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By F. N. Rhines, B. H. Alexander

MUCH attention has been directed to the effects of grain size upon the properties of alloys, but there has been scant study either of the conditions that determine the pattern and dimensions of den-drites in metal systems, or of the influence of their shape and size upon the overall properties of cast-ings. The aim of the research that is about to be described has been to investigate the effect of vari-ous factors upon the mode of formation of dendrites in alloys by measurements of the distance between adjacent dendrite arms (dendrite spacing). Early investigators, including Grignonl and Tschernoff,2 showed that a metal dendrite is com-posed of a tree-like system of stalks and branches arranged in a simple geometrical pattern. North-cott and Thomas3 demonstrated that, in the face-centered cubic solid solutions of copper-base, these stalks and side arms all lie in (100) directions in the crystal. Several investigators, including Sauveur and Chou,0 Sauveur and Reed,' and Martin and Mar-tina have reported that the addition to steel of alloy-ing elements, such as nickel, chromium, and molybdenum, not only makes the dendrites easier to reveal by etching, but makes them coarser. The latter authors8 proposed that the coarsening of the dendrites is roughly proportional to the increase in the temperature range of freezing, caused by adding the alloying elements. Sauveur and Chou6 showed, in addition, that the dendrites are coarsened by a decreased rate of cooling of the casting. Measurement of Dendrite Arm Spacing Among the physical conditions that could be ex-pected to have an influence upon the dendrite arm spacing, that appears in a cast metal, are: composi-tion, rate of freezing, crystal structure, and type of constitution. The relationships obtaining between these variables and the dendrite dimensions have been examined, in the present research, by measur- ing the arm spacing in a wide variety of alloys, listed in tables II through VI. Alloy compositions are recorded in the tables by showing the symbol of the major metal followed by the percentage and symbol of the alloying agent; thus, "Al-10Ag" is an aluminum-base alloy containing 10 pct of silver. Although none of the alloys were analyzed, an im-pression of their degree of purity may be obtained from that of their component metals given in table I. Five hundred grams of each alloy was made by melting in small clay-graphite crucibles in an elec-tric muffle furnace. After alloying the temperature was adjusted to 50" to 75°C above the liquidus and the melts were poured into cast iron molds, at room temperature, the molds having a wall thickness of 1 in. and a cavity 11/2 in. sq in cross-section. Each ingot, thus cast, was sectioned at mid-height and the sectioned surface was polished and etched for metallographic examination. Dendrite spacing meas-urements were made at three positions, namely, ad-jacent to the mold wall, midway between the wall and the center of the ingot, and at the center (desig-nated e, m, and c respectively, in the tables). A typical series of microstructures is presented in fig. 1. For each measurement, the average was taken of the dendrite spacing of several grains covering a zone about 2 mm wide. Only those grains which had a major dendrite axis nearly in the plane of polish were selected in order to eliminate corrections for orientation differences from grain to grain. Although the dendrite spacings were measured to the nearest thousandth of a millimeter, the values listed in the tables are thought to be significant only to the nearest hundredth of a millimeter. The larg-est difference in readings found, when various ob-servers rated the same specimens, was 0.012 mm; the largest difference between corresponding meas-urements upon duplicate specimens was 0.027 mm.

Jan 1, 1951

By William F. List, Marvin A. Schuster

Monolithic electrooptical mosaics of 2500 photo-transistor elements with internal row and surface column interconnections have been fabricated by epitaxial-planar diffsion techniques. Unique access to any elemed of the mosaic is provided through one of the fifty X and one of the fifty Y external leads. The sensor mosaic can be used for imaging applications and has a 1:1 aspect ratio, a resolution of 100 lines per in., a dynamic range in excess of lo3, a sensitivity of 0.5 per pw, element response within a 2:l range over 75 pct of the mosaic, and a minimum detectable signal of the order of 10-' w. Design considerations which ilnpose particclar fabrication yequirements are disctussed along with some of the problems peculiar to the epitaxial and planar-dijfision techniqes by which this device is fabricated. The solid-state silicon monolith has an imaging area of 0.5 by 0.5 in. and an element center -to- center spacing of 0.010 in. J monolithic solid-state electrooptical device has been developed as the photon-sensing mosaic for use in an image-converter system.' This system is the solid-state equivalent of the vidicon and can image radiation in the visible and near-infrared regions of the spectrum. The electrooptical image converter has the desirable size, weight, reliability, and low-power characteristics inherent in solid-state devices. It is read out by direct-wire means rather than by beam-scan techniques. The packaged unit is shown in Fig. 1. A selection of material for the sensor was based on considerations of both reliable fabrication techniques and material spectral response. Silicon was selected both for its response from the lower end of :he visible to the long-wavelength cut-off above 11,000A and for its well-developed epitaxial planar-diffused technology. The electrical image is composed of M x N discrete information bits with each bit emanating from one of the individual phototransistor sensors. The interconnected mosaic concept was introduced to provide a structure which is both manageable in its number of leads and compatible with conventional viewing systems which accept XY data. Interconnections along the Y direction are provided by internally diffused strips, while interconnections along the X direction are formed by vacuum-deposited metal surface bars. Unique access to any individual element of the M x N mosaic is available through one of the M and one of the N external leads. PHOTOTRANSISTOR DESIGN A phototransistor structure2 was selected for the discrete photon detectors of which the mosaic is com- posed. Basically, the mode of phototransistor operation is such that incident quanta are absorbed in the base area of the element where they generate electron-hole pairs. If the electrons are liberated within a diffusion length of the depletion region around the collector junction, they will diffuse to this depletion region and be swept across the junction where they account for a small component of the photocurrent. Similarly, the holes which are created within a diffusion length of the emitter junction will diffuse to this region where they forward bias the emitter and so induce injection of minority carriers into the base. This accounts for the substantial transistor photocurrent. This mechanism of operation implies several design and fabrication goals for the individual sensor elements: high electrooptical conversion efficiency, sufficient carrier lifetime in the base regions, and a maximum volume in which photons can be absorbed within a diffusion length from the depletion layer about the junction. Moderately high transistor gain is desirable to permit readout at low light levels; however, very high gain has a deleterious effect on mosaic dynamic range. The mosaic must also be characterized by good uniformity of element response as well as by good isolation between elements. The above set of conditions imply that junction depths must be optimized with respect to photon ab-

