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By E. Miller, J. M. Eldridge, K. L. Komarek

The liquidus curve of the Mg-Pb system was accurately redetermined. The compound Mg2Pb decomposes peritectically at 538.2° ± 0.3°C to liquid and to a compound p' which melts congruently at 35.0 at. pct Pb and 549.0° ± 0.3°C. The solidus curve of ß' was determined. X-ray diffraction studies indicate that 4' has an orthorhombic structure. Activity values of magnesium calculated from the phase diagram agree with those published in the literature. EXPERIMENTAL thermodynamic properties of binary metallic systems have to be consistent with values calculated from the phase diagram. In systems forming intermetallic compounds the shape of the liquidus curve near a compound is determined by the thermodynamic properties of the coexisting solid and liquid phases. Hauffe and Wagner' neglected the temperature dependence of the chemical potentials and obtained the potential differences of the components of the liquid alloys, relative to stoichiometric liquid. Their calculations were based on the liquidus curve and on the heat of fusion of the compound, and were only valid near the congruent melting point. Steiner, Miller, and Komarek2 developed equations which account for the temperature dependence and obtained the chemical potentials of liquid Mg-Sn alloys over the entire phase diagram from the liquidus and solidus curves and from enthalpy values with the pure components as the standard states. The Mg-Pb phase diagram has been studied by several investigators whose results have been compiled and critically evaluated by Hansen.3 Although the liquidus curve was poorly defined, the general features of the diagram, i.e., one congruent melting compound, Mg2Pb, of essentially stoichiometric composition, two eutectics, and limited terminal solid solubilities, seemed to be suitable for a similar thermodynamic analysis. A careful redeter-mination of the liquidus by thermal analysis revealed, however, the existence of another compound. The liquidus curve between the two eutectics was precisely delineated and the structure and solidus curve of the new compound were investigated. The revised phase diagram was thermodynamic ally analyzed to evaluate the activity of magnesium in the liquid alloys. EXPERIMENTAL PROCEDURE The magnesium metal (Dominion Magnesium Ltd., Toronto, Canada) had a purity of 99.99+ pct; lead (American Smelting and Refining Co.) contained 99.999 pct Pb. Most experiments were carried out in graphite crucibles. Several experiments were made in high-purity alumina (Triangle R.R., Mor-ganite, Inc.) and in Armco iron crucibles to test the inertness of the graphite crucibles. Chemical analysis of magnesium and detailed description of the procedure for thermal analysis have been given previously. For the determination of the solidus curve of the compounds, specimens of initial composition Mg2Pb were equilibrated in a closed isothermal system with magnesium vapor. The source of the magnesium vapor was an alloy which had a gross composition lying in the 0' + L field at the temperature of equilibration. As equilibrium was approached, the specimens lost magnesium to the two-phase reservoir thereby lowering the activity of magnesium in the specimens until activity and composition equaled that of the ß'/ß' + L boundary. Crucibles (1.9 cm ID by 2.2 cm OD by 4.1 cm high) and tightly fitting lids were machined from a molybdenum rod; small, shallow trays were fashioned from thin (0.005 in.) molybdenum sheet, and all the molybdenum components were degreased in hot carbon tetrachloride and then dried. The pieces were then degassed in vacuum at 950°C for about 6 hr. The two-phase alloy was placed at the bottom of the crucible and small specimens of the Mg2Pb compound, weighed on an analytical balance, were placed in two molybdenum trays above the two-phase alloy. The crucible was closed by forcing its lid on and then inserted in a titanium crucible. This crucible was evacuated, flushed twice with argon, and welded under argon. The specimens were equilibrated for about 1 week in a resistance furnace regulated by a Celectray controller, and the runs were terminated by water quenching. The specimens were again weighed and the equilibrium compositions were calculated on the basis that the weight losses were solely due to a loss of magnesium to the two-phase alloy. The structure of the B' phase was investigated by the Debye-Scherrer X-ray diffraction technique. Selected ingots from thermal-analysis experiments containing about 35 at. pct Pb were re-melted, slowly cooled, and crushed in an argon-filled glovebox until the entire ingot passed through a 50-mesh sieve. The powder was thoroughly

Jan 1, 1965

By R. E. Somers

I. Introduction...........................604 1. Location, Topography, and Climate...............604 2. Scope of Work and Acknowledgments...............606 3. History and Mining......................606 11. General Geology.........................609 1. Introduction...........................609 2. Granite. :..........................610 3. Quartz Porphyry......................... 612 4. Monzonite........................... 614 5. Volcanic Breccia........,................ 618 6. Gravels............................. 619 111. Economic Geology......................... 619 1. Introduction........................... 619 2. Mineralogy........................... 619 3. Occurrence of the Ores...................... 622 4. Oxidation and Downward Enrichment............... 630 5. Rock Alteration........................639 6. Genesis of the Ores........................ 643 I. Introduction 1. Location, Topography, and Climate The Burro Mountains are located in the southwestern part of New Mexico, in Grant county. The group is made up of two distinct mountain masses, known as the Little Burros and the Big Burros, the former lying about 6 miles southwest of Silver City, and the latter about 9 miles farther in the same direction. They are separated by the valley of the Mangas River, a tributary of the Gila, and a stream only in name, except after a heavy downpour of rain. The Little Burros attain an elevation of 6,625 ft. above sea level, and the Big Burros 8,054 ft., with the surrounding country averaging about 6,000 ft. To the south of these mountains stretches the desert plain, while to the north are the more frequent elevations of the mountainous country.

