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By L. S. Allen, R. L. Caldwell, W. R. Mills

Borehole models used in the study of nuclear well logging are reviewed and the merit of heterogeneous us homogeneous formation simulation is discussed. .A heterogeneous model for simulating sandstone formations of variable porosity is described. Simulation adequacy was checked by steady-state and pulsed-neutron measurements. INTRODUCTION In the course of developing new methods of nuclear well logging, the problem of testing new logging instruments under controlled conditions always arises. This testing is usually done in wells of known lithology, porosity and fluid saturation, or in laboratory test facilities which simulate the borehole environment. Although the former approach is possibly more satisfying, it is frequently difficult or inconvenient to find wells with enough variation in the cited parameters for a truly comprehensive study, On the other hand. laboratow- test facilities can simulate a wide variety of formation and borehole conditions if care is exercised to maintain adequate simulation under all conditions. Workers concerned with the development of nuclear well logging methods have reported several types of research facilities in the past. Tittle, et a1 used cubical tanks filled with Ottawa silica sand to study the steady-state behavior of thermal and epithemal neutrons in simulated sandstone logging environments.1 In addition to the effects of fresh vs salt water, a wide variety of casing sizes and compositions were investigated. Tittman also used a large tank of Ottawa sand to measure the slowing down length of sio2;2 for making the same measurement in CaCO3, however, an assembly of solid Vermont marble blocks was used. More recently a very useful and carefully planned test pit for nuclear logs was constructed under the auspices of the API.3 This facility consists of three massive limestone sections, each 6-ft thick and more than 5 ft in diameter. The blocks are buried, one on top of the other, in a concrete- lined pit having a total depth of 24 ft. Each section is made of a different limestone to achieve porosity variation, the selection being Carthage (2 per cent), Indiana (19 per cent) and Austin (26 per cent). The blocks are traversed by a 7 7/8-in. diameter borehole and are saturated with fresh water. Great care was taken to insure total saturation of the stone. Homogeneous mixtures and materials have not been used exclusively for simulating earth formations. Tittle, et a1 4 showed that a heterogeneous lattice of water and graphite could be used to simulate Liquid furfural with very little effecton measured thermal and epi thermal neutron distributions. Subsequently, a lattice-type model for simulating limestone earth formations was designed and built by Berry This limestone model was constructed of 7/8- x 11/4- x 36411. marble rods glued together with a plastic resin to form a 36-x 42- x 42in. cube. The cube was honeycombed vertically with 7/8- x 7/8- x 3641-1. holes for porosity and had a 111/2-in. diameter hole in the center to serve as the borehole. Lower porosities were simulated by placing marble rods in the square holes. The finished cube was used with the borehole vertical and set in a tank to hold liquid for filling the holes in the rock matrix. A second type of heterogeneous borehole model has been proposed by Kukharenko, et a1.6= In this concept the model is composed entirely of solid material. The hydrogen equivalent of formation fluids is simulated by making the model of alternating layers of dense rock and celluloid. Additional hydrogen is included by drilling vertical holes in the rock sections and filling them with solid forms of hydrogeneous material. The volume of the holes is equal to the volume of the celluloid layers, so an axial and radial dispersion of the hydrogeneous material is thus obtained. One such model was composed of alternate 50 mm-thick sand layers and 2 mm-thick celluloid sheets. Approximately 200 appropriately spaced plastic tubes were used in each sand section. The plastic tubes were filled with paraffin for additional hydrogen concentration. This arrangement yielded a model with a water-equivalent hydrogen concentration of 10 per cent. Experimental data taken in this model and in a model consisting of the same material but homogeneously dispersed showed that the heterogeneous system adequately

Jan 1, 1966

By Herty, C. H.

