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By Frank L. Antisell

Certain physical and chemical properties of copper are so intimately related that a change in variation of the physical properties indicates a certain chemical change. The standard specifications of copper of the American Society for Testing Materials are based upon physical characteristics with one exception, namely, the copper contents. The physical standard includes electrical properties, defects in the "set or casting," variation in dimensions, weight, etc. Paragraph 4 of the specifications states, " Wire bars, cakes, slabs and billets shall be substantially free from shrink holes, cold sets, pits, sloppy edges, concave tops, and similar defects in set or casting." Shrink holes and concave tops indicate both physical and metallurgical defects; cold sets, sloppy edges, etc., indicate physical defects only; small pit holes may be indicative of either or both physical and metallurgical defects, depending on conditions under which they originated. To the refiner, a copper casting, no matter how made, is known as a "shape," irrespective of whether it is wire bar, ingot, cake, slab, billet, etc. As practically all shapes are cast in an open mold, that is a mold without cope, the surface of the shape cools in contact with the atmosphere and has a coating of oxide. Certain phenomena of the surface indicate the adaptability of the metal for forging or rolling. The writer believes that it is much simpler to produce shapes that are metallurgically correct than those that are mechanically satisfactory. When copper is to be rolled into thin sheets or drawn into very fine wire, the slightest physical defect becomes evident. It is, therefore, of the utmost importance to consider every characteristic of the shape and ascertain the physical and chemical relationship. Pitch and Set.—The appearance of the surface of the copper when cooled is considered as to its "pitch," or the general contour of the surface of the shape (which may vary from a concave to a convex); and the '" set,"' or the detail appearance of the surface of the shape (the wave-like structure). When the shape presents a concave surface, it is known as "low pitch;" a convex surface is known as "high pitch" or "tough pitch;" and a level surface is called "flat pitch." The set of the copper is, in a very large measure, directly related to the pitch; and so intimately are

Jan 1, 1921

By G. Townsend Harley

STOPING methods in which shoveling plays an important part are gradually being replaced by other and cheaper methods. But there will always be considerable shoveling done underground in stopes as well as in drifts, tunnels, urinzes, and shafts. At the mines of the PhelpsDodge Corporation at Tyrone, N. M., the cost of shoveling in all stopes in 1917 amounted to 24c. per T. In the top-slice stopes for the same period, it cost 27 c. per T. or 16 per cent, of the total cost of these stopes. The tonnage for shovelers from all stoping was 9.3 T. per man, and for topslicing 8.2 T. per man. These stopes were not unduly hot, and there was not more than the usual amount of timber to interfere with the work of the men. The tonnages obtained per shoveler were considered low; first, because of a poor grade of Mexican labor, many of the men having come in from railroad grading camps; and second, because of a poor spacing of raises, especially in the top-slice stopes, where, in general, they were spaced 25 ft. by 66 ft. (7.6 by 20.1 m.) centers. The average wage per laborer shift was $2.67 during the year. It was thought, however, that even under these conditions the men were not producing the tonnage that they should, so, with the consent of the management, the writer undertook to determine how the general efficiency of the underground shoveling could be improved. No predetermined plan for conducting these experiments was arranged because we had no definite ideas as to the scope of the work or the number of elements into which the investigation would resolve itself, before all of its phases could be determined. We were sure, however, that any work that would thoroughly cover the ground would have to be in the nature of a systematic time study, combined with a course of instruction in correct shoveling methods and adequate and intelligent supervision of the work. Two or three companies in the Southwest have done some work to determine the proper shovel to be used undcrground, but so far as is known the work has been limited to equipping certain parts of their mines with a particular type and size of shovel and thereafter watching the cost and efficiency records. In each case it seems to have been the shovel that held the 21-lb. (9.5-kg.) load that gave the bcst results. Excepting personal communications from these companies, the only data available on scientific shoveling are contained in F. W. Taylor's book, "The Principles of Scientific Management," and D. J. Haucr's article, in The Contractor for March 29, 1918, "A Hundred Hints for Shovelers." This paper discusses and draws conclusions from several thousand time-study readings, taken both on the surface and in the mines for nearly a year. A sufficient number of readings were taken on each factor in the problem for the plotting of curves of the performances and to obtain accurate indices of the work to be expected from this class of labor. The work is not as complete in all of its details as we would like to havc it, because we were forced to stop the work temporarily, owing to the numbcr of men going into the National service and our inability to get others who could make time studies. The results obtained so far, however, have been of such a startling nature that we have decided to submit them at this time, subject to future modification. It is hoped, also, that a free discussion of this paper will lead to a disclosure of any errors that may have becn embodied and offer some valuable suggestions for the conduct of future work.

