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By Herbert H. Kellogg

RECENTLY the long-chain primary amines have been used extensively for the flotation of silicate minerals. The use of amines to float sulphide minerals has been investigated by several authors1-5,18 but most of this work has been done with the short-chain (less than six carbon atoms) primary amine compounds or the more expensive secondary, tertiary and quaternary amines. Perhaps the fact that the long-chain amines are good collectors for the common gangue minerals has led investigators to omit them from consideration as collectors for the selective flotation of metallic sulphides. The work reported in this paper was designed to investigate the use of a typical long-chain amine salt, lauryl amine hydrochloride, as a collector for the flotation of galena-sphalerite ores. The results show that lauryl amine hydrochloride (LAmHCI), when used in small amounts, is a good collector for the selective flotation of sphalerite and galena from the common gangue minerals. The differential flotation of sphalerite from galena was not accomplished but the amine flotation of sphalerite after the standard xanthate flotation of galena is possible. The experimental work reported herein is not complete enough to be able to say whether amine flotation of lead-zinc ores would prove superior to xanthate flotation, or whether the method is even applicable to a more complex ore than the one used for this work. However, the apparent reagent costs for the flotation operations described in this paper seem to be less than for xanthate flotation. This fact alone should be sufficient to encourage the millman to investigate the use of these amine reagents, especially as these reagents are available on a commercial scale at a reasonable price. This paper has as its secondary purposes to illustrate how contact-angle measurements have aided in this investigation, and to bring forward some evidence concerning the mechanism of the collecting action of primary amines. CONTACT-ANGLE TESTS The contact-angle measurements were made by the method described by del Giudice6 and used in recent work by Taggart and his collaborators.7-9 The mineral specimens for the contact-angle tests were carefully chosen, to avoid cracks and inclusions of other minerals. All specimens were mounted in "transoptic" plastic mounts and the surfaces were cleaned by polishing with levigated alumina on a cloth-covered glass polishing wheel. Distilled water was used on the lap during the polishing and at all subsequent steps in the contact-angle tests. The mounted mineral specimens were handled with glass forceps and special care was exercised to prevent exposure of the dean surface to air or any other source of contamination.

Jan 1, 1945

By H. l. Burghoff, J. S. Porter

THIS paper presents the results of an investigation of the effect of cold-working and annealing treatments upon the occurrence of preferred orientation in annealed brass wire. The subject has received less consideration than has the same phenomenon in annealed brass sheet or strip, and perhaps very properly so in view of the obvious and undesired results obtained in the forming or drawing of strip having preferred orientation, which results are in contrast with the lack of any spectacular visual evidence in wire. The factors of cold-working and annealing that control preferredness in strip are naturally expected to function similarly in wire. Indeed, one might expect the condition to be commoner in annealed wire, because the severity of the cold-working between anneals in commercial practice is usually much greater for wire than for strip. For example, a wire that is to be finished in the annealed condition on a diameter of 0.040 in. is commonly subjected to a final reduction of 96 per cent between the last two anneals, the large reduction being accomplished in the successive drafts of a multiple-die machine. Wire for rivets, for instance, on 0.125-in. diameter, although given a slight reduction of about 10 per cent after the final anneal, may have been given a prior reduction of 75 to 80 per cent. Barrett1 states the fiber axis of annealed 70-30 brass wire to be [111] with some indication of [100] as a secondary fiber axis. Croft and Sachs2 have reported briefly on some differences in brass wire with random and with preferred orientations. They showed statistical plots of the twin-band angles with respect to the wire axis or direction of drawing as observed on an axial plane. They also pointed out that the resistance of the wire to corrosion-cracking when externally stressed and exposed to a mercurous nitrate solution decreased as the degree of the preferred orientation increased. MATERIAL AND PROCEDURE All the wire for the investigation was processed from one. portion as cut for extrusion from a cast billet of the following analysis: 70.13 per cent copper; 0.01 lead; 0.01 iron; 0.02 nickel; 29.83 zinc (by difference). The billet section, 8 in. in diameter, was extruded hot to 3/4 -in. diameter, after which it was processed by alternate cold-drawing and annealing treatments as indicated in Fig. I. The earliest anneals in process were at about 1100°F. and the next to the last reductions by drawing were 58 per cent. The diameter of the finally annealed wire was 0.132 in. Semifinal anneals were at 800°F., 950°F. and 1100°F. and reductions of 47.5, 74, 83.5 and 89.5 per cent were employed in drawing to 0.132 in. The final anneals were at 875°F., 1050°F. and 1250°F. and were

