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By Frank M. Monroe, James R. Cost

The solubility of nitrogen in vanadium is determined from 275" to 575°C by measuring the height of the nitrogen internal friction peak of equilibrated V-N alloys. The proportionality constant at 275°C between the internal friction peak height (Q- 1) and the atom percent nitrogen in solution is found to be 0.095 per at. pct for nitrogen concentrations up to 0.8 at. pct. The heat of solution of the nitride in vanadium is 5500 cal per mole. The solubility of nitrogen in the Group V metals is discussed. LITTLE work has been performed on the vanadium-nitrogen terminal solid solution. Hahn1 found the solubility for nitrogen to be very small and reported the existence of a hexagonal phase of composition near that of V2N at the solubility limit. Rostoker and Yamarnoto2 reported the solubility to be at least 3.5 at. pct at the melting point and to be less than this value at 900°C. In addition, they reported from X-ray diffraction studies that nitrogen in solution produces tetragonality in the vanadium lattice. An X-ray study by Schonberg3 has confirmed the results of Hahn but indicated that the tetragonality observed by Rostoker and Yamamoto was due to the presence of oxygen in their specimens. Beatty4 has performed lattice parameter and hardness measurements on terminal solid solutions and found the upper limit of the solubility to be at least 0.66 at. pct N. No measurements have been made of the pressure-temperature-composition relationships (P-T-X) for the terminal solid solution. As a part of a research program on gas-metal equilibrium, an attempt was made to study the P-T-X relationships in the V-N system using both the internal friction and the gas equilibration methods which have been successful with the Nb(Cb)-N and Ta-N systems (see Ref. 5 for a review of this work). Extensive investigation, using the gas equilibration methods, showed this method not to be applicable with vanadium This was presumably due to the gettering action of vanadium sublimed on the walls of the Sieverts apparatus. Thus, the nitrogen pressure relationships with temperature and composition were not obtained. The internal friction methods were, however, found to be applicable, and the temperature-composition relationships are reported in this paper and compared with similar results for the Nb-N6 and Ta-N7 systems. The existence of a Snoek internal friction peak due to nitrogen in solution in vanadium has been clearly demonstrated. 8-10 Powers and Doyle found the peak to be at approximately 275°C for frequencies near 1 cps.8 In a subsequent paper10 they reported the proportionality constant at 275°C between the internal friction peak height (Q-1) and the concentration of ni- trogen in solution (in atom percent) as 0.06 per at. pct. The studies of Stanley and wert9 indicated qualitatively that the height of the Snoek peak decreased with aging at the peak temperature and thus suggested that internal friction methods were suitable for study of the solubility. EXPERIMENTAL METHOD The vanadium for this investigation was of particularly high purity. It was obtained from the Ames Laboratory of the U.S. Atomic Energy Commission, Ames, Iowa in the form of a 1/2-in. diam, three pass zone-refined ingot. The electrical resistivity ratio (p300ºk/p4ºk) was 160. The initial composition was determined as follows: Carbon 200 ppm Oxygen 150 ppm Chromium <50 pprn Iron 125 ppm Silicon <50 ppm Other metallic 100 pprn The initial vanadium ingot was fabricated to 30-mil wire by swaging and wire drawing without the need of intermediate annealing. Lengths of this wire were then further purified (particularly for oxygen) by outgassing at 10-6 torr at 1400°C for 4 hr. The outgassing treatment resulted in specimens with a bamboo grain structure and a lustrous appearance. Desired amounts of nitrogen were added to the outgassed wires in a Sieverts apparatus in which known amounts of nitrogen were equilibrated with the wire at 1300°C. Nitrogen concentrations were produced in the desired range from less than 1 to 10 at. pct N. Monitoring of the partial pressure of nitrogen in the Sieverts apparatus indicated that at 1300°C equilibrium between the nitrogen gas and the vanadium was obtained within 10 min. Relatively rapid cooling from the nitrogen addition temperature was obtained simply by turning off the specimen heating current and cooling to room temperature in the partial pressure of nitrogen. Internal friction measurements of wire specimens were made under forepump vacuum in a torsional pendulum at frequencies near 1 cps. The torsional pendulum was of low thermal inertia and was designed so that specimens could be heated both by a conventional tube furnace and by the joule heating of a separate current through the wire specimen." Use of a static atmosphere of helium gas as a quenching medium made it possible to cut the specimen current, rapidly cool the specimen to the measurement temperature, and make a measurement of the internal friction in less than 1 min. Because of the large solubility of vanadium for nitrogen, the internal friction peak heights were in some cases greater than Q-1 = 0.1. This high damping resulted in an estimated relative uncertainty in the damping measurements of approximately 10 pct. X-ray analyses made to identify the precipitated ni-

Jan 1, 1970

By Carl Henrich

The Ducktown copper-mines are located in the southeast corner of Tennessee. The name Ducktown was originally given to a district occupying the southeast corner of Polk county, which in turn occupies the southeast corner of the State. Fig. 1 is a map of the vicinity of Ducktown, taken from the topographical surveys of the United States Geological Survey. The Ducktown district is bounded on the east by Cherokee county, North Carolina (the boundary-line between the two States running here a little east of north along the western slope of Pack mountain), and on the west by the eastern foot-hills of Little Frog mountain. On the north, Stansbury mountain, really a chain of low mountains or hills, forms the dividing-line between Ducktown and Turtletown districts. On the south, the Ducktown district extends beyond the Ocoee river to the Georgia State line.. This line, in going west, gradually recedes southwards from that river into the foot-hills of Big Frog mountain, the highest mountain of the neighborhood, which rises about 4300 feet above sea-level, while the surface of the Ocoee river, where it leaves the Ducktown district, is less than 1500 feet above sea-level. It will be seen from this description, and from a study of the map, that the Ducktown district occupies the northern part of a kind of basin, bounded on the east by Pack mountain and on the west by Little and Big Frog mountains. Between these mountains the Ocoee river, draining the basin, cuts its way to the Hiwassee and the Tennessee rivers in a narrow gorge, through the crystalline slates and schists, which from their excellent exposure in this Ocoee gorge have received the local

