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By G. R. Leverant, C. P. Sullivan

To evaluate the effect of a dispersion of nondeform-able, incoherent, second-phase particles on high-strain cyclic deformation and fracture, recrystallized TD-nickel (Ni-2ThO2) and a commercially pure nickel, Ni-200, were fatigued under strain control at total strain ranges varying from 0.009 to 0.036. Relative to the Ni-200, the slip at the surface of the TD-nickel was more wavy and discontinuous due to the presence of the thoria particles. This made crevice formation (incipient cracking) within slip bands more difficult in TD-nickel than in Ni-200. Both materials cyclically hardened to a constant (saturation) flow stress which increased with increasing plastic strain amplitude. Cellular substructures were developed in both materials during cycling. The cell size in TD-nickel was controlled by the thoria particle distribution and was independent of plastic strain amplitude over the range investigated. The cell size in Ni-ZOO was larger than that in TD-nickel at similar plastic strain amplitudes and was a function of plastic strain amplitude. These results, together with the cyclic stress-strain curves for both materials, are discussed in terms of a model for fatigue strain accommodation at saturation recently proposed by Feltner and Laird. NUMEROUS fatigue investigations have considered the interrelation of slip character, dislocation substructure, and cracking in pure metals and solid-solution alloys. However, except for the studies of the low-strain fatigue of internally oxidized copper alloys1 and cast, dispersion-strengthened lead,&apos; little is known about the effects which small, incoherent, nondeform-able, second-phase particles have on cyclic deformation and cracking processes. Effects due to the particles alone are often obscured by a dislocation substructure introduced during thermomechanical processing of dispersion-strengthened metals. In the present study, recrystallized TD-nickel and a commercially pure nickel, Ni-200, were employed to evaluate the effect of a thoria dispersion on high-strai fatigue deformation and cracking at room temperature. I) MATERIAL AND EXPERIMENTAL PROCEDURE The TD-nickel was supplied by DuPont as a 5/8-in.-thick stress-relieved plate which had been subjected to a proprietary schedule of thermomechanical treatments, and the Ni-200 as 3/4-in. bar which was subsequently annealed for 2 hr at 850°C in argon resulting in an average grain diameter of 0.05 mm. The compositions of these materials are given in Table I. The microstructure of the TD-nickel consisted of elongated grains parallel to the primary working direction with an average width of 0.16 mm, Fig. l(a). Many fine annealing twins were present indicating that the starting material was in a recrystallized condition; this supposition was confirmed by the absence of of any extensive dislocation substructure, Fig. l(b). Sheetlike stringers parallel to the rolling direction were occasionally seen both within grains and at grain boundaries. Some approximately spherical particles about 2 in diam, which may correspond to exceptionally large thoria particle aggregates, were also present. The average Young&apos;s modulus of the plate material in the rolling direction was 21.8 X 106 psi which is consistent with a {100}<001>recrystalliza-tion texture3&apos;* being prominent. In transmission microscopy, the 2.3 vol pct of thoria particles generally appeared to be uniformly distributed although some clusters, 0.1 to 0.3 in diam, of larger particles were observed as previously reported for TD-nickel sheet,5 and stringering of particles was present in some areas as welt. The average diameter of the thoria particles was 450A with a calculated mean planar center-to-center spacing of 2100A, as determined by quantitative metallographic analysis.= The 0.2 pct offset yield stress was 36,000 psi which agrees with the value predicted by the modified Orowan relation7 for edge dislocations bowing between thoria particles of the size and spacing observed in the present investigation. Fig. 2 illustrates the specimen design employed for the axial high-strain fatigue testing. Adapters were screwed onto the threaded portions of each specimen so that testing could be performed in the same manner as that reported for buttonhead specimens.8 Stressing was coincident with the working direction for both materials. The gage section of each specimen was electropolished and lightly etched prior to testing. The total strain was controlled, being varied between zero and a maximum tensile strain ranging from 0.009 to 0.036. In addition to these tests, a circum-ferentially notched TD-nickel specimen was cycled over a total strain range of 0.0075. The same strain

Jan 1, 1969

By C. A. Heiland

WITH seventeen papers submitted. and thirteen presented in three sessions, the geophysicists had a most successful meeting at New York in February. The first paper on Monday morning dealt with the location of a diabase dike near Chapel Hill, N. C., by magnetic and resistivity methods. The magnetic indications were pronounced directly over the dike. whereas the anomalies of apparent resistivity were less distinct and displaced away from the dike. In the second paper, Professor Keys reported on the results obtained with four different methods of depth calculation on known portions of the Falconbridge

