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

In the iron-cobalt system there are several property-composition relationships of theoretical importance. The alloys are ferromagnetic exhibiting a maximum saturation at approximately 33 at. pct cobalt;' the interatomic distances at room temperature show large positive deviations from Vegard's rule;2 and in the region of 50 at. pct cobalt there is an order-disorder transition2 which has a large effect on other properties. The thermal expansion data for the system have been reported only from room temperature to 100 C and for this temperature range a minimum in coefticient in the rcgion of 50 at. pct cobalt is well established.3,4,6 This paper reports the expansion properties in the iron-cobalt system for temperatures from 30 to 850°C, shows the correlation with other physical properties, and proposes an explanation for the tcrrelation. Experimental Procedure The thermal expansivities of iron-cobalt alloys in 10 pct steps in composition were determined from 30 to about 850°C. The major series of alloys was prepared by induction melting from Armco iron and cobalt rondelles with the addition of about 0.6 wt pct manganese. This series was supplemented by three compositions: high purity electrolytic iron, high purity electrolytic cobalt, and an alloy of 52.1 wt pct cobalt prepared from the high purity electrolytic iron and electrolytic cobalt by vacuum-melting. The compositions of both series of alloys are given in Table I. The specimens for measurement were prepared from the cast ingots by first hot-swaging followed in most instances by cold-swaging to 0.180-in. diam rod. Some alloys in the region of 5c pct cobalt, because of inherent cold-brittleness, were swaged hot to the final diameter. The expansion specimens were approximately 2 1/2 in. long with flat-ground and polished ends. Before measurement they were annealed in hydrogen for I hr at 900°C. In the apparatus used for the thermal expansivity measurements (Fig I), a modification of that designed by Hidnert and Sweeney,? the differential expausion between the specimen and vitreous silica was measured by a dial micrometer reading to 0.001 mm. An invar fixture supported the dial gauge, and this fixture, in turn, was connected to a split invar collar which supported the outer silica tube. A pyrex "T" was placed over the outcr silica tube and was sealed to the invar collar by Apiezon Q sealing compound. A movable hollow vitreous silica rod which rested on top of the test specimen slid through a flexible rubber diaphragm cemented to the top of the pyrex "T." The specimen rested On a vitreous silica pedestal fused into the outer tube and was kept centered by a silica sleeve. A nonoxidizing atmosphere was obtained by admitting hydrogen into the