Jan 1, 1916

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By R. Maddin, C. H. Mathewson, W. R. Hibbard

Recent publicationsl.2 establishing the presence of cross-slip in strained metallic single crystals oriented wholly within the area of single slip as predicted from the generalizations of Taylor and Elam3 described these markings as they appeared during the initial stages of the deformation process. At that time, the plane having a common glide direction with the primary slipping plane was reported as the cross-slip plane although the specific direction was not confirmed. Consequently, in continuation of the research, it seemed advisable to investigate the micro-graphic appearance of cross-slip together with the Laue back-reflection X ray analysis and stress-strain data during the later stages of the deformation process. Accordingly, a single crystal of brass (72.75 pct Cu, 0.01 pct Fe, 0.01 pct Pb, 27.23 pct Zn) was polished mechanically and repolished electrolytically after the manner described in the earlier paper.' Three pairs of flat surfaces, parallel to the specimen axis, and (1) perpendicular to the plane containing the pole of the primary glide plane and the specimen axis, (2) perpendicular to the plane containing the pole of the cross-slip plane and the specimen axis, and (3) perpendicular to the plane containing the slip direction and the specimen axis, were polished mechanically and repolished electrolytically, resulting in a final minimum gauge diameter of 0.4864 in. in a gauge length of 3.36 in. The specimen was elongated in tension and load-extension readings were taken following the method described in the initial investigation.' Observed reorientations were obtained from a series of Laue back-reflection photograms at the center and ends of the gauge length and at various positions around the circumference of the specimen. These were interpreted after the manner of A. B. Greninger.4 Cross-slip (Fig 1 and 2) was found with the first appearance of the primary slip clusters and usually joined members of these clusters. In addition, a third set of entirely different markings (Fig 3) could be noted. The displacement of this third set by the primary slip lines was measured as 8300 at. diam (3.04 microns). Since the specimen was carefully observed at high magnifications before any deformation and no markings of any type could be noted, it would appear that this third set was formed during the deformation process prior to the initiation of classical primary slip. Additional extensions produced no unusual change in the appearance of either cross-slip or the third set of markings. The number of lines increased with increasing elongation and appeared, generally, in areas where earlier markings were present. The continuity of the clusters of cross-slip lines in Fig 4, 5 and 6 illustrates that they are neither noticeably displaced by nor do they displace the primary lines at this stage. In Fig 7, cross-slip appears in a long narrow localized band approximately 45 degrees from the stress axis. This somewhat resembles a twin band except for the lack of a sharp boundary. After a shear of 0.257, suffcient additional glide occurred on the cross-slip plane to displace the primary slip lines (Fig 8). Generally, where a large number of cross-slip lines could be observed in an area on one flat surface, few cross-slip lines appeared on the diametrically opposite position on the parallel flat (Fig 9). These, of course, were not matched observations on the same glide ellipses. It was extremely difficult to make such comparisons. The third set of markings (Fig 10) was extensively displaced by glide on the primary slip planes. A plot of the width of primary slip clusters versus their displacement of the third set of lines is shown in Fig 11. The slope and the linearity of the plot suggest that each primary glide plane slips to a constant maximum value of shear before further slip is transferred to another plane. A shear value of 0.28 was determined in this case. Heidenreich5 has presented a similar schematic representation of glide for aluminum. After the specimen had attained an elongation of 51.8 pct, corresponding to a shear of 0.973, cross-slip appeared very prominently in certain areas as shown in Fig 12, yet at diametrically opposite positions very little cross-slip could be noted, Fig 13. Classical conjugate slip was found at this advanced stage in the deformation, Fig 14, which corresponds to the axial location shown at 12 in Fig 15. It should be noted that cross-slip occurs within the conjugate slip clusters and on the same plane as the cross-slip associated with the closely spaced primary lines which constitute a background in less distinct focus. The third set of markings noted at all stages in the deformation of the

Jan 1, 1950

By AIME AIME

TWO technical sessions, an excursion through the Midwest refinery and a smoker, marked the first day of the meeting of the Petroleum Division at Casper, Wyo., on Aug. 28. Ninety-nine members and guests registered and there was an excellent attendance at 'all functions. The -local committee under the general chairmanship of J. C. Lindsay, general manager of the Western Pipe Line Co., had made every possible arrangement for the convenience and comfort of the visiting members and the Program Committee under E. L. Estabrook, vice-chairman of the Petroleum Division, had brought together a most interesting series of technical, papers. The meeting centered mainly on the various features of the Salt Creek field but there were also contributions from the technology of production in California, the Mid-Continent, and the Texas fields. The opening session was called to order by Mr. Estabrook at the Townsend Hotel on Friday morning. The members and visitors were welcomed appropriately by Ex-Governor B. B. Brooks, president of the "Rocky Mountain Oil and Gas Association, who recalled the changes that had taken place as Casper, a frontier cow town, became a thriving oil metropolis. F. Julius Fobs, chairman 'of the Petroleum Division, responded and then took the chair. He introduced H. Foster Bain, Secretary of the Institute, who expressed the regret of those members members who found it impossible to stop over en route to Salt Lake City and his own pleasure at meeting with the Division in the field. Following these introductory ceremonies the technical session began with a "Sketch of the Geological Formations of Central Wyoming," presented by J. G. Bartram of the Midwest staff. It was brief and to the point and contributed greatly to the easy under¬standing of the succeeding papers by those unfamiliar with the region. The talk was illustrated by a large scale columnar section -and a copy of the excellent, geological map of the State recently issued by the U. S. Geological Survey.