Jan 1, 1937

(Members are urged to send in for this column any notes of interest concerning themselves or their fellow-members) The following is a partial list of members and guests who called at Institute headquarters during the period May 10,1917, to June 10, 1917. F. J. Anderson, Cali, Colombia. W. F. Jahn, Kirkland Lake, Ont., Canada. George J. Bancroft, Denver, Colo. W. McA. Johnson, Hartford, Conn. W. F. B. Berger, Denver, Colo. J. E. Jopling, Marquette, Mich. F. J. Brulé, Toronto, Ont., Canada. William Kelley, Vulcan, Mich. J. Murray Clark, Toronto, Ont., Canada. H. M. LaFollette, La Follette, Tenn. Will L. Clark, Jerome, Ariz.. Dorsey A. Lyon, Washington, D. C. G. H. Clevenger, Palo Alto, Cal. James F. Magee, Lancaster, Pa. Paul S. Couldrey, Sound Beach, Conn. M. Ortin, Nijni-Novgorod, Russia. C. W. Crispell, Kingston, N. Y. - C. H. Palmer, Jr., Los Angeles, Cal. George A. Easley, La Paz, Bolivia. Edison S. Pettis, ?Mill Valley, Cal. Bancroft Gore, Butte, Mont. Mortimer A. Sears, Paintsville, Ky. John B. Guernsey, Roanoke, Va. W. J. Uren, Houghton, Mich. Rush M. Hess, St. Louis, Mo. C. E. Visel, New Haven, Conn. E. Hibbert, Nickelton, Ont., Canada. Percy E. Barbour, has resigned his position as managing editor of the Engineering & Mining Journal, to accept the appointment of Deputy Superintendent of the New York State Troopers, with headquarters at Albany, N. Y., with the rank of captain.. He has also been commissioned as captain in the 22nd Regiment, N: Y. N. G., having been formerly 1st Lieutenant.

Jan 7, 1917

The following is an incomplete list of members and guests who called at Institute headquarters during the period Jan. 10, 1918 to Feb. 10, 1918: K. Baumgarten, San Diego, Cal. J. A. Meyerovitch, Petrograd, Russia. F. J. Brine, Toronto, Ont., Canada. C. Naramore, Washington, D. C. W. A. Castleton, Salt Lake City, Utah. Orrin P. Peterson, Wausau, Wis. J. Ross Corbin, Boyerton, Pa. William H. Rea, Pittsburgh, Pa. W. M. Corse, Buffalo, N. Y. W. Murray Sanders, Tucson, Ariz. W. A. Deane, Summitville, N. Y. Edmund F. Saxton, Philadelphia, Pa. S. E. Doak, Philadelphia, Pa. William C. Schmidt, Humboldt, Ariz. F. G. Downs, Jersey City, N. J. G. J. Sielaff, Oakland, Cal. Albert H. Fay, Washington, D. C. A. D. Sproat, Bound Brook, N. J. F. Julius Fohs, Tulsa, Okla. J. A. Stader, Joplin, Mo. A. L. Gholz, Minneapolis, Minn. A. K. Stewart, Mine La Motte, Mo. Ruger W. Hay, Easton, Pa. Geo. W. Tower, Jr., New Rochelle, N. Y. Stanley C. Herold, Pittsburgh, Pa. Henry Traphagen, Toledo, Ohio. A. A. Holland, Montreal, Canada. H. E. Treichler, Chuquicamata, Chile. T. Z. Humphrey, Anaconda, Mont. Paul M. Tyler, Fairlee, Vt. H. M. LaFollette, LaFollette, Tenn. F. R. Van Campen; Seattle, Wash. J. B. Lain, Goldfield, Nev. Thor Warner, Phoenix, Ariz. J. R. Lashbrooke, Los Angeles, Cal. Clarence Woods, Narrows, Va. W. F. Lewis, Ewen, Mich. E. N. Zern, Pittsburgh, Pa. C. E. McQuigg, New Haven, Conn. Robert J. Anderson has resigned his position as chief chemist and metallurgist of the Cleveland Metal Products Co., Cleveland, Ohio.

Jan 3, 1918

Herbert A. MegRaw, San Luis de la Paz, Guanajuato, Mexico (communication to the Secretary *):—I am in entire accord with the basis of Mr. Lamb&apos;s argument, that the stamp

Jan 1, 1911

By Anthony Anable

HOOVER DAM, rapidly nearing completion in the Black Canyon of the Colorado River at Boulder City, Nev., taxes the superlatives of the vocabulary to describe. For by all odds, it is the largest construction project of its type ever essayed by man and the plants providing the essential materials of construction are also in a class by themselves not only in size but in advanced design, mechanization, and accurate control. Picture, if you will, the great aggregate plant, as it is called, situated about 4 mi. upstream from the site of