Jan 1, 1949

By R. E. Reed-Hill, W. H. Hartt

The second order, {1011}-{1012} twin bands observed in critically deformed magnesium are often accompanied by an unusual form of kinking. These kinks, which lie adjacent to and run more or less parallel to the twin band habit, allow plastic deformation that occurs inside the twins to be accommodated into the matrix. The bend planes of these kinks cannot be explained using slip dislocations with Burgers vectors lying in the basal plane. A mechanism involving a single set of {1012)(1011) dislocations is proposed to account for the kink band habit, in good agreement with the experimental observations. It has been shown that second order, {101l)-{1012} twinning is an important phenomenon for magnesium deformed in the ambient temperature range. A detailed study of these twins has recently led to a better understanding of their irrational habit plane1 and their relation to fracture in magnesium.' This paper is concerned with a third aspect of these twins; this being the kink bands, originally referred to as shear accommodation kinks,3'4 that are often induced in the adjacent matrix. A twin band and its shear accommodation kink usually appear as a single macroscopic deformation, as seen in Fig. 1. The complex nature of these deformed regions is easily revealed, however, with the aid of a suitable microscope. It has been proposed374 that the primary function of these kinks is to accommodate the nonhomogeneous deformation that normally occurs in the second order twins. The twins tend to form as small discrete lamellae lined up approximately one in front of the other.''' Very large plastic deformations varying in magnitude from one twin to the next, may occur inside these lamellae. The kinks serve both to pass this strain into the matrix and to accommodate strain variations between twins. Deformation within the kinks, subsequent to their formation, has also been observed;3,4 and it is thought that this contributes to the strain accommodation process. The bend planes of the kinks have a habit near that of the twin band itself, which lies about 56 deg from the matrix basal plane. This orientation does not bisect the angle formed between the basal plane to either side of the bend plane and therefore differs markedly from the kink structure usually observed in hcp metals.'-' The present paper reports the results of a study of shear accommodation kinks and proposes a possible solution to the problem of the orientation of the bend plane. EXPERIMENTAL PROCEDURE Rectangular cross-section tensile specimens with axes parallel to (1010) and faces to (1210) and (0001) were cut and acid machined from a high-purity magnesium single crystal. After straining on an Instron machine the specimens were examined by both optical and replica electron microscopy. The basic procedures have been previously reported."' EXPERIMENTAL RESULTS AND DISCUSSION Structure of Shear Accommodation Kinks. A typical, large (101l)-{1012) twin band with its associated shear accommodation kink is shown running diagonally from upper left to lower right in Fig. 1. In this optical micrograph the twin band, consisting of a row of small, highly deformed twin lamellae, is visible as a narrow dark band along the left hand edge of the structure in question. The kink lies to the right of the twins, is approximately three times as wide, and is lighter in contrast. The horizontal slip lines visible on the general specimen surface correspond to matrix basal slip and are parallel to the tensile axis. Note that on the right-hand side of the band these slip lines can be followed from the matrix into the kink. At the kink band boundary the slip lines suffer a clockwise rotation of about 25 deg. Rotations of this magnitude are not uncommon. When a surface such as that in Fig. 1 is given an etch1 making it sensitive to polarized light, it has been observed that the slip traces in the kink are parallel to the basal plane trace in this region. This is in excellent agreement with the assumption that these regions are indeed kinks. Fig. 2 is an electron micrograph of this same twin band and kink. Note that a row of small supplimation pits has formed

Jan 1, 1969

By James K. Stanley

PREFERRED orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.1 In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurgical literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanical properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important in- formation, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational under- standing of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing 'stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required-it is only necessary punch or machine a disk of the sheet material and insert it into the testing device.

Jan 1, 1943

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann' and Pilling and Bed-worth. wott and Gurney' have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.' According to Wagner','' silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,' silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By R. L. Featherly, J. R. James

The replacement or reconditioning of oil storage tank bottoms due to external corrosion is an expensive maintenance item to the oil industry. Cathodic protection as a means of mitigating this problem has proved very successful in the past few years. One pipe-line company recently used magnesium anodes to cathodically protect two 55,000 bbl and two 20,000 bbl tanks. The tank bottoms were protected as individual units with considerable factual data being taken on one of the 20,000 bbl tanks. Twelve 60-lb anodes were installed about 2½ ft from the tank on approximately 17-½ft centers around the tank. Previous installations and tests have shown that sufficient protection is provided when the tank-to-soil potential using a copper-copper sulphate half-cell as a reference electrode is — 0.90 volts at the edge of tank. Potential measurements taken a few months after completing the installation indicated that the potentials were higher than were needed for protection. Resistors were then inserted in the individual anode circuits which increased the life of the anode installation and still provided adequate protection for the structure. All connecting pipe lines were then insulated from the tank. This limited the anode current strictly to the tank resulting in a greater degree of protection with a still longer anticipated anode installation life. The total installation cost for this tank was less than $300 which amounts to $20 per year The corrosion of metallic structures in contact with soil or water has been a very serious and costly problem for centuries. The annual loss to our nation's pipelines alone is estimated at $200,000,000. Mitigation of this problem by various methods has been carried on quite successfully for a number of years. An electrical method called cathodic protection has been used with considerable success to control corrosive influences on pipelines, tank bottoms, cable sheathing and other buried metal structures. Corrosion of oil storage tank bottoms has been a serious problem among the oil industries for years. In addition to damage costs and loss of oil, the replacement of one tank alone represents several thousand dollars. A reconditioning program at periodic intervals was instituted by several organizations and found to be a very expensive process. A few years ago two of the pipeline companies installed cathodic protection units at their tank farms.3'4 The average current required for protection of the tank bottoms varied from 0.7 to 1.0 milliampere per square foot. The results indicated that adequate protection was obtained at a cost of approximately 10 pct of the previous reconditioning program. The Republic Pipe Line Company experienced severe corrosion on their oil storage tanks. One of their 55,000-bbl tanks

