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By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead-producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741." Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832." Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead, the zinc, and the rock or waste materials. The first record of zinc production from the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1953

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By C. O. Dale, W. J. Rundle

THE upper Mississippi Valley zinc-lead area was the first major lead-producing section in the United States. The lead ore, found near the surface in crevices, was relatively pure galena that could be smelted directly into lead, at first in log hearth furnaces and later in more efficient blast type furnaces. French Canadian fur traders encouraged the Indians to mine the lead ore and showed them how to smelt it into lead that had a high value for bullets1 Nicholas Perrot found lead ore on the Mississippi River bluffs near the junction of Wisconsin and Illinois and in 1690 established a trading post on the Wisconsin side of the river opposite the present site of Dubuque, Iowa.2 Shortly after 1720 discovery of Mine La Mott in Missouri diverted considerable attention from the Upper Mississippi area. Mining continued on a desultory basis with operations concentrated in the Galena, Illinois-Dubuque, area. In 1740 at least 20 miners were at work in the Fever River area around Galena and are reported to have shipped 2500 70-lb pigs of lead to Kaskaskia in 1741." Julien Dubuque established a mining and smelting operation in 1790 near the city that bears his name and was granted sole right to exploit the mining operations on the lands of the Sauk and the Fox Indians. He is reported to have produced 30,000 70-lb pigs of lead in 1805. Following the death of Dubuque in 1810 the Indians refused to let the white miners enter their lands, and little was done on the Iowa side of the river until the Indians were removed by treaty with the United States government in 1832." Early mining was entirely for lead but as the crevices were followed down, increasing percentages of zinc sulphide and zinc carbonate were encountered and at first discarded. Later a market became available for the zinc ores, and hand jigging devices were made to separate the lead, the zinc, and the rock or waste materials. The first record of zinc production from the area is for 1860. Production of zinc passed that of lead before 1900, reached a peak of 64,000 short tons in 1917, fell off rapidly and continually to about 2000 short tons in 1938, and since 1940 has ranged from 11,000 to 19,000 short tons. Lead has been of considerably less importance since 1900, and at present only about 10 pct as much lead as zinc is produced. Practically all of the zinc ore has come from orebodies that are rather flat and wide with considerable length as compared to width. Most of the early lead came from the crevice type deposit, but present production is from the predominately flat zinc orebodies. The Graham-Snyder orebody, scene of Eagle Picher operations, is practically all zinc with little or no lead being recovered. Marcasite, present in varying amounts, makes production of finished concentrates by gravity separation impractical. Satisfactory lead and zinc concentrates have been produced since flotation was introduced in the area in 1927. An acid recovery plant was operated for about 20 years after World War I, but it has been dismantled, and no recovery of the iron sulphides in the ores of the district is being made at the present time. In June 1950 there were three companies operating mines and mills, Tri-State Zinc Co., Calumet & Hecla Consolidated Copper Co., and Eagle Picher Mining and Smelting Co. The Vinegar Hill Zinc Co. had completed a shaft at a new orebody and had started to develop the mine which will supply the Cuba City mill. The Cuba Mining Co. was holding the Andrews Mine inactive. The Dodgeville Mining Co. was not operating but was exploring for additional reserves. Several small mines were selling ore to the Eagle Picher mill. A general area map is given in Fig. 1. The Eagle Picher Mining and Smelting Co. entered the area in 1946 with an active exploration campaign. Leases on a block basis were secured for the area south from the Wisconsin-Illinois line near

Jan 1, 1953

By H. L. Teichman, E. M. Sipprelle

ENACTMENT' of Public Law 290 by the 78th Congress authorized the U. S. Department of the Interior, Bureau of Mines, to conduct an experimental program to develop the technology for obtaining oil from oil shale. In adopting and later extending this legislation, the Congress recognized the impending necessity of supplementing ground petroleum reserves with synthetic fuels. Under the provisions of this legislation, the Bureau of Mines, among other things, was charged with the responsibility of developing mining techniques, methods, and equipment for mining the oil shales of the Green River formation of Colorado, Utah, and Wyoming. The oil shales of western Colorado are apparently richer, more accessible, and more amenable to exploitation than elsewhere in the Rocky Mountain region. The site chosen for the Bureau's Experimental mine is about 10 miles west of Rifle in northwestern Colorado. It is within a 1000-sq-mile area from which, it has been estimated, 300 billion barrels of shale oil could be produced from a 500-ft measure near the top of the formation. One hundred billion barrels of this amount could be produced from the Mahogany ledge, a 60 to 100-ft section near the bottom of the 500-ft measure. This ledge is considered to have economic importance at present. The Green River formation was laid down as sediment in the bottom of vast, shallow inland lakes during Eocene time. The deposit is flat-lying, and there are no faults, fissures, or local rolls. Oil shale is actually a strong, tough magnesium marlstone, which will stand unsupported over relatively wide spans. These and other natural physical characteristics favor mechanized, low-cost mining, which is essential for establishment of an oil-shale industry. It was realized from the outset that an extensive research program would be necessary to develop mining methods, equipment, and techniques for a mechanized, low-cost operation. The program was designed to include research. into all the productive phases of mining, such as drilling, blasting, loading, transportation, and maintenance of the mine structure. The methods, equipment, and techniques developed as a result of this research have established a production of 116 tons per man-shift total labor at a direct cost of $0,292 per ton. Another important phase of the research program that has received little publicity because of its theoretical nature is study of the roofstone behavior and determination of mine structure stresses. This paper purposes to discuss this phase of the research program. Preliminary studies of the physical properties of the Green River oil-shale formation were made in the Barodyramics Laboratory at Columbia University during the latter part of 1945 and the early part of 1946.* The purpose of these studies was to determine the maximum size of unsupported underground openings that would be commensurate with safety and still permit the use of large, efficient mining equipment. Also to be determined were the pillar support to extraction ratio and the shape, size, and spacing of supporting pillars. Selected samples of possible roofstones near the top of the Mahogany ledge, as well as representative samples of different rock types found within the ledge, were obtained from the Bureau's oil-shale mine for these studies. The maximum safe unsupported roof span calculated from this work was 200 ft. Using a safety factor of four, it was theoretically determined that openings 60 ft wide could be advanced under a roofstone at the top of the Mahogany ledge. To support the overburden, 60-ft-sq pillars would be left in a checkerboard pattern. From visual observations made of core samples through the selected roofstone at the oil-shale mine, it was determined that the roofstone was actually a plate 6 to 8 ft thick. Because the calculations were theoretical and allowance had to be made for unknown cracks and fractures in the formation, openings 50 ft wide and pillars 60 ft sq were originally contemplated in the Bureau's Experimental mine. This would be the minimum allowable width that would permit use of large underground mining equipment. For lower mining costs and greater efficiency larger openings were desirable. Different but analogous approaches were made to the problem at the Bureau of Mines Applied Physics

