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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 N. I. Fisher, J. Shepherd

A rapid method of determining natural fracture trends in collieries has been developed. The method will yield information that is precise enough to permit fracture domain boundaries to be delineated in a coal seam. Instead of a survey of cleat trends in a colliery taking several man-weeks or even man-months, a reconnaissance survey can be carried out in only a few man-days. At each of a sequence of sampling sites along a traverse, five measurements of trend are recorded for each set of fracture directions. A sequential plot of the medians of each fracture set is then made manually underground or by a computer in the mine office. Changes in fracture pattern can be detected easily in colliery development work if a geologist visits advancing faces regularly, and forecasts can be made about the likelihood of forthcoming faults and dykes. A full description of this method is given in Shepherd and Fisher (1981). The concept of mapping fractures rapidly in a colliery is based on using a geological traverse (Compton, 1962), along which observations can be made at chosen, regular intervals. The technique has been widely used for surface mapping across outcrops and in follow-up work in photogeological studies (Hepworth and Kennerley, 1970). In these cases, the geologist surveys the traverse line as mapping proceeds. In a colliery, however, ready-made traverse lines already exist in panels and along main roadways, often in several directions. It is thus possible to traverse a colliery in different directions and record the fracture trends at intervals, generating a reconnaissance fracture map. This can also be done on a continuing basis as mine development takes place. Generally, a sampling traverse should be longer than 0.5 km with sampling sites at relatively close-spaced intervals along the traverse. For example, in room-and-pillar mines pillars are commonly formed on 40-m centers and the sampling sites can then be arranged at 20-m intervals [(Fig. 1)]. The sites might have to be closer together for mines known to have bad mining conditions. The predominant fracture trend is normally the face cleat and the subordinate trend is the butt cleat (McCulloch et al.. 1974). Various changes can occur in the cleat or joint pattern: the face and butt sets may disappear or an entirely new set or sets may appear. Therefore, it is best to record all prominent fracture sets. Sometimes there is only one; in other cases there may be as many as three or more. An odd number of measurements of each fracture set are made (generally five or more) to enable the median value to be determined easily. The median value can be plotted underground using graph paper or a computer plot can be made in the laboratory or mine office [(Fig. 2)]. The sequential linked median (SLIME) plot draws the median trend for each sampling site as a unit line segment. The segments from successive sampling sites can be connected together to form a long chain [(Fig. 2A)]. The needle plot, on the other hand, draws a straight line to represent the traverse and then plots out the median trend for each sampling site [(Fig. 2B)]. The SLIME plot is better for visual display, as it highlights small irregularities and gross changes in trend. However, some work is required to relate the individual segments to their site location along a traverse. In this respect, the needle plot is more convenient because each segment -can be plotted-at a point corresponding to its location. Also, there is precise match-up if needle plots of face and butt cleat are compared. A description and listing of the SLIME program is given by White et al. (1981). An example of the use of this method is given for Wallsend Borehole colliery in New South Wales (Australia) [(Fig. 2)], where domains II and IV are associated with mining hazards. Domain II is coincident with a normal fault of 2.6-m throw, and domain IV with a basic dyke 12 m thick. These hazards were approached driving in a southwesterly direction, and a pronounced change in trend of the cleat to a northwesterly direction occurred at a distance of approximately 45 m from each one. The northwestern joint trend is parallel to that of the dyke and fault, and it occurs at a higher frequency close to these structures. The association of a particular joint set with faults has been found elsewhere (Shepherd and Creasey, 1979). The two minor cleat direction changes within domain V are narrow joint zones that are less than 5 m wide. The fracture trends derived from a SLIME traverse can be verified by collecting larger quantities of data at selected sites, as shown in the balloon density (rose) plots depicted in [Fig. 2C]. We are grateful for the financial support provided by Thiess Bros. Pty. Ltd. and the National Energy Research, Development, and Demonstration Program administered by the Commonwealth Department of National Development and Energy. R.W. Miller Holdings Ltd. and Thiess Bros. Pty. Ltd. are thanked for their permission to publish data from their collieries.

Jan 1, 1982

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.' 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, anortho-site, 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 plagio-clase, 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.V he 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 15". 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, 1953

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 H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

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

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.' 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, anortho-site, 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 plagio-clase, 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.V he 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 15". 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, 1953