No attempt will be made here to review the previous work done by investigators on the general subject of inclusions, because it was discussed sufficiently in an early cooperative bulletin of this series (No. 36, 1928), and reference was then made to general bibliographies. The work described in this present bulletin deals directly with the study of the mechanism of deoxidation of steel with aluminum and the formation of inclusions containing alumina. Unquestion- ably, such inclusions are encountered in most steel-making practices and little has been done to determine their characteristics. Aluminum is used to ensure rapid deoxidation during the solidification stages of the steel. For this reason the possibilities of inclusion elimination are slight and alumina-containing particles will undoubtedly be present in the ingot. Besides this common practice, aluminum is often used in the ladle with other deoxidizing agents such as silicon and manganese. Ladle additions of aluminum are made to rimming steels to obtain the correct partial deoxidation desired in this type of steel. In killed steels the aluminum is added to ensure soundness, as far as blowholes are concerned, in the ingot. In either rimmed or killed steels, alumina or alumina-containing inclusions are found therein, the amount and type depending on the oxidation of the metal, the amount of aluminum added, and the addition of other deoxidizers.

Jan 1, 1957

Discussion, at the Virginia Beach Meeting, February, 1894, of the Paper of Prof. Posepny. (Trans., xxiii., 197, 587.) Including communications subsequently received. a T. A. Rickard, Denver, Colorado (communication to the Secretary) : The paper of Professor Posepny was printed so short a time

Jan 1, 1895

Coal - Surface Mining Coal Preparation Coal Utilization Research and Development Health and Safety

Jan 3, 1976

By Akira Yazawa, Alžbeta Gubcova

RECENT lead-smelting techniques have tended toward use of high-grade concentrates with minimum amounts of flu, accompanied by profitable employment of roast reaction.1-5 In order to better understand these smelting processes, thermodynamical calculations have been carried out on the Pb-S-0 system, and the results obtained have been presented in isothermal reaction diagrams in which log Ps, and logPo, were the axes. The diagram thus constructed seems to be more convenient to grasp the equilibrium aspect than those published hitherto.6-8

Jan 1, 1968

By C. W. Allen, L. C. Moore

THE Mather mine, of the Negaunee Mine Co., is within the limits of the City of Ishpeming, on the Marquette iron- range in Michigan's Upper Peninsula. It is named for William G. Mather, who has served as President, and Chairman of the Board, of The Cleveland-Cliffs Iron Co. for well over 50 years. The property comprises nearly the square mile of section 2, T.47 N. R.27 W., which, except for 20 acres in the northeast corner, was leased by The Cleveland-Cliffs Iron Co. to the Negaunee company. The latter is a partnership of Cleveland-Cliffs and the Bethlehem Steel Co., organized to equip the property, retaining Cliffs in charge as operator. Shipments of ore from this area are mainly through Marquette, which is 16 miles to the northeast on Lake Superior, or through Escanaba, a Lake Michigan port, 65 miles to the south. Cleveland-Cliffs, in 1943, operated 12 mines in the Lake Superior district, with shipments of 6,635,576 tons for the year. GEOLOGY The north footwall of the Marquette Range synclinorium outcrops near the north line of sec. 2, the iron formation dipping to the south at an angle of about 40º. The south side of the trough reappears at a distance of 4 ½ miles on sec. 26 and the surface geology between shows iron formation or intrusive diorites. The latter are harder than most phases of the iron formation and, as a result of glacial action, appear as buttes or low-lying hills. The general elevation of sec. 2 is about 1450 ft. above sea level, or 850ft. above Lake Superior, and the higher diorite outcroppings about 1600 ft. above sea level. The geological structure has been complicated by a series of major and minor faults, one of which may be illustrated by the diorite sheet, which tilts south with the iron formation in the north half of the section and then reappears near the center to repeat this sequence. Sectionally the geological series includes a nearly eroded capping of Goodrich quartzite followed by the considerable thickness of Negaunee iron formation, which is cut by intrusive dikes or diorite sheets, and underlain by the Siamo slates grading into quartzites. The ore deposits occur mainly in troughs formed by the intersection of impervious dikes and the footwall slate, but include locally enriched lenses or bands in the iron formation and also interbedded with the Siamo slate. The ore is a soft red hematite with an indicated dried analysis from the surface drilling to date of 61.50 per cent Fe, 0.134 per cent P, 5.40 per cent Si, 2.87 per cent Al and 0.015 per cent S. EXPLORATION A diamond-drilling campaign started in 1937 actually had its inception in 1917, when a number of shallow test holes were put down for the purpose of locating ore that might be quickly developed and mined