Jan 1, 1951

By Ikuya Takase

INTRODUCTION Since the occurrence of the first oil crisis, coun-tries of the world, especially oil-importing countries have made sustained and vigorous efforts to lessen the dependency on oil as a source of energy supply. The adoption of "Principles of Coal Policy" by the IEA Ministerial Governing Board Meeting in May, 1979 was the first formal action taken by major energy consuming countries. At the Venice Summit in June, 1980, it was agreed that production and use of coal should be doubled over the next ten years. In fact, the world coal use in 1980 showed around a 10 percent increase over the previous year. Recently, we have seen an indication that the balance of oil supply and demand in the short term have eased. But I believe that it remains vital that we continue to encourage the development and introduction of alternative energy sources. Because, from the medium and long range viewpoint the recovery of the worldwide economy will lead us to increased oil requirements and thus we will be faced with the cyclical, structural tightening situation between the supply and demand of oil. Moreover, we are still convinced that the constraint of the supply capabilities of the Middle-East nations may be increasing in the long-term, since there still remains political uncertainties among these nations. Consequently, above all, coal is viewed as an alternative energy resource available for immediate expansion of use and is given as high a priority as nuclear power. In Japan, we regard coal as the most reliable alternative energy resource to replace oil. According to the "Alternative Energy Supply Targets" approved by the Cabinet in November, 1980, the level of coal imports is estimated to approximately double by 1990, while our domestic coal production will remain nearly at the same level. The transition from oil to coal is found in the recent import levels of coal---73 mil¬lion tons in 1980, a 23 percent increase over the 59 million tons imported in 1979. There was an upsurge in steaming coal imports, reflecting the transition in feedstocks---7.2 million tons in 1980, four times over the previous year's amount. Henceforth, from the medium to long range view, the demand for coal, especially that of steaming coal is forecast to continue to grow. The timely expansion of supply capabilities is our utmost concern and should be one of the most significant goals of our comprehensive policy. The Overseas Coal Investigative Committee, a privately organized advisory panel to the Director-General of the Natural Resources and Energy Agency of the Ministry of International Trade and Industry (MITI), investigated means to secure a stable supply of overseas coal. The panel presented its interim proposals in August, 1981, recommending the diversification of coal import sources, extensive use of low rank coal, as well as enhanced international cooperation between coal producing and importing countries. THE CONTENTS OF THE COMMITTEE'S REPORT Four Points for Major Consideration In order to ensure a stable supply of overseas coal, Japan needs adequate policy measures consistent with the characteristics of coal resources and environmental requirements, giving consideration to Japan's status and the role she is expected to play in the areas. From the above, great importance should be attached to the following four points: All the components of the "Coal Chain" (Namely, the development of mine sites, construction of railroads, port loading facilities, coal shipping vessels, port receiving facilities, including coal centers and international transport facilities etc.) should be reviewed and reformed with steps taken to assure efficiency consistent with the entire coal chain system. The complete formation of a coal chain system requires such lengthy lead times and huge amounts of investment that necessary measures should be undertaken well in advance utilizing long-range projections of future demands and various economic surveys. Policy planning should be conducted taking into account of harmonizing stability and economics of the supply structure. For ensuring the long-term stability and expansion of the coal trade, international cooperation on a bilateral and multi-national basis should be encouraged. Mutual understanding and close relationships are essential to facilitate the formation of the supply system and to promote the extensive use of coal. Direction and Problems Related to Supply Stability Expansion of Supply Capabilities. World coal imports in 1979 amounted to 229 million tons, of which Japan's share amounted to 59 million tons, or one fourth of the entire amount. The imports of European and Asian countries accounted for 83 million tons and 7 million tons respectively. According to the examination of the Investigative Committee, Japan's coal requirement is estimated to be between 140-150 million tons by 1990, nearly the same level as announced in the Provisional Long-Term Energy Supply and Demand Outlook in 1979. This fore¬cast is-to be revised in April, 1982. Japan's demand is expected to be met through fiscal 1985; however, by 1990, the supply is estimated to fall short of demand, particulary, in the field of steaming coal. For the expansion of supply capability, first, mine development should be accelerated. The proposed

