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By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By F. R. Hensel

PuRe silver and silver-lead alloys have been studied as to their suitability for bearing~.' A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materia1s. t The silver-rich end of the diagram as reported in the literatureg-" was found to be sketchy and it was necessary to carry out corisiderable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. Test Materials In the beginning of the work, only fused alloys were investigated. Later, research Table i.—Composition of Fused Silver-thallium Alloys Tested for Antifriction Properties Percentage Alloy No. of Thallium 1533...................... 0.48 1534.................... 1.06 a31 HT................... 2.04 231....................... 2.10 232 HT................... 3.83 Balance 232....................... 4.07 Silver 233 HT................... 5.86 a33....................... 6.38 a34....................... 9.84 a34 HT................... 10.07 was carried out on electroplating methods and diffusion processes. In preparing the fused alloyst care was taken to exhaust the toxic fumes caused by the thaillium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in, diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr207, 8 C.C. H2S04, and IOO C.C. H20. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475OC. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not iesiilt iii complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1946

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By Lewis Reeve

As part of a program of investigation of the properties of electric arc welds carried out in the laboratories of the A. 0. Smith Corporation, considerable work has been done on the determination of the oxygen, nitrogen and hydrogen content of different types of weld metal, employing for this purpose the so-called "vacuum fusion method." It is the purpose of this paper to describe certain improvements that have been introduced in this method of determining the gas content of metals, with particular references to the steel specimens examined in this investigation. The method and apparatus used at the beginning of the investigation were essentially those of the Bureau of Standards as described by Vacher and Jordan.' Later a number of changes were introduced which resulted in more rapid evacuation of the graphite crucibles employed and which enabled larger volumes of gas to be dealt with than could be handled conveniently in the Bureau of Standards equipment. In addition, the analyzing of the gases evolved from a melt in the same apparatus as collected was abandoned in favor of analysis outside the equipment using standard methods of gas analysis. The time required for gas analysis in the apparatus itself, as described by the Bureau of Standards, was found to be considerable, and during this time the rest of the equipment was tied up, preventing its use for the analysis of further steel samples. As a result of the modifications introduced, the time required for the analysis of a steel sample for gas content was reduced from about 8 hours to less than 3 hours. Subsequently, the whole procedure of melting the sample and collecting the gases evolved was modified so as to enable a distinction to be drawn between the easily reducible oxides such as iron oxide and the more stable oxides such as silica and alumina. At the same time evidence was obtained indicating the probable existence in the steels of other nitrides than those of iron alone and making possible their quantitative etermination.

Jan 1, 1934

By B. F. Fackenthall

The Durham Iron Works of Messrs. Cooper & Hewitt, near Riegelsville, Pa., occupy a site which has been almost continuously the scene of iron-manufacturing industry since 1727. Doubtless if Anthony Morris and his thirteen associates, who in that year erected a blast-furnace on the Durham Creek, a short distance above where the Durham Iron Works now stands, could have had a vision of the improved and enlarged apparatus of their successors, they would have been not less astonished by the huge stack, the hot-blast ovens, and the blowing-engines of the modern blast-furnace, than by the railroad which now follows the bank of the river on which their clumsy " Durham boats " once floated pig-iron to Philadelphia. In one particular, posterity must confess their snperiority. We are told that in November, 1728, they shipped three tons of Durham iron to England. The proprietors of the Durham Iron Works are not now shipping iron to England. The present Durham furnace was built (in place of two smaller ones) in 1874 and 1875, and made its first blast in 1876. A description of it, with other works of the same proprietors, at Trenton, N. J., by A. L. Holley and Lenox Smith, was published in London Engineering for January 31st, and February 21st, 1879. Since that time, a number of improvements, dictated by experience, have been made in the details of the furnace and fittings; and the recent roilclusion of a long and successful blast presents a convenient opportunity for a description of the works and a statement of the results of practice. The accompanying drawings will show the general arrangement of the works. The furnace, Plate I., Figs. 1 and 2, is 75 feet high by 19 feet bosh. The hearth is 11 feet 4 inches in diameter, with seven tuyeres 5 feet 6 inches above hearth-line. The tuyeres project 9 inches into the furnace, making the interior tuyere-circle 9 feet 10 inches in diameter. The front is a modification of Luermaun's