Jan 1, 1945

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By M. A. Grossman

The harden ability of most steels can be predicted within 10 to I5 per cent provided the complete chemical composition is known, including "incidental" elements; and provided the as-quenched grain size is known; and provided, finally, that the composition and heating temperatures for hardening are such as to result in austenite free from carbide particles. In the method proposed herein, the steel is considered as having a base hardenability due to its carbon content alone (the hardenability of a "pure steel" of the given carbon content, without any other elements), and this base hardenability is multiplied by a multiplying factor for each chemical element present. After multiplying all these together, the final product is the hardenability. Grain size may be taken into account either in the base hardenability or after the multiplication. Hardenability is stated in terms of "ideal critical diameter", namely, the diameter of bar, in inches, that will just harden all the way through (absence of un-hardened core) in an "ideal" quench, and the calculation may also be related to the Jominy test The data bring out certain features rather clearly. For example: i. It is quite useless to attempt to predict hardenability unless all elements, including "incidentals,,) are known; thus an "incidental,, chromium content of 0.20 per cent increases the hardenability by about 50 per cent. 2. The relative effectiveness of different alloys is sometimes unexpected; thus molybdenum when calculated in this way appears to be of the same order of effectiveness as manganese, rather than much more powerful, as would appear to be common experience; observe that an increase from no manaanese to 0.20 per cent Mn provides a multiplying factor of 1.67, and an increase from no molybdenum to 0.20 per cent Mo provides a factor of 1.63, an increase of over 60 per cent in each case. However, if to a steel containing 0.50 per cent Mn there is added "20 points of manganese," the factor is raised from 2.65 (for 0.50 per cent Mn) to 3.35 (for 0.70 per cent Mn), or an increase of only 26 per cent. Thus the fist small addition of an element has a much more powerful percentage effect than an equal further addition when some is already present, and in most cases the effect of molybdenum is considered in relation to a steel in which molybdenum is absent. 3. If two elements are equally effective, a greater hardenability will be obtained by using, for example, 0.5 per cent of each than by using I.o per cent of either of them alone. 4. A knowledge of the as-quenched grain size is essential for precise work, since a difference of only one grain size number (say No. 7 instead of No. 6) makes a difference of almost 10 per cent in hardenability (in these units); this, however, does not apply to certain It should be emphasized that in chromium steels (over 0.30 per cent Cr) and chrome-molybdenum and chrome-vanadium steels, un-dissolved carbides are likely to be present in the steel as quenched, and that in such cases the charts can indicate only a maximum Passible hardenability, whereas the extent of hardening actually obtained may be much less. Thus tests on a number of chrome-molybdenum steels have indicated a degree of hardening amounting to only 50 to 65 per cent of the maximum possible, and in chromium steels from full hardening (100 per cent) down to as low as 70 per cent. On the other hand, when the amount of such elements is small (Cr under 0.30 per cent, Mo up to 0.25 per cent in the