Jan 1, 1948

By R. L. Featherly, J. R. James

The replacement or reconditioning of oil storage tank bottoms due to external corrosion is an expensive maintenance item to the oil industry. Cathodic protection as a means of mitigating this problem has proved very successful in the past few years. One pipe-line company recently used magnesium anodes to cathodically protect two 55,000 bbl and two 20,000 bbl tanks. The tank bottoms were protected as individual units with considerable factual data being taken on one of the 20,000 bbl tanks. Twelve 60-lb anodes were installed about 2½ ft from the tank on approximately 17-½ft centers around the tank. Previous installations and tests have shown that sufficient protection is provided when the tank-to-soil potential using a copper-copper sulphate half-cell as a reference electrode is — 0.90 volts at the edge of tank. Potential measurements taken a few months after completing the installation indicated that the potentials were higher than were needed for protection. Resistors were then inserted in the individual anode circuits which increased the life of the anode installation and still provided adequate protection for the structure. All connecting pipe lines were then insulated from the tank. This limited the anode current strictly to the tank resulting in a greater degree of protection with a still longer anticipated anode installation life. The total installation cost for this tank was less than $300 which amounts to $20 per year The corrosion of metallic structures in contact with soil or water has been a very serious and costly problem for centuries. The annual loss to our nation's pipelines alone is estimated at $200,000,000. Mitigation of this problem by various methods has been carried on quite successfully for a number of years. An electrical method called cathodic protection has been used with considerable success to control corrosive influences on pipelines, tank bottoms, cable sheathing and other buried metal structures. Corrosion of oil storage tank bottoms has been a serious problem among the oil industries for years. In addition to damage costs and loss of oil, the replacement of one tank alone represents several thousand dollars. A reconditioning program at periodic intervals was instituted by several organizations and found to be a very expensive process. A few years ago two of the pipeline companies installed cathodic protection units at their tank farms.3'4 The average current required for protection of the tank bottoms varied from 0.7 to 1.0 milliampere per square foot. The results indicated that adequate protection was obtained at a cost of approximately 10 pct of the previous reconditioning program. The Republic Pipe Line Company experienced severe corrosion on their oil storage tanks. One of their 55,000-bbl tanks

Jan 1, 1948

By S. R. Zimmerley, S. F. Ravitz

High-grade cobalt concentrates were produced from the complex Blackbird ore with very good recovery in continuous pilot-plant operations in which a low-grade bulk cobaltite-pyrite flotation concentrate was roasted in a multiple-hearth furnace to oxidize the pyrite selectively. The cobaltite was floated from the resulting calcine.