Jan 1, 1920

By A. W. H. Morris, G. H. Laurie, J. N. Pratt

Using- galvanic cells of the form Sn(liq)/Sn" (LiCl-KC1-SnCl,)/Sn-Ag (alloy), measurements have been made of relative thermodynamic properties of the a, C, E, and liquid phases of the Ag-Sn alloy system. Partial heats of solution of the components in the liquid alloys lzave also been observed by direct cal-orimetric measurement in an isoperibol calorimeter. The thermodynanzic quantities are disczlssed in relation to structural and other properties and the existence of anomalous minor fluctuations in the partial heats and entropies of solution in liquid alloys is tentatively suggested. In the course of a recent electro motive-force study of the thermodynamic properties of Sn-Ag-Pd liquids,' some measurements were also performed on the Ag-Sn binary system. Most previous thermodynamic studies of this system have been concerned with the liquid state. Measurements confined to the limiting heat of solution of silver in liquid tin have been made by many calorimetric workers2 while high-temperature calorimetric measurements of the heats of formation of the full range of liquid alloys are reported in the early work of Kawakami~ (1323°K) and more recently by Wittig and Gehrin~(1248°K). Electromotive-force studies on liquid alloys have been made by Yanko, Drake, and Hovorka' (606" to 686°K; 86 to 99.4 at. pct Sn) and by Frantik and Mc Donald' (900°K; 30 to 90 at. pct Sn). The only known measurements on the solid state are of heats of formation of the a, £, and c phases; these values were obtained using tin-solution calorimetry, at 723"K, by Kleppa,~ whose investigation also yielded heats of formation of liquid alloys containing more than 64 at. pct Sn. The present experiments on the Ag-Sn alloys include a re-examination of the liquid phase and, because of the dearth of free-energy data for the solid state, attempted measurements on the a, c, and E phases. The principal new feature of electromotive-force results obtained for the liquid phase was an indication of anomalous fluctuations in the partial heats and entropies of solution of tin at certain compositions. However, since the values for these thermodynamic quantities were determined from the temperature coefficients of cell potentials, which are commonly subject to considerable error, confirmation by calorimetric measurements was considered desirable. A detailed investigation of the partial heats of solution of the components in the binary liquids was made using a liquid metal solution calorimeter. I) GALVANIC CELL STUDIES a) Experimental Details. Measurements were made, as a function of alloy composition and temperature, of the potentials of reversible galvanic cells of the form: ~n(liq)/~n++/~n-Ag (solid or liquid alloy) Details of the apparatus and experimental techniques have been given elsewhere.' so that a brief account will suffice here. Molten salt, 58 mole pct LiC1-42 mole pct KC1, containing small amounts (1 to 2 mole pct) of stannous chloride was used as the electrolyte. The salts were dehydrated by pre-electrolysis and vacuum -drying techniques. Cells were established under an argon atmosphere by immersing tin and alloy electrodes in the molten salt contained in a large silica tube, heated in a vertical resistance furnace. The tube was sealed at the top by a head plate provided with openings permitting the simultaneous insertion of six electrodes, a central thermocouple sheath, and connections to vacuum and argon lines. Temperatures were controlled to *0.2"C over prolonged periods, with maximum variation over the electrodes at any time of 0.l°C. Temperatures were measured with a standardized Pt/13 pct Rh-Pt couple. The electromotive force of this and the cell potentials were measured on a Cambridge Vernier potentiometer and short-period galvanometer. Alloys were prepared from Pass "S" tin (99.999 pct) and Johnson-Matthey high-purity silver (99.999 pct) by melting in evacuated silica capsules and quenching in cold water. For liquid phase experiments, pieces of the resulting alloys were remelted into prepared silica electrode units, while solid electrodes were prepared by remelting into 3-mm bore tubing, inserting a cleaned molybdenum lead wire, and quenching to produce uniform rods about 3 cm in length, with soundly attached leads. In all cases remelting was done under an argon atmosphere. The solid electrodes were subsequently annealed in evacu ated silica tubes for 14 days at about 20°C below the solidus and quenched. Analyses showed that these techniques produced uniform electrodes with no significant change from weighed out compositions. b) Results and Discussion. Measurements were made on about forty alloys in the solid and liquid states, over varying ranges of temperature between 550" and 1050°K. Stable, mutually consistent, and reproducible electromotive-force data were obtained with most liquid alloys and these are shown in Fig. 1. Investigations were extended below the liquidus tem-