Jan 1, 1967

By Benjamin Petkof

The mineral mica, which has been known to man since ancient times, has played an impor¬tant role in the development of our modern industry. In the latter part of the 19th century sheet mica began finding use as a dielectric insulating material in the newly developing electrical industry. Later, when modern elec¬tronics began to develop, it became a vital insulating and dielectric material for use in electronic equipment. Both the electrical and electronic industries were greatly dependent on some form of natural mica. The manufacture of electric motors of varying sizes, electronic tubes, and other electronic items was dependent on an adequate supply of sheet mica. During World War II this material was so vital to national defense that special efforts were made to mine it in the United States as well as to obtain it from overseas mica-producing areas. However, advancing technology has successfully begun the progressive development of man-made mica-based and non-mica-based materials that can replace mica for many uses. In addition, developing technology has dictated changes that have made sheet mica unnecessary for some uses. As the demand for sheet mica declined, the demand for scrap and flake mica has continued to increase. In fact, today the domestic production and use of scrap and flake mica far outshadows the necessity for good¬quality sheet mica in this country. Historically the United States has always been dependent on foreign sources of material for good-quality sheet mica and imports practically its entire requirement. In the case of scrap and flake mica, the United States is the dominant world producer and consumer. End Uses Sheet mica (Chowdhury, 1941; Rajgarhia, 1951; Skow, 1962) is available in many com¬mercial forms, but these forms can be broadly classified into manufactured and unmanufac¬tured mica. Manufactured mica consists of mica that has been shaped, punched, or other¬wise processed into some form, suitable for a particular end use. Unmanufactured mica con¬sists of partially hand-trimmed or processed material that has not been prepared for any particular end use. Unmanufactured mica is broken into two commercial classes consisting of sheet mica and scrap and flake mica. These classes of mica differ greatly in their ultimate end uses and marketed forms. Sheet muscovite mica can be classified by color, degree of prep¬aration of the crude material, thickness, size, visual appearance, and electrical quality. In addition, phlogopite mica is also classified by its thermal stability. Scrap and flake mica consist of mine, trimming shop, and factory scrap that occurs as remnants from mining, processing, and manufacturing operations, and small particle size mica that is available from the beneficiation of pegmatites, clays, schists, or other mica-rich host rock. The end uses for sheet mica vary so greatly from those of scrap and flake mica that it is necessary to discuss them separately. Sheet Mica Sheet mica consists of relatively flat sheets of material which have been mined as naturally occurring books or runs of mica. These sheets are hand-trimmed to remove any imperfections and are punched or stamped into specified shapes for industrial use. Sheet mica can be further processed and is described or specified as block, film, or splittings based on thickness. Block mica is not less than 0.007 in. thick with a minimum usable cross-sectional area of 1 sq in. Film mica is split from the better quali¬ties of block mica to specified thickness groups ranging from 0.0012 to 0.004 in. Splittings are sheets of mica with a maximum thickness of 0.0012 in. and a minimum usable area of 0.75 in. Other small sized, lower quality block mica

Jan 1, 1975

By G. R. Wilms

A study has been made of the structural changes in polycrystalline high purity aluminum during the tertiary stage of creep under conditions of constant tensile load. It appears that there is no basic modification in the particular mechanism of deformation that characterized the preceding secondary stage of creep, but that the changes in crystalline structure produced during the tertiary stage are only a consequence and not a cause of the accelerated strain. Intercrystalline fissures were observed on entry into the tertiary stage, and these might supplement the accelerated rate of strain owing to local stress concentrations. There is evidence that the formation of these fissures may be associated with the presence of surface imperfections, and it is suggested that a more generalized treatment of the results may explain certain creep characteristics of commercial alloys. IN previous work'-4 a study was made of the changes produced when specimens of annealed aluminum were deformed at various temperatures and rates of strain, especially under conditions leading to creep under constant tensile load. It was shown that, as the temperature was increased or as the rate of strain was decreased, elements of the substructure produced within the grains became coarser, and with the strain rate constant at a given temperature, their size tended to an equilibrium value. The preliminary process of the breaking down of the grains into a substructure was identified with primary creep.' The subsequent equilibrium, condition was associated with secondary creep. The question then arose whether the tertiary stage corresponded to any further significant change in the substructure. The question is also of interest in view of the opinion, expressed for instance by Andrade,5 that the tertiary stage is merely an accelerated rate of strain due to the reduced area of section of a specimen under continuous tensile load, and the other opinion, as suggested by the observation by Sully, Cale, and Willoughby6 of a tertiary stage in com-pressive loading, that this third stage is a real effect in its own right. The object of this paper is to record some observations on the tertiary stage of high purity aluminum. Experimental Procedure The material was aluminum of 99.98 pct purity as previously used. The specimens had a rectangular section of l/8 x l/2 in., and extensions were measured over a 1 in. gage length. After machining to shape, the specimens were annealed to give a standard grain size of 0.2 mm and then electropolished. The general procedure involved metallographic and X-ray diffraction examination at progressive stages of elongation (marked by arrows on the curves shown in Figs. 1 and 2), the specimen being extended to fracture under constant load at a given temperature. The X-ray tests were made by the back-reflection method from a stationary specimen, using CoK radiation. The longer edge of the micrographs in the paper corresponds to the direction of applied stress. Results The previous work showed that, in the secondary stage of creep in aluminum, three basic types of structure could be developed according to the temperature and rate of strain. These were: 1—slip, which predominated at the lower temperatures and higher rates of strain and produced the finest and least perfect substructure; 2—cell structure, which superseded slip as the temperature was raised and the rate of strain decreased and which was characterized by a coarser and more perfect structure and an absence of slip lines; and 3—a stage termed "boundary microflow," which predominated at still higher temperatures and lower rates of strain when the cell size had increased and become comparable