By Thomas P. Forbath

THE sudden realization that known sulphur reserves amenable to mining by the Frasch hot water process are nearing exhaustion focused attention on widely scattered surface deposits throughout the world. These deposits are not necessarily of lower sulphur content than ores located underneath Louisiana or Texas salt domes which usually average about 30 pct sulphur disseminated in limestone matrix. Their near surface occurrence, however, renders exploitation by the Frasch process impossible. As is well known, the Frasch process depends on the presence of 500 to 1000 ft of overburden and cap rock above the sulphur deposits to permit melting underground sulphur in place by diffusing hot water under pressures of 200 to 600 psig in the formation and raising the molten sulphur to surface by air lift. This process renders possible the production of pure sulphur which is 99.5 pct pure without any subsequent treatment. Surface deposits contain sulphur in the same range of concentrations as the salt dome deposits, i.e., from 10 to 50 pct sulphur, associated with various gangue materials such as silica, limestone, and gypsum. The pirincipal distinction, then, does not lie in the percentage of sulphur contained in the ore, but in the geological nature of the deposit. A recent study' of the world sulphur supply situation estimated 1950 sulphur production in the free world countries at 5.6 million long tons, of which the United States produced 5.2 million tons, or 93 pct of the total. While America's domestic needs alone would have been covered by national production, about 1.4 million tons were exported during the same year. Despite all the steps which are being taken to restrict use of elemental sulphur and to force the fullest possible development of alternate sulphur sources here and abroad, the deficit in elemental sulphur production will probably increase with time. As a result of intensive prospecting for oil throughout the Gulf Coast area discovery of significant new salt domes is held unlikely. With the growing scarcity of sulphur and what appears to be an inevitable rise in price, recovery from deposits not amenable to Frasch-process mining assumes greater economic importance. Untapped Reserves The most important deposits in this category are located in Sicily, where elemental sulphur occurs in Miocene limestone and gypsum formation. Sulphur content of these ores ranges from 12 to 50 pct with an estimated average of 26 pct. Although quantitative estimate of these reserves is not available it is held that they exceed 50 million tons of sulphur. Similar deposits occur also on the mainland which contribute about one-third of Italy's total current annual production of 230,000 tons, but these are known to be nearing exhaustion. Significant surface deposits of volcanic origin are located in South America, Japan and western United States, silica being characteristic gangue con-stituent. The largest of these deposits are in South America. More than 100 extend over a zone 3000 miles long, paralleling the west coast of South America. 'Total sulphur content of these deposits has been estimated to be as high as 100 million tons. The main islands of Japan also possess at least 40 known volcanic sulphur deposits with probable reserves of 25 to 50 million tons.' Prospected reserves in western United States might amount to 2 million long tons, principal deposits being located in the northwestern part of Wyoming, southern Utah, and eastern California. Volcanic deposits of lesser importance are found around the Mediterranean, in Turkey and Greece, and in Africa, Egypt, Abyssinia, and Somaliland. Beneficiation Methods Different methods of beneficiation have been used in these various locations. In Italy the Calcarone kiln and Gill regenerative furnaces are used exclusively. Both utilize heat liberated by burning part of the sulphur in the ore to liquify or vaporize the remaining sulphur, which is recovered by solidification or condensation. The Calcarone kiln is of conical shape, generally 35 ft in diam at base and 18 ft high. A kiln of 25,000 cu ft capacity burns for about two months and yields about 200 tons of sulphur. The Gill furnace consists of a series of chambers with domed roofs. Sulphur is burned and melted in one chamber at a time and the hot combustion gases are used to preheat the ore charge in the subsequent cell. These furnaces operate on a cycle of 4 to 8 days. The recovery yield of both systems is about 65 pct. Sulphur losses amount to 25 pct through the combustion to sulphur dioxide; about 10 pct is retained in discarded calcines. Ores containing less than 20 pct are not considered suitable as furnace feed. These methods are not only wasteful because of the low recovery obtained, but represent a serious atmospheric pollution problem. Sulphur produced ranges from 96 to 99 pct purity and thus does not match Texas or Louisiana sulphur. Owing to the present shortage, sulphur in the Middle East sells