Jan 1, 1967

By Emerson F. Heald

A systematic study was made of new and old data on chemical activities in Fe-Pt alloys at elevated ternperatuves. Experimental results may be expressed in terms of the excess free energy using Least-squares analysis of the data gave the following values for the constants: for the temperature range 1130° to 1350°C, and tentatively to 155O°C, B = -3.326564 and C = 0.221051; for the temperature range 650" to 850°C, B = -2.555690, C = 1.762735, and D =0.097196. In the study of iron-containing silicate systems, it is sometimes desirable to have a direct experimental measure of the activity of iron in the system. The well-known solubility of iron in platinum, often a headache in experimental work on iron compounds under reducing conditions, can be used to advantage in this respect. If the activity of iron in an Fe-Pt alloy in equilibrium with the silicate is known as a function of the composition of the alloy, chemical analysis of the alloy will give a knowledge of the activity of iron in all of the phases in the system. The present study was undertaken in order to elucidate the characteristics of Fe-Pt alloys as iron activity indicators. This work is intended to tie together some previous work, which may be summarized as follows. Larson and Chipman1 determined the activity of iron in Fe-Pt alloys at 1550°C by equilibrating platinum metal with calcium oxide-iron oxide-silica melts of known iron activity. Compositions of the resulting alloys were determined by chemical analysis. A similar study was carried out by Taylor and ~uan,' who worked at 1300°C. They brought the Fe-Pt alloys into equilibrium with iron oxide under conditions of known partial pressure of oxygen, and thus, from the work of Darken and ~urr~,~ conditions of known iron activity. Compositions were determined indirectly, by following the change in weight of the sample. Sundaresen et el* used the electromotive force of cells in which the alloy formed one electrode in order to measure the activity of iron in the alloy at 650" and 850°C. These temperatures were chosen to be above and below the first-order phase transition which takes place upon the ordering of Fe3Pt and the second-order transition which occurs upon the ordering of FePt3. EXPERIMENTAL 1) High Temperatures. The starting materials used were thin platinum foil, about 0.002 mm thick, and Fisher Certified reagent ferric oxide, Fez03, which had been heated for 24 hr at 1000°C. An intimate mixture of 80-mesh Fez03 and platinum platelets was placed in a thin platinum foil envelope. The latter was suspended from thin platinum wires in the hot zone of a vertical-tube, platinum-wound furnace of the type described by Muan and ~sborn.~ A capillary gas mixer similar to that used by Darken and Gurry3 was used to prepare a precisely known mixture of carbon dioxide and hydrogen, which was allowed to flow upward through the furnace tube. The partial pressure of oxygen in contact with the sample was thereby fixed at a value which was calculated from the charts prepared by porter? Temperatures were measured with a Pt-10 pct Rh-in-platinum thermocouple, which was calibrated using the melting points of gold (1062 .@C) and diopside, CaMgSizOB (1391.5"C). Temperature control was maintained to within i3"C with a Geophysical Laboratory proportional controller, using the furnace resistance as the sensing element. Samples were quenched by passing a small current through the platinum suspension wires, allowing the sample to drop into a bath of dibutyl phthalate at the bottom of the furnace tube. Prior to chemical analysis the samples were washed with acetone and dried. 2) Chemical Analysis. It proved possible, in almost all cases, to separate the Pt-Fe platelets physically from particles of iron oxide. The platelets were dissolved in a small volume of aqua regia, evaporated to dryness, and redissolved to 0.1 M HC1. In order to determine iron in the platinum alloy potentiometrically, it is necessary first to remove the platinum. A 10-cm column of Amberlite IR-120 cation exchange resin in the hydrogen form provided separation quickly and quantitatively: The mixture of iron and platinum in 0.1 M HC1 was added to the top of the column, and washed with about 100 ml of 0.1 M HC1. Under these conditions, the iron, principally in the form of cations such as FeC1" and FeCl;, is held quantitatively in the uppermost centimeter of the column. The platinum, in the form of anions such as PtC&- , is washed through without being adsorbed. After a qualitative test with stannous chloride indicated all of the platinum was removed, the iron was

Jan 1, 1968

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By Eric R. Morgan, J. C. Shyne