Jan 1, 1944

By M. R. Geer, H. F. Yancey

Although the use of dense suspensions for coal cleaning was pioneered in the United States with the Chance sand flotation process, and during the past year a pilot plant using a magnetite suspension has started operation in this country, the more recent developments in this field of coal cleaning have occurred principally in the Netherlands. During the thirties the Dutch developed the Barvoys process, in which a medium of barite and clay is employed, the Tromp process, which utilizes a magnetite suspension, and the Loess process, in which is used the air-borne earth or soil known as loess.1-3 All these processes are finding increasing use in European coal-cleaning practice. Now a fourth process, the cyclone cleaner, is under development by the Netherlands State Mines. A cyclone thickener for reclaiming and thickening the dense suspension is a novel feature of the Loess process. Through accident, the discovery was made that the cyclone could be utilized as a cleaning device for fine coal. When the cyclone thickener at the Maurits mine plugged, the overflow was found filled with clean coal free of refuse, and from this observation developed the concept of the cyclone as a coal cleaner. In June 1945 the cyclone cleaner was observed by one of the authors,' and in September 1945 it was described by Dries-sen6 in a paper presented in London before the Institute of Fuel. As the cyclone seemed to offer unusual promise as a means of extending heavy-medium cleaning to the finer sizes of coal that cannot readily be treated in existing heavy-medium processes, the Bureau of Mines, following Driessen's, presentation, launched an investigation of the cyclone as a coal cleaner. Added impetus was given to this study by the present increased interest in heavy-medium cleaning in this country. Object and Scope of Investigation Driessen's report, although comprehensive in many respects, did not include a detailed description of the cyclone cleaner, and contained almost no information on the influence of the various operating variables of the cyclone. It was necessary, therefore, to investigate the influence of the cyclone adjustments on its performance before studying the application of the cyclone to various coal-washing problems. The present report is confined entirely to these preliminary tests, designed to demonstrate the operating characteristics of the cyclone. The investigation has been in progress

Jan 1, 1949

The present paper records a chapter in the history of the development of an electrolytic manganese industry in the United States.l A relatively large pilot plant at Boulder City, Nev., for the production of electrolytic manganese was conceived as part of the national defense program to make this country independent of foreign importation of manganese ore. The first authorization, in November 1940, however, was for a plant of only several hundred pounds capacity. Improvements in process and subsequent additions to some sections authorized by subsequent appropriations have enabled the plant to produce as much as 2000 lb. of manganese a day for substantial periods of time. Since in pilot-plant operation frequent changes are made in the flowsheet, the electrolytic manganese plant was constructed so that equipment could be rearranged with a minimum of expense and time. Several different kinds of the various ¦ types of equipment were installed for many of the operations, so that the one most suitable for the process might be chosen. Pilot-plant operations were begun in November 1941 and have been continuous except for brief shutdowns for installation of new equipment. More than one-half million pounds of manganese have been produced. The improvements in process, selection of equipment, and operational procedure developed are recorded here. Development of the Process The work of early investigators on the electrolysis of manganese solutions has been reviewed by Shelton. Until the method of continuous production of manganese by electrolysis was perfected by SheltonZm4 and coworkers, no practical procedure had been devised. The method as originally developed by the Bureau of Mines will be described here only briefly. The manganese dioxide ore was reduced in a rotating kiln-type furnace at 650°C. in an atmosphere of "city" gas. The calcine was leached with spent electrolyte and enough sulphuric acid to produce a neutral leach solutioil containing 2 5 grams manganese per liter as manganese sulphate and zoo grams per liter of ammonium sulphate. Arsenic was removed from the solution by the addition of 0.0j gram iron per liter as ferrous sulphate followed by oxidation with manganese dioxide, and aeration, which precipitated the iron as ferric hydroxide. The solution, free from iron