Jan 1, 1982

By J. A. Goebel, S. Rosen

IN the NiAl phase diagram the NiAl (CsC1-type) phase field extends over a large composition range. At elevated temperatures the nickel-rich phase boundary extends to a composition of about 70 at. pct Ni, a value which is within 5 at. pct of the Ni3A1 (Cu 3 Au-type) phase boundary.' At room temperature, however, the maximum nickel content is only about 60 at. pct. Experiments have shown that alloys containing greater than 63 at. pct Ni when quenched from temperatures below 1000°C contain the equilibrium phases NiAl and Ni3A1. On the other hand, when these same alloys are quenched from temperatures above 1000°C and examined microscopically, a typically martensitic decomposition product appears in the microstructure as shown in the micrograph of Fig. 1. The structure of the martensitic phase has been determined by employing powder X-ray diffraction techniques to be an "ordered" AuCu type (Strukturbericht Llo, space group P/4 mmm - DL). The diffraction pattern of this phase differs from that of AuCu in the appearance of superlattice lines. The structure is shown in Fig. 2. The open circles represent nickel atoms and the half-shaded circles represent nickel and aluminum atoms which are randomly distributed. The sites represented by half-shaded circles would be occupied solely by nickel atoms at a stoichiometry of Ni3A1. The alloys used in this investigation were prepared from 99.99 wt pct Al and 99.99 wt pct Ni by arc melting charges of varying compositions in a water-cooled copper hearth using a tungsten electrode in a gettered argon atmosphere. In all cases chemical analysis agreed within $ at. pct with the nominal compositions of the alloys. Annealing treatments were carried out in a vertical resistance furnace through which a stream of argon gas was flowing. Specimens, which were wrapped in tantalum foil, were quenched by allowing the specimens to drop into a bucket containing iced brine. X-ray diffraction patterns were obtained from -325 mesh powder specimens by using a 114.8-mm

Jan 1, 1969

By J. L. Kenty, J. P. Hirth

The concept of a critical super saturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, is discussed with reference to vapor-solid nucleation. The necessary and sufficient conditions deduced for observations of this type of behavior are: 1) the nucleation rate must exhibit a sharp dependence on super saturation, 2) the growth rate must be sufficiently large that nuclei become observable in the time period of the experiment, and 3) the number of highly preferred nucleation sites must be small. Experiments reveal that the nucleation of silver on sodium chloride is visually detectable at all experimentally accessible super saturations and does not exhibit critical nucleation behavior. Failure to observe a critical super saturation is attributed to the insensitivity of nucleation rate to supersaturation as a consequence of the particular values of the contact angle and the surface free energy for this system. THE concept of a critical supersaturation, below which the nucleation rate is essentially zero and above which it is essentially infinite, arises naturally in homogeneous nucleation theory. Experimentally this type of behavior has been found by Volmer1 and others for water and other low surface tension liquids, as reviewed by several authors.2'3 The same type of behavior has been predicted and observed for heterogeneous nucleation of solids by Yang et al.4 and others,596 as also recently reviewed.2,7,8 In the work reported here on the heterogeneous nucleation of silver on NaC1, however, no critical super-saturation was found. Similar observations have been made recently for other systems.9-11 These results led to a reexamination of nucleation theory which revealed that there are conditions for which critical behavior is not predicted, either for homogeneous or heterogeneous nucleation. Although heterogeneous nucleation is of primary importance in this paper, some insight into critical behavior for such a case can be gained by considering homogeneous nucleation. Accordingly both types of nucleation theory are reviewed briefly. The requisite conditions for critical supersaturation behavior are then considered. The experimental results for the nucleation of silver on NaCl are presented and interpreted in terms of the theoretical presentation. REVIEW OF NUCLEATION THEORY There are essentially two approaches to nucleation theory, the so-called classical theory involving the concepts of bulk thermodynamics, and the statistical mechanical theory in which nuclei are regarded as macromolecules. The classical theory is based on the work of Volmer and Weber12,13 and Becker and. Doring14 and has been extended by Pound et al.15 The crucial assumption in the classical theory is that the small clusters or nuclei can be characterized by the same thermodynamic properties as those of the stable bulk phase. Thus, the nuclei are assumed to have a surface free energy, y, and a volume free energy of formation (relative to the vapor phase), ,, identical to that of the bulk. For deposition under low super-saturation conditions, the nuclei are large and this assumption is satisfactory. However, in many cases of interest, the nuclei contain only a few atoms and this assumption is highly questionable. The statistical mechanical models originated, for the specific case of a dimer as the critical nucleus, with the work of Frenkel16 and were extended later to larger sizes by Walton,17,18 Hirth19 and, more recently, Ht Zinsmeister. These models describe the nucleus in terms of a partition function, the estimation of which is tractable for clusters of 2 to 10 atoms, but extremely difficult for clusters larger than 10 atoms. Although the classical and statistical mechanical models are expected to apply for the limiting cases of large and small nuclei, both are uncertain for intermediate sizes. In this paper we shall treat only the classical model, recognizing that it is exact only for large nucleus sizes and regarding it as a phenom-enological description for small nucleus sizes. When analyses of experimental data using bulk properties show the nucleus size to be small, the resulting parameters should be regarded as largely empirical parameters describing the relative nucleation potency of the system. Considerable justification for the continued use of classical theory is provided by its general success in predicting nucleation behavior as a function of supersaturation and temperature. We emphasize that the qualitative features of the statistical mechanical models, particularly the critical super-saturation behavior that is central to the present work, are the same as those of the classical model. Of course, potential energy terms and surface partition functions replace the volume and surface energy terms of the latter model. The most recent versions of classical nucleation theory have been extensively reviewed.2,3,7 so that only the results are presented here. For homogeneous nucleation of a condensed phase from the vapor phase, the volume free energy change is ?Gv=vrT = =^ln£ [1] where v is the molecular volume of the condensing species. The supersaturation ratio,