Jan 1, 1896

By Charles S. Barrett

The experiments reported in this paper have been fruitful in disclosing the mechanism of the deformation of iron in compression. They have established the nature of "deformation bands," "etch bands," or "X-bands," that have been a recognized but little understood feature in the structure of cold-worked metals since the early days of metallography, and have shown the role of the bands in the development of preferred orientations by cold-working. The work has also shown the relation of the orientation of individual grains to the preferred orientation of the aggregate. Some of the methods previously used in the determination of the indices of slip planes and slip directions are shown to be untrustworthy in the presence of deformation bands. The conclusion is reached that many slip planes and slip directions must operate during each stage in the compression of a single crystal, and that theories failing to take account of this require revision. In conducting the experiments a method of compression has been used by which extreme reductions can easily be reached, even to the limit set by the metal&apos;s capacity to deform without fracture. The work is a portion of a research program on the plastic properties of iron and steel. It is being used as a foundation for studies of orientntions resulting from recrystallization and is being extended to other metals and other types of deformation. Previous Work The previous experiments are few and have given confusing results Onol compressed a polycrystalline alpha-iron specimen between two flan plates of a testing machine and found that severe deformation oriented the crystals into a duplex preferred orientation, one set of crystallites having a cube diagonal of the body-centered cubic lattice parallel to the compression axis, and another set having a cube axis parallel to the compression axis. We shall speak of this structure as a double fiber texture of the type [111] + [100]. Wever2 also made an X-ray determination of the texture

Jan 1, 1939

By R. A. Grange, H. M. Stewart

Man.; steel parts may crack if quenched directly into a bath near room temperature, but not if quenched at a temperature just above the range where martensite forms and then allowed to cool slowly to room temperature. This latter procedure, which is the basis for such modern hardening techniques as "martempering" and "isothermal quenching," may entail some sacrifice in depth of hardening but very little, if any, in intensity of hardening. In planning such treatments, it is necessary to know the upper limit of the martensite range, and often desirable to know the proportion of martensite that would form on cooling to any lower temperature; furthermore, the tendency of a particular steel to crack when quenched is unquestionably associated with the temperature range of martensite formation, and consequently knowledge of this range aids in selecting the optimum composition for a given application. Certain puzzling phenomena associated with the properties of quenched and tempered steel may be at least partly clarified as the manner in which martensite forms is more fully understood. Information on the temperature range of martensite formation, particularly with respect to how much martensite results from quenching to a given temperature, is lacking for most commercial types of carbon and low-alloy steel. These considerations led us to study martensite formation in 14 carbon and low-alloy steels. The resultant data may be directly used in the following ways: (I) for selecting the lowest quenching temperature at which no martensite will form; (2) for selecting the highest quenching temperature at which virtually all marten . site will form, thereby avoiding quenching to an unnecessarily lower temperature with attendant danger of cracking; and (3) in producing a mixture of tempered martensite and bainite, which in high-carbon steels has been found to possess somewhat better ductility than tempered martensite, yet does not require the full transformation time necessary for a completely bainitic (austempered) structure. PART I. OBSERVATIONS OF MARTENSITE FORMATION IN FOURTEEN CARBON AND LOW-ALLOY STEELS Transformation of austenite to pearlite or bainite can be conveniently studied by observing the change that occurs over a period of time at constant temperature; such studies are the basis of the isothermal transformation diagram (S-curve). This isothermal technique is not applicable to martensite formation, which occurs within a time interval too small to measure, at least by any ordinary means. For all practical purposes, therefore, martensite may be regarded as forming only during cooling and not during a period of time at constant temperature. As austenite is cooled below

Jan 1, 1947

By G. Ansel, J. O. Betteron

THE PURPOSE OF THIS PAPER is to give a brief picture of present day magnesium rolling practice, to elaborate on laboratory and development rolling experiments; and finally, to discuss the possible Future rolling of magnesium. The present production practice is so varied between various mills that it can only he concluded that no single producer is now using a process that is outstandingly superior to others. In view of this, only the general features of present day production practice have been presented and attention is focussed on the results of laboratory find development rolling of magnesium-base alloys as indications of the Future trend of magnesium rolling. MAGNESIUM ROLLING LITERATURE The literature relating to magnesium rolling is divided into three groups: the deformation mechanisms of the hexagonal magnesium crystals, the metallurgical aspects and laboratory type experiments in rolling, and finally, the articles on production rolling methods. This literature was reviewed and is summarized below. In the first group of references, the existence of basal slip in magnesium single crystals was shown by Schiebold and Siebel1 and of {102} twinning by Mathewson and Phillips2, Schmid3 predicted and partially established {101} slip at hot working temperatures. Bakarian and Mathewson4 confirmed the above and eliminated {101} twinning as a probable deformation mechan-