Jan 1, 1942

By R. M. Waterstrat

The phase VPt has been reported to have a crystal structure of the B19 (AuCd) type at low temperatures.''' A recent investigation3 has indicated that this phase forms by an ordering reaction from the disordered fcc Pt(V) solid solution which is stable at high temperatures. olander4 has shown that there exists a close structural relationship between the orthorhombic B19 structure and a fcc structure possessing the L1 , (CuAu) type of atomic ordering. One may derive the B19 structure by a shear-like displacement of the atoms in the (002) plane of the ordered fcc lattice along the (010) direction through a distance equal to one eighth of the unit cell dimension, see Fig. 1, followed by an orthorhombic distor; tion of the cube axes such that a = 2.693A. h = 4.413A. and c =4.767A (estimated uncertainty 0.005A). Filings of this phase were produced by grinding a VPt alloy having the B19 structure with a diamond dental grinding disc. When these filings were subjected to X-ray diffraction examination, a pattern of a severely cold-worked fcc structure was obtained. higher solution temperature used (1200 C) or to a much lower oxygen pressure than he reported, due to transfer through many bends and tubes in his complicated apparatus. An interesting observation was made when an oxygen addition was attempted in a cylindrical sample of columbium in the cold worked condition rather than in the annealed condition. The interior of the sample re-crystallized during the oxygen addition at 900°C. The periphery, however. (1 mm) did not recrystallize. A similar sample without oxygen recrystallized throughout the entire cross section. It appears that the re-crystallization is hindered by interstitial oxygen. Presumably, the interior recrystallized before appreciable oxygen could diffuse into the core. This work was supported by the United States Atomic Energy Commission. When the filings were annealed in a high vacuum furnace for 15 min at 110O0C, however. they returned to the B19 structure perhaps as a result of reordering. Subsequent less-severe cold-working of these filings by grinding in a hardened steel mortar and pestle at room temperature produced a transformation into a cold-worked L1, structure which was slightly tetragonal. Thus it appears that the degree of deformation may influence the final structure. Considerable line-broadening was observed in X-ray diffraction patterns obtained from the cold-worked filings and therefore no attempt was made to obtain accurate lattice parameters. Vacuum annealing treatments at 1100'C intended

Jan 1, 1970

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500' to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"' times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

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 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 James R. Holden, Frederick E. Wang

Through both single-crystal and powder X-ray diffraction methods, ten A6B23-type compounds have been confirmed to exist between lanthanides (A) (plus scandium and yttrium) and manganese (B); A = Y, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, and Lu. The formation of a compound of this type is shown to he extremely atomic size-sensitive; hence it can be classified as a "size-factorH compound. The "enveloping effect", a geometrical consideration observed in its crystal structure, is proposed as the reason for the A6B23-type compound being size-sensitive. The approximate ideal geometrical ratio of the radii R/r is 1.31 while experimentally A6B23-type compounds have a radius ratio lying within the range 1.2 to 1.4. FLORIO t al.' characterized the structure of Th6MnZ3 as fcc, space group Fm3m, with 116 atoms in the unit cell. Since then, a number of isotypic binary compounds, and recently Gd n,,' have been confirmed to exist. The fact that strontium and barium form A6Bz3-type compounds with magnesium strongly suggested the possible existence of Ba6Liz3. However, investigation3 showed the compound Ba6LiZ3 to be absent. Since both strontium and barium are group 11-a elements and are therefore "open metals",6 the nonexistence of Ba6LiZ3 can hardly be explained satisfactorily by valence-electron considerations. On the other hand, the consistent atomic-radius ratio, (R/r),* observed for the known A6Bz3-type compounds,3 strongly suggests that the formation of compounds of this type is atomic size-sensitive. Therefore, one is tempted to explain the nonexistence of Ba6LiZ3 entirely on the basis of the atomic-size difference between strontium and barium. However, this approach is not entirely without objection. Atoms are not rigid spheres and are known to vary in size within certain limits.7 Since the atomic-radius difference between strontium and barium (0.07 to 0.09A) is within these limits, it is reasonable to assume that the size difference would have a negligible effect on the formation of Ba6LiZ3. This view is further supported by the fact that the radius ratio, R/r, in other known "size-factor" compounds is observed to range widely—for example, from 1.08 to 1.45 for ABz-type compounds (C15, MgCuz type)' and from 1.37 to 1.58 for AB5-type compounds (D2d, CaZn5 type).g The present investigation was undertaken in order to find a more satisfactory explanation for the non-existence of Ba6LiZ3 and, consequently, a better understanding of the nature of the A6Bz3-type compound. The primary objectives are to confirm the previous conclusion3 that the A6B23-type compound is indeed a "size-factor" compound and subsequently to determine the atomic-radius ratio range in which the A6Bz3-type compound can exist. In order to achieve these objectives, stoichiometric A6Bz3 alloys, where manganese (B) was alloyed with various lanthanide elements (A), were selected for investigation. The atomic-radius ratios of lanthanide elements with manganese range from 1.26 for Lu/~n to 1.46 for Eu/Mn. This radius ratio range includes and exceeds the range of all previously reported A6Bz3-type compounds—1.32 for Th/Mn' through 1.38 for Sr/Li. Furthermore, the atomic-size difference between successive elements of the lanthanide series in order of atomic number) is of the order of 0.01A (europium and ytterbium are exceptions). The series of lanthanon-manganese alloy systems is ideally suited to a precise determination of the limits of allowable atomic-radius ratio for A6Bz3-type compound formation. EXPERIMENTAL PROCEDURE The lanthanide metals, in ingot form, supplied by Michigan Chemical Corp. (St. Louis, Mich.) and Nuclear Corp. of America (Burbank, Calif.), were guaranteed by the suppliers to be at least 99.9 wt pct pure (traces of silicon, calcium, and other minor constituents present on occasion, not to be more than 0.05 wt pct) as shown by spectrographic analysis. Manganese metal, in polycrystalline form, was redistilled from the commercial, chemically pure grade and was analyzed to be at least 99.95 wt pct pure. In all cases, the atom ratio between the two elements in each charge was A (rare-earth meta1):B (manganese) = 6:23 and a constant weight, 3 g, of