Jan 1, 1955

By Donald A. Brobst

The minerals barite (BaSO4 barium sulfate) and witherite (BaCO3 barium carbonate) are the chief commercial sources of the element barium and its compounds whose many uses are nearly hidden among the technical complexities of modern industrial processes and products. Barite, the major ore mineral, is extremely vital to the petroleum industry which in 1973 consumed at least 80% of the world's produc¬tion of 4.4 million tons as a major ingredient of the heavy fluid, called mud, that is circulated in rotary drilling of oil and gas wells. The re¬maining 20% of the barite production was consumed chiefly in the manufacture of barium chemicals and glass and as a pigment, filler, and extender. Barite occurs throughout much of the world and is available from three major geologic types of deposits-vein and cavity fill¬ing, residual, and bedded-in sufficient quantity at competitive prices to meet current demands. The world's demand for barite is expected to increase, and geologic circumstances are favor¬able for the discovery of new deposits of com¬mercial value. Witherite is much less common and abun¬dant than barite, although it is more desirable in many ways as a raw material for the pro¬duction of barium chemicals. The United States has not produced witherite since about 1950; England is currently the chief producer of witherite. End Uses Most of the world's barite production since 1926 has been used as a weighting agent for the muds circulated in rotary drilling of oil and gas wells. The muds fundamentally are mixtures of water, clay, and barite in different proportions that vary according to local reservoir condi¬tions. Muds with a specific gravity as great as 2.5 are used. The mud is pumped down the hollow drill stem, passes through the bit at the bottom of the hole, and rises to the surface in the space between the drill stem and the wall of the hole. In the course of this circulation the drill bit is cooled, cuttings are removed, the drill stem is lubricated, the walls of the hole are sealed, and the hydrostatic head of the column of weighted fluid helps to confine high oil and gas pressures. The latter feature aids in prevention of gushers, thus reducing both environmental pollution and waste of oil and gas resources as well as conserving the natural reservoir pressure for greater production and rate of recovery of the products contained in the rocks. Barite is particularly well suited for drilling mud because it is clean, easy to handle, soft (nonabrasive), heavy, virtually inert chemi¬cally, and relatively inexpensive compared to many other available heavy materials. Barite is used in the manufacture of glass in continuous tanks. The addition of barite ho¬mogenizes the melt and gives greater brilliance and clarity to the finished glass. Ground barite, both unbleached and bleached by sulfuric acid, is a common industrial filler, extender, and weighting agent. The rubber in¬dustry is a major consumer of barite as a filler. Barite also is added to bristolboard, heavy printing paper, playing cards, rope finishes, brake linings, clutch facings, plastics, and li¬noleum, to name but a few uses. Bleached barite has long been an extender in white lead paint because of its weight. The low index of refraction of barite, however, makes its ability to cover marks poorer than some other sub¬stances, but its low capacity for absorption of oil is a good feature. Off-color or unbleached barite can be used as a filler in colored paints. In the construction industry, some lump barite is used in concrete aggregate to weight down pipelines buried in marshy areas and to shield nuclear reactors. Because barite absorbs gamma radiation well, its use reduces the amount of expensive lead shielding otherwise

Jan 1, 1975

By E. V. Kleber, V. F. Novy, R. C. Vickery

The constitutional diagram has been determined in part for the sgstem Gd-Fe. Seven intermetallic compounds have been found at compositions corresponding to the following Gd-Fe ratios; 2:3, 1.2, 1:3, 2:7, 1:4, 1:5, and 2:17. The GdFe, com-pound has a congruent melting point above 18000C, whereas all of the remaining compounds melt incongruently, A eutectic exists at 13 wt pct Fe at a temperature of 860°C. ALTHOUGH an increasing amount of information is becoming available on the metallurgy of pure rare earth metals, relatively few studies have been made on alloy systems of the rare earths with the transition metals; iron, nickel, and cobalt. Even less data are extant on gadolinium alloys although it could be expected that such alloys might possess interesting structural and magnetic properties. In this paper, we report investigation of the gadolinium-iron alloy system. Studies on systems containing nickel and cobalt will be presented in subsequent papers. Previous data on gadolinium-iron compounds have been reported by Endter and Klemm1 and Jep-son and Duwez.2 Both reports agree on the existence of the GdFe2 phase, which crystallizes with the C-15type structure (face-centered cubic). This is in accord with results of the present work. EXPERIMENTAL The gadolinium metal used was prepared by met-allothermic reduction of high purity gadolinium fluoride. A typical analysis of the metal thus produced indicated the principal impurities to be oxygen, 0.24 pct, and tantalum, 0.2 pct. The iron metal used for alloying was a reagent grade material. Alloys were prepared by arc melting mixtures of the respective metals. Appropriate quantities of the two component metals were carefully weighed, blended and compacted. The compacts were then melted in an arc furnace consisting of a water-cooled copper hearth plate and a water-cooled tungsten-tipped counter electrode contained in a brass vacuum chamber. The furnace was evacuated to an absolute pressure of less than 1 with the leak rate established as being less than 20 per min. The furnace was then back-filled to a pressure of 25 mm of Hg, with a 75 pct He-25 pct Ar mixture. Arc melting at 25 v and 300 amp was maintained for about 30 to 60 sec until the entire visible area of the sample became molten, by which time surface tension had drawn the molten metal pool into a large bead. After allowing the furnace to cool, the alloy button was inverted and the melting process repeated. A series of melts was made covering entire composition ranges from 100 pct Gd to 100 pct Fe. All samples were examined metallographically in the as-melted condition. As the phase diagram became rationalized, and differential thermal analysis had given indications of temperature arrests, annealing was carried out in vacuo or in argon. Generally, compositions containing more than about 60 pct Gd were heat treated at 750°C and alloys containing less than this quantity of gadolinium were annealed at 1000°C. Prolonged annealing times were of the order of 100 to 200 hr. Metallographic examination was repeated on the annealed materials. Although little material loss was noted during alloy preparation, chemical analyses were made on all specimens prepared. The following standard, analytical techniques were used. Samples were dissolved in hydrochloric acid; insoluble material was filtered off, ignited and fused with potassium pyro-sulfate. The cold melt was leached with dilute acid and the solution thus obtained added to the main sample solution. Gadolinium was always determined gravimetri-callv as oxide from oxalate ignition. Iron was removed from an aliquot sample by electrolysis on a mercury cathode at approximately six volts. Gadolinium in the iron-free electrolyte was then precipitated as oxalate which was subsequently ignited to oxide. Iron was determined volumetrically in an aliquot solution by reduction with stannous chloride fol-

Jan 1, 1962

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By H. O. Hofman

INSTITUTE OF TECHNOLOGY, In deternlining experimentally the fusibility of clays, two kinds of methods may be distinguished—the direct and the indirect. Of the direct methods, that of Seger has found

Jan 1, 1899

The United States has never been a large coal exporting nation, and normally such shipments, aside from those to Canada, have been relatively small. Since the first railroad was built across the Allegheny Mountains, the imports have been quite small also, although fairly large tonnages of Canadian coal have moved into the extreme northeastern and northwestern states at times. In Table 21 are shown all data available about these shipments from 1790 to 1939, inclusive.

Jan 1, 1942

By John J. Cioston

THE steadily rising flood of gold production from all parts of the world has created an avalanche of rumors regarding the stability of the present price of this metal. Markets have been unsettled from Johannesburg to London from New York and Toronto to Melbourne, despite repeated denials from, American and British authorities of any immediate intention to alter the price. Various economists and financial writers have blossomed forth with predictions that the price would be set at the old level of $20.67 per oz.; some have even been so brash as to state That a price of $15 would be necessary to bring production within control. These effusions, based entirely upon monetary theories and with no regard to production costs, serve to confuse rather than clarify the situation.