Jan 1, 1886

By CYRIL W., William Campbell, Henry M. Howe

THIS paper gives the results of an investigation of the behavior of the argentiferous cobalt-nickel arsenides of Temiskaming, Ontario, in roasting, made in the metallurgical laboratories of the School of Mines, of Columbia University in the City of New York. The ore was kindly given by the owners of the La Rose and Trethewey properties at Cobalt, Ontario, and Mr. E. J. Hall, Tutor in Assaying in Columbia University, has helped us much. I. OBJECT OF THE INVESTIGATION. The object of the investigation was to learn:- 1. The temperature at which the arsenic is most rapidly expelled; 2. The thoroughness with which it is expelled by prolonged roasting at this temperature; 3. The effect of adding charcoal (a) near the end of the roast and (b) at the beginning of the roast. II. NATURE OF THE ORE. The important ores mined in the Temiskaming deposits are native silver-with small amounts of dyscrasite (Ag6 Sb), argentite (Ag2S), pyrargyrite (Ag3SbS3)-smaltite (CoAs2), chloanthite (NiAs2) and niccolite (NiAs). Mispickel (FeAsS) and cobaltite (CoAsS) also occur in smaller quantities. The average composition of the ore shipped from this district for the first six months of 1905 -was: silver, from 4.1 to 4.8 per cent.; cobalt, from 6.9 to 8.2 per cent ; nickel, from 3 to 4.7 per cent ; and arsenic, from 30.9 to 34.6 per cent. The ore which we treated consists chiefly of smaltite ; In our laboratory-work

Jan 1, 1907

Discussion of the paper of F. C. NEWTON, presented at the New York meeting, Feb-ruary, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 473 to 477. H. 0. HOFMAN, Boston, Mass.-The results of these large-scale experiments, which were carried on at Perth Amboy, show that there are many differences between theoretical conceptions and their applications to work on a large scale. The author has given reasons why the results of bringing a desilverizing kettle to the high melting point of the zinc-silver alloy, Zn3Ag2, melting at 665° C., are not satisfactory. In all probability the alloy is dissolved in the lead; it may also be decomposed by the lead; the practical result is that this high temperature does not work. It remains now for the laboratory man to carry on systematic experiments

Jan 5, 1915

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature 1135°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By Roland D. Parks

Corundum, little publicized as an industrial abrasive, has, in its small way, contributed greatly to the production of many specialized items vital to our war program and to Our allies. Optical elements Of the highest quality for range finders, bombsights, and scientific instruments; precision metal parts for torpedoes and airplane engines; quartz crystal plates for military radios; armorplate and malleable castings for tanks and guns; and eyeglasses for everyone; these are some Of the products that corundum has helped to produce in the quantities needed and on time. Unlike metals and many other raw materials, corundum is not incorporated into any Of these finished products. It is simply a grinding medium used to produce the desired finish or precision; an operating supply or tool, so to speak. With a Mobs' scale index of 9, corundum ranks next to the diamond in hardness among the natural minerals and is superior to emery and garnet. The gem varieties of corundum, including the Oriental ruby and sapphire, are frequently more highly prized as jewels than the diamond. It is the intent Of this paper to deal Only with a description of the corundum industry, the administration of wartime control, and certain economic aspects as seen by the author. Several references are listed to assist anyone who wishes further information on the geological occurrence of the mineral. Ore Production and Consumption For the past two decades, south Africa has been the world's sole producer of corundum ore. A possible exception is Russia, where, it is understood, there was considerable production during the thirties for domestic consumption but for which statistics are lacking. The United States is the world's principal consumer of corundum ore; imports lor the period 1934 through 1940 averaging 3000 Short tons per year, The years 1935 and 1936 were close to the 5000-ton mark, and imports during 1941, the last prewar year for which statistics have been released, were approximately 6000 Short tons. Again lacking statistics on Russia, the United Kingdom ranks second, but far below the United States in consumption of ore. Historically, corundum has been found in some 35 countries throughout the world, but the principal deposits are in South Africa, Canada, Madagascar, Russia and the united States. Deposits are generally small and subject to rapid exhaustion. Thus, the United States was the principal world producer for the period 1870 to 1900, when operations ceased except for two years during World War I. India was a producer of ore from 1898 through 1921, with peak output in 1916 through 1918 Canada came into production in 1901 with substantial output of ore and finished grain until 1914; the production thereafter was smaller until 1921. Madagascar has produced ore since 1910 but has had important output in only a few scattered years. South African production started in 1912