Jan 1, 1934

By Frederick Beckett

WIDESPREAD experimentation has been conducted in recent years to devise a means of preventing intergranular corrosion in austenitic chromium-nickel steels of the 18 per cent chromium-8 per cent nickel type. Additions of titanium to these steels have been used commercially to overcome this difficulty, as advocated by Krupp of Germany, and the latest literature reference concerning improved details of this method is the article by Bain, Aborn and Rutherford.1 Extensive work by the present authors has shown columbium also to be a particularly valuable agent for inhibiting intergranular corrosion. This paper does not deal with steels that are largely or wholly aus-tenitic ; it is limited to a discussion of the results obtained through the use of titanium and columbium in plain high-chromium steels. For many years titanium has been used commercially by some steelmakers as a cleanser, and to a lesser extent as a hardener, but then in greater per-centages. The results of the work to be described disclose that titanium and columbium in proper proportions act as effective softeners in the high-chromium steels. It is well known that chromium intensifies the hardening effect of carbon in steel; it imparts pronounced air-hardening properties within a rather wide range of chromium content; it provides increased ductility in steels of given strength and hardness; and it enhances resistance to corrosion and oxidation at elevated temperatures to a marked degree. However, in applications requiring a combination of some of these valu-able properties great hardness is frequently a detriment rather than a merit. When the objective is a soft and ductile steel having optimum corrosion resistance, the producer strives for a carbon content as low as commercially practicable.

Jan 1, 1933

By J. W. Pugh, J. D. Nisbet

F. B. Foley—The use of data published by Wever and Jellinghaus in 1931 to fix boundaries of the sigma phase in the Fe-Cr system, in the face of the author&apos;s own references to the suggestions of Bradley and Goldschmidt, Aborn and Bain, and Hougardy that the phase is much more extensive, and the very much more accurate work, which weighs heavily in favor of these suggestions, of Cook and Jones, published in 1943 and evidently disregarded by the authors, makes their derived ternary diagram, especially fig. 15 for 400°C, quite inaccurate on the Fe-Cr side and affects the extent of phase boundaries in the most controversial and important part of this ternary system. In commercial Fe-Ni-Cr alloys the occurrence of sigma has been observed time and time again at lower chromium contents than that of the 24 pct Cr, 16 pct Ni, 60 pct Fe alloy which is the lowest permitted by fig. 15 of practically carbonless metal. Newel1 reports sigma in 27 pct Cr-Fe even with some carbon present to be one of the greatest detriments to its extensive application, whereas Pugh and Nisbet set a low limit of 36 pct Cr for sigma in the binary Fe-Cr system. J. J. Heger—The diagrams presented by the authors do not agree with observations made on commercial Fe-Cr and Fe-Cr-Ni alloys, nor do they agree with two recent investigations made on the Fe-Cr and the Fe-Cr-Fe systems. I refer first to the investigation made by Cook and Jones1&apos; on the sigma region of the Fe-Cr system. On the basis of their results which were published in 1943, Cook and Jones established new boundary limits for the sigma and the alpha plus sigma regions. These new limits have been accepted and are incorporated in the Fe-Cr diagram that appears in the 1948 edition of the Metals Handbook. This diagram is shown here as fig. 34. As will be noted, the boundary limits of the alpha plus sigma region in this diagram extend to much lower chromium contents than do those in the diagram presented by the authors in fig. 2. These new limits indicate that sigma phase should form in an Fe-Cr alloy containing 26 pct Cr, and experience with commercial alloys confirms this finding. Indeed, recent studies on a commercial Fe-Cr alloy containing 17 pct Cr have shown sigma phase to be stable in this alloy at 550°C. I recognize that the authors&apos; work did not include studies on the sigma region; however, I believe this is a serious omission because sigma phase may profoundly affect the physical properties of these alloys and should be evaluated in any investigation which attempts to relate physical properties to the equilibrium diagram. The second investigation to which I refer is that made on the Fe-Cr-Ni system by Rees, Burns, and Cook,&apos;&apos; who used pure alloys and employed heating 17 W. P. Rees, B. D. Burns, and A. 3. Cook: Journal Iron and Steel Institute. (July 1949) 162, Part 3. p. 325. times that extend to 200 days. These investigators published their results in July 1949 and from these results constructed isothermal sections at 800" and 650°C. The isothermal section at 650°C is shown here as fig. 35. This diagram indicates sigma phase should form in a pure 18 pct Cr-8 pct Ni alloy. Although sigma phase has not been observed after 10,000 hr at 1200°F in commercial 18-8 alloys containing carbon and nitrogen, it has been observed under the same conditions in 18-8 alloys modified with titanium and columbium, both of which serve to reduce the effect of carbon and nitrogen. This section and the one at 800°C suggest that the constant iron sections which are presented by the authors, should be considerably altered, if they are to represent an accurate picture of the system. A few of the suggested alterations are as follows: In fig. 9, the section at 50 pct Fe, the gamma plus sigma region should be widened, not narrowed at 800" and 650°C. In fig. 10, the section at 60 pct Fe, the gamma plus sigma region should be widened at 800° and 650°C. In fig. 11, the section at 70 pct Fe, an alpha plus sigma, an alpha plus gamma plus sigma, and a gamma plus sigma region should be added. In fig. 12, the section at 80 pct Fe, the alpha plus gamma region should be widened at 800°C. In fig. 13, the section at 90 pct Fe, the alpha plus gamma region should be widened at 650° and 800°C. Undoubtedly, the chief reason for the discrepancies between the authors&apos; data and those of Rees, Burns, and Cook is that the authors did not employ long enough heating times to allow for transformation. In this connection, I wish to warn that transformations in these alloys, particularly transformations at temperatures below 800°C, are extremely sluggish and may require a year or more to approach completion. Therefore, unless extremely long heating times are employed or steps are taken to accelerate these transformations by such means as mechanical working, the results will not yield an accurate picture of the alloy system. Certainly, an accurate picture is needed for the development of better high-temperature materials. E. J. Dulis-The purpose of this work is not clear. If an improvement of the ternary equilibrium diagram of the Fe-Cr-Ni system was wanted, it seems logical that testing techniques superior to those previously used would be a prime requirement. To approach equilibrium in this system, long holding times are needed; a fact established long ago but apparently ignored by the present authors, who used the continuous heating and cooling tests in equilibrium studies. A publication on the same system by Bradley and Goldschmidt6 was criticized by Monypenny in a