Jan 1, 1937

By ERNEST A. HERSAY

ACCURATE ore-sizing with screens is drawing attention to certain details that now, more than ever before, require attention. There are many tests that must be preceded by careful sizing. The assayer often could profit by a more careful selection of screens. In milling, more attention is given the slimes produced. Cement-manufacturers are pulverizing and screening finer than they formerly did, and others are reducing materials to fine sizes at high cost, with screens used to govern the fine¬ness of the pulverized product. Fine screens are expensive, easily injured by mis-use, are carried in stock sparingly by most dealers, and are handled often by those who know little about them except their designated number. More attention, on the whole, needs be given the actual size of the mesh-openings, and less emphasis placed upon any custom or conventionality in numbering. An effort to classify wire screens, in this respect, leads at once into computations, where one is confronted with details of sizes and standards, of different wires, different gauges, and different customs. There is always uncertainty about the exact working-size of a screen until one gives the matter special attention, and devotes more time to it than its simplicity seems to demand. To know only the number is not sufficient for all uses. Often, in sets, superfluous sizes are used; and sizes are omitted that are of critical importance. In wire screens, the use of different standard sizes of wire makes important differences in dimensions that must be taken into account. The dealer usually grades screens by the number of openings per linear dimensions, regardless of the size of the openings or of the wire. Certain 100-mesh screens in use are found, by measurement, to he actually coarser than others of 90-mesh, a result which is due, of course, to the use of larger

May 1, 1906

By Winston W. Spencer

ALTHOUGH by far the largest A consumer of platinum metals in the world, the United States until recently has been in- significant as a producer. Writing in the "Minerals Yearbook" for 1939, H. W. Davis states that 1938 probably marked the beginning of an- other period of transition in the world production of the platinum metals. In that year, he says, their production in the United States jumped to 49,380 oz., or fourth in the rank of world output. In the ten-year period 1925 to 1934 United States output ,averaged only 8300 oz. Practically all of this sudden in- crease in production is attributable to the introduction of mechanized equipment at the placer deposits in the Goodnews Bay district of Alaska. This district adjoins the Bering Sea and Kuskokwim Bay (accented on the first syllable), and is approximately 120 miles south of the mouth of the Kuskokwim River. The nearest village and post office is Platinum, which lies about eleven miles north- east of the Goodnews Bay Mining Company's camp. A good gravel road connects the mine camp and the village.

Jan 1, 1940

By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The microhardness of single crystals of tungsten disilicide has been investigated by the Knoop method. The average random room-temperature hardness of the WSi, matrix was 1350 kg per sq mm. Hardness crnisotropy was noted with respect to plane and indenter orientation as determined by single-crq.stal X-rny studies. Annealing at 1600" and 1800°C decreased the average hardness to 1310 and 1230 kg per sq tnm, respectively, and produced a second phase identified by X-ray diffraction and electron-microprobe analysis to be wSio.7. Ball-impact experiwzents produced rosettes at 850°C. Optical and electron microscopy showed evidence of slip and cross slip and twinning produced by microhardness indentations. Prismatic (100), [001] slip was found and cor~elated with hardness data. THE present study was undertaken to investigate the hardness anisotropy of as-grown and annealed single crystals of tungsten disilicide. The existence of the silicide WSiz in the W-Si system has been well-established and its structure thoroughly investigated zachariasen2 found WSi, to have a tetragonal C type of structure, similar to that of MoSi, with lattice parameters a = 3.212A, Kieffer et al. studied the W-Si system and measured the density and microhardness (at a 100-g load) of both polycrystalline WSi, and WSi,.,. The values found were 9.25 g per cu cm and 1090 kg per sq mm for WSi,, and 12.21 per cu cm and 770 kg per sq mm for WSi0.7, respectively. According to Samsonov et a1.5 the microhardness of polycrystalline WSi2 is 1430 kg per sq mm (at a 120-g load). EXPERIMENTAL The WSi, single-crystal boules investigated in this paper were grown by a Verneuil-type process using an electric arc by the Linde Division of the Union Carbide Corp.6 The largest specimens were 8 mm in diameter by 16 mm long. The crystals had an average density of 9.01 g per cu cm with a tungsten • silicon content of 99.9 wt pct. The major impurities were: 87 ppm O, 41 ppm N. 54 pprn C, 500 ppm Zr, 50 ppm Na, and 50 ppm Mn. The crystals were silicon-poor, the average silicon content being 22.20 pct (stoichiometric value is 23.40 pct), and tungsten-rich, the average tungsten content being 77.70 pct (stoichiometric value is 76.60 pct). As-received single crystals were ground and analyzed by powder X-ray diffraction technique using Cu Ka radiation. Laue and layer line rotation patterns were obtained on cleaved sections of WSi, single crystals. Electron-microprobe traverses of representative crystals were done using a Phillips-AMR electron microanalyzer. Carbon replicas were used to prepare electron micrographs. This work was done with a JEM-6A electron microscope. Prior to the metallographic examination, the specimens were mounted in Lucite and then polished for short times on polishing wheels using 9-, 3-, and 1-p diamond-grade pastes. Finally they were fine-polished with Linde A powder for 24 hr on a Syntron vibratory polisher. The samples were etched with 4H 2 O:1HF:2HNO3, which is a medium fast-acting etchant. The combination 1HF:2HNO3:5 lactic acid is also a satisfactory etchant. Annealing runs for selected specimens were made at 1600" and 1800°C for 3 hr at 1.0 to 3.0 x 10-5 mm Hg. A Brew tantalum resistance furnace with WSi2 powder for setters was used. The WSi2 powder was the same as that used for the crystal growth. Temperatures were measured with a calibrated W, W-26 pct Re thermocouple and a microoptical pyrometer. Powder X-ray diffraction, emission spectrographic, and electron-microprobe analyses were done after the annealing runs. For microhardness measurements a Tukon Microhardness Tester Type FB with a Knoop indenter was used. Although measurements were taken at loads ranging from 25 to 1000 g, the 100-g load was chosen as the standard load. All measurements were taken at room temperature. Only indentations of cracking classes 1 and 2 were considered.' DISCUSSION OF RESULTS Powder X-ray diffraction analysis showed the as-received crystals to be single-phase WSi2. Laue and layer line rotation patterns obtained on cleaved sections of WSi2 single crystals proved them to be tetragonal WS 2 2 The results also indicated that the c axis of the crystal was oriented parallel to the boule or growth axis. Electron-microprobe traverses across the matrix of the as-grown crystals showed them to be homogeneous WSi,. Optical and electron microscopy of etched crystals, however, revealed that they contained minute amounts of the "golden" and the "blue" second phases as opposed to the "white" or WSi2 phase. These two second phases were concentrated in inclusion and etch-pit