Jan 1, 1944

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a very general loosely used term that includes virtually all finely divided types of limestone as well as burned forms of lime. However, actually (and according to Webster) lime is only calcined limestone (known as quicklime, calcium oxide, or calcia). It also embraces the secondary product of quicklime-namely hydrated lime or slaked lime (calcium hydroxide). Fundamentally there are two basic types of limestone-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts in terminology. The only difference is that the dolomitic types are a combination of the elements, calcium and magnesium, whereas high calcium limes contain only 0.5 to 2 pct of magnesium. Both types, which are made through calcination at high temperatures, are shown chemically as follows: [ ] In the above reactions either type of limestone is burned (calcined) in furnaces known as lime kilns so that the carbon dioxide content of the stone is expelled as a gas. With high calcium limestone 44 pct of the weight of the stone is lost; with dolomitic limestone the loss is 48 pct. Also, both reactions are chemically reversible since quicklime absorbs carbon dioxide readily and in so doing transforms itself back to the original carbonate form. Most quicklimes correspond in size to the original rock, which varies from one to eight inches, depending upon the type of kiln employed. Slight shrinkage occurs during calcination. A few limestones when calcined will decrepitate (break down) into a fine powdery form; however, chemically it is the same as the pebble or lump-sized material. For some uses the lumps of quicklime are pulverized and packaged. Since quicklime has great affinity for moisture and carbon dioxide, it is perishable. When it absorbs moisture and CO2 slowly from the atmosphere, the resulting product is "airslaked." Consequently, it must be stored in dry, moisture-proof areas that are free from CO2. Because of its fugitive nature, it is usually consumed within a few weeks after manufacture. A more stable form of lime is hydrated lime-commercially made by adding water to the quicklime until the lumps break down into a fine, white powder. This product, which is usually packaged, can be stored more safely; and many of its uses are interchangeable with quicklime. The irreversible chemical reactions of hydrated lime for both high calcium and dolomitic types are: [ ]

Jan 1, 1960

By A. J. Jacobs, J. W. Spretnak, R. Speiser

The activities of nickel in liquid iron-nickel solutions containing from 10 to 90 at. pct Ni were measured over the temperature range .1510° to 1600°C. A special function was devised whereby activities can be computed by a graphical integration using the results of chemical analyses on the vapor phase alone. The liquid solutions studied exhibit negative deviation from Raoult's law, but they approach ideality as the temperature is raised from 1510° to 1600°C. The maximum heat of solution is less than -8.0 kcal per mole. The entropy of solution is less than —2.5 kcal per mole deg at 1510°C, and changes negligibly as the temperature is raised. The liquid iron-nickel solutions do not follow regular solution behavior. THE activities of the components of a liquid alloy system can be determined in favorable cases from the partial pressure of the vapor in equilibrium with the liquid alloy.' Assuming that the vapor over the alloy behaves as an ideal gas, the activity of component i is given by the expression, Where the superscripts 1, v, and o signify the liquid, the vapor, and the pure component, respectively; the f's are the fugacities, and the P's, the pressures. The quantities Pi and Pi can be determined by the

Jan 1, 1960

By W. H. Emmons

INTRODUCTION MINERAL deposits that have formed by the various geologic processes, when exposed to air and water at or near the surface of the earth, break down and form new compounds that are stable under surface conditions. Mechanical disintegration of the ores proceeds along with chemical alteration which generally is attended by oxidation, carbonation and hydration. Essentially all minerals are affected-silicates, carbonates, native metals, sulphides, etc. Where iron sulphides are present, oxidation yields sulphuric acid, and in the presence of oxygen and iron, ferric sulphate, a powerful solvent, is formed. Above the water level, in the vadose or shallow zone, both air and water are present. Below the water level air is excluded and that which is carried down with water is removed from the solution by reactions with reducing materials. Above the water level, solution is the pre-dominating process; below the water level, precipitation generally is equally important. In some deposits, particularly above the hater level, valueless materials are removed from the ore, leaving certain metals in a more highly concentrated state. This type of alteration, which has been termed negative enrichment, is common in ores of iron, aluminum, manganese and certain other metals. Some gold deposits, particularly those in which the environment is unfavorable for solution of gold, have been enriched near the surface by removal of material other than gold. Certain metals are readily dissolved in an oxidizing acid environment. These include copper, silver and, under certain conditions, gold. In the presence of iron sulphides, deposits of these metals are likely to be leached above the water level. The metals are carried downward to depths where air is excluded, and where they may be redeposited, generally below the water level. Such enrichment by addition of metals has been termed positive enrichment.