STRAIN aging is the name given to time-dependent changes which occur in the properties of cold-worked metals and alloys during storage. These changes are best observed through a study of mechanical properties, as illustrated in Fig. I for low-carbon steel. The effects of strain aging are usually regarded as being detrimental, particularly in deep-drawing steels. For example, an increase in yield strength and loss in ductility lead to buckling and tearing during drawing. At the same time the return of the yield point results in the formation of Luders bands or stretcher strains during the pressing operation. As a result of these effects many attempts have been made to eliminate strain aging from low-carbon steel. The problem still remains, however, because all known methods of preventing strain aging result in a more costly steel. The present work is an assessment of the situation in terms of theoretical, practical, and economic factors and suggests a new solution to the problem. Previous Work According to the Cottrell theory,' strain aging in a-iron may be regarded as the migration of interstitial atoms to free dislocations and the anchoring of dislocations by the resulting atmospheres. It may be concluded that the important factors which will govern the degree of strain aging are the diffusivity, the effective amount of interstitial element in solution, and the time of aging. The diffusivities and effective amounts of carbon and nitrogen in solution in low-carbon rimming steel are such that significant aging occurs in a few hours' storage at room temperature. Strain aging in deep-drawing steels cannot be controlled by controlling the time of aging because in commercial practice this is determined by economic factors concerned with inventories and may be several weeks. The diffusivity of nitrogen is twice that of carbon at room temperature but the diffusivities can be controlled by controlling the storage temperature. The retardation produced by only a 25 °C drop in temperature is significant but the cold storage of large steel inventories is an impractical solution to Table I. Analysis of Base Materials Alloy Pet C Yet 0 Pet N Vac 0.0037 0.052 0.0003 H 0.0044 0.013 0.0008 C 0.06 0.0014 0.0001 the problem. By far the most simple and effective ways to control strain aging are through control of the amount of carbon and nitrogen in solution. This may be effected through alloying, controlled precipitation, or by eliminating the carbon and nitrogen. Consider first the control of the amount of carbon in solution. The simplest approach would be alloy -ing in which strong carbide-forming elements are added. Examples of this approach are the additions of titanium' and niobium9 0 steel. These elements also combine with nitrogen and oxygen and when added in sufficient quantity result in a completely killed and non-aging steel. They are, however, impractical additions because they result in a costly steel. Carbon and nitrogen are often removed from iron on a laboratory scale by annealing in wet hydrogen, but because of cost this process has never been adopted on a commercial scale. In practice the amount of carbon in solution is controlled by the rate of cooling from the annealing temperature (710°C or 1310°F). In commercial box

Jan 1, 1958

By A. M. Gaudin, C. S. Chang

Adsorption was measured for barium ion and laurate radical, using radioactively marked agents, over wide range of concentrations. Laurate adsorbed in absence of barium fails to float. With barium, flotation-effective laurate coating needs not exceed 5 pct of monolayer. Barium adsorption then is several fold larger. No barium laurate coating is obtained. IN general, fatty acids or their alkali salts do not cause clean quartz to float. However, the presence of multivalent ions, such as the alkaline-earth metal ions and heavy-metal ions, can activate quartz and thus make it respond to soap flotation. The mechanism of activation and soap flotation of quartz has been studied.'-' The problem was attacked by making flotation tests rather than by careful adsorption measurements on suspensions of ground quartz in solutions containing the activator and the collector. Attempts have been made to determine the adsorption of barium ion and calcium ion on quartz. The results have only qualitative value as the analytical methods were not adequately precise. Artificial radioactivity and progress in radioactivity detection have introduced a new analytical tool, which can have a sensitivity several orders of magnitude greater than that of other methods."-" In the experimental work described in this paper the radioactive tracers, barium 140 and carbon 14, were employed. Lauric acid was synthesized, having a radioactive carbon atom and was used with Ba" to study the adsorption of barium and laurate ions from aqueous solution on ground quartz. Flotation tests, using the vacuum flotation technique,' were run in conjunction with the adsorption experiments. The object of this investigation was to understand better the reaction mechanism of barium activation and soap flotation of quartz. Methods and Materials Quartz Sample Preparation: Lumps of hand-picked quartz, washed free of stains, were reduced in size to —20 mesh in laboratory crushers. The product was boiled in concentrated hydrochloric acid to remove the abraded iron. The cleaned product then was ground dry in a laboratory porcelain mill, using siliceous pebbles, to pass through a 200 mesh screen. The ground product was deslimed by sedimentation at 37 microns. This —200 mesh +400 mesh material was subjected again to boiling with concentrated hydrochloric acid, followed by washing with distilled water and further desliming. The cycle was repeated until no trace of iron could be detected in the wash liquor. During the final washing, the pH of the wash water was checked to insure the complete removal of the acid from the mineral. The quartz then was rinsed with conductivity water. The resulting product was dried in a drying oven and stored in mason jars. The impurities (spectrographic) were as follows: Al, 0.01 to 0.001 pct; Li, Mg, Mn, Na, each less than 0.001 pct; Fe and Cu not detected. The specific surface of the quartz sample was determined by the krypton gas adsorption method.' The average of two measurements was 881 sq cm per g. The calculated specific surface for 37/74-micron quartz particles, using a surface factor of 1.96; is 900 sq cm per g. This is in good agreement with the measured value of 881 sq cm per g. Beta-Counting Method: The radioactive isotope of barium used in the experimental work was barium 140. It has a sufficiently long half-life, 12.8 days, emits high-energy beta particles (up to 1.0