Jan 1, 1965

By John S. Crandall

THE mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sandpaper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where Occurrence: Garnets in the Emerald Creek area occur as disseminated crystals in beds of micaceous schists of the Belt Series, which in this section are estimated to be close to 4000 ft thick. The schists are high in alumina and silica with iron, manganese, and magnesium. Subjection of the original sediments to high temperatures and pressures caused metamorphism to take place with the resultant re-crystallization of high alumina-silica minerals such as garnet, mainly spessartite and almandite varieties, cyanite, sillimanite, chlorite, actinolite, tourmaline, biotite, and muscovite, with minor amounts of ilmenite and magnetite. Quartz is also present in considerable amounts. Fast erosion of the soft mica schists on exposure to weathering has created extensive alluvial deposits containing up to 10 pct garnet having a maximum grain size of 3/16 in. These alluvial sands and gravels are now being treated for the recovery of garnet sands. Treatment: Overburden of 1 to 4 ft must be stripped to expose the garnetiferous gravels. This operation and the subsequent feeding of the gravels to a trommel-screen washing plant are performed by a % yd dragline. The trommel-screen openings are 3/16 in., thus allowing a separation and concentration based on grain size, since over 95 pct of total free garnets are minus 3/16 in. All plus 3/16-in. material is wasted at this point. The minus 3/16-in. material is further concentrated in a sand-drag classifier, where the slimes and silts are washed out and wasted. The sand product from the classifier varies in garnet content from 20 to 60 pct according to the particular section of ground being worked. This sand product is trucked to a jig plant where two sized fractions are made in a trommel-screen. The minus 3/16-in. plus 10-mesh portion is fed to a Pan-American two cell 42-in. jig. The minus 10-mesh portion is treated in a Bendelari three cell 42-in. jig. The jig concentrates are combined to form a 98 pct garnet sand. The jig tailings contain 3 to 5 pct garnet which is mainly flat crystals and chips which will not settle into the jig hutch. Subsequent treatment of these tailings in a scavenger jig followed by drying and electromagnetic separation will, according to tests, reduce the garnet losses in the tailings to something around 1 pct. Jig treatment of this feed approaches ideal as the major portion of the garnet crystals are the natural dodecahedrons and so are, in general, close to spherical. The specific gravity of pure garnet is 4.2, while the next heaviest mineral in the feed is cyanite with a specific gravity of 3.6, then quartz with specific gravity of 2.6. The garnet concentrate is practically free of quartz. The predominant impurity is cyanite which amounts to about 1.5 pct. The rod-like crystals of cyanite appear to up-end in the jig and go into the hutch with the garnets. Some ilmenite and magnetite appear in the concentrate but in very minor amounts. Subsequent washing in a sand-drag classifier removes fine silts and iron oxides. The gravel feed to the washing plant will average 8 pct recoverable garnet content. Concentration ratio in this plant runs about 2.5 to 1. Washing-plant concentrate as fed to the jigs will average 45 pct garnet by weight. Concentration ratio of jigging runs about 2.2 to 1. The garnet concentrate is dried in a rotary oil-fired drier and then fed to vibrating screens in closed circuit with crushing rolls. Practically any grit from 10-mesh down to 150-mesh grain size may be graded to specifications in two 3-deck vibrating screens. The present production, however, is approximately 75 pct No. 36, 15 pct No. 60. and the balance No. 80 and No. 100. Metal-screen cloth is used for sizes down to 36 mesh. From 36 mesh and finer, silk-screen cloth is used since it has less tendency to blind. All garnet sand is bagged in 100 lb self-sealing, sleeve-type paper bags. Practically all shipments are made in carload lots. Car loading is convenient since the plant is in Fernwood on the tracks of a branch line of the Milwaukee railroad. Truck shipments can and are made occasionally.

Jan 1, 1951

By John S. Crandall

THE mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sandpaper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where Occurrence: Garnets in the Emerald Creek area occur as disseminated crystals in beds of micaceous schists of the Belt Series, which in this section are estimated to be close to 4000 ft thick. The schists are high in alumina and silica with iron, manganese, and magnesium. Subjection of the original sediments to high temperatures and pressures caused metamorphism to take place with the resultant re-crystallization of high alumina-silica minerals such as garnet, mainly spessartite and almandite varieties, cyanite, sillimanite, chlorite, actinolite, tourmaline, biotite, and muscovite, with minor amounts of ilmenite and magnetite. Quartz is also present in considerable amounts. Fast erosion of the soft mica schists on exposure to weathering has created extensive alluvial deposits containing up to 10 pct garnet having a maximum grain size of 3/16 in. These alluvial sands and gravels are now being treated for the recovery of garnet sands. Treatment: Overburden of 1 to 4 ft must be stripped to expose the garnetiferous gravels. This operation and the subsequent feeding of the gravels to a trommel-screen washing plant are performed by a % yd dragline. The trommel-screen openings are 3/16 in., thus allowing a separation and concentration based on grain size, since over 95 pct of total free garnets are minus 3/16 in. All plus 3/16-in. material is wasted at this point. The minus 3/16-in. material is further concentrated in a sand-drag classifier, where the slimes and silts are washed out and wasted. The sand product from the classifier varies in garnet content from 20 to 60 pct according to the particular section of ground being worked. This sand product is trucked to a jig plant where two sized fractions are made in a trommel-screen. The minus 3/16-in. plus 10-mesh portion is fed to a Pan-American two cell 42-in. jig. The minus 10-mesh portion is treated in a Bendelari three cell 42-in. jig. The jig concentrates are combined to form a 98 pct garnet sand. The jig tailings contain 3 to 5 pct garnet which is mainly flat crystals and chips which will not settle into the jig hutch. Subsequent treatment of these tailings in a scavenger jig followed by drying and electromagnetic separation will, according to tests, reduce the garnet losses in the tailings to something around 1 pct. Jig treatment of this feed approaches ideal as the major portion of the garnet crystals are the natural dodecahedrons and so are, in general, close to spherical. The specific gravity of pure garnet is 4.2, while the next heaviest mineral in the feed is cyanite with a specific gravity of 3.6, then quartz with specific gravity of 2.6. The garnet concentrate is practically free of quartz. The predominant impurity is cyanite which amounts to about 1.5 pct. The rod-like crystals of cyanite appear to up-end in the jig and go into the hutch with the garnets. Some ilmenite and magnetite appear in the concentrate but in very minor amounts. Subsequent washing in a sand-drag classifier removes fine silts and iron oxides. The gravel feed to the washing plant will average 8 pct recoverable garnet content. Concentration ratio in this plant runs about 2.5 to 1. Washing-plant concentrate as fed to the jigs will average 45 pct garnet by weight. Concentration ratio of jigging runs about 2.2 to 1. The garnet concentrate is dried in a rotary oil-fired drier and then fed to vibrating screens in closed circuit with crushing rolls. Practically any grit from 10-mesh down to 150-mesh grain size may be graded to specifications in two 3-deck vibrating screens. The present production, however, is approximately 75 pct No. 36, 15 pct No. 60. and the balance No. 80 and No. 100. Metal-screen cloth is used for sizes down to 36 mesh. From 36 mesh and finer, silk-screen cloth is used since it has less tendency to blind. All garnet sand is bagged in 100 lb self-sealing, sleeve-type paper bags. Practically all shipments are made in carload lots. Car loading is convenient since the plant is in Fernwood on the tracks of a branch line of the Milwaukee railroad. Truck shipments can and are made occasionally.