Jan 1, 1948

By Charles S. Barrett, L. H. Levenson

Plastic flow in metal crystals and the changes in orientation resulting from it are generally understood to take place by the following fundamental mechanisms: (1) slip on crystallographic planes, (2) homogeneous crystal rotation resulting from the slip, (3) bending of the 1attice between the planes of slip, and, under certain circumstances, (4) twinning. This paper and a preceding one on iron subjected to uniaxial compression1 concern two additional processes that must now be added to this list: (5) the formation of deformation bands, and (6) the bending and rotation of these bands. The present investigation yields a new understanding and definiteness to the common terms so loosely used when speaking of cold-worked metals —(&apos;grain fragmentation," "elongated grains," and "deformation twins," "deformation bands," "etch bands," or "X-bands." Bands have been noted on the polished and etched surfaces of cold-worked metals by various investigators for more than 25 years, ‡ yet their nature and their significance have been so little understood that they are not treated in the most comprehensive modern texts on the deformation of crystals. The experiments in this series show that they are one of the fundamental processes in the deformation of metals, of importance in the development of preferred orientations, in work-hardening (since they have the effect of reducing the effective grain size and interfering with slip), and in the recrystallization process. The present experiments were performed on the same stock of material that was used in the earlier compression experiments1—hydrogen-purified mild steel in which the carbon content had been reduced to the limit detectable under the microscope and in which single crystals could be grown by a strain-anneal treatment.2

Jan 1, 1939

By James M. Barker

Sulfur is a nonmetallic element of great physical and economic importance to the world. It is widely but sparingly distributed throughout the hydrosphere, lithosphere, and biosphere. Sulfur is the tenth most abundant element in the universe and eighth most abundant in the sun. In the earth&apos;s crust, which is mainly igneous, it ranks 14th, but is eighth or ninth in sediments (Kaplan, 1972; Stanton, 1972). It apparently is very abundant in the core of the earth, because it is a strong chalcophile, and it is fifth in abundance in stony and iron meteorites (Field, 1972) where it occurs as trolite (FeS). In ancient times sulfur was called brimstone, literally "burning stone." Today the term brimstone is used interchangeably with the term elemental sulfur. Shelton (1979) summarized most of the common definitions of terms, grades, and specifications for the sulfur industry as follows (with minor additions): Sources of Sulfur: Combined sulfur-Sulfur that occurs in nature combined with other elements. Cupriferous pyrites-Pyrite containing relatively minor amounts of copper sulfide minerals. Hydrogen sulfide-A toxic gas (H2S) occurring in natural gas and petroleum. Involuntary sulfur-Sulfur produced primarily as a result of legislative or process mandates. Native sulfur-Sulfur that occurs in nature in the elemental (uncombined) form. Nonferrous metal sulfides-Copper, lead, zinc, nickel, and molybdenum sulfides that are processed for their metal content. Organic sulfurs-Complex organic sulfur compounds occurring in petroleum, coal, oil shale, and tar sands. Pyrites-Iron sulfide minerals that include pyrite, marcasite, and pyrrhotite. Sulfate sulfurs-Sulfur in anhydrite and gypsum. Voluntary sulfur-Sulfur produced in response to market forces. Basic Sulfur Products Produced and Marketed: Acid sludge-Contaminated sulfuric acid usually returned to acid plants for reconstitution. Brimstone-Synonymous with crude sulfur. Bright sulfur-Crude sulfur free of discoloring impurities and bright yellow in color. Broken sulfur-Solid crude sulfur crushed to -8 in. Byproduct sulfuric acid--Sulfuric acid produced as a byproduct of a metallurgical or industrial process, generally relating to combined sulfur sources. Crude sulfur-Commercial nomenclature for elemental sulfur. Dark sulfur-Crude sulfur discolored by minor quantities of hydrocarbons ranging up to 0.3 % carbon content. Elemental sulfur-Processed sulfur in the elemental form produced from native sulfur or combined sulfur sources, generally with a minimum sulfur content of 99.5%. Formed sulfur-Elemental sulfur cast or pressed into particular shapes to enhance handling and to suppress dust generation and moisture retention. Frasch sulfur-Elemental sulfur produced from native sulfur sources by the Frasch mining process. Hydrogen sulfide-Associated with natural gas or petroleum and produced at refineries and coke oven plants; used to make sulfuric acid or recovered sulfur. Liquid sulfur-Synonymous with molten sulfur. Liquid sulfur dioxide-Purified sulfur dioxide compressed to the liquid phase. Molten sulfur-Crude sulfur in the molten phase.

Jan 1, 1983

By E. Miller, K. L. Komarek

Equatiorzs have been derived which related maximum solid solubilities in semicondcting compounds having retvograde solidus curves with 1iqllidus data. Liquidus curves in Lke Pb-Te, Pb-Se, ard PB-S systetris have been defermined by thertrzal aralyses. Fvotrz expevimental maximum solibilities ia CdTe, PbTe, uxd PbS vetvograde tetrperatures hale beep1 calculated. TIze resllts support the concept that under certaiz conditiots pronounced itjlections in the liquidis curves arc indzcatiz:e of retropade solidus curves and that the tenlperatltre of the lmaximum solid solubility will be close to the temperature of the point of inflection in the liquidus curve. The maximum solid solihility within a gvoup of homologous cottrpoods SeetlLs to increase with increasing flatness ol the liquidus curvres. The phenomenon of retrograde solubility in metals, i.e., maximum solubility in a solid terminal phase in equilibrium with a liquid phase, has been theoretically predicted by Van aar&apos; in his calculations of hypothetical binary phase diagrams. It was not until 1926, however, that retrograde solubility was experimentally verified in the Zn-Cd system.&apos; Since then many sys- tems with retrograde solubility have been found, so that at present approximately fifty binary diagrams with a retrograde solidus curve are known.3 Meijering4 has critically appraised the accumulated data and has presented calculations which alloy predictions as to whether or not a solidus line will be retrograde. Interest in retrograde solubility increased when it was found that the solidus curves of germanium and silicon alloyed with a great many doping elements are retrrade. The problem was treated thermody-namically by odkinson,% d all available data on solid solutions in germanium and silicon were summarized by Trumbore.7 Although it is to be expected that intermetallic compounds will also exhibit retrograde solubility, experimental evidence is much more limited. Until now retrograde solidus curves have been reported for the compounds de,&apos; be, Ps:" ne," SnSe," and SnS.13 All these compounds are semiconductors, and the solidus curves were usually obtained by determining the carrier concentration at room temperature of samples equilibrated at elevated temperatures and then quenched. It has been hown,&apos;&apos; however, that it is not always possible to quench in the equilibrium compositions from above a certain temperature. Theoretical discussions have either explicitly excluded intermetallic compounds4 or not treated them with respect to retrograde slubilit.j In the following a thermodynamic treatment of retrograde solu-