Jan 1, 1933

By L. A. Mekler

The recirculating furnace is primarily a heating apparatus of the convection type in which the heat-absorbing surfaces are heated by a mixture of fresh products of combustion and a portion of the combustion gases that have already given off a part of their heat in their previous passage over the heat-absorbing surfaces. In its basic conception, the recirculating furnace can be considered as a closed thermal system in which the heat-absorbing surfaces are constantly swept by a fixed quantity of products of combustion at a given initial temperature with the gases being constantly returned to the furnace and reheated before they again enter the heating zone. Gases equal in amount to those produced by the fuel burned to reheat the circulating gases are constantly ejected from the system to the stack. The recirculating furnace is the most suitable apparatus for heating by convection where low furnace temperatures must be maintained and where only a small portion of the available heat is taken out of the gases, particularly where the maximum allowable furnace temperature is low and where the final temperature of the gases is only a few hundred degrees below their initial temperature. In such cases, recirculation not only provides a method of reducing the rather high combustion temperatures of the fuel when burned without a large amount of excess air, but, by returning to the furnace the heat content of the gases at their final temperature, recovers a large portion of heat that otherwise would have been lost through the stack. The convection-type oil still is particularly suitable for the application of flue-gas recirculation. In an oil still, the heating of the oil is accomplished by applying to the tube surfaces a given quantity of heat of a certain predetermined quality, usually with the initial temperature of the gases not over 1500" F. as measured by thermocouples placed above the tube bank. To obtain the full benefit of the heating surface of the coil, the final temperature of the gases, after passing over the coil, is kept 200" to 300" higher than the temperature of the incoming oil. This final temperature varies from 500" F. for a topping still with only a slight or no

Jan 1, 1928

By R. G. Treuting, W. C. Ellis

D. Whitwham, M. Mouflard, and P. Lacombe (British Council Research Fellow, Labratoire du Professor Chaudron, Vitry-sur-Seine; Inqenieur de Recherches, Labratoire de Vitry; and Maitre de Recherches, Labratoire de Vitry, Professeur Adjoint de Metallurgie, Ecole des Mines, Paris)—The authors' work is of great interest in bringing out the geometrical relations existing between twinned lattices, and for the notion of a coincidence super lattice developed from this. We should like to point out that a similar idea was put forward by Friedel8 in his book on the subject of lattice merohedrism "merihedrie réticulaire:"—When two crystals A and B are twinned with respect to a mirror plane, there exists a common superlattice, "réseau periode," which is independent of the contact surface between the two crystals. The volume V of this superlattice is a simple multiple of the volume v of the lattice of crystals A, or B, (Fig. 5). This "multiple cell" is defined by the twin plane (p q r) and a row of atoms [h k l] normal to this plane, the base being taken as the smallest unit (two-dimensional) of this plane. Two cases must be considered. First when the multiple cell, as defined, has no atom site at its center nor at the center of its faces other than (p q r), v the twinning index is defined by —. In the second v case, when one of the two above conditions does not v apply, then the twinning index is V 2v A more intuitive definition of the twinning index would be the proportion of atoms of C, which would coincide with those of C1 when the C, lattice is imagined to extend on the other side of the contact surface. In the case of cubic crystals, the twinning index

Jan 1, 1952

By George K. Foster, Charles D. Borror

THE Jeffrey mine of the Canadian Johns-Manville Co., Limited, is in the town of Asbestos, situated approximately 100 miles northeast of Montreal and about the same distance southwest of Quebec, in Richmond County, Quebec. Mining operations were started in 1881 on outcrops on a hill, as a side-hill cut, followed by a second and third cut. This development was the forerunner of the present large open-pit operations, the mine now ranking as the largest openpit asbestos mine in the world. Operations were first carried on by hand, then by horsepower and later by stem cableways. By 1924 the derrick spans, 2000 ft. or more long, became unwieldy. To overcome this, and also to eliminate hand labor as much as possible, steam shovels and railroad haulage were introduced. The steam shovels were replaced in 1928 by larger electric shovels of the full-revolving type. THE ORE BODY The ore body is a serpentinized peridotite rock mass. The chrysotile fibers form a network of veins throughout, varying from microscopic width to two or more inches measured across the veins (Fig. I). These veins may be continuous for a few or many feet; they may increase or decrease in width within a few feet. The veins in which the fibers occur perpendicular to the veins are known as cross fiber. Those in which the fibers lay parallel to the veins are known as slip fiber. The cross fibers are of better quality, and more in demand. The majority of the fiber [ ]