Jan 1, 1953

By John T. Thorndyke

MOST important of the naturalcalcium silicates is the meta¬silicate, CaSi03, known as wollastonite, after W. H. Wollaston. A large deposit of this mineral was dis¬covered some seven years ago near Code Siding, Rademacher mining dis¬trict, Kern County, Calif., the deposit being some 7500 ft. long and of an average width of 300 ft. It consists of a series of small domes striking north¬erly and southerly and with a dip of 81 ° to the south. This deposit was opened up by a series of small quarries showing a potential tonnage of 12,000,¬000 tons, allowing of cheap mining and transportation, the Southern Pa¬cific R.R. spur track being one mile north of the workings. Numerous sam¬ples taken from different points on the deposit, tested by Mr. Brinker, of the California Testing Laboratories, Los Angeles, showed an average as fol¬lows: Per Cent Silica (SiO2) 47.12 Lime (CaO) 41.72 Magnesia (MgO) 2.72 Alkalies (R,0) Trace Iron (Fe.,O,) 1.60 whereas the theoretical composition of of wollastonite, as given by William Shirley Bayley, is as follows: Silica 51.75 Lime 45.25 The tonnage and purity of this de¬posit led to investigations into its com¬mercial development. Early work es¬tablished the fact that wollastonite was ideal for the manufacture of a tough, almost unbreakable, glass similar to Pyrex. It also established the fact that wollastonite was particularly adapted for use in the manufacture of mineral wool, towards which further research was then directed. Briefly, the prin¬cipal advantages were the substantially unvarying chemical composition of the naturally occurring mineral and its characteristic of being relatively flexi¬ble and highly resilient when fused into a glass. A mineral wool produced therefrom is thus not only of highly uniform composition and color but is most desirable because of the high mechanical strength and length of the individual fibers constituting the wool. It is well known that mineral wool may be prepared by melting a suitable charge of raw material and then intro¬ducing a stream of a suitable fluid, such as air or steam, into a stream of the molten raw material. By this means the molten material is blown into threads or fibers, which are collected in a suitable chamber similar to a tun¬nel, from which they are removed from time to time or continuously. Com¬mercial manufacture of mineral wool has been carried on for only about 50 years, but volcanoes, specifically Kilauea in the Hawaiian Islands, have

Jan 1, 1936

By H. M. Chance

Recent research work has shown that coal can be produced, at reasonable cost, from almost all coal-mining districts containing not more than 3 to 8 per cent. of ash. From coal so produced, an abundant supply of coke, suitable for blast-furnace operation, can be made containing from 12 down to 6 per cent. or less of ash. These statements apply broadly to the Appalachian coal belt, including most of the mining districts in Pennsylvania, Ohio, West Virginia, Kentucky, Tennessee, and Alabama. The exceptions will generally be found among those coals carrying a prohibitive percentage of sulfur. Any gravimetric heavy fluid method of separation will effect a reduction in the percentage of sulfur, but this reduction may not be sufficient to produce, from coal unfit for metallurgic use, a product that can be so used. When a large part of the sulfur is in the form known as "organic sulfur, "or is present as very finely disseminated and homogeneously distributed pyrite, possibly it cannot be eliminated from the low-ash coal produced. When the sulfur exists as pyrite in distinct layers, bands, or nodules, or when it is finely disseminated but is irregularly distributed, often a low-ash coal low enough in sulfur to make good metallurgic coke can be produced from relatively impure coals. It has generally been assumed that the quality of coke on which blast furnaces must be operated depends on the geographic location of the furnace, and that the grade of coke on which a blast furnace must operate is that produced from the best coal obtainable by careful mining; or if the coal is prepared by washing, hand picking, or other means by which the foreign impurities are removed, that the grade of coke on which the furnace must operate depends on what has been termed the "inherent ash" of the particular coal. The term "inherent ash " is generally understood to mean the percentage of ash present after all removable (free) impurities, slate, fireclay, high-ash bony coal, and pyrite have been removed, and is usually applied to the percentage of ash present in run-of-mine coal from any mine after these impurities have been removed. Perfect washing, or perfect preparation, is understood to be attained when the percentage of ash in the washed coal is reduced to the percentage of inherent ash; that is, of ash that cannot be removed by the washing processes in common use. Wash-