Jan 1, 1967

By Carmine D. &apos, Lemuel Tarshis, Joel Hirschhorn, Antonio

Vapor-deposited nickel films in the thickness range 700 to 4360A were tested in uniaxial tension utilizing a microtester designed specifically for this study. Contrary to the findings of some investigators, a definite thickness-strength relationship was observed below 3000 A with a four-to sevenfold increase in strength over that of bulk nickel. The films were characterized by high elastic strains and little plasticity. On the basis of these and other reported data, it is suggested that the high strength level in metal films is related to the manner in which they are produced. Vapor deposition, owing to its severe quenching effect. is believed to promote the formation of point defects which inhibit dislocation movement. IN recent years it has been reported that metals, when in the form of thin films, exhibit extraordinarily high strengths. The data published to date have been primarily concerned with silver and gold because of the ease with which these metals can be vapor-deposited and their high resistance to surface oxidation. Previous investigations into the mechanical strength of thin films has uncovered an apparent dichotomy of view on film behavior. Beams and his co-workers have reported a definite dependence of strength on film thickness. Other workers,"-&apos;6 however, in separate studies on the strength of poly crystalline and single-crystal films have found no such thickness-strength relationship. The study of thin-film strength is extremely difficult because of the many variables associated with film preparation, handling, and testing. Moreover, the manner of test employed by different investigators has varied quite radically, ranging from simple uniaxial-tension to biaxial-bulge testing. The work reported herein was conducted in order to determine the mechanical behavior of a structural metal when in the form of a vacuum-deposited thin film and to gain some insight into the reasons for the high strengths exhibited by metals having such a con- figuration. In this study a method of test was chosen which would yield results which are easily interpreted and lend themselves to comparison with properties of the same material in bulk form. Moreover, specimen-preparation parameters and film-handling techniques are set forth so that other investigators can properly compare their findings with ours. EXPERIMENTAL PROCEDURES A) Film Preparation. Vacuum deposition was performed in an 18 by 30 in. bell jar using a standard New York Air Brake Co. vacuum station with a 6-in. oil-diffusion pump. Before evaporation the system was pumped to a pressure of less than 2 x 10"5 torr. A shield was employed to protect the substrates from the emission of contaminants during the critical melting and outgassing of the evaporant. The source consisted of from one to six filaments (0.020 in. diam). The length of each filament was about 5 in. and was placed 6 to 8 1/2 in. from the substrate in such a manner that the substrate face was at 90 deg incidence with respect to the evaporant beam. The temperature of the source was 2000"~ during evaporation. The films were deposited onto a substrate arrangement which was composed of four basic components, that is: 1) a 3 by 1 in. glass slide; 2) a 22-mm sq micro cover glass on 1); 3) a 22 by 50 mm micro cover glass coated with collodion on 1); and 4) a stainless-steel sheet mask containing twelve rectangular openings of 1-mm and 2-mm widths and lengths of 5 mm laid over 3). Thus, test specimens of 1-mm and 2-mm widths are deposited onto a collodion substrate which precludes epitaxial effects in the specirnens. 17-le The rectangular cover glass and square cover glass were positioned in such a manner that a strip of film would be evaporated along the length and across the width of the large glass slide. This boundary of evaporated film was used to determine the film thickness by multiple-beam interferometry. The square cover glass was used for X-ray and chemical analyses. Thickness of the deposits was varied by changing the number of filaments used (one to six). The duration of evaporation was 30 sec for each filamgnt which resulted in a deposition rate of 8 to 20A per sec. Evaporations were all performed at room temperature; however, radiant heat from the source raised the substrate temperature to 40" to 60°C. All substrates were cleaned by ultrasonic agitation in a solution of spectranalyzed isopropyl alcohol. Collodion was deposited on the micro cover glass by immersion in solution of collodion in amyl acetate. B) Thickness Control and Measurement. Film

Jan 1, 1963

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,&apos; the gold film marker of Kofstad and ~jijllesdal,&apos; and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.&apos; reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By W. N. Miner, R. O. Elliott