Jan 1, 1946

By Ira B. Joralemon

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

By Ira B. Joralemon

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

By A. M. Gaudin, J. G. Morrow

FLOTATION requires the existence of a definite contact angle. This contact angle, the surface tension of the solution, and adsorption at the solid-fluid interface are quantitatively related. Adsorption of dodecylammonium acetate on hematite was measured for a wide range of concentrations of reagent in solution. Similar measurements for quartz have already been made. Contact angle measurements were then made on polished surfaces of hematite and of quartz immersed in aqueous dodecylammonium acetate solutions, and a functional relationship was sought between adsorption density at the mineral-solution interface and the contact angle. Finally, the surface tension of the aqueous amine acetate solutions was measured. These data were combined to give an evaluation of the work of adhesion for the three-phase system. Specular hematite was crushed and then ground dry in a laboratory porcelain mill, with flint pebbles, to pass a 200-mesh screen. The ground product was sized in a Haultain infrasizer, and one of the granular sizes (cone No. 3) was used in all adsorption tests. A hand magnet was used to remove magnetite and abraded iron. Quartz was removed in a Frantz isodynamic magnetic separator. The purified hematite was leached in aqua regia, washed with distilled water until the washings appeared free of electrolyte by conductance measurement, dried in a low-temperature oven, and stored in a pyrex container. The specific surface of the closely sized hematite was determined by the krypton gas adsorption method.' Three measurements gave an average value of 1350 sq cm per g. Chemical analysis showed Fe -69.37 pct, insol = 0.72 pct. The quartz used in the flotation tests had been prepared by Chang" for an earlier investigation. Demineralized distilled water was used for all test solutions. Dissolved salt content was of the order of 0.03 ppm, expressed in terms of sodium chloride, as estimated from conductance measurements. Dodecylammonium acetate was obtained from Armour & CO. in two forms, the unmarked compound and a preparation marked by carbon 14 in the hydrocarbon chain of the aminium ion. Specific activity of the active salt was 0.134 millicurie per g. The important physico-chemical constants for the primary amine salt have been reviewed by de Bruyn. The calculated effect of hydrolysis of amine salt on pH of aqueous solutions and the effect of pH on the distribution ratio of the alkylammonium ion to free amine are of particular interest. All other chemicals used in this investigation were of analytical reagent grade. A column method' was used for adsorption work. Attainment of equilibrium distribution in the adsorption column depends on the solid-solution contact time, hence upon the volume of solution passed. It was assumed that contact time required for equilibrium would be a maximum for the lowest reagent concentrations. On this premise it was demonstrated experimentally that the passage of 500 ml of solution through the mineral bed was adequate. An aliquot (1 to 5 cc) of the solution to be analyzed was transferred to a small pyrex cup and allowed to evaporate to dryness at room temperature; 4 or 5 mg of unmarked amine acetate were added to the dried sample and the cup and its contents were transferred to the combustion system for analysis. Evaporation at room temperature must be emphasized, as even slightly elevated temperatures result in loss of reagent. A laboratory model G Beckman pH meter equipped with a glass electrode was used to measure pH of amine acetate solutions. The technique of internal gas counting of radioactive carbon dioxide in a Geiger-Muller counter was used. Developed originally by Brown and Miller,- his method was adapted to the analysis of carbon-14 marked flotation reagents by Chang, de Bruyn, and Bloecher. nalytica1 method and procedures have been described in detail by Bloecher.' Contact angles were measured by the captive-bubble technique." The mineral specimens were carefully selected to avoid cracks and inclusions of other minerals. All specimens were mounted in plastic and polished to produce a smooth surface. The final polishing and contact-angle measuring

Jan 1, 1955

By Ira B. Joralemon

Neighboring mines, like men who live in the same environment, often assume similar characteristics. In the Bridge River area of the Lillooet district in central British Columbia there is a remarkable exception to this rule. The Pioneer mine has a simple fissure over 3000 ft. long, with no faults of more than a few feet and with only minor variations in width; the Bralorne mine, 2½ miles away at the other end of the same intrusion, has developed one of the most intricate vein and fault systems in the West. Hinged faults displace the main vein for hundreds of feet, and sometimes become valuable veins themselves. The width of ore varies in a few yards from 2 to 60 ft. Changes in grade of ore are just as abrupt. The rocks that follow the veins or are cut by them often grade into one another or into the ore with no definite contacts. Although the complexity of the structure has left many problems unsolved, the development has indicated a fascinating geological pattern. The Bralorne is in the eastern portion of the Coast Range, 55 miles by spectacular mountain road from the Pacific Great Eastern Railway station of Bridge River. The adit tunnel runs easterly from Cadwallader Creek, a tributary of Bridge River that flows into the Fraser River. Steep mountains rise from 3300 ft. elevation above sea level at the creek to peaks and ridges at 8000 to 9000 ft. altitude. The lower slopes are heavily wooded while above 5000 ft. bare rocks, glaciers and snow-fields extend far above timber line. See Fig. 1. Story of the Bralorne The Lorne claim, staked in 1897, was one of the earliest lode locations in the Bridge River district. At that time it was 70 miles by steep and treacherous trail from the railway. For the next 15 years Arthur Noel, Will Haylmore and other local prospectors mined the small, irregular, oxidized quartz veins to a maximum depth of 200 ft., and treated the ore in arrastres and later a five-stamp mill. The total production to 1912 was only $55,000. Noel and associates later formed the Lorne Amalgamated Mines Co., which they worked in a desultory way until 1925. Increasing sulfide and arsenide content in the veins