Jan 1, 1965

By R. W. Armstrong, D. H. Feisel

Self-diffusion in pure crystalline solids has been described through extension of the Cohen and Tum-hull volume -fluctuation model originally proposed for diffusion in simple liquids. It is shown, for a number of crystalline solids, that the self-diffusion coefficient, D, obeys the relationship where a is the lattice spacing, v the Debye frequency, Z' the lattice-volume fluctuation per atom required for a diffusion jump, and (?V/Vo) the relative increase in the lattice volume resulting from thermal expansion between O°K and the temperature under consideration. The calculated value of Z' is dependent upon the difiusion mechanism and the lattice geometry. ThE need for an increased understanding of mass-transport processes in crystalline solids has resulted in much research to determine rates of self-diffusion.' For several metals (e.g., copper, silver, and iron), the experimental values of the self-diffusion coefficient, D, have been determined over a large interval of temperature and the accuracy of D has been investigated through repeated experiments. Also, a number of empirical and theoretical diffusion studies have established a rational basis for understanding the D values for the different elements.2"6 The empirical diffusion analysis by Sherby and simnad6 supplied the main stimulus for the present study. Sherby and Simnad, reviewing the self-diffusion data for a substantial number of pure crystalline solids, suggested that sufficient data were available to establish with some certainty the apparent intrinsic material properties which influence D. Without explicit regard for any mechanism of diffusion, these investigators obtained an empirical relationship for D which correlated the self- diffusion coefficient for each element with the melting temperature, crystal structure, and valence of the particular element. Their analysis is only unsatisfactory in that the effect on D of crystal structure is not very clear and the valence to be assigned to an element is not always straightforward. The present study is an attempt, from a very different viewpoint from that of Sherby and Simnad, to establish a basis for understanding the self-diffusion coefficients for crystalline solids. This analysis was undertaken for the purpose of developing a general expression for D which would explicitly depend on the mechanism of diffusion. The main result of the study is that diffusion in crystalline solids may be described in terms of a volume-fluctuation model which was originally proposed by Cohen and Turnbull7 to describe diffusion in simple liquids. The model appears to be useful for predicting self-diffusion coefficients in crystals. The following sections describe the volume-fluctuation model for diffusion, the application of this model to crystals, and the resultant agreement with experimental data. 1) THE VOLUME-FLUCTUATION MODEL FOR DIFFUSION Cohen and Turnbull7'8 developed their model for liquid self-diffusivity for the purpose of describing certain properties of liquids, glasses, and the liquid-glass transition. A hard-sphere model for the liquid structure is used. In this model, the size of a spherical molecule or atom is fixed for all temperatures by the interatomic spacing at the absolute zero of temperature. At any temperature above O°K, the atom is viewed as being contained within a larger spherical cage defined by the interatomic spacing of the atoms at that temperature. A random distribution of varying cage sizes is assumed to exist in the liquid. An individual diffusion jump occurs when the free volume of an atom (the volume of the cage containing the atom minus the volume of the atom) is large enough for the atom to jump out of its cage. With this physical picture of diffusion in liquids, Cohen and Turnbull derive the following equation for self-diffusivity: D=Doe-yv*/vf [1] where Do is the product of three factors which are the diffusion-path geometry, the diffusion-jump distance, and the velocity of the diffusing atom, v*