Jan 1, 1948

By Roland D. Parks

Corundum, little publicized as an industrial abrasive, has, in its small way, contributed greatly to the production of many specialized items vital to our war program and to Our allies. Optical elements Of the highest quality for range finders, bombsights, and scientific instruments; precision metal parts for torpedoes and airplane engines; quartz crystal plates for military radios; armorplate and malleable castings for tanks and guns; and eyeglasses for everyone; these are some Of the products that corundum has helped to produce in the quantities needed and on time. Unlike metals and many other raw materials, corundum is not incorporated into any Of these finished products. It is simply a grinding medium used to produce the desired finish or precision; an operating supply or tool, so to speak. With a Mobs' scale index of 9, corundum ranks next to the diamond in hardness among the natural minerals and is superior to emery and garnet. The gem varieties of corundum, including the Oriental ruby and sapphire, are frequently more highly prized as jewels than the diamond. It is the intent Of this paper to deal Only with a description of the corundum industry, the administration of wartime control, and certain economic aspects as seen by the author. Several references are listed to assist anyone who wishes further information on the geological occurrence of the mineral. Ore Production and Consumption For the past two decades, south Africa has been the world's sole producer of corundum ore. A possible exception is Russia, where, it is understood, there was considerable production during the thirties for domestic consumption but for which statistics are lacking. The United States is the world's principal consumer of corundum ore; imports lor the period 1934 through 1940 averaging 3000 Short tons per year, The years 1935 and 1936 were close to the 5000-ton mark, and imports during 1941, the last prewar year for which statistics have been released, were approximately 6000 Short tons. Again lacking statistics on Russia, the United Kingdom ranks second, but far below the United States in consumption of ore. Historically, corundum has been found in some 35 countries throughout the world, but the principal deposits are in South Africa, Canada, Madagascar, Russia and the united States. Deposits are generally small and subject to rapid exhaustion. Thus, the United States was the principal world producer for the period 1870 to 1900, when operations ceased except for two years during World War I. India was a producer of ore from 1898 through 1921, with peak output in 1916 through 1918 Canada came into production in 1901 with substantial output of ore and finished grain until 1914; the production thereafter was smaller until 1921. Madagascar has produced ore since 1910 but has had important output in only a few scattered years. South African production started in 1912

Jan 1, 1948

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By Kenneth Seaver

(San Francisco Meeting, September, 1915) INTRODUCTION IT is rather gratifying that in the field of the manufacture 'of refractories, in which, as a whole, foreign practice has surpassed us, the United States stands pre-eminent in the making of silica brick. In some instances European manufacturers have refused point-blank to credit the possibility of making to such specifications as are common with us, until the actual 'completed shapes were shipped for inspection. But both the manufacturer and consumer in foreign lands are now frankly learning from us, and benefiting by our advanced practice in this field, as is evidenced by the orders placed here and the efforts put forth abroad to come up to the standard of American-made material. In no metallurgical operation has the employment of silica brick spread with. such leaps and bounds as in the building of plants for the carbonization of coal, particularly in the byproduct coke oven. Today, in practically all types of oven, the structure above the floor level (except the facings) is of silica, while in the recuperative and in some regenerative types, its use is extended to that portion of the oven below the floor as well. By reason of the fact that there are a number of classes of refractories of higher silica content than the usual so-called fire-clay brick, there is sometimes a misunderstanding as to the class of material referred to as "silica" brick. We here refer only to a brick having a silica content of 94 per cent. or more and made usually from quartzite rock with a small percentage of lime as a binder. The term "silica" brick is sometimes rather loosely applied to brick front highly siliceous clays, or to a quartzite refractory of mingled fire-clay and quartz rock; but such products are not considered in this discussion.