Jan 1, 1950

By Anal J. Mehta, Theodore D. Tiemann

Growing demand for steel and increasing dependence upon foreign ore makes the need for developing the technology for treatment of low-grade iron ores greater than ever before• Representative of these added interests were the studies carried on at the University of Wisconsin• These studies included among others: anionic and cationic flotation, magnetic separation, roasting followed by magnetic separation, electrostatic separation, a hydrogen reduction process,6,7 and caustic digestion• The idea of removing silica by caustic extraction is not new•-1; The principle of concentrating siliceous iron ores by this method is based on the fact that silica is soluble in sodium hydroxide solution while iron oxides are essentially insoluble• For this process to be economically feasible, it is believed that some method of recovering silica from solution as a marketable by-product, with recycling of spent liquor is necessary. Precipitation of silica with carbon dioxide will allow subsequent causticizing of the spent liquor with lime• Caustic thus produced can be recycled for digestion• A flowsheet of the envisioned process is given in [Fig• 1] The purpose of this paper is to describe results obtained from the investigation of carbon dioxide precipitation of silica from sodium silicate solutions, which could be later applied to the caustic extraction process to treat low grade siliceous iron ores, particularly taconites.15 Theoretical Considerations The soluble silicates of sodium include sodium orthosilicate (2Na2O•SiO2), sodium metasilicate (Na20•SiO2), sodium disilicate (Na1O•2SiO2), and more highly siliceous products approaching Na2O•4SiO2• These materials have been described in detail by Vail•16 Stones has reported that the extraction of silica is not significantly affected by the amount of silica in solution until the Si02/Na20 ratio exceeds that of orthosilicate (Ratio = 1/2)• However, as the Si02/Na2O ratio exceeds that of metasilicate (Ratio = 1), silica extraction is significantly impaired• The present experimental work was confined to orthosilicate and metasilicate solutions, as to be successful the envisioned commercial process for the extraction of silica from siliceous iron ores would operate in this region. The mechanism of extraction of silica from aqueous sodium silicate solutions is complex in nature. For the carbon dioxide process-18 of core and mold making in which silica is also precipitated from sodium silicate solutions by gassing with carbon dioxide, the reaction of aqueous silicates with gaseous carbon dioxide has been represented by the equations: [ ] However, these equations are very much oversimplified• It has been shown that the reaction between aqueous sodium silicates and carbon dioxide gas is ionic in nature 18 Considering this fact and the mechanism for digestion of silica in aqueous sodium hydroxide, the overall conversion of aqueous sodium silicates to solid silica may be represented in ionic form by the following equations: [ ] Silicon in the silicate ion is shown here with a coordination number of 6• This may be in doubt, but it is known that ion (SiF°)-2 exists; it seems logical that the Si (OH) e 2 ion should be equally capable of existence•

Jan 1, 1977

By Louis A. Rosales, Kanji Ono

The anomalous behavior of hydrogen in iron is examined and a new model is proposed It is postulated that hydrogen single and di-interstitials are in equilibrium with each other. When the binding enthalpy of the di-interstitial, B, is assumed to be about 10 kcal per mole, the predicted temperature dependence of the solubility agrees reasonably well with the reported data. Effective diffusiuity is calculated assuming the di-interstitials to be immobile. Since the number of mobile single interstitials is greatly reduced at lower temperatures, the effective diffusivity is decreased. A good agreement in the temperature dependence of diffusivity between theory and experiment is provided with B - 10 kcal per mole. The predicted diffusivity is also a function of total concentration of hydrogen and this appears to be Partly responsible for the large scatter in the reported data. HYDROGEN is known to form an interstitial solid solution with iron.''' At elevated temperatures, it has been well-established that hydrogen enters iron in the dissociated form and occupies the interstices, and that diffusion of hydrogen in iron is via the interstitial mechanism. The concentration, c, permeability, P, and diffusivity, D, of hydrogen in iron have been separately determined and are consistent with each other under the steady-state condition for temperatures above approximately 400°C; that is, the relationship P = c-D holds. At lower temperatures, however, anomalous behavior of hydrogen in iron has been observed by many investigators. The results of experimental studies4-'' of the diffusion of hydrogen in iron are summarized in Fig. 1, in which the values of D are plotted against the reciprocal temperature. Although there is an increasing divergence in observed values of D with decreasing temperature, the values of D at temperatures below approximately 200°C are definitely small as compared with the extrapolation from high-temperature data. The lines shown bracket the region containing the most probable data. The observed values of c6," are plotted against the reciprocal temperature in Fig. 2, where the dashed lines represent Geller and sun's'' most probable isobars at 1 and 100 atm. At high external hydrogen pressure and low temperatures, the values of c observed are higher than those expected from high temperature data. It is generally accepted that certain trapping mechanism is responsible for the anomalies, but the nature of the trapping mechanism has not been clarified. Various types of hydrogen traps were suggested in the literature, such as "rifts" in the lattice dislocations, voids, microcracks, and so forth. However, no quantitative account of the observed behavior has been given in terms of these trapping mechanisms. Formation of methane in hydrogen-charged steel was found by ~odgurski." This appears to explain the existence of the so-called "residual" hydrogen,4 but not the observed anomalies of hydrogen in iron. McNabb and Foster' proposed a mathematical analysis in terms of a trapping mechanism. However, the physical significance of the traps was not clarified. The necessity of evaluating five parameters in their theory made comparison with experiment difficult. In the present paper, a model is proposed in which the anomalous behavior of hydrogen is attributed to the formation of hydrogen di-interstitials at lower temperatures. In this model, it is postulated that single and di-interstitials are in equilibrium with each other. (The hydrogen di-interstitial is to be distinguished from a hydrogen molecule which may exist in voids.) It can then be shown that most of the anomalies can be explained by assuming that the di-interstitials are virtually immobile and that the binding enthalpy of the di-interstitial, B, is approximately 10 kcal per mole. Predictions of the theory agree with the available experimental data reasonably well. THEORY The basic postulate of the present analysis is that single and di-interstitials are in equilibrium with each