Jan 1, 1970

By Fred E. Carter

AT first sight, the platinum group of metals seem of little import to we, the people," although actually the life of the common man is much influenced by them; this influence is usually indirect, hence his lack of knowledge and interest. He generally associates platinum with high-class jewelry and lets it go at that. Were 11e to go deeper, he would find that platinum metals play their part in his food supply, his clothing. his health, his transportation, his home. And the technical man is in general only slightly better informed, for he usually does not realize how necessary platinum metals are in the manufacture of the many construction materials and chemical products with which he is acquainted. Certainly, our daily lives would be profoundly affected if platinum were suddenly to become unavailable.

Jan 1, 1944

The San Manuel district of Arizona was first prospected prior to the Civil War, but there was little or no production until 1881. Small operators tried to develop ore bodies from time to time after that without success. Then, in 1917, a drilling program was carried out; but it did not indicate a copper content of interest. Finally, in the 1940s, the U. S. Geological Survey drilled the property and obtained indications of a mineralized area. At that time, Magma Copper and its principal owner, Newrnont Mining Corporation, drilled many deep holes through the gravels and conglomerates and in 1948 proved an ore reserve of 367 million tons of 0.785% copper sulfide ore. Underground exploration and development were started in early 1948, and in 1953 design and construction of the surface facilities commenced. By the end of 1955 plant construction was completed. The ore deposit of disseminated pyrite, chalcopyrite, chalcocite, molybdenite, silver, and gold is in quartz monzonite porphyry gangue. Mine production, which is entirely underground, is by full-gravity block-caving. Initially, ore mined at a rate of 36,000 tpd was hoisted through two identical shafts. From the 5,000 ton coarse ore bins located at the collar of each shaft, the ore was hauled by a shuttle service rail- road in 100-ton bottom-dump rail cars a distance of seven miles to the rail bin. Fragmentation from block-caving supplemented by underground grizzlies at the loading stations controlled the oversize material to give a feed size acceptable to the two 7 ft standard Syrnons crushers. During operation, however, it became evident that a large amount of secondary breaking in the grizzlies was necessary to produce a suitable feed for the standard crushers. The decision was then made to install primary gyratory crushers on the surface adjacent to the shaft site ore bins. Under each 5,000-ton coarse ore bin, an 8ft by 20 ft (2.44 m by 6. 1 m) apron feeder transfers the ore to a 13 ft 6 in. by 10 ft (4. 1 m by 3. 05 m) grizzly set at 6 in. (152 mm) and sloped at 45 degrees. About 65% of the ore passes the grizzly and thus bypasses the 42 in. by 65 in. (1.07 m by 1. 65 m) Allis -Chalmers gyratory equipped with a Hydroset mechanism and having an open side setting of 5 ½ in. (140 mm). Grizzly undersize and crushed ore drop onto a 6 ft by 30 ft (1. 83 m by 9. 14 m) variable- speed apron feeder for transfer to a 54 in. by 90 ft 5 in. (1.37 m by 27.6 m) inclined conveyor equipped with a tramp iron detector. Indication of tramp iron automatically stops the conveyor and both apron feeders. When the iron is removed from the belt by the operator,

Jan 1, 1978

By D. H. Forbes, H. M. Manasevit, F. L. Morritz

Single-crystal thin films of molybdenum have been grown. by the pyrolytic decomposition of molybdenum hexafluoride in a hydrogen ambient on various insulating substrates at temperatures front 650° to 900° C. Single-crystal discs of various orientations of magnesium aluminate spinel, a aluminum oxide, magnesium oxide, and the natural facets of beryllium oxide were all observed to exert epitaxial control on the depositing film. Determinations of the crystallographic relationships existing between film and substrates have been made, using X-ray diffraction three-circle goniometry and Laue back-reflection techniques. Using these data, crystallographic overlays have been constructed which suggest a possible interfacial geometry on the basis of a match between metal deposit atoms and metal ion sites in the substrate. A continuing program has been in effect in the Auto-netics Laboratories over the past several years aimed at the development of electronic materials in new and useful forms using chemical vapor deposition techniques. During the course of these investigations, the epitaxy of silicon1"5 and tungstenep7 on single-crystal metal oxide insulators was studied extensively. The deposition of molybdenum is a logical extension of the tungsten work since the crystal structure is identical and the lattice dimensions differ by less than 1 pct. The pyrolytic decomposition of molybdenum hexafluoride in hydrogen was used to grow molybdenum films on the oxide substrates AlzOs, MgA1~04, MgO, and Be0 at from 650" to 900°C, depending on the substrate material. Under the experimental conditions to be described, monocrystalline films of controlled orientation were obtained. The materials investigated and their crystal structure are listed in Table I. EXPERIMENTAL The molybdenum depositions were effected by the hydrogen reduction of molybdenum hexafluoride (MoFe) in a flowing system of hydrogen at atmospheric pressure. The schematic of the apparatus is shown in Fig. 1. The hydrogen, purified by passage through a heated palladium thimble, was mixed with the vapor of the liquid MoFe maintained in a steel bottle at room temperature (25°C). The mixture was passed over the substrate, which was heated by rf induction of a sup-