Jan 1, 1925

By E. P. Abrahamson, S. L. Lopata

A general relalionship between the amount of glide shear (due to slip) and the macroscopic shape change has been developed. Since the deformation can be large, finite strain analysis is employed. In this treatnzent, the shape change is expressed by a deforlnation gradient matrix, F - [axi/aXj/ where X and x refer lo the initial and final positions of a particle. This matrix is readily evaluated in termas of the amounl of glide shear, a , and the direction cosines of the slip-plane normal and the slip direction for a single active slip systena. In the case of deforma tion from slip on several systems, the product F(a) of the several deformation gradient matrices is first calculated. Then, by assuming that the final configuration is reached by a long series of small shears of magnitude a, occurring more or less alternately in the several slip sys- IN problems of crystal plasticity, it is often necessary to relate the amount of glide in the operating slip systems to the macroscopic strain components. This relationship is relatively simple when only small strains are considered. In this case the separate strain contributions from several slip systems are additive. Such a procedure is incorrect in the case of large plastic deformation. To the authors' knowledge, no general treatment of the latter problem has appeared in the literature. In specific instances, Mark, Polanyi, and schmid3 have derived the relationship between glide and axial elongation during tensile pulling of a single crystal when only one slip system is active. A similar relationship for duplex slip was worked out by v. Göler and Sachs.4 Taylor and Elam1 have also studied in detail problems of large plastic deformation. Due to uncertainties as to the slip systems at the time, ! terns, the final deformation gradient matrix can be obtained. Mathematically, the problem is reduced to finding the limit of F(aN as N — m while a — 0 in such a way that the Product Na = a finite conslant designatzng the accumulated amount of shear. It turns out that this limit is simply eafF1, where F, is the matrix whose elements are the coefficients of a in the F(a) twatrzx. Application is made of the present treatment to a fcc crystal of Permalloy compressed on the (110) plane and contrained to elongate in the [112] directzon. In addition, it is shown that one rnay readily obtain from the general analyszs the well-known formulas relating elongation, amount of glide shear, and amount of lattice rotation for crystals deforming by single and double slip under tension. however, they were mainly concerned with proving that slip occurs on {111}(110) systems in fcc metals. The present general treatment arose out of recent investigations of magnetic anisotropy in cold-worked Fe-Ni alloys6 as well as some related problems in strength anisotropy of single crystals.' Detailed application of the general analysis will be provided in the case of a Permalloy single crystal compressed on the (110) plane and constrained to elongate only in the [112] direction. It will be seen that, as expected, the small strain approximation leads to significant errors after moderate straining. It will also be shown that the present general treatment yields the formulas of Mark et al. and of v. Goler and Sachs in those specific cases. GENERAL CONSIDERATIONS Consider a homogeneous deformation in which a material point initially at moves to (xl,xz,x3), both positions being referred to the same set of Cartesian axes. Such a deformation can be

Jan 1, 1967

By A. W. Bethune, L. M. Pidgeon

The equilibrium vapor pressure of zinc has been determined over the systems: ZnS(s) + Fe(s) = FeS(s) + Zn (vapor) and ZnS(s) + 2Cu(s) = Cu2S(s) + Zn (vapor) by reacting the components in an evacuated tube containing a thin copper fiber, and allowing equilibrium to be established with respect to the brass formed and the zinc in the vapor phase. The composition of the brass formed was determined and equilibrium vapor pressure values obtained from existing data. Between 850' and 1000°C, values for the first reaction ranged from 8 to 58 mm Hg; for the second reaction from 1.8 to 22 mm Hg. THE direct reduction of metallic sulphides may be indicated by an equation of the form MS + X = XS + M [1] where X is some suitable reducing agent. In the case where M is a metal of relatively high volatility, the use of vacuum will displace the equilibrium to the right at comparatively low temperatures in the face of the usually unfavorable thermochemistry. For this technique to be feasible, MS, X, and XS, must of course be nonvolatile compared to M. In this regard, zinc becomes an obvious metal both from the point of view of its volatility and the fact that most commercial ore deposits of this metal occur as the sulphide, and its direct reduction would avoid the expensive roasting process necessary prior to present day reduction methods. Two reducing agents are of interest, namely copper and iron, with the former having the added attraction of being relatively easily regenerated by oxidation in the copper converter. The possibility of these reactions has been considered before. Imbert1 patented a process whereby zinc sulphide was reduced by either copper or iron. The process as described took place at atmospheric pressure and, at the high temperatures required, the system was molten, resulting in the formation of a matte with the consequent reduction in the activities of the reactants. Peterson2 did further experimental work on these reactions and, although promising results were obtained on a small scale, attempts to increase the size of the furnace led to excessive "blue powder" formation. The early workers failed to realize the large reduction in temperature afforded by the use of vacuum and its desirable results. More recently, the direct reduction of zinc sulphide by iron has been the subject of a thermody-namic investigation by Kelley,3 and Gross and War-rington' have studied the kinetics of the reaction in the temperature range 900" to 1000°C, their experiments being conducted using vacuum and indicating that the reaction would proceed practically to completion in 1 to 3 hr, depending on the temperature. A qualitative examination of the system ZnS-Cu carried out at this University indicated that 98 pct of the theoretical zinc in the charge could be recovered in 1 hr at 1000°C when operating under reduced pressure. The purpose of this research program was to study the equilibrium of the two reactions. During the investigation, reference to the experimental work of Schenk5 was found but, due to lack of detail in the report, it was felt that it would be desirable to continue the equilibrium measurements. Selection of Method The measurement of vapor pressure of metals presents obvious problems resulting from the high temperatures which must be employed. In the present case, the production of the "reaction pressure" introduces a further difficulty since a chemical reaction must proceed before any metal vapor pressure is produced, resulting in depletion of the re-