Jan 1, 1951

By J. A. Rowland, C. W. Funk

THIS investigation is a part of the United States Bureau of Mines work in conserving the Nation's resources. The isothermal sections presented were developed as a guide to a comprehensive investigation of the properties and fabricating characteristics of copper-base alloys containing manganese and tin. These alloys are being investigated as possible replacements for the commercial bronzes containing substantial quantities of tin. Development of the isothermal sections has, therefore, been limited to the area between 0 to 20 pct Mn and 0 to 25 pct Sn. Since Heusler1 reported the ferromagnetic properties of the Cu-Mn-Sn alloys in 1903, the system has been the subject of several investigations. These studies were largely concerned with correlation of magnetic properties and crystal structure.2-6 Vero,' however, established the solidus surface of the system, between 20 pct Mn and 40 pct Sn, by thermal and microscopic methods. The a, ß, and y solid solutions were also observed by Vero and reported to extend into the interior of the ternary system. For the present study, the annotated diagram of the Cu-Sn system prepared by Raynor' and the Cu-Mn diagram by Dean and coworkers9 were used as the binary borders of the ternary system. Procedure The metals used in this investigation were electrolytic manganese, washed cathode copper, and three-star tin. The manganese, produced at the Boulder City pilot plant of the Bureau of Mines, had a purity of 99.9 pct; the copper contained less than 0.004 pct Bi and 0.001 pct S; the tin contained 0.070 pct Pb, 0.070 pct Sb, 0.050 pct Fe, and 0.065 pct Si. Heats of 1 lb were melted in alundum crucibles with a 3-kw induction furnace. The heats were chill-cast in iron or copper molds to form 6-in. ingots 3/4 in. in diameter. Molds were washed with graphite or zirconia, depending on the manganese content, and preheated to 150°C. The maximum impurity content of any alloy was 0.03 pct Fe, 0.02 pct Si, and 0.02 pct Al; in most cases, they contained less than half this quantity of any of these impurities. Composition of the alloys and their treatment prior to homogenizing are shown in Fig. 1. Designations adjacent to each composition refer to the heat numbers. With a few exceptions, ingots containing 20 pct Sn or less were hot-swaged. These ingots were swaged, after a 24-hr preheat at 650°C, to obtain a total reduction of 70 pct in cross section. Intermittent reheating was necessary, and reductions were limited to either 0.025 or 0.050 in. in diameter per pass. Selection of a 200-hr homogenizing treatment was based on extensive experiments which indicated that virtual equilibrium was reached after 150 hr. Structures were retained by quenching in water. Grain sizes in the specimens homogenized at 350" and 450°C were generally small. These homogenizing treatments were preceded by a 50-hr anneal at 650°C to facilitate phase identification by increasing the grain size in these specimens. The specimens were furnace-cooled from this temperature to the homogenizing temperature, and the heat treatment was continued for the standard 200-hr period. The homogenized samples were bisected to provide an internal section for metallographic examination. Optimum definition of the microstructure was obtained by successive polishing and etching. Quarter-strength ASTM copper reagent No. 13 gave the most satisfactory results.10 Filings from interior sections of the samples were used for diffraction studies. These filings were annealed in evacuated glass tubes at homogenizing temperatures for periods exceeding 50 hr and quenched in water. During this treatment the manganese content was reduced by significant amounts, probably by vaporization. This change in composition was considered in applying the diffraction data, which were used only as a means of identifying phases where the data were consistent with the metallographic evidence. Phase Identification The a solid solution is readily distinguished by the copper-colored, twinned, polyhedral grains, as shown in Fig. 2, and a face-centered cubic X-ray pattern. Tukon indentations, using a 25-g load, indicate a Knoop hardness of 155 for a quenched from 650°C. Using white light developed by a Wratten 78 A filter, the ß grains in etched specimens have a dark brown tint in contrast to the lighter copper-colored grains of the a phase. Knoop hardness values of 284 were obtained for the ß structure in specimens quenched from 650°C. The ß structure was also distinguished from the a phase by its body-centered cubic lattice. The acicular structure appearing in Fig. 3 was evident in several alloys of higher tin content after quenching from either 750' or 650°C. Since a trans-

Jan 1, 1954

By Thomas E. Wayland

AN isopachous map is one on which lines connect points of equal thickness of a given unit. This type of map is used by the Florida Phosphate Project of the U. S. Geological Survey to represent the economic phosphate deposits known as matrix and the waste material, or overburden, that overlies the matrix. The top of the bed on which the phosphate was deposited is known as the basement and a subsurface contour map of this old buried erosion surface is known as a basement map. Recent experiments have been made in preparing maps that show tonnages and grades of the phosphate content of the matrix. Few of the operating companies in the Florida phosphate district have applied isopachous (Greek isos, equal and pachys, thick) to mapping. The writer believes there is a need for the techniques discussed herein and that they can be applied to mapping other geologically similar areas in either economic or scientific investigations. The land-pebble phosphate district of Florida occupies a compact area in the west-central part of the state. It includes mainly the following land survey divisions: Ts. 27 S. through 32 S. and Rs. 20 E. through 26 E. The town of Mulberry, Fla., is in the approximate center of the district. The strata of the area, which is part of the Gulf Coastal Plain, occur in thin formations with broad outcrop belts, and low dips. The topography is subdued and gently rolling with three marine terraces, which are found at 30, 100, and 150 ft above sea level,' accounting for most of the relief. Occasional small sinkhole lakes are present, most of them above the 150-ft shoreline. The phosphate deposits occur in unconsolidated sediments such as clays, sands, and sandy clays. They are overlain by a heterogeneous assemblage of sands, clays, muck, and iron-cemented sand, easily penetrated, in most cases, by a hand auger or drill. Limestone, locally called bedrock, or a calcareous bedclay, thought to be a residue of the limestone, directly underlies the phosphate deposits. General Requirements Most companies and independent prospectors operating in the district have furnished prospecting data to the U. S. Geological Survey. The information is recorded on either field logs or prospecting maps and includes the following information for each hole drilled: location of the hole, thickness of the overburden, thickness of the matrix, phosphate content in long tons per acre, grade of the phosphate content expressed as the percentage of bone phosphate of lime (P2O5 x 2.18) or BPL, and the per- centages of iron-aluminum oxides and insolubles. The phosphate is classified according to size as either pebble or flotation material. The milling processes of the companies vary, and the size classification is necessarily different in many cases. However, pebble may be considered as larger than 14 mesh and flotation material as smaller than 14, but larger than 150 mesh. Some prospecting data include the exact depth at which bedrock or bedclay was reached, and these figures greatly increase the reliability of the data both for isopachous mapping and for mapping the basement. A drilling density of four holes per 40 acres of land furnishes a minimum amount of data for isopachous and related mapping. From the minimum of four, densities up to 32 holes per 40 acres are used. The various drilling densities may influence the choice of the proper scale. Selection of the proper scale is dependent upon the known drilling densities, the subsurface variations to be shown, the extent of the area to be mapped, and the detail desired in the completed map. Scales of 1:24,000, 1:4800, and 1:2400 are used in isopachous and related mapping by the Florida Phosphate Project. The 1:24,000 scale is used most effectively with drilling densities not exceeding eight holes per 40 acres. The subsurface variations should be relatively low and uniform, permitting the use of smaller intervals without undue crowding of the lines. Comparatively large areas can be mapped on this scale, but minute detail is necessarily sacrificed, because the information is drawn from a maximum drilling density of only eight holes per 40 acres. Isopachous and related maps of the 1:4800 scale are made of areas on which the drilling information covers from 4 to 16 holes per 40 acres. Moderate subsurface variations with relatively sharp gradations can be shown accurately. The area represented by the maps is reduced considerably in favor of detail. The 1:2400 scale is most frequently used by the Florida Phosphate Project. It lends itself particularly well to isopachous and related mapping, being easily adapted to the multiform drilling data available. Maps of this scale are prepared with information ranging from 4 to 32 holes per 40 acres; however, use of the minimum drilling density on the