Jan 1, 1924

By A. M. Skov, L. F. Elkins

First response to large-scale water flooding in the fractured very low permeability Spraberry sand has led to a new unique cyclic operation. Capacity water injection is used to restore reservoir pressure. This is followed by marly months production without water irzjection and the cycle repeated. Expansion of the oil, rock and water during pressure decline expels part of the fluids but capillary forces hold much of the injected water in the rock. At least with reservoir pressure restored and with partial water flood development, field performance has proved this cyclic operation is capable of producing oil from the nzatrix rock at least 50 per cent faster and with lower water percentage than is imbibition of water at stable reservoir pressure. INTRODUCTION The Spraberry Field of West Texas presents unusual problems for both primary production and water flooding. Extensive interconnected vertical fractures in the fractional-md sandstone permitted recovery of oil on 160-acre well spacing, but they made capillary end effects dominant. Primary recovery by solution gas drive is less than 10 per cent of oil in place. The concept of displacement of oil from the sand matrix by capillary irnbibition of water has led to field techniques which promise greatly increased oil recovery. Free exchange of laboratory research, reservoir information and results of field pilot tests among the various companies has been very important in development of this technology. Five units covering a total of 170,000 acres have been formed for water flooding, and 10 other areas covering an additional 175,500 acres are in various stages of unitization. Part of the Driver Unit reaching fillup first has demonstrated very unusual waterflood behavior and indicated numerous operating problems that will develop within and among the various units. SPRABERRY ROCK AND PRIMARY PERFORMANCE The Spraberry, discovered in February, 1949, is a 1,000-ft section of sandstones, shales and limestones with two main oil productive members: a 10-15 ft sand near the top and a 10-15 ft sand near the base. In part of the field some thinner intermediate sands are oil productive, and others are water bearing. All sands have permeabilities of 1 md or less and porosities of 8-15 per cent. Ordinary core analysis and electric and radiation logs are ineffective in differentiating between oil productive and nonprcductive sands. Sands capable of containing producible oil are best identified by mercury injection capillary pressure measurement and, in some cases, by core water saturation. About 3,500 wells have been drilled in the 500,000-acre trend. Vertical fractures were observed in practically all Spraberry cores. Continuity and interconnection of fractures were confirmed by pressure interference among wells during early development.' Major fractures trend northeast-southwest as indicated by oriented cores and confirmed by five fluid injection tests, by analysis of the pressure transients observed during development,''' and by three interference tests in the Driver Unit Water Flood reported herein. Fracture spac- ing probably averages inches to a few feet. Spraberry wells typically produced 100-400 BOPD initially after hydrauLic fracture treatments. By 1962 oil production had declined to an average of 12 bbl/well/day, near the economic Limits of operation. Reservoir pressure had declined from 2,300 psi initially in the Upper Spraberry and 2,500 psi in the Lower Spraberry to 500-1,000 psi. Partial closing of the fractures with declining reservoir pressure is believed to be the cause of such low oil production rates at these relatively high reservoir pressures. Cumulative recovery of 208 million bbl of oil is 80 to 90 per cent of that recoverable by primary means. Performance of the entire reservoir is summarized in Fig. 1. IMBIBITION WATER FLOODING By 1952 reservoir performance indicated low primary recoveries. Most engineers, expecting serious channeling of injected fluids through the fractures, held little hope for secondary recovery. With its extensive background of research on the fundamentals of fluid flow within reservoir rocks, Atlantic's Research and Development Division on short notice in 1952 conceived that displacement of oil by capillary imbibition of water into the rock might significantly increase Spraberry recovery. Laboratory data reported by Brownscombe and Dyes scaled to probable reservoir conditions showed potential waterflood recovery equal to or greater than primary recovery with a 10-15 year flood life.= A pilot test using three 40-acre injection wells, one central producing well and 18 surrounding observation wells demonstrated technical feasibility of the process. Injection of 1.5 million bbl of water from November 1952 to August 1955 proved water entered the rock and displaced oil

By F. H. Willcox

In Bessemer-steel practice, air is blown through a bath of iron, or projected strongly upon its surface to burn out silicon, manganese, and cafbon. Toward the end of the blow, when the iron is not protected from oxidation by these elements and the excess of air becomes great, there is oxidation of the iron. In open-hearth practice, the same difficulty is experienced with dissolved gas and oxides in the product, though not to as great or severe a degree as in the Bessemer process because the oxidizing conditions grow less severe as the end of the heat is approached, and if the bath is allowed to boil for a time it undoubtedly frees itself from a large part of the gas and oxides which have been absorbed in the earlier part of the process. Basic open-hearth steel is usually assumed to contain a larger proportion of oxides than acid open-hearth steel, but it may be said that all steel, Besserner and open-hearth, contains more or less oxide of iron dissolved in the fluid metal at the end of the "blow" or "heat." That certain metals are solvents for their respective oxides has been shown, in the case of copper, by Heyn, and, in the case of iron, by Law. It is indicated that the solubility of iron oxide in iron increases with the purity and temperature of the metal. This confirms what is observed and known by operating men, and these observations may be summarized as follows: 1. Cast iron. is rarely subject to oxidation, as is logical from its composition. 2. Normal steel, unless deoxidizers are added, contains blow holes. 3. Steel known to be oxidized is full of blow holes. 4. The addition of deoxidizers prevents, to a greater or less degree, the formation of blow holes in normal steel. With these observations in mind, it is logical to deduce that the cause of blow holes lies in part in the presence of dissolved oxide of iron in the molten steel and its consequent reaction with the carbon of recarburizers, when these are added, to form gases. (Another factor in the origin of blow holes is, of course, the solubility of gases themselves in the steel and