Jan 1, 1954

By Walter R. Hibbard, Harold Margolin

The effect of ten ternary additions on the aging of a Cu-Ag alloy was measured by X ray, microstructure and hardness. A supersaturated copper-rich transition structure was found. The effect of the ternary element was related to differences between transition and precipitate lattice parameters and analogies with solution and strain hardening. IN addition to the prerequisite of diminishing solid solubility with falling temperature, the theory of coherency hardening1 proposes that the principal source of hardening during precipitation is strain caused by coherency between the matrix and precipitate. For a given system greater coherency hardening would result from lengthening the period of coherent growth and/or increasing the number of nuclei, other things remaining equal. However, the hardness change during aging is a function of a number of phenomena in addition to coherency hardening, such as dispersion hardening, loss of coherency, solute depletion, matrix recovery or recrystal-lization, coalescence, and their relative time sequences. The present investigation was undertaken to study the effect of ternary additions on the age-hardening of Cu-Ag alloy. For this purpose a series of alloys were made containing as ternary constituents Mg, Al, Si, P, Mn, Ni, Zn, As, In, and Sb. These elements were added to a master 5 wt pct Ag in Cu alloy in such amounts as to obtain alloys listed in Table II containing the following approximate atomic percentages: 96 pct Cu, 3 pct Ag, 1 pct ternary addition. A 97 atomic pct Cu, 3 atomic pct Ag alloy was used as a comparison standard. There have been numerous investigations of age-hardening in Cu-Ag alloys2-lo but few of ternary Cu-Ag alloys. Pfister and Weist" found that 1 wt pct Ni reduced the solubility of Ag in Cu above 600 °C and that the rate of precipitation was slower than in polycrystalline Cu-Ag alloys of similar silver content. More recently Hodge, Jaffee, Dunleavy, and Ogden12 investigated the effect of ternary additions of Mg, Li, P, Cd, Zn, Zr and Be on strength properties of Cu-Ag alloys. Mg, Cd, and P were found to increase strength in the aged and cold-worked condition. Experimental Procedure Charges weighing 7.5 lb were melted in a closed carbon crucible under a reducing atmosphere* of nitrogen and hydrogen. A Durville-type casting procedure with a hot-top arrangement was used to obtain a sound casting, 2x2x43/4 in. Prior to rolling and annealing of the ingots, a trial solution anneal of rolled sections of the hot-top portions indicated that at 780°C melting was avoided except for the Cu-Ag-Sb alloy. This alloy could not be produced as a single phase within the limits of temperature control. i 3" to 5oC, since melting occurred at 64O °C, and below this temperature precipitation was

Jan 1, 1952

By H. E. Mills

THE local auditorium of a little Alabama mining town was crowded with expectant men, women and children, as the bulletin board had announced the addition of visiting entertainers to supplement the local talent and motion pictures which usually made up the program of the regular monthly safety meeting. In the audience, near the stage, sat a group of bright-faced boys in boy scout uniforms, discussing the picture just completed. As the lights flashed on a crash and scream was heard from the outside, a shrill whistle and word of command from the scoutmaster, and five of the scouts ran out of the hall, while the mine super-intendent stepped on the stage and requested everyone to keep their seats. The scouts returned, three of them carrying a limp figure in their arms, while the other two cleared the doorway and aisle of excited spectators. They marched to the stage and, placing the apparently badly-injured boy on the floor, proceeded to give an expert demonstration of first aid to the injured. The scoutmaster then explained to the audience that the whole affair had been arranged for their benefit, and invited the local first-aid men to come up on the stage to examine and criticize the boys' work. This gave an opening for several talks on the value of first-aid training and accident prevention, which is the main object of the monthly meetings. This demonstration was given by the first-aid team of Troop One, and the entertainment was provided by members of Troop One and Twenty-eight of the Bir-mingham Scout Council, organized by the writer for the purpose of promoting interest in the welfare and safety meetings in the mining villages of the State. During the past year they have visited a number of such meet-ings and presented programs similar to the one men-tioned above. However, in order to assure a good attendance, entertainment features must also be pro-vided, and the serious part of the evening program was interspersed with excellent vocal and instrumental mu-sic, dancing and novelty acrobatic acts furnished by the visiting scouts. In addition to the numerous first-aid teams of the Birmingham Council, there are hundreds of scouts scat-tered throughout the mining district whose knowledge of first aid, safety first, life-saving, personal health and public health are a constant source of protection to their community. All of these subjects are covered by merit badge pamphlets and are required of an eagle scout.