Jan 1, 1935

By M. C. Flemings, P. J. Ahearn

Dendvite morphology of unidirectionally solidified Sn-12 pct Bi alloy was determined with the aid of X-ray and macroetch techniques. Columnar growth direction (growth direction of primary arms) in this alloy is [110]; secondary arms grow in the [lii], [111), and [112] directions. Interstices between [112] dendrite arms fill in during early stages of solidification so that well-defined (110) planes are seen in the final structure (parallel to the heat-flozo direction). Similarly, interslices betweex the [111] secondary arrlls fill in to form (112) planes, and interstices between [1111 ] arms fill in to form (112) planes. DENDRITE morphology in alloys is conveniently studied in unidirectionally solidified castings. In this type of solidification, heat is extracted from a single chill surface of the casting while other surfaces are insulated. Solidification progresses from the chill and results in cast grains that are columnar with the long axis of the grain perpendicular to the chill. Dendrite morphology is conveniently studied by examination of etched surfaces parallel and perpendicular to the chill, as previously described.'" Experimental studies on the growth direction for tin are in general agreement. The major growth direction is [110]:-' although this is altered somewhat by supercooling. In one study, tin dendrites pulled from a supercooled melt had a growth orientation 12 deg away from the [110] direction toward the [002] direction.' This orientation could be changed back to the [110] or close to the [110] direction by changing the tempera- ture gradient in the melt. In a study using autoradio-graphic techniques, (111) directions were shown to be directions of preferred growth in addition to the [110) direction.7 PROCEDURE The samples employed in this study were cut from 12 pct Bi-88 pct Sn castings, 1.5 in. in diam and 3.5 in. tall. The casting procedure consisted of heating the charge to 390°C and then pouring the molten alloy directly into a gypsum sleeve mounted on a massive copper chill. Specimens were cut from the ingot, mounted, polished, and etched with Taffs reagent [FeC13 .6H2O, 2 g; HC1, 5 cu cm;H20, 30 cu cm; CzHaOH (95 pct), 60 cu cm].' The dendritic pattern was clearly visible after etching. Photomicrographs at about 8 and 35 times were taken on surfaces parallel and perpendicular to the chill. Laue back-reflection patterns were obtained from three different columnar grains in a singIe polished face 2 in. from the chill. The cut face was polished and positioned in the beam of a Laue camera, so that diffraction occurred from a single dendritic grain. The resulting diffraction pattern was interpreted to determine crystal log raphic orientation in relation to the heat-flow direction and in relation to microstruc-ture of the given grain. RESULTS Fig. 1 shows a horizontal and vertical section of the columnar structure, at low magnification. Light regions are rich in tin, and darker regions tin-poor; the primary phase is tin-rich a phase. The two sections shown were taken orthogonally from the same metallographic specimen. It is readily seen from Fig. 1 that the dendrites have