Jan 1, 1964

By R. G. Knickerbocker

THE copper smelter and refinery of The Messina (Transvaal) Development Co. Ltd., at Messina, South Africa, was erected in 1920 and 1921, but initial operations were deferred until late in 1922 on account of the collapse of the copper market in the interim. Because the anticipated production was to be only 20 tons of copper per day from a high-grade matte containing 60 per cent copper, and because the ore did not contain gold or silver in quantities sufficient to pay for separation from the copper bullion, it was decided to design the plant along lines quite different from the modern smelteries treating large quantities of sulfide ores carrying appreciable amounts of gold and silver. The plant was built, therefore, for the production of copper by the Nicholls-James process. By this method two-thirds of the copper matte produced was roasted in a Merton calciner and charged into a bath of the remaining one-third portion of unroasted matte in a reaction furnace. The original design was not only novel in providing for the Nicholls-James process, but also in comparison with new plants built elsewhere, because of factors inherent in the locality. Sources of supply for machinery were very remote; it takes three months after the placing of an order to accomplish delivery of machinery into Messina from the United States. Native labor was available at 30 to 40¢ per 8-hr. shift. These factors permitted plant design which provided no overhead cranes, no matte ladles, no slag pots or other usual mechanical means of transportation between departments. The design resulted in a compact simple plant with furnaces arranged close together and. terraced so as to provide for gravity transfer of molten material from one furnace to another and for manual disposal of products. Fig. 1 shows the relative location of furnaces. The three furnaces are parallel on successively decreasing elevations. A superimposed feed floor was provided above the furnaces. All three furnaces were provided with coal-dust burners served from a Bonnot system of coal-dust transportation, and the waste gases were discharged into waste-heat boilers.