Jan 2, 1927

G. D. Kneip, Jr., and J. 0. Betterton, Jr. (Union Carbide & Carbon Corp., Oak Ridge, Tenn.)—The authors have contributed to the theory of zone melting by considering the effects of the solidification of the final zone on the distribution curves for the finite length bar. However, they do not consider in sufficient detail the restrictions imposed by the particular metals involved. Eq. 4 has the analytical solution which is equivalent to Pfann's' equation for normal solidification of the final zone. For distribution coefficients less than one, it is apparent from this form of the equation that, as the solidification approaches completion, the concentration attains extremely large values which are inconsistent with the density of physical materials. The necessary restrictions then are that the solute concentration cannot exceed the density of the alloy, or more frequently, the solubility limit in the solid phase. Secondly, the distribution coefficient cannot be constant from 0 to 100 pet solute unless the liquidus and solidus coincide over this whole region. It would thus be more correct to impose limits on the solubility such as would be indicated by a typical eutectic diagram. Furthermore, in this case the assumption that the distribution coefficient remains constant is more likely to be realized. Eq. 4 should then be replaced by the following C,,(x) =k/L-x [ ?11 3 C11 (x)Ddx - ?11 4 Cn(x)dx= k[Cn (L-l)/k] [ L-x/l]x-1 L-l = x = L-l [kCenterlie/Cn (L-l)]1/k-1 The typical shape for the distribution curve in the final zone is indicated schematically in Fig. 12 for the simple eutectic case. The solidification proceeds according to Pfann's' expression until the concentration reaches the maximum solubility in the solid phasc. At this point, the concentration changes abruptly to the eutectic composition and remains at this value for the duration of the solidification. The width of the flat region, and the back reflection of this effect into the concentration curve on subsequent passes, depends upon the ratio of the eutectic concentration to the original concentration, upon the distribution coefficient, and upon the number of passes. Similar effects on the concentration curves in the first zone length would be expected in many systems for which the distribution coefficient is greater than one, and where the maximum solubility is not too much larger than the original concentration. The discussers agree with the authors that the assumption that the liquid is uniform in concentration should be considered with caution. Kneip and Better-ton' have shown, however, that in floating zone refining of zirconium, using induction heating, the distribution of iron agrees with theory which assumes a uniform liquid composition. Hence, in this case, the experimentally realized distribution coefficient agrees with the present phase diagram within the experimental uncertainty. L. Burris, Jr., C. H. Stockman, and I. G. Dillon (authors' reply)—The authors are happy to have received the comments of G. D. Kneip, Jr., and J. 0. Betterton, Jr., which provide additional insight into the zone refining process. It is true that the equations developed are inapplicable if the solute solubility in the solid phase is exceeded. However, this restriction on the use of the equations was clearly stated in the paper. A closer approach to

Jan 1, 1957

By W. P. Sykes

SINCE Honda and Murakami1 in 1918 proposed their constitutional diagram of the carbon-free iron-tungsten system, considerable effort has been expended by several investigators in attempts to define more positively the structural features of the alloys. The existence of an intermediate phase corresponding to the formula Fe3W2 (68.7 per cent W) was proposed from evidence of a purely metallographic nature by one of the present authors2 in 1926. Since that time the identity of this phase has been confirmed by Arnfelt3 and by Takeda,4 both of whom employed X-ray methods as well as the microscope and the chemical analysis of isolated microconstituents. According to Arnfelt, Fe3W2, as crystallized from the iron-rich melts at a temperature above 1450'C., contains by analysis 68.7 per cent W. The lattice of this phase is characterized by trigonal symmetry. Arnfelt, moreover, proposed a second intermediate phase formed at some temperature between 1450° and 1000° C. by a peritectoid reaction involving Fe3W2 and the iron-rich solid solution. A melt containing 25 per cent W was cooled to 1000° C. and heated for. 100 hr. The precipitated tungsten-rich constituent was separated and found by analysis to contain 62.6 per cent W. This composition agrees closely with that represented by the formula Fe2W (62.2 per cent W). Diffraction patterns from the concentrated precipitate showed a hexagonal unit cell. Takeda confirmed the data of Arnfelt regarding Fe3W2 but was unable to detect Arnfelt's second intermediate phase. While Takeda. failed to describe in detail the treatments employed, he stated that in alloys containing 40 per cent W which were quenched after heating at various temperatures between 1200° and 1450° C., no evidence of the second phase (Fe2W) was observed either in the microstructure or in the diffraction patterns of isolated residues. He therefore considered the existence of this low-temperature hexagonal compound as disproved.

Jan 1, 1932

By T. C. Campbell

Copper is extracted from the Chuquicamata oxide ore by a hydro-metallurgical process. The ore is crushed to 3/8-in. sizing, and leached with a sulfuric acid electrolyte. Chlorine is precipitated. and the ferric iron reduced in the enriched electrolyte, after which the copper is recovered by electrolysis with insoluble Chilex and lead-antimony anodes, the spent electrolyte being returned to leaching. Cathodes are melted and refined in market furnaces and cast into commercial wire-bar and cake shapes. Sulfuric acid for the process is supplied by the brochantite in the ore. Water for washing the ore is advanced through the solution system and finally after cutting by electrolysis to from 6 to 16.0 grams per liter is completely stripped by the cuprous chloride method and run to waste. The cuprous chloride so obtained plus that resulting from precipitation of chlorine from strong solution is dissolved in ferrous chloride brine and the copper cemented on scrap iron. The cement so obtained is in part used to reduce ferric iron in electrolyte, and as it is of exceptional purity is also furnace refined and cast into an exceptional quality of fire-refined copper. Fig. 1 is flow sheet of the operation. The reduction plant is composed of seven divisions as follows: (1) crushing, (2) leaching, (3) tailings disposal, (4) dechloridizing, (5) sulfur dioxide treatment, (6) electrolytic tank house, (7) smelting and melting. A brief description of each of these divisions will be given. Crushing Ore that is frequently blocky and up to 5 ft. in section is crushed in four stages to 3/8-in. mesh. The first stage of crushing is called primary and the next three stages are known as secondary crushing. The first stage is accomplished with two 60-in. Superior McCully gyratory breakers by which the ore is broken to 9 in. The second coarse gyratory breakers crush the ore to 3-in. sizing. There are seven No. 10 McCully gyratories in this service, for one of which recently has been substituted a No. 7 cone crusher. The third and fourth stages of crushing are accomplished by fifty 48-in. disk crushers. In the third stage 14 disk crushers break the ore to 1 in., and in the last stage 36 disk crushers turn out the final product of 0.371-in. sizing. Reference to the flow sheets of Figs. 2 and 3