Jan 1, 1951

By W. C. Ellis, E. S. Greiner, M. E. Fine

C. H. Samans and W. R. Ham (Chicago, Ill., and Dix-field, Maine, respectively)-—For several years we have been studying transitions of this basic type in metals, alloys, glasses, etc. Usually, however, they are not so clearly marked as those which the authors have found, and hence are much more difficult to determine accurately. Since our studies indicate that most of them occur virtually unchanged (as far as temperature is concerned) regardless of the form in which the element appears, we believe that they are a characteristic of the atom. Specifically, we believe that there is an additional rotational degree of freedom possessed by the nucleus which has not been considered heretofore. This nuclear rotation is made up of several components, each related to the several quantum shells of electrons. In chromium there are four of these shells and hence four separate series of characteristic transition temperatures. The lowest temperature at which any transition occurs, based on the present state of our computations, is 125°K, 4° higher than the authors&apos; value of 121°K. A convergence of this series, we believe, shows up at the higher temperature of 2085 °K, surprisingly close to the transformation temperature of 2103°K recently announced by N. J. Grant of M.I.T. for a body-centered to face-centered transformation in chromium. Likewise, our computations indicate a temperature of 311°K for the second transition temperature, reported by the authors as 310 °K. A convergence of this series, we believe, shows up at a higher temperature as the melting point at 2163°K. Although our work on these series must, in a sense, still be regarded as empirical, since we do not understand fully as yet just what the series mean, it is based on a reasonably firm picture. The individual constants, from which the various series are computed for each element, comes directly from the X-ray K absorption limit. Furthermore, the same basic method has accounted for transformation and melting temperatures in about 50 of the chemical elements, which is all we have tried thus far. In many cases the only known transformation is the melting point, but in others the occurrence of transformations or other transitions, equally as well marked as those of the authors, has been pointed out by others. These observations have assisted us greatly. Consequently we were very pleased to see the authors&apos; excellent work in finding these two transitions in chromium. With these confirming data, our picture of this element is clarified considerably, so we expect that at least some of our work can be published in the near future. R. C. Ruder (E. I. du Pont de Nemours & Cu., Wilmington, Del.)—The authors&apos; interpretation of these transitions in terms of 3d to 4s electronic structure transitions is most interesting. It would be interesting to have additional experimental evidence of such transitions from the temperature dependence of the Hall coefficient in the neighborhood of the property changes discussed in this paper. Simple theory15 suggests the Hall coefficient as a measure of the free electron (or s electron) concentration per unit volume. It has been shown that for paramagnetic&apos;" and ferromagnetic1? metals the simple theory is in fact too simple. However, the existence of a discontinuity in the Hall coefficient would provide information which should aid both in our understanding of these transitions and the significance of the Hall coefficient in these metals. It was rather surprising that no significant paramagnetic effects were observed. In this connection the recent work of McGuire and Kriessman18 is cited. They measured the magnetic susceptibility of chromium from 20" to 1460 °C. They also observed no large change in the susceptibility although there might be a change in slope in the vicinity of the 40 °C transition. The existence of these 3d to 4s electronic transitions has been discussed in connection with the paramagnetic susceptibility behavior of nickel and nickel alloys.&apos;"-" Assuming a correspondence principle between classical and quantum mechanical paramagnetic theory and using classical theory to calculate the effective Bohr magneton number from the Curie constant for substances obeying the Curie-Weiss law," it is found that the effective magneton number is a function of temperature. The process of calculation involves the inverse of the differential of the 1/x4 vs. temperature curve so that good and numerous data are necessary to obtain significant results. The data of Fallot23 show a discontinuous increase of about 12 pct in the effective magneton number between 850" and 900 oC, followed by a continuous increase up to the melting point. The data of Sucksmith and Pearce24 show a possible 8 pct increase. The older data of Terry25 and Weiss and Foex26 show a continuous increase. It is possible that small amounts of impurity atoms change these electronic transitions significantly. Fallot&apos;s23 data on a nickel alloy with 4.5 atomic pct Fe indicate that the discontinuity occurs around 1300 °C. Systematic investigation of the transition metals for transitions of this nature should provide information which would be very valuable for our understanding of these metals. The absence of antiferromagnetic structures in chromium has been shown by Shull27 using neutron diffraction techniques. M. E. Fine, E. S. Greiner, and W. C. Ellis (authors&apos; reply)—The remarks by Drs. Samans and Ham are certainly very interesting, in particular those pertaining to the close agreement between the theoretically calculated values for transition temperatures in chromium and the experimental values reported by a number of investigators. This is a remarkable achievement and we shall look forward to a more detailed presentation of the method followed in their calculations. We do not believe that the transition in pure chromium near 40 °C remains temperature invariant with alloying, as was reported by Samans and Ham for a number of the substances that they studied. We have not done any work with alloys but base our belief on the results of earlier studies in which less pure chromium was included and considerably lower transition temperatures were observed. The transition tempera-