Electrical-resistivity )measurments were made be-trueetz room temperatrive and 1.5 oK on five different stocks of cerium metal, and the results were correlated with the types, amounts, and distribution of the impurities present. Magnesium, which appeared to be distributed as a solute throughout the cerium matrix, was found to have a large effect on the residual resistivity, 1 at. pct Mg being sufficient to increase the residual resistivity by about 10 microhm-cm. The formation of ß by repeated thermal cycling between room temperature and liquid-helium temperature is attributed to the deformation and faulting that occurs during the ? D a transformation. In preparation for starting a proposed study of cerium-rich alloys, we examined samples from severa1 stocks of cerium metal in order to choose the purest stock for future use in making the alloys. Low-temperature electrical-resistivity data were used to gain initial information about the purities of the stocks. Additional information was subsequently obtained from chemical analyses, density measurements, optical metallography, and electron-micro-probe analyses. Cerium that has been annealed at high temperature and cooled to room temperature has the fee crystal structure (? phase) with a = 5.16Å. When cooled further, in the region between about 250" and 150°K, some of the fee phase transforms to the double hcp form (ß phase) with a = 3.68 and c = 11.92Å. The remainder of the room-temperature fee form (and perhaps some of the hexagonal phase) transforms electronically in the vicinity of 100° K to the more dense or "collapsed" fee form (a phase), a - 4.85A, by transferring about 0.5 electron per atom from the 4f level to the valence band. Very little work related specifically to the effects of impurities on the physical properties of cerium has been reported in the literature. Gaume-Mahn1, 2 has studied the effects of calcium, magnesium. iron, silicon, and tantalum on the electrical resistivity and magnetic susceptibility of cerium between 60o and 300°K. Gschneidner, Elliott, and McDonald3 have discussed the effects of total impurity content on the hysteresis of the a —? (reversible) transformation and on the formation of the 4 and "a-? intermediate" phases. Smith and Morrice* have reported the effect of total impurity content on the resistivity of cerium at 4 and 293°K. In none of these reports, however, is it apparent that the distributions of the impurities were determined, L.r., whether the impurities were present in inclusions or in solid solution in the matrix is not mentioned; nor does it appear that the phase purity of the cerium was always considered. In the present study, five different stocks of cerium were involved. One was represented by a single sample of electrowon cerium, which was all that had remained from a stock of high-purity material obtained from the U.S. Bureau of Mines, Reno, Nev., in 1959. The other four stocks were recently purchased from commercial sources and were specified to be 99.9 wt pct pure. EXPERIMENTAL Cerium stocks designated as #1, #2, #4, and #5 were obtained from commercial suppliers for the specific purpose of finding a reliable source of high-purity cerium. Although the purity level of the cerium was specified to be 99.9 pet, the specifications did not include limits as to the amounts of various impurities that would be acceptable. Consequently the chemical analyses of the different stocks varied widely. Stock #3, which had been obtained from the U.S. Bureau of Mines and which was the purest on the basis of chemical analyses, consisted of a single specimen of electrowon cerium. It was included in the examination for purposes of comparison. Table I contains the chemical and spectrographic-

Jan 1, 1968

By Charles S. Barrett, Robert F. Mehl

A study of the structures arising from the decomposition of the ß solid solutions in the Cu-Zn and the Cu-A1 systems is of peculiar interest in the study of the mechanism of precipitation from solid solutions. It is possible in these alloys, by varying the composition within the ß field, to precipitate from the same basic lattice phases having different lattice structures. It has been rather generally assumed heretofore that the type of structure originating from the decomposition of a solid solution— the Widmanstätten structure—-is determined by the lattice structure of the parent solid solution alone. In the first paper of this series1 evidence was advanced which threw doubt upon this hypothesis; but definite proof of the correctness or incorrectness of the hypothesis should be forthcoming from a study of these alloys, for if the structures originating, for example, from the precipitation of the a phase from ß and of the ? phase from the ß in the Cu-Zn system should be shown to be crystallographically different, the hypothesis would necessarily be held as definitely disproved. Furthermore, the newer proposal enunciated in the first paper of this series—that the origin of the Widmanstätten structure lies in a cooperation between the lattice of the parent solid solution and that of the precipitate-—which at present seems the only a1ternative hypothesis, would in such an event be given added weight. The work here reported shows that the Widmanstätten structures originating in the precipitation of the a phase from the ß and in the precipit&apos;at.ion of the y phase from the y in the Cu-Zn system are indeed crystallographically different; and incidentally presents some new descriptive information on the Widmanstätten structure from a more general point, of view.

Jan 1, 1931

By Roger L. Beals, George A. Tweedy

The results of the cyanide-operations, given in detail in the following paper, show the progress that is being made at the Minas del Tajo. The old pan-amalgamation process, in operation up to and including 1905, while paying a profit on high-grade ores, was no longer able to treat profitably the ores in sight at that time; hence an alteration in the process was imperative. The success of this alteration is eloquently expressed by the following data : Pan-Amalgamation. Cyanidation. 1905. 1905. " 1908. Tons treated,.... 51,387 58,983 69,200 Value per ton (U. S. currency),. $ 10.78 $8.39 $8.28 Extraction, per cent.,.. 65.00 88.56 87.45 Extraction, per ton,.. $7.00 $7.43 $7.24 Total cost, per ton treated, . 6.50 4.36 4.01 Profit, per ton treated,.. 0.50 3.07 3.23