Jan 1, 1934

By R. P. Carreker, J. C. Fisher

Cheep tests are normally constant load tests. Such tests approximate some types of service conditions and therefore are justified from the engineering point of view. Coupled with this consideration is the advantage of simplicity inherent in constant load tests, as contrasted with the comparatively complex requirements of a constant stress test. It is not surprising that the vast majority of creep tests reported are of the constant load type. Despite the enormous amount of accumulated creep test data, plastic flow is by no means completely understood. The widespread use of constant load tests is at least partly responsible for this lack of understanding. Any attempt to analyze deformation must involve the more fundamental quantity stress, rather than load. It is possible to predict constant load behavior from known constant stress data, but the reverse is much more difficult. When a metal specimen elongates, as in a creep test, the cross section decreases, maintaining constant volume. Thus For a constant stress test the force on the specimen must be decreased as the cross section decreases, that is, this force must be inversely proportional to the elongation of the specimen. An-drade has described three methods of obtaining the constant stress condition,l-3 each of which is relatively complex. The most recent proposal,³ suggests a major simplification which maintains the simplicity of the constant load test while approximating quite closely the desirable condition of constant stress. Andrade's device is admittedly more accurate but the method described below has definite advantages Consider a specimen in the form of a "V" supported at its ends. If a weight be applied at the vertex of the angle, the stress in each leg of the "V" If this stress causes an elongation ?1 in each leg of the "V," the angle decreases from a. to a smaller angle a1. The quantity sec — thus decreases with specimen elongation while the quantity 1/A increases. By selecting proper initial conditions it should be possible to hold S/So very nearly constant at unity. The proper initial conditions are realized when a0 is made equal to approximately 90°. Fig 1 compares the ratios of S/S0 for a0 = 85, 90, 95, 100°, with a0 = 0, that is, a straight speci- men, for true strains up to e = 0.10. It may prove convenient to measure X, the movement of the vertex, rather than the true elongation 1. Contour lines of X/lo are also plotted in Fig 1. The method for obtaining constant stress described above is especially suited to the testing of small wires, but may easily be extended to rods of any diameter through the use of a suitable grip which serves as the vertex joining two identical rods forming the legs of the "V." References 1. E. N. da C. Andrade: On the Viscous Flow in Metals, and Allied Phenomena. Proc. Roy. Soc., A, 84, 1, (1910-11). 2. E. N. da C. Andrade and B. Chalmers: The Resistivity of Polycrystalline Wires in Relation to Plastic Deformation, and the Mechanism of Plastic Flow. Proc. Roy. Soc., A, 138, 348, (1932). 3. E. N. da C. Andrade: A New Device for Maintaining Constant Stress in a Rod Undergoing Plastic Extension. Proc. Phys. Soc., 60, (3). 304, (March, 1948).

Jan 1, 1950

By Everett Carpenter

THE average daily production of crude oil-in Kansas a1 the beginning of the year was about 71,000 1 bbl. and, at its close, 82,000 bbl.-an increase of 11,000 bbl. per day. The total production for the state during the year was about 28,250,000 bbl., or an average of practically 77,500 bbl. per day for the year. This increase in the production was the result of the discovery of several new pools of high-grade oil. COWLEY AND SUMNER COUNTIES One of the principal factors in bringing the production of the. state back to its former level was the newly discovered pools in western Cowley County. During December, 1923, the Waite Phillips Co. completed its Johnson No. 1 in Sec. 20, T. 33 S., R. 3 E., which opened up the Rainbow pool about 12 miles southwest of Winfield. In this pool, the production comes from the Burbank sand, locally called the "Rainbow," found at a depth of 3200 ft. The sand varies in thickness from 25 to 40 ft. in the seventeen wells completed during the year, and the initial productions ranged from 300 to 3000 bbl. per day of 40° Be. oil. The Rainbow pool is purely a wildcat discovery, for no. rocks suitable for the use of the geologist are present. To determine the geologic conditions, the larger companies core-drilled the Rainbow area immediately after the discovery. The Marland Refining, Co., drilling on the Graham farm in Sec. 9, T. 33, R. 3, failed to find the Burbank sand and continued to the Siliceous lime, often erroneously called the Wilcox, at 3505 ft., where a well with an initial production of 900 bbl. of 40 Be. oil was obtained. In the development following this discovery, 4 additional wells were completed, 3 of which encountered pay sand at 2500 ft., the initial productions each being about 200 barrels. Judging by the sands already proved and the area indicated as probably oil bearing by the development to date, these pools have a very promising outlook for the future. It is not unlikely that a field second only to El Dorado may have been opened.