Jan 1, 1952

By J. B. Newkirk, A. H. Geisler

INTRODUCTION CERTAIN of the permanent magnet alloys provide ideal systems for the study of the kinetics of the precipitation reaction and the correlation of structure with properties. One such system, Cu-Ni-Fe, was found by Bradley1,2 to exhibit a coherent transition state in the precipitation process analogous to that reported for Al-Cu alloys somewhat earlier.3 The attractiveness of some permanent magnet alloys for study lies in the fact that vertical sections of the ternary phase diagram in certain regions of composition (Fig I) have as their prototype the binary Ni-Au diagram. Alloys of this type decompose into products that have the same crystal lattice type but only slightly different lattice parameters. The advantages that such alloy systems offer for study over the usual in which an intermetallic compound is formed are many: I. Since the precipitate has the same crystal structure as the matrix, complex atomic movements are not required to form the new lattice. 2. Similarly, complex orientation relationships are not involved for both the matrix and the precipitate would be expected to have the same orientation. 3. Small disregistry of the decomposition products at equilibrium (in contrast with Cu-Ag alloys) is conducive to extensive coherent growth in the transient state and thus the transition lattice can be detected by the usual X ray diffraction methods. 4. Finally, the relative quantities of precipitate and depleted matrix can be varied from o to 100 pct* thus permitting wide freedom for the study of the effect of composition on coherent growth and properties. In the Cu-Ni-Fe alloys of appropriate composition, the face-centered cubic precipitate and also the depleted matrix when first formed are coherent with the parent matrix.1,2 The two have the same [ao] parameter as the original matrix but they are both tetragonal; the precipitate has an axial ratio c/a < I while that of the depleted matrix is c/a > I. When coherency is lost they assume the normal face-centered cubic structure with the depleted matrix having a lattice parameter greater than the original matrix and that of the precipitate less. Such a mechanism would also be expected for Cu-Ni-Co alloys because of the similarity in constitution but this had not been demonstrated. The present investigation was conducted on a Cu-Ni-Co alloy. The constitution diagram and magnetic properties of these alloys have been fairly well established 4,5 however, no previous determinations of mechanism of precipitation and no correlation of structure with properties had been made. Thus, an alloy of this system was chosen for a comprehensive investiga-

Jan 1, 1948

By F. Keller

ALUMINUM alloys containing magnesium and silicon are susceptible to strengthening and hardening by suitable heat-treatments, and they constitute a class of alloys of considerable commercial importance. Generally, they contain these two elements in the proportions required for the formation of the intermetallic compound Mg2Si, or an excess of silicon; no commercial wrought alloys are made with an appreciable excess of magnesium. The reason for not having excess magnesium is obvious from the results given in this paper, since it is shown that excess magnesium results in a proportional decrease in the solubility of Mg2Si. This is the eighteenth1 of a series of papers from the Aluminum Research Laboratories dealing with the equilibrium relations in aluminum-alloy systems; most of the previous publications concerned binary aluminum-alloy systems; this is the fourth of a group pertaining to ternary aluminum-alloy systems. The work on this system was com-pleted in 1930, but the results were not published because of the pressure of other work. Hanson and Gaylor2, in 1921, presented the results of an extensive investigation of the aluminum-magnesium-silicon system. Their results indicated that an excess of magnesium over the amount required to form the compound Mg2Si caused a noticeable decrease in the solid solubility of Mg2Si in aluminum. A more recent investigation3 in these laboratories showed that the solid solubility of Mg2Si in aluminum was 1.85 per cent at 595° C. and decreased to 0.30 per cent at 300° C. The results of the latter investigation were used as the basis for the present work.