Jan 9, 1915

By T. R. Cass

THE renewed interest in titanium, resulting from its increasing application as a structural material, has stimulated basic deformation studies on this metal. In the course of our work, we have developed a dislocation etchant and applied it to a perfection study of melt-grown single crystals as well as to a preliminary investigation of plastic deformation in titanium. The etchant, Keller's etch (21 cu cm HF, 64 cu cm HC1, 106 cu cm HNO3, and 160 cu cm H20), reveals the emergence of both grown-in and fresh dislocations on pure titanium and a-phase Ti-Al single crystals. Pits are produced only on surfaces within a few degrees of the basal plane; the more exactly parallel to a basal plane the surface is, the more distinct are the pits. The observed pit density, however, does not appear to depend on the surface orientation; the pits simul- taneously become less distinct as the misorientation from a basal plane increases. Etch times are short, a few seconds, for pure titanium; longer times are necessary for alloy crystals.

Jan 1, 1968

By L. A. Dale, D. A. Dahlstrom

Closed-water circuits are justified today from two standpoints: economical operation and prevention of stream pollution. In today's modern preparation plant, it has been found very desirable to have the plant circulating water maintained at a relatively low solids concentration of around 3%. In so doing, bene-ficiation equipment can operate at a much higher efficiency. However, makeup water requirements would become excessive if the fines were to be removed from the preparation plant by bleeding a 3% solids concentration to a tailings pond. With the ever increasing percentage of —200 mesh coal, clay and slimes in the raw coal, coupled with the creation of these fines within the preparation plant, the need for water conservation for economy reasons becomes even more important. Because of stream pollution laws, tailings ponds have become very costly to operate and maintain, resulting in the necessity of employing an in-plant method of water recovery. Accordingly, the primary system employed in water recovery in the coal preparation plant today consists of a solids concentration device to thicken refuse solids while at the same time producing a sufficiently clarified effluent that can go back to the preparation plant for water reuse. The thickened product is then normally passed to a dewatering device that will produce a handleable solid that can be disposed of

Jan 1, 1965

By H. J. Ramey

Conventional calculation of total system isothermal compressibility for a system containing a free gas phase involves, among other things, evaluation of the change of oil and gas formation volume factors and the gas in solution with pressure. Preferably, this information should be obtained from laboratory measurements made with particular oils and gases. Often, experimental measurements are not available. In this case, it is necessary to obtain pressure-volume-temperature relationships from general correlations such as those of Standing' for California oils. In order to speed estimates of compressibility, generalized plots have been prepared of the change of both oil formation volume factors and gas in solution, with pressure from Standing's correlations. A generalized plot for estimating the change in the two-phase (oil and gas) formation volume factor with pressure is also presented. Usually, the effect of gas dissolved in reservoir water upon the total system compressibility is neglected for gas saturated systems, due to the low solubility of gas in water. Results of this study indicate that the increase in total system compressibility caused by solution of gas in water is often as large as the compressibility of wafer, and can be magnitudes larger for low pressure systems. Generalized results for estimating the change of gas in solution in water with pressure are presented in tabular and graphical form. INTRODUCTION During the past decade, pressure build-up and drawdown techniques have gained an important place in reservoir engineering. Build-up and drawdown analyses are only two special applications of the broad field of transient fluid-flow theory. All solutions of transient fluid-flow problems contain a parameter called the total system isothermal compressibility. This property of fluids and porous rock is a measure of the change in volume of the fluid content of porous rock with a change in pressure, and it may vary considerably with pressure. Evaluation of total system isothermal compressibility is not difficult, but it is tedious and time-consuming. Often compressibilities are estimated roughly, or transient flow methods are neglected completely. The benefits of using accurate system compressibility in properly-executed build-up or drawdown analyses are: 1. Better planning of pressure build-ups may be achieved to avoid unnecessary loss of revenue due to excessively long shut-in periods, or to shut-in periods too short to yield useable data. 2. Better and more reliable estimates of static formation pressures for reserves estimates and rate performance estimates. 3. Reliable information for evaluation of well completion effectiveness, and planning and interpretation of well stimulation efforts. The purpose of this paper is to clarify the nature of the total system isothermal compressibility, and to present useful methods for estimation of compressibility, particularly for systems containing a gas phase. DEVELOPMENT Numerous publications have presented solutions to transient single-phase flow of slightly compressible fluids, stressing pressure build-up applications. In transient flow, a compressibility* term arises to permit volume content of fluids in porous rock to change as pressure changes. The basic nature of the compressibility term is usually taken for granted. Problems arise in practical applications of transient fluid theory because most published works consider only one flowing fluid—in an ideal porous system containing only one fluid. In 1956, Perrine2 presented an intuitive extension of single-phase flow pressure build-up methods to multiphase flow conditions. Later, Martin- established conditions under which Perrine's multiphase build-up method had a theoretical foundation. Perrine has shown that improper use of single-phase build-up analysis in certain multiphase flow situations can lead to gross errors in estimated static formation pressure, permeability and well condition. It is likely that, much pressure build-up data for oil wells should be analyzed on the basis of multiphase flow. For both single-phase and multiphase build-up analysis, the isothermal compressibility term in dimensionless time groups often should be interpreted as the total system compressibility. All real reservoirs contain one or more compressible fluid phases. In addition, rock compressibility can contribute in an important way to the total system compressibility. The proper total system compressibility expression may contain terms for compressibility of oil, gas, water, reservoir rock and terms for the change of solubility of gas in liquid phases.