Jan 3, 1925

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954

By Ö. Valla, A. Muan, K. Grjotheim

The solid miscibility gap between CaO and "FeO" in the system CaO-"FeO" in contact with metallic iron gradually closes as MnO is added as a third component. On the liquidus surface of the system CaO-"FeO"-MnO, this situation gives rise to a boundary curve which originates in the bounding system CaO-''FeO", proceeds a short distance into the composition triangle of the ternary system, and then vanishes. A new approach has been used to follow the course of this boundary curve. It is shown that the curve vanishes at a much lower temperature and at much lower MnO contents than has been inferred previously. The oxides CaO, "FeO", and MnO together with SiO2 are the major components of the slag phase formed in the basic oxygen process. Hence, the system CaO-"Fe0"-MnO is of considerable technological interest. In addition, the system is theoretically interesting. The three oxides above all have sodium chloride structure. The size differences among the cations are such that in the bounding "binary"* systems CaO-MnO and "FeO"-MnO complete solid-solution series are formed,1,2 whereas in the system CaO-"FeO" there is only limited mutual solubility in the solid state,3 see Fig. 1. Hence, a solid miscibility gap exists in a part of the "ternary"* system Ca0-"Fe0"-Mn0, and a liquidus boundary curve originates at the peritectic point, point a in the insert in Fig. 1, in the system CaO-"FeO", extends a certain distance into the ternary system, and then vanishes. Very little quantitative information on the system Ca0-"Fe0"-Mn0 is available in previous literature. Fischer and Feischer4 sketched isothermal sections at 1600° and 1700°C, and estimated that the vanishing boundary curve extends to approximately 1650°C and a composition of 42 wt pct MnO. The work to be described in the following was aimed at locating experimentally the "vanishing" liquidus boundary curve, determining its end point, and deriving representative isothermal sections below and above the temperature of the end point of this curve. EXPERIMENTAL METHODS The phase relations were determined by the well-known quenching method. (For a description of this method as applied to oxide systems, see the original paper of Shepherd, Rankin, and wright.5) Prereacted oxide mixtures of desired compositions were contained in iron crucibles and heated in a vertical tube furnace in an atmosphere of purified nitrogen. After equilibrium was judged to have been attained, the samples were quenched to room temperature, the phases present were identified by microscopic and X-ray examination, and total iron oxide contents were determined by chemical analysis. "Fisher Certified" reagents (MnCO3, CaCO3, Fe2O3, and Fe) served as starting materials. The calcium carbonate and ferric oxide were heated in air at 400° and 800°C, respectively, for 24 hr prior to use. Manganese oxide was prepared by decomposing the carbonate in a graphite crucible in hydrogen atmosphere at 1000°C. The product was ground under acetone to -100 mesh. The iron powder was used directly without any preparation. Dicalcium ferrite was used as a starting material for some mixtures. It was made by mixing some of the above prepared CaCO3 and Fe2O3 in proportions corresponding to the formula 2CaO. Fe2O3. This mixture was then fired in air for

Jan 1, 1969

By H. E. Cline

Solidification of Pb-Sn alloys ranging in composition from 1.2 to 56 at. pct Pb ws observed with polarized light. Lamellar structures were observed over a larger range of compositions in alloys containing excess tin than excess lead, as expected from constitutional supercooling. The occurrence of pools of supercooled liquid surrounded by lead is explained by the difficulty in nucleating tin. Cells and dendrites weve observed in tin-rich alloys. Evidence was found that the degenerate structure formed at low growth rates, the formation of faults, and abrupt changes in composition and structure can be attributed to non-steady-state growth. The apparent interface shape was observed to have deep grooves at the interphase boundaries. HUNT and Jackson have observed the shape of the interface during growth of organic eutectics. They observed the formation of lamellar faults and shape instabilities upon changes in growth rate. The lamellar structure in these organic eutectics was not restricted to the eutectic composition. Recent work by Mollard and Flemings2 indicated that Pb-Sn alloys from 12 to 26 at. pct Pb could be solidified with a lamellar or rodlike structure if a sufficiently steep temperature gradient was used at a slow growth rate. Observations of the solid liquid interface of the Pb-Sn eutectic were made by Davies3 using polarized light. Photographs were at too low a magnification to determine the interface shape, but he has concluded that tin was the leading phase. In the following experiments, solidification of a range of Pb-Sn alloys from 1.2 to 56 at. pct Pb was observed using polarized light, to determine the factors controlling stability of the lamellar structure. EXPERIMENTAL Procedure. One hundred-gram ingots of alloys prepared from 99.999 pct pure Pb and Sn were cast into graphite molds under argon. The compositions of the alloys were 1.2, 6, 12, 26, 36, 46, and 56 at. pct Pb. Two-gram pieces were melted between two cover glass slides which were squeezed into a 1-mm separation. Samples were then observed under polarized light in a hot stage shown in Fig. 1. A long working distance objective designed for viewing at 500 times was used. Photography was made difficult by the lack of illumination and contrast at these high magnifications. By using an elliptical polarization compensator, as suggested by A. Holik, the contrast and illumination could be optimized. Photographs could be taken only at slow growth rates to avoid excessive interface motion during the 15-sec exposure used. The solidification rate was varied by increasing or decreasing the power to the heater. It was found that insulation was necessary to avoid undesired growth rate fluctuations. The temperature gradient, as measured with two thermocouples 1 cm apart, was 80" ± 20°C per cm during all the experiments reported here. The advantage of this procedure is in being able to observe solidification while it is occurring. However, the observations are restricted to the glass-metal surface and may be influenced by this surface. Also, one has no knowledge of the interior of the sample, in contrast to studies of the freezing of transparent organic eutectics.' Observations. The alloy near the eutectic composition (26 at. pct Pb) solidified in a lamellar structure when the growth rate was uniform. If the growth