Jan 1, 1917

By C. W. Burrows

The burden a man can endure depends on its magnitude and the number of times it is applied, as well as on many other factors. The resisting power of steel likewise is dependent on many factors. The maximum load it can support indefinitely is much less than its possible momentary burden. A light load straining the metal far within its elastic limit, if repeated indefinitely, ruptures the metal. The magnitude of the stresses that may be alternately applied and removed without rupturing the material depends on the number of repetitions of the cycle; the intervening periods of rest; the thermal, electric, and magnetic conditions, as well as the presence of secondary streessses. While we are unable to formulate the law between the magnitude of repeated stresses necessary to produce rupture and the length of time during which these alternating stresses may be applied before rupture, my experience is that the time increases as the magnitude of the force decreases, according to a law which! to a first approximation, is exponential. In other words, F = Ce-t where F= magnitude of alternating stresses; t= time for which stresses are continued; C = constant, which depends on the conditions under which the operations are carried out. It is quite probable that the same type of law holds for the magnitude of a continuous force and its duration. When a rod of steel is subjected to the blows of a drilling hammer several things happen. First, one end is struck by the hammer and the other end is driven into the rock, thus causing a bodily displacement of the entire material of the steel drill. The greatest stresses involved in this bodily displacement are located at the two ends of the steel and manifest themselves by the distortion of these parts. Second, after the blow has been delivered, the steel drill, due partly to its own resiliency and partly to the resiliency of the rock, experiences a vibratory motion as a whole, this motion is quite similar to the bouncing of a rubber ball thrown violently upon a smooth pavement. Third, the free vibration of the drill is determined only by its own natural period of vibration. This motion involves all the characteristics of any vibrating body emitting sound. Certain elements of the rod will experience alternations of condensation and rarefaction and, in these regions, the individual steel

Jan 1, 1922

By Walter O. Snelling

In the course of some experiments more than five years ago, made for a totally different purpose than the investigation of the oil used, I placed a small quantity of a transparent yellow lubricating oil in a bomb-like vessel and heated it to a relatively high temperature. At the end of the experiment I removed the oil from the vessel and was amazed to find that instead of bearing any resemblance to the oil which I had put in, it now had the appearance of ordinary crude oil. The green color by reflected light and the rich red-brown by transmitted light were so unmistakable as to at once lead to further investigation. I subjected the material to fractional distillation, and the surprise which I experienced at the appearance of the oil, changed to amazement when I found that it yielded, on distillation, 15 per cent. of gasoline and 30 per cent. of burning oil, and that its constitution resembled crude oil quite as much as did its appearance. Furthermore, the gasoline and kerosene distillates which it yielded were of a clear water-white color, entirely without treatment with acid or alkali, and were entirely free from the odor familiar in "cracked" petroleum distillates. The result of this experiment was quite too remarkable to be credited without further confirmation, and I at once filled the vessel with some of the same oil that I had used before, and again heated to about the same temperature that I had previously used, and for the same period of time. Upon opening the vessel and removing the contents I found, not the material resembling crude oil that I had obtained before, but apparently only the same oil that I had put in, somewhat darkened in color, but nevertheless far different in appearance from the material obtained in the previous experiment. Evidently some condition existed in the first experiment that had not existed in the second test, and here began a series of tests in which I sought by the change of one variable after another to arrive at the identical conditions which must have existed in the first experiment. Only the fact that the bottle of heavy oil used in the first test was still in its place,

Jan 1, 1915

By G. S. Rice

Some form of longwall mining is generally used in Continental Europe; also in Great Britain where the coal is weak and friable, or the coal bed provides material for pack walls and filling, or where the bottom is soft and squeezes up easily, or the roof is pliable, or the bed is thin and brushing provides building material, or the thick multiple seams are mined in layers, such as the 24-ft.seam at Weymss, Scotland, or the 10-yd. pitching bed near Coventry, England. Pillar methods have been retained in British fields where the coal beds are from 5 to 9 ft. (1.5 to 2.7 m.) thick, and free from thick partings or binders or without draw slate, which would provide waste rock for pack walls, or where the roof is hard and requires shooting to bring down, and also the bottom or floor is comparatively hard. The room-and-pillar system, by which probably 95 per cent. of the coal of the United States is produced, is now found in only a few mines in Wales, where it is known as the pillar and (single) stall method. The American room-and-pillar system is not equivalent to the bord-and-pillar or stoop-and-room system. The essential difference between the bord-and-pillar and the average American room-and-pillar system is probably due to natural conditions. The majority of the coal mines in the United States have a depth of less than 700 ft. (213 m.). The bulk of the coal mined in Europe comes from a depth of more than 1200 ft., while the deepest mines in Great Britain, Belgium, and France reach 3500 to 4000 ft. In deep workings wide spans are impracticable, even with the use of abundant timber; accordingly, as the mines in the United States become deeper the rooms will become narrower and the pillars thicker, and the bulk of the coal will be extracted on the retreat. It is generally conceded, without reference to the cost of production, that the larger the pillars left on the first mining, the more thoroughly can the coal be extracted. In Europe complete extraction is generally compelled either by the lessors or by the governments; whereas in this country it has been more largely a question of competitive cost of production, or the support of the surface in the flat farming districts of the