Jan 1, 1965

By G. H. Matheson, J. M. W. Mackenzie

The flotation rate of coal has been studied using a continuous laboratory flotation cell and a multiple exposure photographic technique. The effects of particle size, reagent additions and cell turbulence on the flotation rate of coal have been investigated. The results have been analyzed in terms of current theories of particle bubble encounter and adhesion. The rupture forces which occur during particle bubble encounter have been shown to have an important effect on the flotation rate of coarse coal particles. The flotation of coal is a time dependent process, and in order to obtain a complete understanding of the operation it is necessary to determine the kinetics of the process. In coal flotation, the flotation rate and the associated values of cell productivity in terms of tons per kilowatt-hour and tons per cubic foot of cell volume are of greater importance than in most other mineral flotation operations. The reasons for this are associated with the low unit value of coal and the relatively high cost of coal flotation compared with other coal cleaning processes. An important aspect of coal flotation kinetics is the design of coal flotation cells. The cells used in many coal cleaning operations are often replicas of those used for the treatment of sulfide ores and are not necessarily suitable for the treatment of coal washing pulps, which usually contain a higher percentage of coarse and floatable material than the sulfide pulps for which the cells were designed. This disadvantage of many coal flotation cells has been recognized by Russian engineers who, by the addition of baffles to their subaeration coal flotation cells have increased the cell capacity by 100%. Investigation of the variables which influence flotation kinetics and cell productivity are, therefore, important to the coal industry where flotation is the only accepted method of cleaning the fine (-1/2mm) coal. The kinetics of the flotation process have been investigated in detail by Schumann10 who developed a continuous flotation cell which permitted the study of flotation under steady state conditions. This technique has been used by Gaudin et a1.,6 Brown and Smith and recently by Jowett and Savfi.7 The latter authors have developed a refined mathematical treatment for interpreting the results of continuous laboratory tests. Attempts have also been made to study flotation kinetics using conventional batch testing techniques. The experimental difficulties, however, and the problems of determining the order of the flotation rate process have made this technique of dubious value. A summary of the proposed rate equations for batch testing and the difficulties associated with this technique is given by Brown and Smith. 2 The experimental techniques described above are concerned with the rate of production of froth product. However, several authors, notably Sutherland, 11 Bogdanov1 and Philippoff, 9 have analyzed flotation