Jan 1, 1968

CORPORAL SHEPPARD B. GORDY Sheppard B. Gordy, a brief biography of whom was printed inn the January Bulletin, entered the employ of the Braden Copper Co. immediately on his graduation from the Sheffield Scientific School in 1912. He remained with this company four years, working up through the various grades to assistant foreman and foreman to one of the individual mines. The last year he was in its employ, he acted as general mine foreman. He was for a short time with the Chile Exploration Co. and then went with the Andes Exploration Co. (Anaconda) and remained with CORPORAL SHEPPARD B. GORDY. the latter, doing mine exploration and development work, until he sailed for home in June, 1918, to give a more personal and active service to his country in her need. He declined a tender of induction into an officers' training camp, at the urgent request of Professor McClelland supplemented by Mr. Potter, because they demonstrated to his satisfaction that he could give more valuable service to his country in helping out with the aircraft production. Being within the draft age, in order to carry out this plan, it was necessary for him to be called by his Local Board and sent to camp. This call came Aug. 26. Two weeks before that time lie had gone to Dayton, Ohio; to begin the study of aircraft production, and was sent by the Dayton Board to Camp Sherman, Chillicothe, Ohio, where he died of pneumonia on Oct. 9.

Jan 3, 1919

Discussion of "The Ordering Transformation in Titanium-Aluminum Alloys Containing up to 25 at. pct Aluminum" by F. A. Crossley, Trans, TMS-AIME, 1968, vol. 242, pp. 726-30. Dr. Blackburn, in his response, pointed out that the c/a ratio of the Ti-26 at. pct A1 alloy quenched from 900°C is 1.6006 and not 1.5965 as plotted in Fig. 19. An error in transcription was made in preparing Table V of Ref. 1 (F. A. Crossley, Trans. TMS-AIME, 1966, vol. 236, p. 1174). The corrected Fig. 19 strengthens rather than weakens the argument that a martensitic transformation occurs in alloys containing from 15 to 18 at. pct Al. A Study of the Factors Which Influence the Rate Minimum Phenomenon During Magnetite Reduction, by P. K. Strangway and H. U. Ross, Trans. TMS-AIME, 1968, vol. 242, pp. 1981-88. Page 1883 Reverse Figs. 5 and 6. Sigma—Its Occurrence, Effect, and Control in Nickel-Base Superalloys, by J. R. Mihalisin, C. G. Bieber, and R. T. Grant, Trans. TMS-AIME, 1968, vol. 242, pp. 2399-2414. Pages 2403, 2407, and 2414 Arrows should appear on Figs. 4 and 9; a sigma is missing from Table IV; line 2, page 2414, change "case" to "cast". These are published correctly in the bound volume. Index, December Issue There were a few omissions in the Author Index. These have been corrected and published properly in the bound volume.

Jan 1, 1970

By B. L. Averbach, E. E. Underwood

The vapor pressure of zinc in equilibrium with solid ß AgZn alloys has been measured by the dew-point method. The thermodynamic activities of silver, and the molar heats of formation have been calculated. Similar measurements have been made for the ternary alloys formed by adding gold to AgZn. An apparent particle size effect has been observed for AgZn filings. The vapor pressure of zinc over filings is 15 to 20 pct higher than over the solid alloys. STATISTICAL methods have been used to inter pret the thermodynamic activities of the components of a solid solution in terms of average equilibrium atomic configurations. In some cases, the atomic arrangements can be measured by X-ray methods, and the results are usually expressed in terms of short range order parameters. Only in the cases of Cu³Au and AgAu have there been sufficient X-ray and thermodynamic data to verify the assumed correlation between the X-ray and the thermodynamic measurements. In Cu³Au the agreement is good; negative deviations from Raoult's law are observed and the number of Cu-Au nearest neighbor pairs predicted on the basis of the thermodynamic treatments agrees quite well with the number of such pairs observed by the X-ray methods. The ß brass alloys present a different set of conditions. The ordering is so rapid in these alloys that the disordered state cannot be retained on quenching. In contrast, the disordered state in CuAu is easily retained on quenching. On heating, the ordered ß brass loses its long range order continuously as the critical temperature is approached; in Cuau the order decreases slightly on heating and then drops discontinuously to zero at the critical temperature. These differences indicate that the short range order configurations in ß brass systems may be of a different character than in Cudu systems. However, X-ray measurements of local order cannot be made in the Cu-Zn alloys because of the similarity in scattering factors. The alloy AgZn is isomorphous with CuZn, however, and recent experiments have indicated that there is a good possibility of observing short range order in this system. Another complication arises in the case of ß AgZn. The disordered body-centered cubic structure exists above 280°C. On quenching from above this temperature an ordered structure of the cesium-chloride type is formed. On slow cooling, however, a complex hexagonal structure, the 3 phase, is produced; and if an ordered quenched alloy is reheated the phase begins to form above 80°C. It is thus difficult to study local order by X-ray methods in single crystals of AgZn since the C phase formed on heating does not necessarily return to a single crystal of the original orientation. This problem has been met, however, by adding a few percent of gold to the AgZn. The gold suppresses the formation of the c

Jan 1, 1952