Jan 1, 1969

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10'' atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10'' to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein' reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By E. M. MacKevett

The only source of uranium ore in Alaska that has been mined commercially is the Ross-Adams deposit, a gently inclined, fusiform orebody in alkali granite in which uranothorite and uranoan thoria-nit? ale the chief ore minerals. In mode of occurrence, apparent genetic association with the granite, and to a lesser extent in mineralogy, this type of deposit is uncommon. The mine is in the southern part of Prince of Wales Island (Fig. 1) at an altitude of about 950 ft on the southeast flank of Bokan Mountain. A steep unpaved road 1 3/4 miles long leads to the dock on the West Arm of Kendrick Bay, which can be reached by boat or seaplane from Ketchikan, some 35 miles to the northeast. The southern section of Prince of Wales Island is covered by dense forests interspersed with swampy tracts of muskeg. Most of the higher peaks support only sparse vegetation, and in areas underlain by alkali granite bare rocky slopes prevail to as low as 800 ft. Numerous fiord-like embayments penetrate this part of the island, and their shorelines provide near-continuous rock exposures. Rainfall is heavy, about 150 in. annually. Throughout the year the climate is relatively mild. History and Production: In May 1955 two members of a Ketchikan prospecting group, Don Ross and his wife, found the deposit while working with an airborne geiger counter. Later they confirmed their discovery by ground investigations. During the summer Climax Molybdenum acquired controlling interest in the property and started exploratory diamond drilling, resuming the drilling on a larger scale in the summer and fall of 1956. Climax began mining in July 1957, shipping the ore by barge and train to the Dawn Mining Co. mill at Ford, Wash. The open pit workings, about 370 ft long, between 25 and 75 ft wide. and 25 ft deep (shown in Fig. 2) were shut down in October 1957. As of September 1958 the pit was still inactive, although a small tonnage of known reserves remains in the southern part. The operators believe the 15,000 tons of uranium ore already produced will average 0.80 pct. GEOLOGY The Ross-Adams mine is within a small stock or boss of alkali granite, about 1000 ft from the southeast margin of the granite (Fig. 3). The area around the boss is underlain chiefly by plutonic rocks of intermediate composition and by metamorphosed sedimentary and volcanic rocks. The oldest rocks in the area probably are the metamorphosed volcanic rocks that are well exposed adjacent to the South Arm of Moira Sound. They are considered by Buddington and Chapin1 to be of Devonian age. These light gray to dark gray rocks mainly represent a layered volcanic sequence. They are commonly porphyritic with plagioclase pheno-crysts in an altered, fine-grained groundmass. The