Jan 1, 1952

By K. P. Gupta, A. K. Pal, L. Chandrasekaran, U. P. Singh

The Mn-Sn binary system, investigated at the high-manganese end and between 500° and 1000° C, shows four phases at temperatures below 727"C, namely the u Mn, the p Mn, the Mn3 Sn, and the Mn, Sn phases, while at higher temperatures only the last three phases remain stable. The solubility of tin in a Mn is very small and the maximum solubility of tin in P Mn phase appears to be abollt 10 at. pct Sn. The solubility range of the Mn,Sn and the Mn, Sn phases is 23.0 to 26.0 and 37.0 to 40.0 at. pct Sn, respectively. The lattice parameter of the 13 Mn phase increases with increasing tin content. The Mn, Sn thase is hexagonal with and appears to be basically of the Ni3 Sn type structure except that for quite a few X-ray diffraction lines the calculated and observed relative intensities do not agree well. The Mn-Sn binary system has been studied by several investigators.''~ Their results indicate that three intermediate phases, namely, the Mn3Sn, Mn,Sn, and MnSn, phases, exist at high concentrations of tin. However, so far the proper phase equilibrium has not been established at the manganese-rich end and very little data is available for the composition range between pure manganese and Mn3Sn. Moreover, earlier investigators differ in their opinion about the exact composition range at which the Mn3Sn and Mn,Sn phases appear and some doubt has been cast by some investigators3 regarding the structure of Mn3Sn phase which has been reported to be isotypic with Ni3Sn (Mgscd type) structure. In this investigation an attempt has been made to establish the proper phase equilibrium between pure manganese and Mn + 50 at. pct Sn composition in the temperature range of 500" to 1000°C. PROCEDURE The raw materials used were from three different sources. For exploratory work five alloys containing 5, 10, 15, 20, and 25 at. pct Sn were prepared using 99.9 pct pure manganese and tin supplied by E. Merck & Co., Germany. The rest of the alloys and one more 25 at. pct Sn alloy were prepared using 99.9 pct Mn supplied by Gallard Schlesinger Chemical Mfg. Corp., U.S.A., and 99.999 pct Sn supplied by Semi Elements Inc., U.S.A. Weighed amounts of manganese and tin were melted in recrystallized alumina crucibles in an inert gas (argon) high-frequency induction melting furnace. By careful control of temperature and time of melting the losses were reduced to below 0.2 pct in all cases. Since the losses were very small, no attempt was made here to analyze the samples chemically. Alloys were wrapped in molybdenum foil and sealed in small evacuated fused silica capsules. The alloys were annealed at different temperatures, controlled within + l°C, for sufficiently long periods to attain proper phase equilibrium, and subsequently quenched in cold tap water. The annealing periods used at different temperatures were 15 days at 500°C, 7 days at 600°C, 5 days at 700" and 750°C, 3 days at 800°, 850°, and 900°C, 2 days at 968"C, and two alloys annealed at 968°C were reannealed for 10 hr at 1000° C. From each annealed specimen, a part was utilized for metallographic study while another piece was used for X-ray diffraction study. 1.0 pct HNO, solution and oxalic acid solutions of concentrations 0.05 to 1.0 pct were used for etching Mn-Sn alloys above and below the MnsSn composition, respectively. Since all alloys were brittle, X-ray specimens were prepared using the as-crushed -325 mesh alloy powders. Only one 25 at. pct Sn alloy powder was reannealed in an evacuated silica capsule at 800°C for 5 min and water-quenched. X-ray diffraction patterns . for the Mn3Sn phase with the as-crushed and the reannealed powders did not show appreciable change. Un-filtered iron radiation at 25 kv, 15 ma was used with either Norelco 114.6-mm-diam Debye Scherrer Camera (for phase identification) or Norelco 12-cm-diam symmetrical focusing camera (for lattice parameter determination of the 6 Mn phase). The estimated accuracy of lattice parameter determination for the focusing camera was * 0.001A. RESULTS AND DISCUSSIONS The results of metallographic and X-ray diffraction study made with different alloys are shown in Fig. 1. The variations in lattice parameter with composition for the p Mn and the Mn3Sn phases are given in Tables I and 11, respectively, and the lattice parameter as a function of composition for the p Mn phase is shown in Fig. 2. The lattice parameter of the p Mn phase increases with increasing tin content while for the Mn,Sn phase the data obtained from two two-phase alloys and one single-phase alloy indicate increase in a,, and decrease in c, parameters with increasing tin content. The results, Fig. 1, indicate that the solubility of