Jan 1, 1954

By S. E. Szasz, E. J. Moore, B. F. Whitney

An accurate value of formation water resistivity R, is essential in calculating formation porosity and fluid saturation from electrical well logs. In the cases where R, has not been measured directly, it must be obtained from other data, e.g., the SP curve. This paper deals with another approach: how to calculate R, from the chemical analysis of the formation water. INTRODUCTION It is known that the resistivity of aqueous solutions of pure salts depends on their concentration and on the temperature; the concentrations are given in MPL (mg of solute per liter of solution), or sometimes in ppm (mg of solute per kg of solution): MPL = ppm X specific gravity. Values for different pure salts are available in the literature, but not for solutions of mixtures which are of practical interest. The major component of the dissolved material in almost all formation waters being sodium chloride, it is customary to express the resistivity of formation waters in terms of equivalent sodium chloride concentration, i.e., the concentration of a solution of pure NaCl which has the same resistivity at a given temperature as that of the formation water under consideration. Thus, the problem of calculating R, from the chemical anaylsis can also be stated as how to convert the other constituents of the solute into equivalent NaCl concentration. Salts dissolved in water are at least partly dissociated into ions, and do not conserve their identity. If known amounts of several salts are dissolved in water, the solution does not necessarily contain the same salts in the original proportion, but perhaps some other combination of the ions, along with free ions in solution. This is why the chemical analysis of formation waters is often given in terms of ions, as if all dissolved salts were completely dissociated. Our problem then boils down to how to convert the concentrations of the various ions to equivalent concentrations of Na' and C1-. Dunlap and Hawthorne' have proposed to convert the concentration of all other ions to equivalent Na' and C1-concentrations by means of constant multipliers; e.g., 0.95 for Ca"; 2.0 for Mg"; 0.27 for HCO 3-; 0.5 for SO, -, etc. Their factors were based on measurements made at 68F on 26 formation water samples from the Texas Gulf Coast, ranging in concentration from 1,500 to 75,000 ppm. The Dunlap method is widely used in electric log interpretation, and is often extrapolated beyond its original concentration range. A comparison of R, values calculated by this method and values actually measured on formation water samples has shown large discrepancies, especially at higher concentrations. Therefore, two new methods were developed at Sinclair Oil Corp.'s Tulsa Research Center to calculate equivalent sodium chloride concentration from the chemical analysis of formation water samples. FUNDAMENTAL CONSIDERATIONS The resistivity of a solution, or its reciprocal the conductivity, at a given temperature is determined by the charge, concentration and mobility of the ions actually present. Monovalent ions such as Na' or C1- always carry the same charge. Compounds of polyvalent ions, however. may show incomplete dissociation, e.g., NaSO; + Na' instead of SO,-- + 2Na'. This happens especially in more concentrated solutions. Only very dilute solutions are completely dissociated, as assumed in the chemical analysis report. At higher concentration, the degree of dissociation depends not only on the nature and concentration of the particular salt under consideration but also on the nature and concentrations of the other solutes. Mobility of the ions depends on the viscosity of the solution. It also depends on the degree of hydration of the ions, which in turn is a function of the nature and the charge of the ions and also of the amount of free water available per ion, i.e., the total ionic concentration. The net effect is that the conductivity increases slower than proportional to the concentration, even if a solution contains only one salt such as NaC1, and is different for different salts (Fig. 1). Conductivity can even decline with a further increase in concentration, e.g., if additional salt is little dissociated but ties up some of the free water and/or causes an increase in viscosity. In solutions containing more than one salt, the contribution of one salt to the total conductivity depends not only on the fractional concentration of this same salt, but also on the concentration of all other solutes. A perfect method would give the conductivity or resistivity of a solution as a function of the concentrations of all solutes present. This is so complicated as to be impractical, and a simpler method must be found which is of acceptable accuracy. The Dunlap method, on the other hand. is too simple because it askmes that at any concentration the contrih-

Jan 1, 1967

By I. R. Kramer

I. R. Kramer (Martin Co.)—In a recent paper Nakada and Chalmers24 reported some observations of effects of surface conditions on the stress-strain curves of aluminum and gold single crystals. It is of interest to compare these observations with the results published previously in this journal and to comment on their general conclusions. In brief, Nakada and Chalmers concluded that the removal of the surface layer of a prestrained specimen lowered the stress-strain curve for aluminum but not that for gold. Further, they concluded that the surface work hardening of aluminum is confined to a depth not more than l0-3 cm. In our results25 published previously, it was pointed out that when prestrained specimens of aluminum and gold were polished to reduce the thickness upon reloading the initial flow stress decreased markedly. Further if a sufficient amount of metal was removed, the yield point failed to appear. With continued application of the load the stress-strain curve became coincident with that of the virgin crystal. We have found this behavior in some 100 determinations to hold consistently for gold, aluminum, and copper in both single and poly-crystalline specimens. The amount of strain required before the curves coincided depends upon the amount of metal removed but it is usually less than 0.01. This type of behavior is the same as that reported for metarecovery by other investigators.29 For aluminum specimens which have been prestrained and then heated to temperatures above 50°C we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen. With respect to Ref. 24 the curves for aluminum are always below that of the virgin curves, while those for gold become coincident. This observation indicates at least for aluminum that the specimens must have been heated to a temperature high enough to cause recovery by an alteration of the internal dislocations. In addition, a recovery would be expected because of the removal of the surface work-hardened layer. Nakada27 had reported that, with his particular apparatus in which a perchloric acid polishing solution was used, the temperature of the specimen increased 65°C. The curves presented in Ref. 24 for gold do not permit one to detect the initial flow stress upon reloading after the surface-removal treatment. In fact, contrary to the method used by Nakada and Chalmers, the change in the stress-strain curve produced by a surface-removal treatment cannot be described in terms of a decrease in stress at strains much higher than that at the initial flow stress because of the coincidence of the curves at the higher strain values. With regard to the depth of the work-hardened surface layer, our data show for aluminum single crystals (7.5 by 0.3 by 0.3 cm) that the initial flow stress remained constant after 12 x 10-3 cm had been removed from the thickness. This depth was independent of the prior strain. For gold crystals this depth is somewhere between 10 x 10-3 and 20 x 10-3 cm. Y. Nakada (author's reply)— Kramer states,28 "for aluminum specimens which have been prestrained and then heated to temperatures above 50°C, we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen." However, Cherian et a1.26 discovered that aluminum polycrystals annealed at 32" and 100°C showed the metarecovery behavior. They showed that the orthorecovery behavior did not appear until the crystals were annealed at 150°C. Kramer suggests28 that the drop in the flow stress of aluminum crystals after the surface removal by electropolishing24 may be due to the recovery caused by the temperature rise which may occur during the electropolishing.27 However, as indirectly stated in Ref. 24, the current density used in these electro -polishing experiments was 0.15 amp per sq cm. According to ref. 27, this current density should cause a temperature rise of only 40°C. This may cause the metarecovery but not the orthorecovery. Furthermore, as stated explicitly in Ref. 24, the surface removal was accomplished by chemical etching as well as by electropolishing. The results were the same for both electropolishing and etching. During the etching, the specimen temperature did not rise above 35°C. Some aluminum crystals were placed in water at 35° C for 30 min. These crystals did not show the decrease in flow stress. Therefore, it is quite clear that the flow-stress drop after the surface removal is not caused by a high-temperature recovery. However, as Kramer points out,28 it is quite possible that the internal dislocation structure may have been altered because of the removal of the highly work-hardened surface layer. However, how much this rearrangement contributes toward the flow-stress decrease is not known at present.