Jan 1, 1969

By Felix B. Shay

THE Agua Fria mine is in eastern Honduras at Lat. 140° 06' N., Long. 86° 36’ W. Danli, the seat of the local municipal government, is the nearest town. The property is approximately 44 miles east of Tegucigalpa, the terminus of a truck road from the Pacific coast. The mine lies at an altitude of 3300 ft. with surrounding elevations as high as 6000 feet. For 20 years the oxidized croppings of the Agua Fria vein had been worked intermittently when in 1927 an attempt was made to open the property. A shaft was sunk 300 ft. and considerable ore was blocked out, but before a mill could be installed financial difficulties arose and the mine reverted to the original owners. Erle P. Halliburton, of Los Angeles, purchased the property in 1934. At that time a careful consideration of all factors involved showed that air transport was the only practical method of moving the equipment and machinery necessary to commence production. The other alternative was by muleback, which required sectionalizing all equipment to a maximum load of 200 lb., and during the rainy season this type of freighting was subject to serious delays. It was decided to purchase a trimotor Ford powered by three Pratt and Whitney Wasp B motors developing 400 hp. each. There were several reasons for the choice: (1) this type of plane was available at a reasonable price, owing to its replacement by faster models on most of the airlines in the United States; (2) the ship was capable of carrying a pay load of 3000 lb. over the required distance; (3) since this airplane had been widely used there would be no difficulty in securing competent personnel or in purchasing spare parts. It was necessary to rebuild the plane for cargo service. The windows were removed and the fuselage was entirely covered. A hatch was cut in the top of the fuselage to receive heavy crane loads and pieces of freight that were too large or too long to go through the rear door. The seats were removed and the interior of the plane was lined with Duralumin sheets. A heavy-duty landing gear was installed and the floor was reinforced. The nearest site for an airport was two miles north of the mine. The necessary grading was done by a small track-type tractor with a wheeled grader, which was brought in overland. Six weeks was required for bring-

Jan 1, 1940

By Carl F. Floe, Michael B. Bever

ACCELERATED by the demands of war, research and development work in nonferrous physical metallurgy has continued at a rapid pace during the past year. In particular, advances have been made in processing and fabrication, especially of the light alloys, and in the surface treatment of metals. Theoretical physical metallurgy, although less active, has not been neglected and the year has brought forth some -notable contributions to our understanding of the fundamental structure of metals and their behavior in service. Of course, much work that has been done cannot be publicly discussed because of wartime restrictions.

Jan 1, 1945

By Z. T. Bieniawski

The importance of understanding the phenomena associated with rock fracture has long been fully appreciated in rock mechanics. This is clearly apparent from the special attention paid to rock fracture in the comprehensive papers published within the past four years.l-5 These papers present a picture of how the knowledge of brittle fracture of rock was gradually enriched and also show that what was often taken for granted three or four years ago is no longer considered as valid today. The Griffith hypothesis,6 thought in the past to predict the strength of rock, is now known to be applicable to fracture initiation only. The knowledge of a failure criterion for fracture initiation is not sufficient, however, as after fracture initiation the rock is still a useful material even possessing increasing load-bearing ability. The importance of the fracture propagation process, subsequent to fracture initiation, is thus obvious. Yet, relatively little attention has so far been paid to brittle fracture propagation in rock. As it is now realized that understanding of this process is a prerequisite for practical rock mechanics applications, studies of propagation of brittle fracture in rock constitute an important aspect of rock mechanics research. It has been pointed out 4 that it is essential that the failure mechanism is fully understood before a failure criterion is postulated. Many failure criteria have been propounded in the past on the basis of theoretical reasoning alone and could not be verified by experimental evidence. Recently, a hypothesis for the mechanism of brittle fracture of rock was propounded, 4 describing the events taking place in the rock from the initial application of gradually increased load to complete disintegration of the material.

Jan 1, 1972

By J. D. Audley Smith

Heine's " blue test" for copper, as described by the authorities generally, calls for a set of standard colors; and there has been some discussion concerning the relative superiority, for this purpose, of sulphate and nitrate solutions. The whole matter evidently hinges on the preservation of the standard colors in well-stoppered bottles. The apparatus described by Q. L. Heath* cannot be much improved, when very accurate readings are required. The following method was devised for the purpose of doing away with preserved sets of standard colors, by making a fresh standard for each batch of assays. The solutions are prepared in the usual way, each ammoniacal solution being filtered into its separate bottle, and then filled up to the containing-mark and thoroughly mixed. A similar color-bottle, with an " S " etched upon it, to distinguish it from the other bottles, which are numbered to correspond with the samples, is kept to run the standard. About 150 C.C. of water is put into it, and then the amount of acid (sulphuric or nitric) present in each determination, followed by 30 C.C. of ammonia (s. g. 0.90), which should make the mixture strongly ammoniacal. The liquid is now made up almost to the containing-mark (200 c.c.), say within 1 C.C. The lowest assay is selected first and placed alongside the standard, which, at the beginning, contains no copper. A copper-solution is then dropped into the standard from a burette ; and after each addition the bottle is well shaken and compared with the assay-sample. This operation is repeated until the two shades match exactly, when the burette is read and the assay-result is calculated. The assay next in order of depth of color is now taken and treated in the same way, and so on, until the batch is completed. It