Jan 1, 1960

By C. Richard Honeycutt, Frederick C. Langenberg, Guenter Pestel

Otto Schaaber (Institut für Harterei-Technik, Bremen-Schönebeck, Germany)— Langenberg, Pestel, and Honeycutt gave an interesting example of the grain refining effect nonstationary magnetic fields may execute on a solidifying metal. Probably some additional comments, based on more than a decade of experience with this method of influencing crystallization, may be useful. They refer to an attempt to explain the mechanism of grain refinement by such fields, and to recent European developments which have not been mentioned in the paper. I. During studies of the temperature distribution in a metal body near the phase boundary solid/liquid, an anomaly was observed under certain special conditions: a) direction of heat transfer as horizontal as possible, b) steady state (equilibrium, i.e,, solidification resp. melting rate exactly zero). In the liquid phase, immediately adjacent to the phase boundary, the temperature was found to be constant over an appreciable distance in spite of a high value of heat transfer (40.000 to 70.000 keal/ m2h).3 Convection, which might explain this phenomenon, could not be observed. Therefore another explanation had to be sought. The assumption that a metallic melt, especially at temperatures near the point of solidification, contains some sort of atomic arrangement with a higher degree of order than the surrounding liquid, now is generally accepted. Considering the differences in energy between such an arrangement and its environs, a transport of heat even in absence of any temperature gradient is conceivable by continued formation and redissolution of regions with a higher degree of order, i.e., with lower energy level.3 At this stage, it was not necessary to postulate any special condition as to the form or size of these regions or the distance between arrangements to be newly formed and those to be redissolved. However, a simple consideration shows that an energy transfer from one region to another will only be possible without loss of energy, if the distance between will be equal to the lattice parameters, and if, secondly, crystallographic axis or planes will be parallel.4 By the way, this assumption might give a reasonable explanation of the well known orientation effect of the heat flow during solidification. Any measures to prevent columnar crystallization should act upon this ordering mechanism: a) the regions with a lower energy (higher order) should not be allowed to arrange themselves parallel to the direction of heat flow, and their growth should be disturbed; b) all conditions leading to an appreciable heat flow of uniform direction should be avoided or removed. Condition a) may be satisfied by a physical force preferably under 90 deg to the main axis of the columnar crystals (i.e., parallel to the solidification front) acting on the ordered regions; condition b) by equalizing any differences in

Jan 1, 1962

By Reuben B. Ellestad, Fremont F. Clarke

Lithium chemical plant extraction methods are discussed with reference to 1) base exchange with alkali sulphates; 2) processing based on roasting with lime; 3) miscellaneous methods; and 4) application of the Lithium Corp. process to extraction of lithium from run-of-mine, low grade spodumene ore, or concentrates. IN the early days of the lithium industry most of the production was from lepidolite, zinnwaldite, and amblygonite. Nearly all the early extraction processes described in the literature involve heating the finely ground mineral with sulphuric or hydrochloric acid. On subsequent water leaching most of the bases present in the mineral (especially aluminum) are dissolved as sulphates. As a result, the leach solution required extensive chemical purification before the lithium could be precipitated as carbonate. Following the remarkable growth of the lithium industry to its present size, zinnwaldite and amblygonite ores must be considered of minor importance only. Attention is now focused on spodumene, abundant enough in North America to be a major source of supply, and there are important supplies of lepidolite and petalite in Africa. The extraction processes described below all apply to spodumene, although several will also operate on other lithium minerals, such as petalite. Base Exchange with Alkali Sulphates: A distinct advance was made with the disclosures of Wadman and von Girsewalt. In these methods the finely ground silicate ore (spodumene or lepidolite) is intimately mixed with an excess of alkali sulphate (usually K2SO4) in at least a 1 to 1 proportion, and the mixture was heated to a relatively high temperature. Base exchange results, with the formation of lithium sulphate. A water leach dissolves the lithium sulphate, together with the excess potassium sulphate. Successful operation of this type of process requires very thorough grinding and mixing, as well as careful temperature control. The use of K2SO4 is objectionable from cost considerations since purification of lithium carbonate requires the use of potassium carbonate, if the K2SO4 is to be recovered and recycled. The lower solubility of K2SO4 as compared with Na2S04 is also objectionable, since it limits the concentration of the Li2SO4 solution to be precipitated by K2SO4. Early laboratory-scale investigation of this process by Lithium Corp. was not encouraging. Other related base exchange processes are those of Lindblad, Wallden, and Sivander3 and Sivander, Gard, Villestad, and Wallen4. The former covers the reaction of lithium silicate minerals with a sodium sulphate solution, at 100" to 300°C (under pressure), while the latter involves the extraction of silicate minerals with molten sodium sulphate. Both these processes would seem to be difficult and expensive to operate.