Jan 1, 1965

By Niels Hansen

The substructure formed by drawing at room temperature in aluminum (99.5 and 99.998 pct purity) and in recrystallized aluminum aluminum-oxide products containing from 0.2 to 4.7 wt pct of aluminum -oxide was examined by transmission electron microscopy, and the flow stress of the drawn materials was measured by tensile testing at room temperature. A sub-grain structure was present after a reduction in area by drawing of 10 to 20 pct, and the subgrain size was observed to decrease with increasing deformation. The tensile data show that the increase in flow stress (0.2 pct offset) by drawing from 10 to 95 pct depends on the reduction in area, not on the composition of the materials. Dispersion strengthening and subgrain bowzdary strengtlzening contribute to the flow stress, and these strengthening processes have been found to be linearly additive. The flow stress (0) can be related to the subgrain size &) by the Petclz relation = uo + k . t, where go is dependent on the composition of the products and k is approximately the same far all materials. THE microstructure of dispersion-strengthened aluminum aluminum-oxide products consists of small oxide plates distributed in an aluminum matrix. The matrix structure depends on the manufacturing history, and in hot-worked as well as cold-worked products the matrix is divided by subgrain (or dislocation) boundaries. For hot-extruded products it has been shown1 that dispersion strengthening and subgrain boundary strengthening are linearly additive, and the flow stress (0.2 pct offset.) at room temperature has been related to the subgrain size (ts) by a Petch equation,2,3 s = so + k . ts-1/2, where s0, increases with increasing oxide content. For cold-worked products containing subgrains no systematic work has been reported, and it was the aim of the present study to examine the microstructure and the relationship between the flow stress and the subgrain size for such products. The behavior of' aluminum aluminum-oxide products depends on the purity of the aluminum matrix, and aluminum of the matrix purity (99.5 pct) was included in the investigation. The literature contains few data about the behavior of this impure aluminum, and aluminum of a higher purity (99.998 pct) was therefore also examined. As regards the relationship between the flow stress and the subgrain size in cold-worked dispersion-strengthened products, no systematic work has been reported. For aged cold-worked structures containing fine precipitates (Fe-Mo carbide) a Petch relation has been found,4 and it has been shown that the k value NlELS HANSEN is Head, Metallurgy Department, Danish Atomic Energy Commission, Research Establishment Riso, Denmark. Manuscriot submitted January 9, 1969. IMD is approximately the same as in iron, whereas the s0 value is higher owing to the presence of the precipi-tates. Investigations of metals such as tungsten,' ferrous metals,4,6 and molybdenum7 cold drawn or swaged at room temperature have shown that the flow stress can be related to the subgrain size by a Petch relation when ts is taken as the subgrain size perpendicular to the direction of deformation. For aluminum no work has been reported on the relationship between the flow stress and the subgrain size after deformation at room temperature, whereas for aluminum tensile strained at different temperatures in the range -183" to 375°C a Petch relation has been found by taking ts equal to the subgrain size.' In the present study two aluminum materials (99.998 and 99.5 pct) and three aluminum aluminum-oxide products (containing 0.2, 1.0, and 4.7 wt pct oxide) were drawn at room temperature to reductions in area from about 10 to about 95 pct. The structures were studied by transmission electron microscopy, and the flow stress (0.2 pct offset) was measured at room temperature. EXPERIMENTAL Materials. The materials are given in Table I together with the chemical analysis. The three aluminum aluminum-oxide products were manufactured from aluminum powder that had been compacted and Table I. Chemical Analysis of Materials Al203 Fe SI Material wt pct wt pct wt pct 99.998 pct* - 0.0004 0.0012 Aluminum 99.5 pctt - 0.36 0.16 Aluminum AlMD13† 0.2 0.16 0.12 Aluminum- -Oxide AlMD105† 1.0 0.26 0.18 Products SAPISML960s† 4.7 0.22 0.19 *Other impurities: O.0004 pct max each of Cu and Zn (supplier's analysis). †Other impurities: 0.03 pct max Cu. 0.02 pct max each of Mn, Mg, Zn, Ti. Table 11. Mean Diameter of Aluminum-Oxide Particles in Extruded and in Cold--Drawn Aluminum Aluminum-Oxide Products Mean Diam. of A1203-Plates* Material State A AlMD105 Extruded 540 Cold Drawn 97 pct 510 SAP ISML 960 Extruded 770 Cold Drawn 95 pct 820 *The standard deviation of the mean is approx. 5 ±pct.