Jan 1, 1901

By ROBERT E. CROCKETT

MAGNETITE mining and milling in New York, New Jersey and Pennsylvania continued to remain comparatively inactive during 1933, owing to the low rate of output of the steel industry and also to unrestricted importation of foreign ores. However, some improvement over conditions existing in 1932 was noticeable, particularly in New Jersey, where one plant, that of the Washington mine of the Alan Wood Mining Co., at Oxford, went on full production in August. At Lyon Mountain, N. Y., the Chateaugay Ore and Iron Co. resumed mining and milling operations in October, on a reduced scale, principally to provide employment during the winter months. The Chateaugay company produces a special low-phosphorus pig iron. During the year they obtained a contract to supply their product for use in the manufacture of the suspension cables of the New. Golden Gate Bridge.

Jan 1, 1934

By J. L. Moriarty, Irving Johnson, H. M. Feder

The crystallization of ternary alloys has been studied as a coprecipitation phenomenon by measuring the substitutional carrying of trace metals with CeCd11 precipitating from liquid cadmium. The Doerner-Hoskins logarithmic distribution law has been found to apply in all cases; the coprecipitation coefficients obtained were: 1.48 (La), 1.06 (Th), 0.63 (Pr), 0.24 (Gd), 0.17 (Sm), 0.13 (U), 0.10 (Er), 0.09 (Sr). Li, Na, K, Ba, Y, Sc, and Zr were not measurably carried. It has been observed that coprecipitation was most extensive for those tracers which form with cadmium an intermetallic compmdnd isostructural with CeCd11 or closely related thereto. For these tracers an inverse relation between Solubility in cadmium and coprecipitation coefficient was noted. THE partition of impurities between the liquid and solid phases of a metal or a congruently melting intermetallic compound has been extensively studied by the methods of zone melting.' However, when the composition of a liquid alloy and of the solid phase crystallizing from it differ grossly, partition of an impurity cannot be investigated in this manner. Partition of the impurity under equilibrium conditions may be studied by investigation of the appropriate phase diagram and partition under nonequi-librium conditions may be studied by observation of coring in the solidified alloys.2 The nonequilibrium case is of special interest in metallurgical practice because many complex alloys are cooled too rapidly to permit the uniform diffusion of impurities throughout the crystallizing phase(s). With this in mind, the present study was undertaken to obtain quantitative data on the phenomenon of coprecipitation via substitutional solid solution in certain metallic systems. It will be noticed that rather than adopting metallurgical ter- minology we have chosen to refer to the partition of impurities during alloy crystallization as coprecipitation.3 In the terminology of coprecipitation the impurity is referred to as the tracer and the precipitating phase as the carrier. From aqueous solution, coprecipitation may occur as a result of adsorption on the surface of the carrier, by occlusion of the liquid within the crystals, or by solid solution of the tracer in the carrier. By slow cooling of liquid metallic solutions it is relatively easy to form large, regular crystals of the carrier; the effects of adsorption and occlusion may be minimized and the influence of substitutional solid-solution formation may be made to predominate. Previous studies of the crystallization of some intermetallic compounds4 and of copper, silver, and gold5 have shown that the coprecipitation or partition behavior of trace metals is entirely analogous to that observed in aqueous systems when ionic substitution occurs, e.g., coprecipitation of Ra++ with BaSo4. The precipitation of CeCd11 from liquid cadmium was chosen for study. This choice was influenced by the following consideration. If the relative atomic sizes of the tracer atom and the atom for which it substitutes determine the tendency to coprecipi-tate, then a lattice having a substitutional site of well-defined size would be desirable. In CeCd116 (structure type cubic BaHg117) the cerium atom is completely surrounded by a cage of twelve nearly equidistant cadmium atoms. Thus, atoms much larger or much smaller than cerium should be poorly accommodated in this cage. The choice of a lanthanide central atom allowed the testing of the size hypothesis with a number of lanthanide tracers which differed in size but not in valence or electro-negativity. EXPERIMENTAL The general technique of this investigation was to prepare a slightly undersaturated solution of carrier in liquid cadmium to which a tracer was added. The concentration of tracer was always so low that saturation over the entire temperature range investigated was never exceeded. The solution was cooled in a stepwise fashion. After each step a por-