Jan 1, 1936

By Peter M. Fozzard

The San Bartolomt silver deposit was discovered by a United Nations team of geologists working with a counter- part team of staff of the Ecuadorian Government&apos;s General Directorate of Geology and Mines (DGGM). The Phase I project over five areas of operation during which this discovery was made was financed through a United Nations Development Program contribution of $860,000 and an Ecuadorian Government participation of about $680,000 equivalent. Existence of mineralization at San Bartolomé was first recognized in 1966 when a reconnaissance geochemical stream-sediment program was carried out over a 10 500 km2 (4,054 sq mile) area centered around the city of Cuenca in southern Ecuador. Over the course of this project more than 10,000 samples of stream-sediment, soil, and rock materials were collected. Average costs per sample were $10.00, as follows: collection, $5; sample preparation, $1.60; assay work, $3.40. Initially in the program (1965-1966) sediments were collected along all motorable roads and tracks. Routine analyses, originally by colorimetry and later by AAS, were for Cu, Pb, Zn and occasionally As, Ni, and Co. Discovery geochemical samples from the San Bartolomé drainage area were among the first to be taken in 1965. As luck would have it, the road along which this traverse was taken passes only some 100 m (328 ft) downstream from the mineralized suboutcrop. The relevant two streams sampled are of inconsequential size, some 1 m (3.3 ft) in width, with a limited flow volume throughout the year. Original anomalies were recognized through cold-extractable Cu/Zn analyses. The pH of all river waters was also recorded at sample sites. Resampling the discovery sediments when AAS became available showed total extractable values of between 150 ppm-300 ppm Zn, 550 ppm Pb, and 10 ppm Ag. In 1967 the first followup was by rough-and-ready means. Dithizone field-kits (THM) were used to rapidly test soils from the surrounding area. The area has no outcrop. This work allowed the definition of an area of interest of some 2 km (1.2 miles) x 500 m (1640 ft). Six approximately 1 km (0.6 mile) to 1.5 km (0.9 miles) lines spaced at approximate 250 m (820 ft) intervals were established and used for IP surveys and soil sampling at 50 m (164 ft) intervals. Where one of the lines crossed the westernmost geochemical discovery creek a first-priority geophysical anomaly coincided with a major Zn/Pb (and later Ag) soil anomaly. A pit was sunk and encountered mineralized vein material at a depth of 1.5 m (5 ft). This lucky glory hole confirmed the geochemical discovery and prompted systematic followup. Immediately, costeaning of the west bank of the discovery creek, the Quebrada Ocashuaico, was carried out and exposed weathered and leached mineralization. Nearly 100 mineralized veinlets ranging in thickness from 0.5 cm (0.2 in.) to 8 cm (3 in.) were exposed across the 180 m (59 1 ft) costean. Sixty mineralized veinlets were determined over a 90 m (295 ft) wide zone. Sampling delineated minable widths averaging between 0.16 and 0.31 kg/t (5 and 10 oz per st) Ag with associated copper (very sporadic) lead and zinc. Over the period 1968- 1972 a considerable amount of detailed work was completed: detailed IP, EM Turam, magnetic and mise-a-la-masse geophysics, very detailed soil- sampling, trenching, drilling and glory-hole drifting, and cross-cutting. Numerous problems were encountered: the area was found to be a most difficult geoelectrical target; zero outcrop; pyrite (nonargentiferous zones) associated with faulting; mineralized groundwater; extensive clay development; loss of diamond drill-core, and no two-dimensional surface information. As the program developed the complexity of the structure was slowly unravelled, using a degree of good guesswork. Apart from photogeological and ground geological mapping at various scales, the following

Jan 1, 1985

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.&apos; However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By H. B. C. Nitze

Monazite is a phosphate of the rare earths, cerium, lantha num, and didymium (Ce, La, Di)PO,. It also contains thoria (Tho,) and silica, which are present in varying percentages, probably as impurities.

Jan 1, 1896

By R. S. Busk

TWO groups of binary alloys were prepared. The first group consisted of those elements relatively soluble in magnesium: Li, Al, Zn, Ga, Ag, Cd, In, Sn, Hg, T1, Pb, and Bi. These are predominately Group B elements. The second group consisted of most of the remaining metallic elements, all of which are relatively insoluble in magnesium: As, Au, Ba, Ca, Ce, Cu, Ir, La, Mn, Ni, Pd, Pt, Rh, Sb, Si, Te, Ti, W, and Zr. These are all Group A, transition, or rare earth elements. Alloys of the first group were prepared by melting sublimed magnesium and elements as pure as obtainable in a graphite crucible, using a standard flux1 for protection. The melts were poured into a small graphite mold to produce 3xY4 in. diam slugs. Spectroscopic analyses were made of each slug. In all cases, the total impurity content was less than 0.05 pct. The slugs were then heat treated 5°C below the eutectic temperature until complete solution, as judged metallographically, was obtained. Filings from the center of the slugs were compacted at room temperature into 1/2 in. long x 1/4 in. diam cylinders, sealed in pyrex under 1/2 atm of purified argon, annealed at the heat-treating temperature for 1 hr, and quenched in water. After the X-ray diffraction patterns were made, each compact was analyzed chemically for the solute. It was found that the Mg-Li alloys reacted during filing to reduce the Li in solid solution. For this series of alloys, the slug was cold worked, annealed in purified argon, the surface dissolved in dilute HC1 to a depth of about 0.005 in., and the X-ray exposure made on the fresh surface. This procedure resulted in sharp, continuous lines and in true values for the lattice parameters. The alloys in the second group were prepared in the same way except that about 1 wt pct of each solute was added. Since the solubility limit was exceeded, not all the solute dissolved. These alloys were analyzed spectroscopically only to confirm the presence of the solute. The diffraction patterns were of the back-reflec-tion type using the characteristic copper radiation* and a flat cassette. Both the film and the specimen were rotated. The specimen temperature was maintained at 25" ± 1°C. The films had sharp lines; their diameters were measured directly to 0.01 cm. The parameters were calculated from the line diameters using a modified version of Cohen&apos;s extrapolation method.2 his method effectively eliminates systematic errors such as film shrinkage, inaccurate alignment, and non-precise film-to-speci-men distance. The random errors were minimized