Jan 1, 1970

By Robert A. Rapp, Ronald L. Pastorek

Solid-state electrochemical measurements by three alternative experimental procedures were made with the cell FeO, Fe3O4 |Zro.85Cao.15O1.85 |Cu| Zr0.85CaO.15O1.85 | FeO, Fe304 to establish the solubility and diffusivity of oxygen in solid copper in the temperature range 800" to 1030°C. The solubility of oxygen in solid copper and the diflusivity of oxygen in solid copper Dgu = 1.7 X 10-2 exp(-16,000/RT) Cm2/sec were determined and confirmed in alternative experiments. The enthalpy of solution of oxygen in solid copper equals —10,000 cal per mole; the partial excess entropy of the oxygen atoms in the Cu-O dilute solution is approximately the same as that found for interstitial atoms in other metals. The diffusivity of oxygen in solid copper is consistent with that expected for an interstitial atom. RELIABLE values for the saturation solubility N(s) and diffusivity DO of oxygen in solid copper have not been unambiguously established in the literature. Following three early determinations by others,1"3 Rhines and Mathewson4 reported that the solubility of oxygen in solid copper increased from 0.007 at. pct 0 at 600°C to about 0.015 pct at 1050°C. Phillips and skinner,, using essentiially the same analytical procedure, reported that the solid solubility increases from 0.0018 at. pct 0 at 550°C to about 0.0075 pct at 1050OC. The only previous value for the diffusivity of oxygen in solid copper was reported by Ransley.6 Ransley deoxidized Cu-Cu2O alloys in an atmosphere of carbon monoxide gas to yield a solubility-diffusivity product. He used the solubility data of Rhines and Mathewson to calculate the diffusivity values. Another method for obtaining the solubility-diffusivity product (N(s) DO) is by measuring the widths of internal-oxidation zones in copper alloys as reported by Verfurth and Rapp.7 However, the calculated N(S)Do products depend upon the alloy content of the specimen, so that the internal oxidation of copper alloys does not follow ideal internal oxidation kinetics. As a result, unequivocal values for the N(s) DO product were not obtained by this procedure. A solid-state coulometric titration technique similar to that employed in this work was introduced by C. Wagner8 to study the dependence on silver activity of the Ag/S ratio in silver sulfide in the temperature range of 160" to 300°C. Similar experiments have been carried out by C. Wagner and co-workers9-11 to study the stoichiometry range of silver and copper tellurides, cuprous sulfide, and cuprous selenide. Numerous authors have carried out electrochemical measurements with a solid oxygen-ion-conducting electrolyte to determine the solubility and/or diffusivity of dissolved oxygen in several liquid metals.12-l6 Rickert and Steiner17,18 have used solid-state electrochemical measurements to determine the diffusivity of oxygen in solid silver from 760" to 900°C. Two different cell geometries were used. In the cell of linear geometry Fe, FeO | ZrO2 + (CaO) | Ag + [0 (dissolved)] [1] oxygen diffused from the interior of the silver electrode to the silver/electrolyte interface where the oxygen activity had been lowered from a fixed initial value to practically zero by the application of voltage to the cell. The diffusivity of oxygen in solid silver was determined from the solution of the diffusion equation and the time dependence of the cell current. However, this determination of the diffusion coefficient depended upon a knowledge of the solubility of oxygen in solid silver. A cylindrical geometry was used for the cell Pt, O2(Po2 = 0.21 atm) | ZrO2 + (CaO) | Ag + [0 (dissolved)] [II] which also allowed the diffusivity of oxygen in solid silver to be determined. These values were in agreement with other available data.l9 Recently, Raleigh20,21 used a method involving the measurement of diffusion-limited currents in a cell involving the AgBr solid electrolyte to determine the diffusion coefficient of silver in Ag-Au alloys at 400°C. Diffusivity values on the order of l0-14 sq cm per sec were measured in the alloy composition range 10 to 60 at. pct Ag in a single experiment. From numerous electrical conductivity and galvanic cell measurements,9'22"26 the solid solution Zr0.85 Ca0.15 O1.85 has been established as an electrolyte with predominant oxygen ion conduction over a wide range of intermediate and high oxygen activities. For interrelating the thermodynamics and the kinetics of the dissolution of oxygen in solid copper in this investigation, a galvanic cell was constructed with FeO-Fe3O4 as the reversible reference electrode, the Zr0.85Ca0.15 O1.85 electrolyte, and a pure copper specimen under-saturated in oxygen as the other electrode. THEORETICAL ANALYSIS Three variations of a high-temperature electrochemical technique were used in this study to provide two determinations each of the solubility and diffusivity