Jan 1, 1964

By N. F. Dyson, T. R. Scott

The iilzfluence of catalytic agents on the oxidation of ZnS has been studied under pressure leaching conditions, using a chemically prepared sample of ZnS which was substantially unreactive on heating at 113°C with dilute sulfuric acid and 250 psi oxygen. Nurnerous prospective catalysts were added at the ratio of 0.024 mole per mole ZnS in the above reaction but pvonounced catalytic activity was confined to copper, bismuth, rutheniuwl, molybdenum, and iron in order of. decreasing effectiveness. In the absence of acid, where sulfate was the sole product of oxidation, catalysis was exhibited by copper and ruthenium only. Parameters affecting the oxidation rate were catalyst concentration, temperature, time, oxygen pressure, and a7riount of acid, the first two being most important. The main product of oxidation in the acid reaction was sulfur, with trinor amounts of sulfate. An electrochemical (galvanic) mechanism has been suggested for the sulfuv-forming reaction, whereby the relatively inert ZnS is "activated" by incorporation of catalyst ions in the lattice and the same catalysts subsequently accelerate the reduction of dissolved oxygen at cathodic sites on the ZnS surface. Insufficient data was obtained to Provide a detailed mechanism for sulfate fornzation, which is favored at low acidities and probably proceeds th'rough intermediate transient species not identified in the preseni work. THE oxidation of zinc sulfide at elevated temperatures and pressures takes place according to the following simplified reactions: ZnS + io2 + H2SO4 — ZnSO4 + SG + HsO [i] ZnS + 20,-ZSO [21 In dilute acid both reactions occur but Reaction [I] is usually predominant, whereas in the absence of acid only Reaction [2] can be observed. Both proceed very slowly with chemically pure zinc sulfide but can be greatly accelerated by the addition of suitable catalysts, as suggested by jorling' in 1954. Nevertheless, an initial success in the pressure leaching of zinc concentrates was achieved by Forward and veltman2 without any deliberate addition of catalytic agents and it was only later that the catalytic role of iron, present in concentrates both as (ZnFe)S and as impurities, was recognized and eventually patented.3 It is now apparent that another catalyst, uiz., copper, may have also played a part in the successful extraction of zinc, since copper sulfate is almost universally used as an activator in the flotation of sphalerite and can be adsorbed on the mineral surface in sufficient amount The importance of catalysis in oxidation-reduction reactions such as those cited above has been emphasized by various writers and Halpern4 sums up the situation when he writes that "there is good reason to believe that such ions (e.g., Cu) may exert an important catalytic influence on the various homogeneous and heterogeneous reactions which occur during leaching, particularly of sulfides, thus affecting not only the leaching rates but also the nature of the final products." Nevertheless relatively little work has appeared on this topic, one of the main reasons being that sufficiently pure samples of sulfide minerals are difficult to prepare or obtain. When it is realized that 1 part Cu in 2000 parts of ZnS is sufficient to exert a pronounced catalytic effect, the magnitude of the purity problem is evident. An incentive to undertake the present work was that an adequate supply of "pure" zinc sulfide became available. When preliminary tests established that the material, despite its large surface area, was substantially unreactive under pressure leaching conditions, the inference was made that it was sufficiently free from catalytic impurities to be suitable for studies in which known amounts of potential catalytic agents could be added. The first objective in the following work was to identify those ions or compounds which accelerate the reaction rate and, for practical reasons, to determine the effects of parameters such as amgunt of catalyst, temperature, time, acid concentration, and oxygen pressure. The second and ultimately the more important objective was to make use of the experimental results to further our knowledge of the reaction mechanisms occurring under pressure leaching conditions. The fact that catalysts can dramatically increase the reaction rate suggests that physical factors such as absorption of gaseous oxygen, transport of reactants and products, and so forth, are not of major importance under the experimental conditions employed and an opportunity is thereby provided to concentrate on the heterogeneous reaction on the surface of the sulfide particles. As will appear in the sequel, the first of these objectives has been achieved in a semiquantitative fashion but a great deal still remains to be clarified in the field of reaction mechanisms. EXPERIMENTAL a) Materials. The white zinc sulfide used was a chemically prepared "Laboratory Reagent" material (B.D.H.) and X-ray diffraction tests showed it to contain both sphalerite and wurtzite. The specific surface area, measured by argon absorption at 77"K, varied between 3.9 and 4.6 sq m per g. Analysis gave 65.0 pct Zn (67.1 pct theory) and 31.9 pct S (32.9 pct theory). Other metallic sulfides (CdS, FeS, and so forth) used in the experiments were also chemical preparations of "Laboratory Reagent" grade. Samples of mar ma-

Jan 1, 1969

By R. L. Bowron

GROWING use of basic slag in the agricultural industry is of special interest and importance to the iron and steel industry of the Birmingham district, providing an increasing outlet for this by- product. Such use of basic slag was first developed in England about fifty years ago where it soon became wide- spread. About twenty years ago the Tennessee Coal, Iron & R. R. Co. began its production in the United States after exhaustive tests had demonstrated its high value here as in Eng- land. It is particularly valuable on heavy clay and acid soils, improving their physical condition, increasing their alkalinity where that is desirable, and providing soluble phosphate and small amounts of manganese to soils deficient in these respects. Its use in agriculture is growing as its advantages are becoming more widely known.