Jan 1, 1956

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By L. W. Casteel

St. Joseph Lead Company's Southeast Missouri mines have been successfully converted to the use of ammonium nitrate and fuel oil as a blasting agent. This is significant to the company because it means a savings of a quarter of a million dollars per year. It is significant to the mining industry because of the unusual conditions involved and the methods and materials used to overcome them. St. Joe has been mining the low grade lead deposits of southeast Missouri since 1864. This ore occurs as disseminated galena in widely scattered pockets within the Bonneterre dolomite. The daily production of 20,000 tons is obtained from several hundred small, room and pillar stopes covering an area 10 miles long and five miles wide. Distribution of explosives and other materials is a real problem. Drilling in the stopes is done with air legs, column- mounted machines or jumbos, depending on the size and location of the stope. Drill hole sizes vary from 1 3/8-in. diam down to 1 1/8-in. Each driller charges his own holes and shoots them at the end of the shift. Numerous shafts provide natural ventilation which is supplemented in isolated areas by churn drill holes equipped with blowers. Water, in most stopes, is not a serious problem, although the mines do produce about 20,000 gpm.

Jan 5, 1962

By E. B. Brauer, B. F. Pennington, E. W. Hough, G. L. Stegemeier

Interfacial tension divided by the difference in density between the liquid and the vapor phases was determined experimentally by the pendant drop method on several isotherms in the two phase region below the critical point for the methane-normal decane system. The density difference data of Sage and Lacey was used in the calculation of interfacial tension. Both interfacial tension and and interfacial tension divided by density difference were found to vanish at the critical point. Interfacial tensions of less than one dyne/centimeter were observed as far as 1,000 pounds per square inch below the critical pressure. EXPERIMENTAL PROCEDURE The interfacial tension divided by the density difference for the methane-normal decane system was determined at the 100°, 130°, 160' and 190°F isotherms, from pressures of about 1,000 psi to the critical pressure, which is more than 5,000 psi for these isotherms. Particular emphasis was placed upon the investigation at pressures slightly below the critical pressure where the interfacial tension is less than 0.5 dyne/cm. Volumetric properties in the two-phase region, including the critical pressures and temperatures, were taken from the work of Sage and Lacey.1 The experimental pendant-drop technique used for the determination of interfacial tensions at high pressures incorporated the ideas of Michaels and Hauser,2 Hough, et a1,3 Walker4 and Heuer.5 In addition, the technique for determination of extremely small interfacial tension by Jennings6 was utilized in the region near the critical points. A detailed description of the apparatus is given in a dissertation by one of the authors.7 Cleaning operations on the stainless-steel sample system included successive washings with chromic acid, tap water and, finally, distilled water. Subsequent cleanings were performed with re-distilled normal pentane, which had an extremely low residue upon evaporation. Specific composition requirements necessitated a fairly precise sample introduction — although, fora two-phase, two-component system, the composition of each phase is completely determined if pressure and temperature are controlled. The normal decane was delivered into the evacuated sample system as a liquid from a burette. The methane was then introduced into the system from a calibrated isothermal container, so that pressure differentials could be used to determine the amount introduced. High pressures were obtained by compressing the sample with a mercury injection pump until the critical pressure was reached for the particular isotherm being studied. Experimental data were then obtained for specific pressures by first decreasing the pressure slightly so that two phases would appear, and then photographing a drop at that pressure. Subsequent photographs were made at increments throughout the pressure range. Calculation of interfacial tension divided by density difference was made from measurements