Jan 1, 1970

By R. H. Frazier, J. M. Hodge, F. W. Boulger

This paper reports the results of studies of the impact properties of quenched and tempered alloy-steel plates as a function of sulfur content. It was found that the impact energy levels decreased continuously as the sulfur content increased and that there was a straight-line relationship between impact energy and sulfur content when plotted on logarithmic coordinates. Cross rolling raised the level of these Lines for transverse tests and lowered the level for logitudinal tests proportionately to the amount of cross rolling. ALTHOUGH it has been generally recognized that, for applications in which notch toughness is critical, the sulfur content of the steels used should be held to a low value, quantitative information on the effect of sulfur on notch toughness has not been available. For such applications, it is a common practice to specify minimum impact values, and in order that these may be met consistently it is important that the steel producer know quantitatively the effect of sulfur on notch toughness so that realistic sulfur content limits can be applied to the steels they produce. In many instances, particularly in flat-rolled products, impact properties are specified in the direction transverse to the principal rolling direction, so that the factors affecting the anisotropy or directionality of impact properties are also of concern to the steel producer. For some applications, furthermore, it is a common practice to increase the sulfur content of steels in order to improve their machinability, and, in such instances, the effect of this practice on notch toughness may often be of concern. This paper reports on an investigation, carried out at Battelle Memorial Institute, designed to furnish this quantitative information on the effect of sulfur on notch toughness and also to furnish further information on the factors affecting the anisotropy of impact properties in wrought heat-treated alloy steels. MATERIALS AND EXPERIMENTAL PROCEDURE The experimental steels were of intended base analysis: 0.30 pct C, 0.80 pct Mn, 0.25 pct Si, 2.5 pct Ni, 0.80 pct Cr, and 0.45 pct Mo. Steels were made with sulfur contents varying from 0.005 to 0.179 pct. The steels were prepared from 600-lb induction-furnace melts. Steels containing 0.020 pct or more sulfur (at meltdown) were melted from a charge of ingot iron (except for one heat): lower-sulfur steels were made from electrolytic iron. The charge consisted of ingot or electrolytic iron, ferrosilicon to give 0.10 pct Si, and ferromanganese to give 0.05 pct Mn. At meltdown, electrolytic nickel, ferromolybdenum, iron phosphide, and pyrite were added followed in sequence by ferrochromium, sili-comanganese, ferrosilicon, and ferromanganese. The slag was then removed and graphite added to give the desired carbon content. Bath temperature was adjusted to 2850°F and, when no other additions were to follow, 2 lb per ton of aluminum was added, immediately before tapping. Compositions of the experimental steels appear in Table I. Analyses are from single determinations, except sulfur which was analyzed in duplicate. A test sample (3 in. in diam by 6 in. long) and a 575-1b ingot were poured from each heat. The test sample was poured in a sand mold; the cooling rates of the test sample and the large ingot were approximately the same. Chemical analysis chips and metal lographic specimens were taken from the test samples. The ingot was 8 in. sq at the base and 9 in. sq at the top. A 5 X 5 X 6-in. sand mold hot top was completely filled in teeming the ingot. After solidification, the mold was stripped from the ingot which cooled to room temperature. Ingots were reheated to 2250"F and rolled to 1.9-in. slabs on a commercial mill. The slabs were box-cooled to room temperature. Sections of the 1.9-in. slabs were heated to 2250°F and rolled on a Battelle laboratory mill according to one of three schedules: 1) rolled straightaway to 0.5-in. plate; 2) rolled straightaway to 1.3-in. thickness, then cross rolled to 0.5-in. plate (29 pct cross rolling); or 3) cross rolled from 1.9-in. to 0.5-in.-thick plate (46 pct cross rolling). The 0.5-in.-straight- or cross-rolled plates were normalized at 1700°F for 1 hr and then water quenched from 1600°F. Plates were then tempered 2 hr at 1240°, 1170°, 1080°, or 860°F to obtain Rockwell C hardness of 25, 30, 35, and 40, respectively. Tempering was followed by quenching to room temperature to avoid temper embrittlement. Slack-quenched plates were isothermally transformed for 26 min at 800°F, quenched, and tempered 2 hr at 1170°F. Pearlitic microstructures were obtained by holding 168 hr at 1200° F, followed by quenching. Charpy V-notch specimens were taken both transverse and longitudinal to the main rolling direction, notched perpendicular to the plate surface, and tested. Slabs and plates which were to be homogenized