Jan 1, 1937

By James K. Gluck, William E. Galloway, Gary E. Smith, John P. Morton, Christopher D. Henry

INTRODUCTION Surface mining and in situ leaching of uranium have the potential to alter ground-water quality around mines and leach sites. Of particular concern is the fate of uranium and its associated trace elements: molybdenum, arsenic, and selenium. We wish to under- stand the natural processes that control trace element concentrations in ground water and how these processes will influence dispersion of the elements from a mineralized zone, both naturally and during and after mining or restoration. For example, it is commonly recognized that the trace elements are soluble in oxidizing ground water but are insoluble, and can be precipitated, in reducing ground water. Thus oxidizing, metal-bearing water leaving a deposit could re- enter reduced ground, causing the water to be re- reduced and the trace elements to be, reprecipitated. In a sense, this is recreating the original mineralization process. To accomplish the above goals, we have (1) examined the theoretical controls of concentrations based on the available geochemical and thermodynamic data, (2) determined the major ion composition and oxidation-reduction status of Oakville waters because of the influence of these factors on trace element solubility, and (3) determined trace element concentrations and distribution in Oakville ground water. The last approach is used to evaluate how well actual behavior follows predicted behavior. This report focuses on two elements, uranium and molybdenum, because they exemplify the results obtained. The report also is restricted to a regional study of Oakville ground water. Results of more de- tailed study in and around major uranium districts in the Oakville and much of the raw data that support the conclusions in this report are presented in Galloway, Henry and Smith (1980). This report is part of that larger study, which concerned the depositional systems, hydrology, and geochemistry of the Oakville. The U.S. Environmental Protection Agency funded the study, under grant numbers R-805357-01 and R-805357-02. Theoretical controls were determined by reviewing the available literature on aqueous chemistry and behavior of uranium and molybdenum. To aid in under- standing water chemistry, Oakville water analyses were run through a modified version of the computer model WATEQF (Plumer, Jones, and Truesdell, 1976). WATEQF calculates speciation of dissolved ions and determines saturation with respect to a variety of minerals. In the discussion below, ion activity products (IAP) are compared with the equilibrium constant (KT) for various reactions and mineral products. Values of log IAP/KT near zero indicate that the water is in equilibrium with a mineral. Values less than -1 indicate considerable undersaturation and values greater than +1 indicate oversaturation. Galloway, Henry, and Smith (1980) give a more complete discussion of the application of this approach to Oakville water chemistry. Eh-pH diagrams have been constructed or adapted from the literature to predict what form -- dissolved ion or stable mineral species -- uranium and molybdenum assume under various conditions. Construction of the diagrams has followed procedures described by Garrels and Christ (1965). This approach is particularly appropriate because the solubility of the elements is Eh-dependent, and Eh varies greatly within the Oakville aquifer. A number of assumptions or approximations are inherent in the use of Eh-pH diagrams and chemical models such as WATEQF and in the interpretation of water chemistry in general. Both Eh-pH diagrams and chemical modeling rely entirely upon available thermo- dynamic data, including free energies of formation and dissociation constants for various reactions. These values are known to varying degrees of accuracy. Most major ions and minerals are relatively well control- led; however, data for trace metals are much poorer. Thermodynamic data are not available for some minerals, and for other minerals, two or more divergent values exist. By necessity, we have relied on the judgment of others to evaluate thermodynamic data. Calculations by WATEQF and constructions of Eh-pH diagrams are based on an assumption of equi1ibrium. Equilibrium may not be comnon in low-temperature aqueous environments; at best, ground-water composi tion may be in a state of dynamic equilibrium, continuously changing due to changes in environmental conditions. Eh-pH diagrams show what phases are stable at equilibrium under given conditions; they do not prove that the phases actually exist. Many minerals persist or form metastably under conditions outside their equilibrium stability field. The kinetics of reactions, which cannot be evaluated here, are important in determining what phases occur. Kinetics may be less of a problem for ground water that travels and evolves slowly through a semihomogeneous matrix than for many other natural systems. Eh-pH diagrams show equilibrium fields only of phases included. They do not indicate anything about stability relative to phases not included in the diagram. WATEQF, obviously, cannot calculate the degree of saturation of a mineral not included in the program or for which the appropriate ions were not analyzed. Thus, a mineral that was not considered may be the most stable phase under a given set of conditions and may control the solubility of a trace element. Also, this study is limited exclusively to in- organic compounds. Organic material is known to be an

Jan 1, 1980

By N. LILIENBERGS

DURING the past few years, the requirements for steel have been raised so high that soundness is more important than ever before. The old practice was to mike steel ingots of sufficiently large sections to permit a considerable reduction of area in rolling and hammering to a given size, relying on the fact that by such rolling and hammering all cavities will be squeezed together and practically eliminated. The finished sizes, if found by inspection of the surface to be faultless, were therefore pronounced to be sound. But when such steel is ?worked up,? the manufacturer is surprised and disappointed to find that it splits, or that streaks and seams make the product unmarketable. Large sections, such as rails, beams or heavy forgings, may, within certain limits, be sufficiently strong, even if the sides of the cavities are only squeezed, and not welded together. But it is well known that, in the interior of heavy articles, under certain conditions, forging may develop small streaks into large cavities. Small sections, steel for ordnance and tubes, and numberless articles in the tool-trade, always show up the defects. It may be doubted whether cavities in steel ingots can ever be completely welded. The old theory, is, that the silver-clear blow-holes, without the blue oxide, can be welded by sufficient working. They are, however, not empty, but are filled with carbonic oxide. It is admitted that the "blue" cavities, resulting from air mechanically drawn down into the mold during the casting, can never be welded, because the oxide does not melt, and there would be no escape for it if it did. The only way in which steel can be made satisfactory for the above-named particular purposes is by having it ?dead molten." But then the trouble of piping is encountered. As is well known, a pipe is the result of the contraction of

May 1, 1906