Jan 1, 1911

By J. B. Newkirk, W. G. Martin

Oxidized cobalt powder is known to have a magnetic hysteresis loop which is asymmetric with respect to the magnetization axis. The experiment described herein shows that the orientation relationship between the basal plane of hexagonal cobalt and the oxide which forms upon it at 400°C is {111}ux//{100.1 }co <110>ux//<11.O> This orientation relationship allows a magnetic interaction between the antiferromagnetic oxide and the ferromagnetic substrate which could account for the offset hysteresis loop. Oxidized nickel powder has a symmetrical hysteresis loop and so is apparently not influenced by any magnetic interaction between metal and oxide. The orientation of the oxide (cubic) was found to be identical with that of the nickel substrate when the oxide forms on a polished surface parallel with {111} Ni. IN 1956 W. H. Meiklejohn and C. P. Bean discovered that fine particles of cobalt which had been prepared in a certain way have a magnetic hysteresis loop which in a strong field is asymmetric relative to the magnetization axis.&apos; The cobalt powder exhibited this unusual magnetic property only after it had been oxidized in air or oxygen; it lost the shifted hysteresis loop when the oxide was reduced in hydrogen. X-ray and neutron diffraction&apos; experiments showed the presence of cobaltous oxide (COO) and hexagonal cobalt in samples exhibiting the biased hysteresis loop and specifically showed no indication of any other compound with the exception of mercuric oxide.* The magnetic hysteresis loop becomes symmetrical above the Nee1 temperature (paramagnetic state) of COO. Therefore, it was concluded that the anomalous magnetic behavior is associated with the influence of cobaltous oxide upon the metallic cobalt. It has been proposed that crystallographic coherency may exist between the cobalt and a plane of some antiferromagnetic material which has unbalanced spin distribution and sufficient magnetic anisotropy to hold its spin in the direction which existed when the specimen was cooled. COO has these properties. Therefore, Roth&apos; has suggested that cobaltous oxide may form with a {111} plane parallel and coherent with the basal plane of the hexagonal cobalt metal and proposed that, as consequence of the antiferromagnetic interaction between COO and the underlying cobalt, the magnetization direction in oxidized fine Co particles may be ro-lated from the easy c-direction.2 Such a relationship, he proposed, would explain the observed magnetic effect in oxidized cobalt powder. The main purpose of this study was to determine the orientation relationship, if any, between the basal plane of cobalt and the oxide which forms upon it. Attempts to produce a film of COO which was strong enough to be handled were not successful. However we did succeed in making a film of CoCo2O, which was strong enough to be removed from the cobalt substrate and mounted on an electron-microscope grid. Because of the close structural similarity of COO and CoCo2O, we believe the orientation relation found for CoCo2O, on cobalt probably also holds for COO on cobalt. The epitaxial relationship of NiO and Ni also was investigated. To date no shifted hysteresis loop has been observed with nickel powder. However, the similarity of atomic array in cobalt and nickel leads to the prediction that a {111} of NiO may be parallel with a (111} of nickel. Experimental Method Cobalt-Cobalt Oxide—A coarse-grained specimen of a (hexagonal) cobalt was prepared by allowing a large crystal of fee cobalt to transform slowly at 400°C. The crystal was then cut to expose a surface parallel with the basal plane. A back reflection Laue X-ray photograph showed that the 00.1 plane was within 2" of the cut surface. The surface was mechanically polished and then electro polished in 85 pet orthophosphoric acid after which the crystal was held for 30 min at 400°C in air. During this heat-treatment the surface darkened slightly due to the oxide film which formed. The film was not thick enough to give an X-ray diffraction pattern, even by a glancing-angle technique. Glancing-angle electron diffraction was not possible either, owing to the interference of the electron beam with the high magnetic fields which exist at the 00.1 surface of the cobalt. However, it was possible to make an electron-diffraction photograph of the oxide film by stripping it from the cobalt substrate using the method described later. By maintaining reference marks carefully, it was possible to preserve the orientation relationship between the stripped film and the substrate on which it was formed. The oxidized surface of the crystal was first covered with a 1 pet solution of collodion (cellulose nitrate) in amyl acetate. When the film was dry, small rectangles were scored on the surface with a needle point. The specimen was then repolished

Jan 1, 1959

By S. S. Clarke

LATE in 1942, the increasing demand for zinc, coupled with the growing shortage of miners and the knowledge that some abandoned mines would have to be reopened for prospecting and development, led to considerable thought as to the possibilities of further mechanization in order to conserve man power. The ore bodies, locally termed "sheet ground," are an important ore bed in some mines and are in the lower part of Boone formation of the Mississippian Series. Some mines contain interbedded layers of nearly pure galena and sphalerite in horizontal sheets ranging in thickness from a thin seam to several inches and is persistent over large areas. This type of ore body offered the best opportunity for study and experiments. The use of jumbo drill carriers was advanced but some doubt was expressed as to the adaptability of jumbos as then in use to mine headings as compared to post and arm mounting (Fig I). Another consideration was the introduction of truck haulage when several mines were trackless. A drill frame, built to carry 2 4-in. drifters, was mounted on a truck chassis. This design proved a failure as it was not rigid and the resiliency of the tires and springs allowed too much play. Long screw jacks were then used to hold the truck firmly in place, but placing the jacks and securing the truck required more effort and time than setting up post drills, so the truck carrier was abandoned. The use of a bull dozer underground had been under consideration for some time to be used in "brunoing" the broken dirt from behind pillars and other inaccessable places so the slusher drags could load without double dragging the dirt. A dozer with hydraulic blade lift was purchased and R. I. Tuthill, Superintendent of Section 30 Mines, suggested that a long drill arm be substituted for the blade, and the drills mounted on the cross member. The hydraulic lift would permit drilling holes at any required spacing. The "cat" was very mobile and answered the problem of a trackless mine. The initial tests showed that the "cat" would make a good carrier, but the hydraulic controls Were not positive enough to keep the drills in alignment while drilling. The next step was to build a small hoist. This hoist was attached to the power take-off on the "cat" and by means of sheaves and a double line of 3/8-in. hoist cable, a positive control for raising and lowering the boom was obtained. To avoid serious injuries to the drillers should the cable break, a safety chain was fastened to the drill boom and hooked into a slot in the back of the "cat" frame. A different power unit was obtained for the "cat," as a state law prohibited the use of internal combustion engines in mines. A custom machine shop had just placed on the market a small hoist powered by a Model A Ford engine that had been very ingeniously converted to a slide valve engine using compressed air. To use this unit on a "cat," our master mechanic de-