Jan 1, 1968

By G. R. Belton, Y. K. Rao

A galvanic cell, using liquid MgCl2 or MgC12-CaC12 mixtures as the electrolyte, has been used to determine activities in Mg-A1 liquid alloys between 700' and 880°C. The incovporation of a chlorine electrode in the cell also allowed measurements to be made of the standard free energy of formation of MgCl2(l). The results are shown to be in good agreement with thermo-chetrlical values from the literature, and this is taken as evidence that the small, known solubility of magnesium in iMgCl2 introduces no significant error in galcanic cell measurements. Within experimental error, the activity coefficients and relative partial molar enthalpies at 800°C are shown to be represented by the following "subregular" solution equations: logy~~ =-0.68(1 -xMgj3 log yAL =-1.02(1 - XMf + 0.68(1 - XMf H.M = -4400(1 - %)3 / cal Mg 7Ag' HZ =-6600(1 - xA1)' + 4400(1 - XMf cal SCHNEIDER and toll' have used a transpiration technique to measure the vapor pressures of magnesium over Mg-A1 alloys between 544" and 594°C. amsstad,' however, has since suggested that the extrapolation to zero flow rate, used by these authors in interpreting their apparent pressure vs flow rate data, gives unreliable results. Rogers, Tomlinson, and Richardson,3 in interpreting the results of solution equilibria between Mg-A1 alloys and liquid MgC12, also considered the measurements of Schneider and Stoll to be unreliable and preferred to derive activities for the alloys from the earlier boiling point determinations of ~eit~ebel~ and the partial molar heats recommended by Kubaschewski and ~atterall.~ These latter heats were based substantially on the early calorimetric work of Kawa-kami but, unfortunately, his work on other systems has sometimes been found to be inaccurate.7 Rogers et al., in the above-mentioned paper,3 tentatively concluded that the most likely species responsible for the limited solubility (0.3 mole pct at 800°C) of magnesium in MgC12 were Mg° (neutral) and Mg2++. Two more recent studies8,9 have supported Mg2++ as the soluble species. In the present study, activities in Mg-A1 alloys have been determined by means of a galvanic cell involving liquid MgCl2 or MgC12CaCl, mixtures as the electrolyte. Since the reactive nature of magnesium precluded simple Faraday yield experiments, a chlorine electrode was incorporated in the cell in order that the performance of the cell could be checked by measurements of the heat and free energy of formation of MgC12. This procedure was considered necessary since it has been suggested1' that the solubility of a metal in a molten salt might introduce electronic conductivity; also, previous determinations of the standard electrode potential for MgC12 differed by as much as 70 mv11-13 EXPERIMENTAL Materials. Analyses of the materials used in preparing the alloys and the electrolyte mixtures are presented in Table I. The alloys were prepared by induction melting weighed amounts of the metals in a graphite crucible held under an argon atmosphere. Pure anhydrous magnesium chloride was prepared by heating the mixture MgCl, . 6H20 +NH4C1(1:1) to 650°C, followed by melting under dry argon. The melting point of the dry MgC12 was found by differential thermal analysis to be 714.8oC, which compares well with the accepted value of 714C.14 This agreement was taken to be an indication of the high purity of the dried salt. Table I. Compositions of Materials, wt pn Impurity Mg Al MgCI2 CaCI, Ba - - 0.005 Ca - - 0.010 Cu 0.02 0.02 Fe - 0.10 0.001 0.010 Pb 0.01 - 0.001 0.005 Mn 0.15 0.001 Si - 0.10 Sr - - 0.005 MBSO* - 0.040 ARGON TUNGSTEN CHLORINE LEAD—411 11 II ALUMINA 'A I / ave GRAPHITE on irA~_ ( ^"l ROD MAGNESIUM S>ILICA~^ /, OR ALLOY-. I /A] ___________ -«^- _ ELECTROLYTE I y FRITTED DISCS Fig. l—Arrangement of chlorine and metal electrodes in electrolytic cell.

Jan 1, 1970

By R. A. Morse, C. R. Stewart, F. F. Craig

This paper preFents the results of a series of model flow test on a number of large limestone cores, having different pore configurations. For limestone cores having substantially sandstone type porosity, the production characteristics for solution and external gas drives are similar. For cores whose pore spaces were microscopically heterogeneous (i.e., consisted of combinations of solution cavities, matrix. and fissures), the production characteristics lor solution and external gas drives vary widely. The degree of divergence between gas-oil relative permeability relationships calculated from solution or external gas drive tests is an indication of heterogeneity of rock pore structure. The results of water floods on cores depleted by solution gas drive for each of these two general types of limestone porosity are also shown. Generalizations are made on the water flood recovery that could be expected from each of these two types of limestone porosity. The similarity between solution drive field performance and model solution drive performance on cores from the same formation is shown for several cases. This indicate? the feasibility of predetermining limestone field performance from such large core tests. Photomicrographs of plastic-impregnated rock thin sections of the samples tested are presented as an aid in understanding the flow test performances. INTRODUCTION During the past 15 years. reservoir engineers and research workers have developed methods of testing rock and fluid samples and applying the results, through calculation, to allow reasonably satisfactory predictions of oil recoveries and performances to be expected in sandstone oil recervoirs. It has been determined that representative fluid flow data can be obtained on rock samples as small as three-fourths in. in diameter by one in. long in most sandstones. However, little has been accomplished toward the laboratory determination of fluid flow characteristics in limestones. There has been a great deal of speculation as to the influence of variations in pore size, shape, and degree of interconnection upon oil recovery processes, and a great deal of thought has been given to the interpretation of limestone field perfomance. It has been generally recognized that predictions of reservoir performance based on oil displacement tests on small limestone core samples the size of those used for sandstone tests can often be misleading because of the improbability of obtaining a representative sample in such a small core. Obviously, if there are present in the rock, pore openings of the magnitude of 1/16 in., or fractures or solution channels up to one in. or more in length, it will be impossible to cut any sample less than one in. in any dimension which would represent the flow geometry of the gross rock system. In some formations, the individual openings in the rock are of such size that it would be impossible to obtain a good sample of the flow system even in the total core available from conventional-sized well cores. However, by increasing to the maximum the size of the sample used, it should be possible to obtain representative flow data from the majority of limestone reservoir materials which can be used for prediction of future primary production performance or response to be expected from secondary recovery measures. The only alternatives to obtaining good laboratory test data to serve these purposes are extrapolation of primary performance data obtained by partial depletion of a field, or obtaining information from pilot tests. It has been shown previously, and will be demonstrated further by the work reported in this paper, that extrapolation of solution gas drive performance for an estimate of gas injection response can be very misleading in reservoirs of heterogeneous type porosity. Although it cannot be expected that laboratory information can ever eliminate the necessity of small-scale pilot operations, it is expected, as is now the situation with sandstone reservoirs, that laboratory tests should provide reliable information for screening of