Jan 1, 1969

By David P. Shoemaker, Clara B. Shoemaker

It has been shown for an important class of complex transition intermetallic compounds (a, P, R, 6, and p phases) characterized by "normal" coordination [CN12 (icosahedral), CN14, CN15, CN16/ that interatomic distances nay be calculated to a good approximation as the sum of characteristic atomic radii. Two radii, one for major ligands and one for minor ligmds, are specified for each atom, except in the case of CN12 where only a miaaor-ligand radius is specified. The same appears to be true of transition-metal phases of simpler struc-ture: Laves phases (CN12, CN16), and p-tungsten phases (CN12, CN14). In the case of known examples of the more complex phases, a simple rule is given which specifies these radii. However, only a fraction of the known examples of the simpler phases obey this rule closely. To include the latter phases the rule may be modified by considering the radii as linear functions of the weighted average of the Pauling CN12 radii of the two kinds of atonzs, with the radii weighted according to the over-all chemical composition of the alloy. With very few exceptions interatomic distances for both tlze complex and the simpler transition phases can b$ predicted with this modified rule to within 0.06A. ManY intermetallic compounds are known of composition A,By, in which A is a transition element to the left of the manganese column in the periodic table and B is a transition element in or to the right of it. Frequently the coordination numbers (CN) found in these compounds are CN12 (icosahedral), CN14, CN15, and CN16 (called "normal" coordinations by Frank and Kasperl). Well-known examples are the cubic and hexagonal Laves phases which have CN12 and CN16, and the 0-tungsten (CrsO) phases which have CN12 and CN14. In the more complicated (often ternary) phases, such as the a phase,2 the Beck phases p3 and R~, the 6 phase,5 and the p p atoms occur with CN12, CN14, CN15, and (except for a) CN16; in many cases several crystallographically independent atoms of one particular CN occur in the asymmetric unit. A large number of independent interatomic distances are found in these complicated phases, varying from 20 in the a phase to 94 in the 6 phase. These distances show a large spread; they vary, for example, from 2.358 to 3.278A in the 6 phase. In our analysis of these distances we found that in each of these compounds every atomic position can be characterized by either one or two radii. The CN12 positions are characterized by a single radius, The higher coordinated positions are characterized by two radii, namely: the CN14 positions by 4 in the direction of the twelve "5-coordinated" ligands3 (called 'minor" by Frank and Kasperl) and by r:, in the direction of the two "6-coordi-nated" ligands (called "major" by Frank and Kasper); the CN15 positions by r15 for the twelve minor and r:, for the three major ligands; the CN16 positions by rlE for the twelve minor and r:, for the four major ligands. We have expressed the experimentally determined interatomic distances in observational equations as the sums of the appropriate pairs of these characteristic radii and the value of these radii have been determined by the method of least Squares. Despite their wide range, the interatomic distances could then be predicted by the sums of these atomic radii with an average deviation in any one compound of 0.06A or less. The results are summarized in Table I. Inspection of the radii thus obtained shows that in the structures in Table I the radii (in A) are given to a first approximation by the simple relationship: Where CN is the coordination number (12, 14, 15, or 16), and A = 1 for major ligands and = 0 for minor ligands. The interaLomic distances can be predicted within about 0.1A by sums of these atomic radii. Another phase belonging in this group with CN12, 14, 15, and 16 is the y phase & B7, in which A is molybdenum or tungsten and B is iron or cobalt. Recently the M%C phase has been refinedE and the observed distances also agree well with those calculated with Eq. [I]. (In the original determination of the structure of W6FeV7 the F$(II)-W(II1) distance was erroneously given as 2.84A, but we have recalculated it fro? the published parameters and found it to b? 2.57i4, in good agreement with the value of 2.6A predicted with Eq. [I.].) Many binary transition alloys are known to crystallize with the simpler structures having "nor-

Jan 1, 1964

By G. M. Schwartz, D. M. Davidson

THE Duluth gabbro outcrops containing sulphides of copper, nickel, and iron are located on both sides of State Highway No. 1 an airline distance of 8.5 miles southeast of Ely in northeastern Minnesota. The region of known sulphide occurrences includes parts of sections 5, T. 61 N., R. 11 W., and parts of sections 25, 26, 32, 33, and 34, T. 62 N., R. 11 W. These sections, given in Fig. 1, are all in Lake County, Minnesota. Part of the area, which lies entirely within the Superior National Forest, is shown on the topographic map of the Ely quadrangle. The original discovery was made in 1948 when a small pit was opened in weathered gabbro rubble for use on a forest access road. A shear zone had caused unusual decomposition in this glaciated area, and the resulting copper stain was noted by Fred S. Childers, Sr., an Ely prospector, who began searching the outcrops along the base of the intrusive. He was joined in further exploration by Roger V. Whiteside of Duluth. In the summer of 1951 a small diamond drill was moved into the area and a hole 188 ft deep was drilled, passing through 11 ft of glacial drift into sulphide-bearing gabbro. This paper is a preliminary report on the geology of the newly discovered ore. The Duluth gabbro is one of the largest known basic intrusives and may be defined as a lopolith.1 It extends northeastward from the city of Duluth as a great crescent-shaped mass that intersects the shore of Lake Superior again near Hovland, 130 miles to the northeast, see Fig. 2. The distance around the outside of the crescent is nearly 170 miles. The form of the intrusive is simple at Duluth where it ends abruptly north of the St. Louis River; at the east end, however, the gabbro splits into two elongated, sill-like masses separated mainly by lava flows and characterized by minor irregularities. The outcrop reaches a maximum width in the central part where it is about 30 miles across, and a maximum thickness of about 50,000 ft. It may be significant that the sulphides occur at the base of the thickest part. The lopolith has segregated into rock types ranging from peridotite to granite. The most abundant types are olivine gabbro, gabbro, troctolite, anorthosite, and granite. Of lesser importance quantitatively are peridotite, norite, pyroxenite, magnetite gabbro, and titaniferous magnetite. Grout estimates that two-thirds of the gabbro at Duluth is olivine gabbro. Variations in the percentages of plagioclase, augite, olivine, and magnetite-ilmenite constitute the only essential differences found among the basic rock types. The predominant mineral is plagioclase, mainly labradorite. Plagioclase and olivine seem to have crystallized early, and the olivine rich rocks, usually troctolite, are found in the lower part. Segregations of titaniferous magnetite are abundant near the base of the gabbro along the eastern part and also occur far above the base. These have recently been described in detail by Grout' Near the top, segregation has produced a gradation to granite, or "red rock," as it is known locally. This consists of quartz, red feldspar, and hornblende. The red rock forms a. zone with a maximum width of nearly 5 miles but is quantitatively unimportant from Duluth northward for 35 miles. In Cook county, where the gabbro splits, each of the two sill-like masses has a red rock top somewhat thicker in proportion to the gabbro below than in the main central mass. The intrusive ranges from coarse to medium in grain size and from granitoid to diabasic in texture. Throughout much of the Duluth gabbro in Minnesota banding and foliation are well developed, as Grout has emphasized! The bands are mainly a result of variation in the percentage of minerals, as in troctolite with alternating bands high in olivine and in plagioclase. A few bands may consist largely of one mineral, as is true of some segregations of magnetite. Many of the banded rocks show a clearly developed parallelism of platy plagioclase crystals, and both banding and foliation are believed to conform to the floor of the lopolith. Throughout its extent in Minnesota the Duluth gabbro dips east and south toward Lake Superior. It is generally believed to extend beneath Lake Superior and is found as a smaller mass exposed along the north side of the Gogebic district in Wisconsin and Michigan. The dip at and near the base ranges along most of its length from 20 to 40°, but at places the internal banding dips even more steeply. The dip of the upper part is much less, and if it is assumed that the flows along the north shore of Lake Superior are a dependable indication, it does not exceed 15º. The formations shown in Table I which are intruded by the gabbro range from Keewatin to Middle Keweenawan in age. They present a significant picture. At the top, the gabbro and its accompanying

Jan 1, 1952