By REED H. HYDE

IN these days of low metal prices and difficult marketing conditions, any treatment that will improve the grade of a product is of interest, particularly when the operation involves little or no addition to the total cost and may even result in a marketable by-product. Such a' combination of circumstances exists, in some cases, in the zinc industry, where it has been found that certain impurities can be removed from .the ore during the Dwight-Lloyd sintering operation, previous to reduction to metal. Consequently it is not surprising that zinc smelters having these sintering machines are paying particular attention to this phase of the operation. Loss of zinc as fume is very low under the conditions obtaining in sintering zinc ores, but impurities such as cadmium and lead are more readily fumed off and it is on this fact that the purification is based. As a result of preferential volatilization of these impurities a sintered product' is made from which purer zinc metal or oxide can be produced, while the fume may be collected and treated to recover the impurity metals. To be effective the operation must be carefully conducted, but no special equipment other than that of a well designed Dwight. Lloyd plant is needed.

Jan 1, 1931

By J. S. FINLAY

OPERATING a "muck stick" never appealed to me. It always seemed a terrible waste of energy to "put rocks in the box" by hand-particularly when my own personal energy was involved. But during the past forty years, there have been periods-more or less extended when I was compelled, against my finer instincts, to muck or quit eating. For about the same length of time, I have devised schemes to make mucking faster and more painless. There was always something mechanically wrong with these designs-too many;" parts to wear out and need replacement, and excessive cost incidental to a complicated mechanism. The idea of a shovel unit comprised of a single, rigid assembly which would roll from a digging to dumping position solved the problem of simplicity and durability. Ingersoll-Rand's utility engine provided a splendid power plant, small enough and powerful enough for the job. In the machine finally developed, known as the Eimco-Finlay loader, roller chains are preferred to gears for power trans-

Jan 1, 1935

Note by the Secretary.-—In the preceding communication of Mr. Rickard, in the present discussion, as printed in Trans., xxiii., the loss of quicksilver at Pestarena, reported on p. 569, as 230 and 234 grammes per metric ton, is stated as equivalent to about 74 pounds per short ton avoirdupois—an obvious error, which escaped correction in my reading of the proofs, and was not discovered until after Vol. XXIII. had left the press. The true equivalent is 0.46 pound or about 7 1/2 ounces (instead of pounds) per short ton.— R. w. R. Philip Argall, Denver, Colo. (communication to the Secretary) : Mr. Rickard's last contribution to this discussion* calls for some reply from me, if only by way of defending myself against the charge (p. 569) that my criticisms of his paper were "unnecessarily hypercritical and occasionally unfair." At the same time I am fully aware that our Transactions are not the place for mere personal controversy, and that the sole object of discussion is to define differences of opinion, and defend opposing views as a means of eliciting the truth. Mr. Rickard disclaims the statement, which he says I attributed to him, that in the slow-crushing Gilpin county mills the pyrites remain longer in the mortar than the other portions of the ore. My understanding of his statement was based on the following passages in his paper: " Particles of ore, which have heen pulverized to a fineness which would permit of their exit through the screen, are enabled to settle towards the bottom of the mortar. It would he expected that the heavy metallic minerals occurring in the ore would, because of their greater specific gravity, be most affected by this feature of the treatment. In practice this is found to be so. The fine slimes contain a large proportion of metallic sulphides, generally valuable on account of their close association with the precious metals, while the coarsest particles to be found in the tailings usually consist of quartz and other minerals forming the less heavy gangue (Trans., xxiii., 139).

Jan 1, 1895