Jan 1, 1951

By V. Kondic, W. M. Rumball

HUNT and Jackson&apos; have recently suggested that binary eutectics might be classified according to the entropy of fusion of the component phases. Such a classification was in fact proposed2 some time ago by the authors and the purpose of this communication is to present some supporting evidence. As pointed out by Hunt and Jackson&apos; typical metals of low entropy of fusion, ?S, tend to form normal eutectics (using Scheil&apos;s terminology3). Where one phase is metallic (low ?S) and the other nonmetallic (high AS) then anomalous structures are formed. These anomalous structures may either be regular (e.g., Bi-Sn)or irregular (e.g., A1-Si). Finally Hunt and Jackson suggest that where both phases are of high ?S regular faceted structures are formed. In the proposed classification2 the ratio of the entropies of fusion is taken as the quantitative parameter, i.e., ?Sa/?SB = E, where e > 1.0. An extensive literature survey has been carried out2,4 for reliable photomicrographs of eutectic structures. The structures, numbering 151, have been classified into two classes, viz., normal (i.e., lamellar and rodlike) and anomalous. The latter group has been arbitrarily subdivided into regular and irregular anomalous eutectics. Details and sources of the structures are given elsewhere.2,4 In the absence of better thermodynamic data the value of E has been determined for each of the systems making the following assumptions and approximations: l) The entropy of fusion of solid solutions may be calculated additively;5 ii) Inter metallic compounds are treated similarly but with the addition of the following term for fully ordered structures.5 -4.573(Ni lOg10 Nl + N2 log10 N2) where Nl and N2 are the atomic fractions. It might be argued that the entropies of fusion are meaningless as the eutectic phases form at some temperature (T,°K) below their true melting point (Ta or Tb). As AS, = Lo/To if La the latent heat of fusion of a, is assumed independent of temperature, the actual entropy change AS& is given by La/Te. The ratio of entropies of fusion then becomes Fig. 1 shows E&apos; plotted against cumulative totals for normal and anomalous systems from which it is seen that normal eutectics predominate at low values of E&apos;; e.g., some 90 pct of normal systems lie below E&apos; = 1.5 with 65 pct of anomalous systems above this value. Fig. 1 also shows that the regular anomalous structures occur mostly at low values of c&apos; possibly suggesting growth more akin to normal than anomalous growth. The choice of c as a classification parameter was based on nucleation concepts, it being observed that metals widely separated in Sundquist and Mondolfo&apos;s8 nucleation series were anomalous and those close together normal. The basis of these classification views is really outside the intended scope of this communication but it is hoped to explain them fully in the near future.7 Having arrived at this entropy of fusion classification by nucleation considerations it is interesting to note that Hunt and Jackson&apos;s ideas are based on growth considerations. Elsewhere one of the authors4 has shown that an even better classification of the metallographic structures reviewed is obtained from purely conventional heterogeneous nucleation concepts. It has been found that systems having a value of the parameter +b less than 0.28 are almost certainly normal and above this anomalous: V, is the gram atomic volume. This parameter is nevertheless closely related to c and c&apos;, these being an approximation of p. The parameter is also related to the other classification3,8,9 which have met with any success in the past. All these classifications are to be reviewed shortly by the authorsU7 A significant thing about the classifications based on