Jan 1, 1960

By Morris Cohen, Robert C. Ruhl

The phases in Fe-C alloys over a wide composition range have been studied after splal quenching from the liquid state. Binary alloys containing 0 to 5.1 wt pel C as /cell as a large number of ternary Fe-C-Si alloys with 2.5 to 5.0 wt pct C and 0.3 to 5.1 wt pct Si were attlong those sludied. Olher Fe-C-X alloys, zcilh X being Co, Cr, ,Wn, Ni, and Ru , were also inrestigated after splat quenching. At high carbon contents, a new hcp phase (designaled 6 phase, but different from e carbide) is retained upon splat quenching. The .fraction of this phase varies up lo 97 pcl for a Fe-4.K-1.9% alloy. The composition of the E phase ranges from about 3.8 10 4.8 wt pet C, and the corresponding laltice parameters increase linearly ulith carbon content, while the c/a ratio remains essentially conslc~nl. The E phrtse appears to he a solulion of carbon in E iron, the latler being nornially found only at high pressures. It is deduced that the unit cell of the E phase corresponds to the formula Fe12C3, and llzal il is relaled to tlie ordered slruclures 0.f 6 iron carbide and c iron nilride. The E phase is compared and contrasted to the olher known carbides and nitrides of iron and nickel. An exlrapolaTion of the atomic volume 1,s carhon conlent of /he E pllase lzcts giz.en a neu7 estitnale jor /he alomic volume of E iron, 11.30 cu A, a1 atmospheric pressure and temperature. Other alomic volume relalionships lead to /he co~zpositioti Fe2.iC tor E iron carbide, /he unit cell fortr~ula being -Fe2rClo The E phase undergoes a lulo-slage decomposition upon healing, .forrning firsl rnarlensile plus E carhide, a/ler 1 hr at 140" lo 200°C, slid then ferr ite Plus cementile, after 1 lir a1 330" to 460°C. A1 carbo,l contents between 1.5 and 3.0 LC/ pcl, (he predo.wirzar/t plzase alley quenching is fcc austenite. The retained carbon content of this phase increases with itlcreasing silicon in certain concentration ranges, reaching a maximum of 2.37 wt pct C itz a Fe-2.6C-4.OSi alloy. This is the highest carbon conten1 reLaitled in austenite to date. These high-carbon aus-tenites can be partially tm?zsforttled lo tnartensile hy severe deformation in the temperature range of — 190 to -50°C. TECHNIQUES for splat quenching from the liquid state have been utilized in numerous recent investigations to produce metastable phases in a variety of alloy systems. Among the several ways of splat quenching, the shock-tube method appears to yield the highest cooling rates1-3, 7, 8 and was adopted here. Estimated cooling rates attained in the present experiments ranged from 10' to 10 80Cper sec.' As a part of a research program on interstitial al- loy phases, the Fe-C system was selected for splat-quenching studies. It was hoped that splat quenching would allow high metastable supersaturations of carbon to be retained in solution. Also of considerable interest were the conditions governing the occurrence of the various intermediate phases upon solidification. The alloys investigated included both binary Fe-C compositions as well as six ternary Fe-C-X alloy systems. The known phases in the Fe-C system are summarized in Table I.* Only the ferrite and graphite are ent investigation.14 and is described in detail herein Table II summarizes corresponding data on Fe-N phases, which are also of interest here because of their similarity to the Fe-C phases. EXPERIMENTAL PROCEDURES Alloys were prepared by melting the elements. 99.9 pct purity, in an inert gas nonconsumable electrode arc furnace. The buttons. weighing about 5 g. were remelted twice. were then fragmented. and their interior surfaces were examined for uniformity: if any doubt existed. they were remelted again. Chemical analyses were performed on all the alloys. the accuracy being about k0.05 wt pct. At high temperatures, carbon-containing alloys react with alumina crucibles as follows: If the atmosphere in the splat-quenching furnace does not contain sufficient carbon monoxide the alloy can be depleted of carbon and contaminated with aluminum. Calculations and experimental observations showed that 50 to 100 torr CO partial pressure effectively blocked the above reaction in all the alloys investigated. The splat-quenching equipment in Figs. 1 and 2 provides for evacuation and back-filling with CO-Ar mixtures. The furnace is capable of operation up to 1650°C. and the gettering action of the graphite heating element reduces the oxygen partial pressure in the furnace atmosphere to below 10-5 torr, thus preventing oxidation of the specimens.

Jan 1, 1970

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By Marius R. Campbell

Does mine-sampling show the commercial value of a coal, and if so, how should it be done? This question is often asked, but seldom answered. During the past summer, while engaged in securing coal for the Government coal-testing plant at St. Louis, I had an excellent opportunity to obtain information on this subject, and the results seem to furnish an answer to the questions propounded above. Sampling for the Geological Survey Coal-Testing Plant. In organizing the work of the testing-plant, it was decided that coal in car-load lots only would be accepted for testing, also that this coal should be loaded under the immediate supervision of a representative of the plant, so as to be certain that the car-load sample would be representative. As an additional check on the work, two mine-samples were to be collected from each mine visited, and these samples, as well as the sam¬ple from the car when it was received at the testing-plant, were to be carefully analyzed at the chemical laboratory, which was established in connection with the plant and operated under the direction of Prof. N. W. Lord, of the Ohio State University, Columbus, Ohio. Mine-Sanmhling:-Mine-samples were collected with great care by me and my assistants, Messrs. J. Shober Burrows, John W. Groves and Frank W. De Wolf. The dominant idea in the regulations which were adopted for mine-sampling was that it should be done in such a manner that the sample would have the same composition as the commercial output of the mine. .