Jan 1, 1963

By E. T. Turkdogan, L. S. Darken, R. J. Fruehan

Further consideration is given to the application of the quadratic formalism to evaluate the thermodynamics of binary metallic solutions from experimental data. The use of the thermodynamic relation, in(r1/r2) dN2= 0, in the evaluation of activity data is discussed. The empirical correlations derived previously for enthalpies and entropies of solutions in Part II are shown to be predicted theoretically for a special case. The applicability of the quadratic formalism to the activity coefficients for binary organic solutions is demonstrated. DARKEN&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. In a subsequent paper (Part II) Turkdogan and Darkeen2 extended this formalism to the enthalpy and excess entropy of binary metallic solutions, and showed that the available data for the activity coefficients and heats of mixing of many solid and liquid binary metallic solutions confirm reasonable applicability of the quadratic formalism. Much variation was noted, however, in the extent of the terminal regions from one system to another, commonly from about 10 to 70 at. pct. For the present purpose, equations derived previously need be given only for one of the terminal regions, e.g. region (I), 0 < N2 < N&apos;2: where subscripts 1 and 2 indicate quantities for components 1 and 2 and superscript ° the values at infinite dilution; other terms are: N = atom fraction, y = activity coefficient, = partial molar enthalpy of solution, ?HM = molar heat of solution, ?Sx = excess partial molar entropy, ?Sx = excess molar entropy. The heat and entropy like terms (constants) el, and S12 are defined in the following expression for the temperature dependence of a12, thus a12 £12 — s12 rnl 2.303RT 2.303 R l J Using this formalism, the thermodynamics of binary systems in the terminal regions may be described over a temperature range of experisental interest in terms of eight quantities: Lº1—Lº2, ?Sx1,?Sxº2 , £12 ,£21,fiai, S12, and S21. In the previous paper, these quantities were evaluated for many solid and liquid binary solutions, and two significant correlations were observed between these thermodynamic quantities pertaining to the terminal regions, thus [10] and [11] Combining Eqs. [9], [l0], and [ll] and rearranging gives a12 -a21 = 1.382R log rº2- 0.08(?S2xº- ?S1xº) [12] Since the second term involving entropies is small and Eqs. 1101 and [ll] are empirical relations, the above equation may be simplified to a12 = 2.74 log rº2 [13] Using the values of a&apos;s and y°&apos;s compiled in Parts I and 11, a12 - a21 is plotted against log(rº2/rº1) in Fig. 1; the line drawn has a slope of 2.74. For Hg-K at 300°C, log(yº2 /yº1)= —5.10, not shown in Fig. 1, and from correlation [13], a12 - a21 = -13.97; this is to be compared with -10.76 derived from the activity data (Part II).

Jan 1, 1970

By Lincoln F. Elkins, John T. Cooke

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949

By John T. Cooke, Lincoln F. Elkins

Injection of gas to increase oil recovery has been considered for almost all important discoveries during the past ten or fifteen years. However, the number of gas injection projects having sufficient history and data is too limited to permit valid generalities of effectiveness of gas injection. Management and engineers are faced with a difficult problem of selecting those reservoirs which are susceptible to profitable application of gas injection. Injection of gas to maintain high pressure favors some factors affecting reservoir performance such as viscosity, surface tension, and formation volume factor of oil by keeping gas in solution and favors some operating features such as extending flowing life of wells and storing part of the produced gas for future use or sales. Injection of gas at low pressure involves lower compression ratio, or at least a single gas-gathering system, larger displacement volume in the reservoir per unit of gas handled, and permits effective utilization of the naturally existing energy and agent for oil displacement that is gas dissolved in oil. Each program is thus a compromise to meet optimum economic conditions while striving to attain maximum recovery of this important nautral resource. The statement has often been made that pressure maintenance would greatly increase oil recovery by permitting abandonment of formation oil inflated with gas in solution rather than abandonment of the same liquid volume of tank oil, if the same terminal oil saturation could be attained. Simple calculations indicate increases in oil recov- ery as high as one hundred per cent on this basis for high formation volume factor oil encountered in current deep drilling. Important in this statement is "if the same terminal oil saturation could be attained." Implicit in this statement are the requirement of physical

Jan 1, 1949