Jan 1, 1953

By M. G. Corson

INFORMATION regarding the use of manganese alloys has hitherto been incomplete and available only from widely scattered sources. This paper attempts a systematic description of properties and uses of alloys other than manganese bronze, manganin and duralumin, which are probably the only non-ferrous alloys associated with manganese in the minds of most metallurgists.1 PROPERTIES OF MANGANESE Manganese can react either acid or basic; it is hard to obtain in the pure state; it has two different crystalline lattice structures, both of the cubic system, one stable above 850° C. and the other below 650° C., both coexisting in the intermediate range. Although the commercial product is hard and brittle, the pure metal seems to be ductile. In fact Zhemchuzhny, in Russia, was able to obtain ductile manganese and draw it to fine wires by the simple expedient of adding about 3 per cent. copper to the alumino-thermic product. Copper most probably brings the silicides, aluminides, nitrides and carbides present in the commercial product into a much less harmful form of distribution. One industrial use that can be foreseen for wrought manganese articles is as anodes for electrolytic processes in sulfate and nitrate solutions, particularly with high voltages. A practically insoluble skin of manganese peroxide is likely to form in such cases and an insoluble and strong anode material will be available. MANGANESE AS A SCAVENGER Because of its activity manganese might become the most efficient scavenger and refiner of copper, were it not for the fact that 0.01 per cent.

Jan 1, 1928

By Homer W. Riley

ANTHRACITE SMALL power-driven, toothed, cast-iron rolls were used first to break anthracite in 1844. Prior to that time, men with hammers, who stood on perforated cast-iron plates, broke the large lumps into commercial sizes. In order to convert run-of-mine into the various sizes required by the anthracite industry, about 20 million tons must be broken, annually, into smaller sizes. This phase of anthracite preparation is of major importance, because the degradation accompanying reduction in coal sizes should be kept at a minimum. The exclusive use of toothed rolls for that purpose indicates that comminution by rolls is the best solution of the problem. Many improvements have been made in tooth design, but the most important was a reduction of the peripheral speed of the rolls from 1000 to 300 ft. per minute. The higher speed was based upon and approximated the velocity of a falling piece of coal when it entered the rolls, Exhaustive roll tests at the slower speed showed that the same size reduction could be affected with less degradation. The adoption, therefore, of slow-speed, compound geared rolls, especially for breaking the larger sizes, became quite general after 1912. A high-speed roll is shown in Fig. 1 and a slow-speed roll in Fig. 2. Anthracite Crushing Problems.-Crushing anthracite presents the problem of selecting a series of rolls that will produce the greatest percentage of the prepared sizes of nut and over. The size distributions to be expected are shown in Table 1. Coal breaking and crushing practices in anthracite breakers involve the use of equipment for comminuting the following classes of material: 1. Run-of-mine-plus 6 ½ -in. coal. 2. Sized coal-steamboat, broken, egg, stove, nut, and pea. 3. Flat coal--coal that is flat and hence not suitable for the market. 4. Bone--a piece of laminated coal and slate, crushed for the purpose of reclaiming the coal. 5. Breaker refuse, reduced to a size suitable for flushing into a mine for back-filling purposes.

Jan 1, 1950