Sep 1, 1905

By W. S. CAYPLESS, H. O. Hofman, E. E. HARRINGTON

I. INTRODUCTION. LIME-ROASTING is a term proposed by Ingalls 1 for the operation of forcing air under pressure through a mixture of galena and lime at the kindling-temperature with the object of oxidizing lead and sulphur and of fritting or fusing the charge. If, finely-divided galena were treated in this manner without the addition of lime, the heat set free by the oxidation of part of the lead and the sulphur would be sufficiently great to fuse undecomposed sulphide, and thus stop desulphurization. Besides the chemical action that the addition of lime, limestone or gypsum to the charge may have, the admixture has the physical effect that it keeps the particles of galena separated from one another and accessible to the oxidizing effect of the air. At present, three methods of lime-roasting are carried out on a working-scale, the Huntington-Heberlein, the Carmichael-Bradford and the Savelsberg2 processes. In the last, which interests us here, an 8-ton charge is made up of galena, limestone and perhaps some siliceous or ferruginous flux; the whole is crushed to pass a screen with 3-mm. holes and moistened with 5 per cent of water. It is fed gradually into a bowl-shaped converter, 6.56 ft. in diameter, supported by trunnions attached to a truck. On the .bottom the converter has a grate with blast-inlet beneath. In starting, the truck with the converter

Jan 1, 1907

By David B. Reger

New discoveries of gas in the southern counties featured the petroleum industry in West Virginia during 194;. Drilling for oil increased slightly over 1944 and a small increase of initial production resulted. Out of 28 wildcats drilled, there were 16 gas discoveries and 12 dry holes. No commercial oil was found in the 28 wells.

Jan 1, 1946

By P. A. Beck, M. V. Nevitt

All binary and a number of ternary u alloys formed by first long period transition elements were examined and found to be ferromagnetic at low temperatures. The Curie temperatures for these alloys were measured. It was found that the correlation of the Curie temperature with composition may be described qualitatively in terms of the contributions of the various component atomic moments to the saturation moment of the alloy. Ternary Fe-Cr-Mo u phase alloys were also found to be ferromagnetic, with a Curie temperature dependent on the iron content and largely independent of the unit cell dimensions. Similar relations were found for the Co-Fe-Cr and the Co-Cr-Mo a alloys, where the Co + Fe content appears to determine the Curie temperature. RECENTLY, it has become increasingly evident that the u phase is some kind of an "electron compound." Several papers1-' discussed the empirical correlation between the composition of the various u phases in alloys of the transition elements and the distribution of electrons in the partially filled d-levels of the component atoms. However, a picture of the latter can be formed only in a more or less intuitive manner, as in the Pauling theory," and the rigorous treatment of these problems is at present prevented by lack of adequate knowledge of the electronic structure of the transition elements in the metallic state. It appeared reasonable to expect that investigation of the magnetic properties, which are related to d-shell electrons, may help in clarifying the physical nature of the foregoing empirical correlation. Qualitative tests of samples of various compositions have shown that certain u alloys become ferromagnetic at liquid nitrogen temperature." The present investigation was undertaken to determine whether or not low temperature ferromagnetism is characteristic of a large variety of u alloys and to establish how the Curie temperatures of ferromagnetic u alloys are influenced by changes in composition and in lattice parameter. In the first portion of the in- vestigation, Curie temperatures were measured for a series of u alloys containing either vanadium or chromium with one or two of the elements manganese, iron, cobalt, or nickel. In the second phase of the work, data were obtained on the Curie temperature of ternary (Fe, Co, Cr)a, (Fe, Cr, Mo)a, and (Co, Cr, MO)U alloys, as a function of composition and of interatomic spacing. Experimental Procedures High frequency vacuum melting in high purity re-crystallized alumina crucibles was employed in the preparation of the u alloys, using metals whose lot analyses are given in Table I. Approximately two-thirds of the alloys were analyzed chemically, the analytical results being in acceptable agreement with the intended compositions, as seen in Tables I1 and 111. The specimens were annealed for homogen-ization in an atmosphere of purified 92 pct He and 8 pct H, mixture or in evacuated and sealed Vycor tubes at temperatures from 780" to 1300°C, depending on the temperature range of the u phase field for the particular composition. The annealing temwerature and time for kach alloy are given in Tables 11 and 111. Curie points were determined by an induction method; the change with temperature of mutual inductance between two coils was observed when the i-u specimen was inserted into the flux path between the coils. The transformer consisted of three coils each containing 1200 turns of 0.0050 in. diam enameled copper wire. The center coil, P in Fig. 1, served as the primary coil, and was linked magnetically with each of the two secondary coils, S, and S? which were connected in series opposition. The primary coil, P, was energized by an audio-oscillator, set at a frequency of 500 cycles per sec, while the signal from the transformer secondary circuit,

Jan 1, 1956