Jan 1, 1932

By W. C. Hayes

The site selected for the United States prototype pumped storage project of Union Electric CO. was Proffit Mountain, five miles from Taum Sauk, the highest point in Missouri. Factors influencing final location were: high local relief; satisfactory rock type and structure; and an economic location in respect to existing transmission systems. The upper reservoir was constructed by excavating rhyolite porphyry from the crest of Proffit Mountain and constructing a rock fill dike encircling the area to form a 4350-acre foot reservoir. A 6564-ft tunnel connects the upper reservoir with the generating and pumping facilities. A concrete gravity dam on the East Fork of the Black River forms the 6350-acre foot lower reservoir. Precambrian rhyolite porphyry forms the crest of Proffit Mountain and the floor of the upper reservoir. The tunnel was excavated in rhyolite prophpy, granite porphyry, dolomite, shales and conglomerate. Abutments and the foundation of the gravity dam are in rhyolite porphyry, and much of the valley floor of the lower reservoir is underlain by dolomite and shale. Core drilling provided data on soundness of rock type, structure, depth of weathered zone and potential water loss in the fractured igneous rocks. After a six-year study of pumped storage and cost comparison with alternate stream generating units, the Taum Sauk pumped storage project was authorized by Union Electric Co. on Dec. 11, 1959.' The site selected is located in the St. Francois Mountains of southeast Missouri approximately 90 miles south of St. Louis (Fig. 1). The lower reservoir was provided by damming the East Fork of the Black River, a small tributary of the Black River with a minimum flow of about 1 sec ft. Construction of the upper reservoir was effected by quarrying the crest of Proffit Mountain - five miles from Taum Sauk Mountain, the highest point in Missouri — to provide material for a rock fill dike surrounding the quarried area. This provided a 55-acre mountain top lake with a water depth of 92 ft (Fig. 2). A vertical shaft and tunnel connect the upper and lower reservoirs through the two reversible pump-turbine motor-generator units operating under 800 ft of hydraulic head (Fig. 3). The output rating of the plant is 350,000 kw with daytime generation of about 2.2 million kw-hr under normal use. Night pumping will replenish water to the upper reservoir in about 91/2 hours3. The automatic operation is remotely controlled from the Osage plant and from the dispatchers office in St. Louis. GENERAL GEOLOGY Mountains of the St. Francois area consist of Precambrian granites, granite porphyries, extrusive fel-sites and basic dikes. Basal conglomerates overlain by Upper Cambrian Bonneterre dolomites and shales onlap the exhumed Precambrian knobs and hills and are exposed in the narrow valleys. Cambrian and Ordovician residuum as much as 200 ft thick is present on the slopes of many hills. Proffit Mountain consists of rhyolite porphyry and granite porphyry. All excavation for the upper reservoir was in rhyolite porphyry, and the same rock is present under the Bonneterre at the plant site and under alluvium at the lower reservoir dam site. The region has been dissected to the stage of early maturity with only small upland flats remaining. Considerable local relief (a requisite for the project) approaches 1000 ft. Streams flowing across the Precambrian ridges have formed restricted narrows, termed shut-ins. A shut-in approximately two miles downstream from the plant site provides an excellent site for the lower reservoir dam. TEST BORINGS Preliminary to final approval of the project, 12 test borings were made to determine subsurface geologic conditions (Fig. 2). Drill hole No. 12 at the lower reservoir dam site showed 20 ft of alluvium over solid rhyolite porphyry. Drill holes No. 1, 2 and 3 were drilled in the tail race area to depths of 66 ft, 75 ft and 95 ft respectively, and all bottomed in Bonneterre. Drill hole No. 4 at the plant site provided NX core to a total depth of 98 ft in Bonneterre. Drill

Jan 1, 1965

By H. D. Hoskold

This instrument, shown in Fig. 1, is not generally known, though it has been used in England, and found very practical, handy and useful in work not requiring a transit or theodolite. It is not only a good miner's dial, but a circumferentor as well; that is, it can measure horizontal angles like a theodolite. The magnetic bearings are conveniently read on the inward-beveled upper divided circle; while another circle, graduated on the base-plate, is used for reading the horizontal angles with a vernier. Two leveling spirit-bubbles are sunk in the same base-plate. The vertical divided semicircle is attached to the compact-box by two short axes, which permit the semicircle, with its plain sights, to be turned down to a horizontal position, and rest upon a pin, which relieves the axes from strain. This adjustment gives a clear view of the needle and vernier, and protects the instrument from injury, when carried through low mine-workings. A groove in the semicircle receives a sliding-bridge which carries the plain sights, and a vernier for reading vertical angles. A ball-and-socket-headed tripod is used; but sometimes the instrument is mounted on parallel-plates and level-ing-screws; and sometimes a telescope is attached, instead of the plain sights. The instrument is admirable for all such Mexican surveys as Mr. E. A. H. Tays describes ;l and saves so much time and labor as to be vastly superior to the less accurate hanging-compass called by him a " bully " instrument. If the hanging-compass was ever used in England, it has long since given way to more modern and superior instruments.