Jan 1, 1968

By G. A. Deitz, J. Halpren

The kinetics of dissolution of silver in cyanide solutions under oxygen pressure have been investigated over a wide range of conditions with a view to establishing the reactions involved and the factors which influence the rate. The results indicate that the rate is determined principally by the transport of reactants in solution to the silver surface. The thermodynamic features of the reaction with particular reference to the influence of pH and CN- are also discussed and summarized in the form of potential-pH diagrams. METALLIC silver is readily attacked and dissolved by cyanide solutions in the presence of oxygen. This reaction has long been recognized and extensively applied1 in the well-known cyanide process for the extraction of silver from its ores. While this process has been subjected in the past to a number of investigations2,3 both of a practical and fundamental nature, some features relating to the chemistry of the reactions involved, the role of oxygen, the nature of the rate-controlling step, and the effects of pH and certain reagents such as lime, are still not fully understood. It was felt that this situation justified a further investigation of the reaction, made with a view to obtaining a better understanding of its kinetics and mechanism. In the present investigation rate curves for the dissolution of silver were determined over an extensive range of carefully controlled reaction conditions. By carrying out the reactions in a pressure vessel, the partial pressure of oxygen, and hence its concentration, could be varied widely. The influence on the reaction of other variables including temperature, pH, and the concentrations of cyanide, peroxide, and other salts was also examined. The results of these kinetic studies are presented and discussed in this paper, together with a summary of available thermodynamic information relating to the possible reactions which can accompany the attack on silver by aqueous solutions of cyanide and oxygen. Chemistry and Thermodynamics of the Reaction The chemistry of the reactions of gold and silver with aqueous cyanide solutions has been the subject of several recent reviews.&apos;." It has been proposed&apos; that the following reaction occurs when silver dissolves in cyanide solutions in the presence of oxygen: 4Ag + 8CN- + 0, + 2H.0 -t 4Ag(CN); + 40H- [la] An equation of this form, for the corresponding dissolution of gold, was first suggested by Elsner." Bodlaender5 proposed a similar overall reaction, but suggested that it took place in two steps, 2Ag + 4CN- + O2 + 2H2O ? 2Ag(CN),- + 2OH- + H2O2 [2a] followed by 2Ag + 4CN- + H2O2? 2Ag(CN); + 20H- [3a] On the other hand, Janin- suggested that the dissolution of gold can occur with the liberation of hydrogen, rather than by reduction of oxygen. The corresponding equation for the dissolution of silver is 2Ag + 4CN- + 2H20 -t 2Ag(CN); + 20H + H2 [4a] All these reactions represent oxidation-reduction processes and may be resolved into the corresponding separate oxidation and reduction components. The oxidation step involves the formation of the argentocyanide ion and is the same for all the reactions, i.e., Ag + 2CN? Ag(CN)2 + e [51 However, reactions la, 2a, 3a, and 4a differ in the nature of the reduction steps which are, respectively, O2 + 2H2O + 4e ? 4OH- [lb] O2 + 2H2O + 2e ? H2O2 + 2OH- [2b] H2O2 + 2e ? 2OH- [3b] 2H2O + 2e? 20H- + H2 [4b]

Jan 1, 1954

D. M. Riordan has been appointed a member of the Institute Com¬mittee of the Engineers&apos; Reserve Corps movement. Our Committee, therefore, now consists of Henry S. Drinker, Chairman, Messrs. Arthur S. Dwight, Warren A. Wilbur and D. M. Riordan.

Jan 1, 1916

By O. B. Hopkins

There was no noteworthy development in the oil industry in Peru during 1933 and all activities were restricted to the producing fields. The output of the country increased above that of previous years but there still remained a substantial shut-in production at the close of the year. The total production during 1933 is estimated at 13,259,891 bbl., of which the International Petroleum Co., Ltd. contributed 11,205,-362 bbl. A relatively small amount of new drilling was undertaken during the year. The International completed only one new well although a number of the old producers were reworked and deepened. Comments on Tables There are four oil districts in Peru, as shown in Table 1, although only three of these are now being operated. The exhausted Pirin field was abandoned eight years ago. La Brea-Parinus.—The La Brett-Parinas fields are on the property of the International Petruleum Co., Ltd. in the westernmost part of Peru. These fields include a number of producing districts that are defined by complex fault blocks associated with anticlinal folds. Data covering all the items listed in the table are not available on these fields but can perhaps be supplied in part in the future. Lobitos and Restin.—These two fields belong to the Lobitos Oilfields Limited and are near the coast, 10 to 20 miles north of the La Brea-Parinas fields. According to the Department of Mines and Petroleum of Peru, 311 wells at Lobitos and 197 at Restin had been drilled to the end of 1927. Since that date there has been enough drilling to increase moderately these figures. The depth of wells is not available but it is believed that their average depth is slightly greater than in the La Brea-Parinas area. The productive horizons are of Eocene age. zorritos.—The Zorritos field is the northernmost in Peru and is operated by the Establecimiento Industrial de Petroleo de Zorritos. The field is on the coast about 70 miles north of Lobitos. The number of wells drilled in this field to the end of 1927 was 343, according to the Department of Mines and Petroleum of Peru. The depths of these wells are reported to range from 300 to 700 ft. The largest wells do not produce

Jan 1, 1934

By Cyril Smith

ALTHOUGH alloys of copper and silicon were examined several years ago,1 and their excellent mechanical properties were shown, it was not until C: B. Jacobs2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass. Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. REVIEW OF PREVIOUS WORK ON, THE BINARY SYSTEMS There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described,3 which indicate that there is a change insolubility with temperature.

Jan 1, 1930