Jan 1, 1947

By A. W. Hesse

The trend of American construction toward permanence and longevity is noticeable in the more recent coal plant installations; also, the policy of many coal operators has changed from seeking to obtain the desired tonnage from several plants of small capacities to designing a single installation to produce the whole amount. The mine openings and plant of the Nemacolin mine of The Buckeye Coal Co., are located on the Greene County side of the Monongahela River, 73 miles south of Pittsburgh. The map (Fig. 1) shows the general location, also the Lambert syncline. This syncline partly accounts for the selection of the site; the other reasons were the possibilities of rail and river shipments. Two shafts and a slope were sunk to the coal, work starting on all three in the second half of the year 1917. The air shaft was sunk to a depth of 243 ft. and completed in February, 1918; the slope was completed in November, and the skip shaft was stopped at a depth of 21 ft. below the coal, then the concrete lining was stopped 8 ft. above the coal August, 1918. Work on the skip shaft was resumed May, 1923, and sunk to a depth of 60 ft. below the coal by September, but it was not until May, 1924, that the lining was poured. Max. Min. WateR Water during after Sinking, Crouting, Depth or Cu. Yd. Cu. YD. Gal. per GaL. per Opening Size Length Excav. Conc. Min. Min. Air shaft..... 20 ft. diam. 251 ft. 8 in. 4788 1902 475 2 Slope........ 11 it. by 19 it. 1 in. 857 ft. 11500 5200 50 2 Skip shaft.... 32 ft. 8 in. by 12 it. 8 in. 296 ft. 6042 2293 300 3 Fig. 2 shows sections of these openings. The surface plan shows the relative positions of the openings. Coal was first hoisted from the air shaft May 7, 1918, and entry driving was continued; but the coal had to be stored, as the railroad had not been extended from Crucible to Nemacolin. As soon as the slope was driven to the coal and the linings concreted, the entries were driven along projected lines to connect with those advancing from the air shaft, and skip shaft. As soon as the underground connections had been made between the two shafts, the hoisting by buckets was inaugurated at the skip shaft and construction on the fan at the air shaft started.

Jan 1, 1927

By Warren Howes, C. O. Anderson, Robert E. Illidge, M. D. Harbaugh, S. J. Burris

The Tri-State zinc-lead mining district embraces an extensive area, including the northeastern part of Ottawa County, Oklahoma, the southeastern part of Cherokee County, Kansas, and adjacent portions of Missouri, mainly in Jasper County. The Oklahoma-Kansas portion of the district, in the vicinity of Picher, Okla., has been the principal producing area since 1917, and the present milling practice in that section is the subject of this paper. This district is the largest zinc-producing field in the United States. In 1926 it produced 55 per cent of the nation&apos;s zinc and 15 per cent of its lead, and in 1933 it produced 35 per cent of the zinc and 10 per cent of the lead. From 1842 to 1933, inclusive, the total output of the district was 18 1/2 million tons of zinc and lead concentrates valued at 818 million dollars. Of this production, the Oklahoma-Kansas, or Picher, field yielded over 9 million tons valued at over 400 million dollars. Mining operations in the Oklahoma-Kansas field near Picher and Baxter Springs began in 1915. The mills built it that time consisted merely of gravity concentration plants employing jigs and tables and the same flow sheets as had proved satisfactory with the free-milling ores such as were mined in the Joplin-Webb City fields in Missouri. The Kansas-Oklahoma ores proved to be much richer but also more refractory to treatment than those in the Joplin area, and contained a considerable percentage of zinc mineral not freed by the amount of crushing usually practiced in preparing the ores for jigging. Thus the old Joplin type of mill, with its usual two or four jigs and a few tables, proved inadequate and resulted in excessive tailings losses sometimes as high as 50 per cent

Jan 1, 1935

By Frank F. Poland

TEE purpose of this paper-is to describe a new process for the refining of secondary copper-base metals and a specially designed high-temperature electric-resistor furnace used in the process for the distillation of zinc from these metals. The process was used for the conversion of nickel silver to cupronickel and to recover the zinc content in metallic form. It also proved applicable and economical for the treatment of scrap brass for separating and reclaiming the copper and zinc. The relatively large furnace developed for the distillation of zinc is described in detail, for it made economically possible the direct recovery of metallic zinc from scrap brass, which is a new step in the processing of such material. Considerable interest has been shown in the utilization of the distillation furnace for other metallurgical processes, where it is of advantage to operate in a controlled neutral or reducing atmosphere, or to avoid having the processed metal in contact with refractories other than carbon, or to operate at temperatures between 3000 and 4000°F. PURPOSE OF DEVELOPMENT It was recognized early in the war effort that nickel would become a critical metal, therefore all nickel stock and alloys containing relatively high percentages of nickel were frozen immediately. Among these alloys were considerable quantities of various grades of nickel silver, an alloy containing copper, nickel, zinc, and in some grades lead, also minor amounts of iron, manganese and other constituents. At the time there was no existing plant or process to eliminate the zinc, lead, and minor constituents so as to convert this metal to cupronickel, one of the important alloys needed by the U. S. Navy for condenser parts. Therefore the Bureau of Industrial Conservation of the War Production Board requested the executives of the leading nonferrous metal companies to have their metallurgical staffs study the problem of converting this metal to cupronickel conforming to U. S. Navy Specification 44T40. The composition specified therein is as follows: nickel, 29 to 32 per cent; zinc, 1.00; iron, 0.00 to 0.60; lead, 0.05; tin, 1.20; manganese, 0.00 to 1.00; total of other elements (maximum), 0.50; copper, remainder. The problem in converting these alloys to cupronickel was the elimination of zinc, lead, iron, manganese, and other elements without appreciable loss of nickel to slags or other by-products. Revere Copper and Brass Incorporated, through its Research and Development Department, undertook to solve this problem. A Government-owned plant was built at Rome, N. Y., and there the con- version was successfully made.