Jan 1, 1905

By J. A. Morgan, R. E. Lund, D. E. Warnes

The design, operation, and performance of an integrated pilot plant for recovering zinc and copper from a complex sulfide ore are described. Metallurqical processing comprised selective sulfate roasting in a fluid bed, leaching in a weak sulfuric acid solution, recovering copper by cementation with scrap iron, air oxidation to remove soluble iron, more-or-less conventional Purification for removal of impurities deleterious to zinc electrolysis, recovering zinc by electrolyzing solutions, and recycling spent electrolyte to the sulfating roaster. The effects of several feed preparation and roasting variables on the sulfation response of zinc, copper, and iron are set forth, together with the electrolyzing characteristics of the zinc solutions. SEVERAL years ago, St. Joseph Lead Co. undertook a research program to develop procedures for winning values from a complex ore. The deposit was a massive sulfide ore body containing upwards of 65 pct pyrite. Gangue, composed principally of quartz, calcite, dolomite, and alumina, comprised only 10 to 20 pct of the mineralized zones. Zinc, lead, and copper values were variable, but averaged about 6.7 pct Zn, 2.6 pct Pb, and 0.4 pct Cu. Early in the exploratory test work, it was established that the intimate physical association of the minerals in the ore made beneficiation by conventional flotation procedures difficult. Accordingly, in addition to a comprehensive program to investigate physical methods of ore beneficiation, a research program was established to develop a direct metallurgical method for processing the ore. After surveying a number of potential methods for recovery of both metal and sulfur values, effort was concentrated on the development of a sulfate roasting process. It is the pilot-plant development of the sulfate roasting-solution purification—electrolyzing procedures which forms the subject of the present paper. PREPILOT PLANT INVESTIGATIONS From a thermodynamic viewpoint, it is feasible to sulfate selectively a host of metals, including Zn, Cu, Pb, Cd, Ni, and Co, in an iron sulfide ore without sulfating iron. Of course, a number of conditions such as roasting temperature and gas composition must be controlled. In addition, as first disclosed by Hybinette,' an alkali metal salt is frequently beneficial in promoting the sulfation reactions. The application of fluid bed roasting to the sulfate roasting of nonferrous metals was pioneered by Stephens of Battelle Memorial Institute.' Subsequently, Falconbridge Nickel Mines, Ltd. developed an unique process for selectively sulfating and recovering nickel, copper, and cobalt from their nickeliferous pyrrhotite, which recently has been described in an excellent paper by Thornhill.3 One of the unique features of the Falconbridge process is that the feed is introduced into the fluidized roasting furnace in a manner such that the feed slurry is broken up into droplets and the droplets lose their moisture before contacting the surface of the fluidized bed. The dried droplets do not tend to cake or fuse, but rather remain as discrete agglomerates of concentrate particles and roast without significant degradation. St. Joseph, aware that Battelle Memorial Institute had participated in the development of the Falconbridge process, obtained permission from Falcon-

Jan 1, 1962

By C. W. Mac Gregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow, 2 Elm,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By D. L. McElroy

SAFETY in coal mining received especial attention by the public in general and the mining industry in particular during 1940 and early in 1941, owing primarily to the six explosion disasters which occurred last year with a total of 276 fatalities. This was the largest number of fatalities due to explosions in bituminous coal mines since 1928, when 347 lives were so lost. But facilities due to explosions have had a definite decreasing trend since 1907, in spite of bad years such as 1917, 1924, 1932, 1937, and 1940. Although the upswing in explosion fatalities in 1940 is lamented by all, none will admit it represents a trend and it will serve mainly to stimulate ways and means of further reducing these disasters.

Jan 1, 1941