Jan 1, 1946

CONTENTS PAGE Need for Research in Foundry Pig Iron. By Richard Moldenke. (With Discussion) 1 Carbon Characteristics of Copper-bearing Pig Iron. By W. B. Coleman. (With Discussion) 12 A Pig Iron, Low in Total Carbon, is in Demand for Use in Various Industries. By Enrique Touceda. (With Discussion) 24 Carbon in Pig Iron. By Ralph H. Sweetser. (With Discussion) 28 Second Session (Discussion) 37 Need for Research in Foundry Pig Iron BY RICHARD MOLDENKE,* WATCHUNG, N. J. So FAR as the quality of the product is concerned, the history of the production of pig iron for foundry purposes is one of constant retrogression. The steps in this deterioration began with cold-blast charcoal pig iron, then anthracite iron, coke iron; then gradually warm to hot-blast coke iron, with the charcoal furnaces also heating their blast to get greater tonnages, and finally the present-day hot-blast coke irons with scrap additions to the ordinary burden that, according to one European report, have gone as high as 65 per cent. Parallel with this quality retrogression is the enormous increase in furnace tonnages from about 15 to over 1000 tons per day in exceptional instances of modern practice. The key to this situation is economic pressure. The effect is a growing differentiation between furnace production for gray iron and malleable foundries and, for the

Jan 1, 1927

By H. F. Bishop, F. A. Brandt, W. S. Pellini

The solidification mechanism of experimental steel ingots (7x7x20 in.) was studied by thermal analysis. It was determined that solidification proceeds in wave-like fashion at rates which are determined by the carbon level, superheat, and mold thickness. The thermal cycles of the mold walls were related to the course of solidification. ESPITE marked advances in the field of solid state transformation, metallurgical research has contributed comparatively little exact quantitative data on the mechanism of solidification of metals. There is, therefore, a great need for such data in the various metallurgical industries. The mechanics of solidification of ingots have been investigated in the past primarily by studies of the rate of skin formation as indicated by bleeding or "pour out" tests. The "pour out" method, however, is a tool which gives only approximate information. In the case of alloys with wide solidification ranges, such as irons and certain nonferrous alloys, the method will not work at all; in the case of alloys of intermediate solidification ranges, such as commercial steels, the information may be misleading. Thus, the general adoption of this method has resulted in divergent conclusions regarding the solidification process. Chipman and Fondersmith1 by means of bleeding tests have shown that the linear growth of a solidifying ingot wall follows a parabola of the general form, D = K C, with the start of solidification delayed until superheat is exhausted, as indicated by the constant C. These tests were carried only to a wall thickness of about 5 in. using an ingot of approximately 17x39 in. in cross-section; hence the latter stages of solidification were not studied. Matuschka2-3 indicated that linear solidification of ingots is rapid at first, then slow, but toward the end of solidification the rate becomes extremely rapid again. Spretnak&apos;s4 bleeding studies indicated that, wall growth is expressed more rigorously by two parabolas, and that their point of intersection corresponds to a change of solidification mode from columnar to equiaxed. Spretnak also showed that the K values of the first parabola are always the same regardless of superheat. Nelson bled ingots of square cross-section and found that linear wall growth is initially rapid but decreases continually until the end of solidification. He also concluded that rate of solidification in ingots of square cross-section increases 2.15 pct for every 10 pct increase in cross-sectional area of the mold. The mold ratios considered (ratio of cross-sectional area of the mold to cross-sectional area of the ingot) were all less than 2 to 1. The subject of solidification has also been treated mathematically in many cases, but because of the lack of accurate thermal constants and the simplifying assumptions required, as their authors generally acknowledge, they represent only approaches to the actual conditions of ingot solidification. A third method of studying solidification is the electrical analogue method promulgated by Pasch-kis6-7 and by Jackson and coworkers.8 This method treats solidification as a heat transfer problem with the solidification cycle synthesized on an electrical circuit. Paschkis in his treatment of solidification considered the fact, which was generally ignored, that solidification of steel is not simply the growth of a plane solid wall but a more complex process occurring over a temperature range as indicated by the constitution diagram. Undoubtedly, the anomalous results obtained by bleeding tests arise from the inability to measure quantitatively this mushy condition. The shape of Paschkis&apos; solidification curves are more nearly in accord with those of Matuschka, in that they indicate rapid linear solidification at the beginning and end of solidification with intermediate solidification occurring at a slower rate. Paschkis indicates a definite lengthening of solidification time with increasing superheat. Thermal analysis is a direct method providing exact information for all types of metals regardless of solidification range and was thus adopted in the present program to follow the entire course of solidification from the surface to the centerline of the ingots. The method has the added advantage of being adaptable to following the thermal cycle of the ingot mold during the course of solidification. Test Methods The ingots studied were of square cross-section, 20 in. long, tapered from 71/4 in. at the top to 63/4 in. at the bottom, and fed with a hot top 7 in. in diam and 12 in. high. The molds were uniform in wall

Jan 1, 1953