Jan 1, 1922

By D. J. Rose, W. M. Armstrong, A. C. D. Chaklader

The wetiability of single crystals of MgO by specimens of vacuum-cast iron was studied using the sessile drop technique in vacuo at 1550ºC. Formation of FeO at the liquid-vapor interface caused the contact angle (6) to decrease from 117 to 65 deg during the first minute. After cooling, all specimens possessed a peculiar annular interfacial deposit of Fe,O,. Within the annulus the interface showed no sign of chemical attack. Chemical reaction occurred where the iron was alloyed with Ti, V, Cr, Nb(Cb), Ta, cmd Zr. Vnriation of 6 with alloy concentration was studied. Although vanadium md chromium improved the wettability of MgO by iron, the effect of Zr, Ti, Nb, and Ta was indeterminable because the 8 derived from sessile drop considerations was that of the metal against a restrictive peripheral volume of liquid oxide wetting the substrate. INTEREST in the nature of metal-ceramic interactions has been stimulated by progressive development of metal-ceramic combinations. One of the more valuable methods used for bond investigation is the sessile drop technique. Recent attempts to improve wettability through solute additions to the drop have revealed that the solute may a) react with the oxide creating new compounds at the solid-liquid interface, b) adsorb at the interface in a monolayer formation, or c) distribute throughout the drop uniformly causing no wettability variation. This work, part m in a series1,2 of investigations of interface reactions between metals and ceramics, embraces a study of the Fe-MgO system. MgO possesses a large negative free energy of formation (-173 kcal per g mole 0, at 1550ºC) compared to FeO at this temperature (-73 kcal per g mole 02). Hence the electronegativity difference between the drop and substrate allows selection from an extensive group of metal solutes with intermediate electronegativity differences that would, in the absence of chemical reactions, be expected to adsorb pre- ferentially at the solid-liquid interface. However, the high oxygen pressure of MgO in vacuo creates an oxidation environment which influences the solute behavior. Recent studies of the Fe-MgO systemJ74 have been restricted by chemical reactions that obscured observations. In view of the current interest in liquid-phase sintering of metal-ceramic combinations under partial oxidizing conditions,5 a more comprehensive study of the Fe-MgO system seemed beneficial. EXPERIMENTAL PROCEDURE 1) Specimen Preparation. Optical-grade MgO single crystals and Ferrovac vacuum-cast iron were used in all experiments. A spectrographic analysis of the iron indicated 0.008 C, 0.05 V, 0.005 Mo, 0.01 Ti, 0.002 S, 0.01 Cr, 0.001 Mg, 0.01 Si, 0.003 A1 (wt pct). The MgO crystals were cleaved along (100) planes into plates approximately 20 by 20 by 1 mm. Following annealing in vactto at 1100°C for 3 hr, surface irregularities were removed by a chemical etch in phosphoric acid at 100°C. The iron rod was machined into small cylinders approximately 0.250 in. in diam and length and these were carefully cleaned in organic and acidic solutions to remove surface impurities. All specimens were weighed to the nearest 0.1 mg. 2) Apparatus. The apparatus described in detail by previous authors1,2 was modified for this work. A Polaroid Land Camera was incorporated into the optical system so that drop measurements at ten-second intervals after melting were possible with ultra-high-speed self-develop ing film. 3) Procedure. The iron cylinders were placed upright on the MgO plates and positioned in the molybdenum susceptor. After furnace assembly the system was pumped down to a vacuum of 1 µ and flushed with H2 at 800°C. The system was again evacuated to 5 x 10-5 mm of mercury and the temperature raised to 1550°C within 2 min. The molten drops were photographed at appropriate time intervals. TWO min after melting the iron vapor pressure caused gas discharge, or corona, within the tube. The specimens were then slowly cooled to room temperature, sectioned and examined metallographi-cally. X-ray identification of interfacial reaction products was attempted by the powder diffraction technique. Alloying elements (Ti, V, Cr, Zr, Ta, Nb) were added to the iron in various concentrations up

Jan 1, 1963

By C. A. Heiland

A. INTRODUCTION (C. A. HEILAND) I. PRINCIPLES OF TEMPERATURE COMPENSATION IN MAGNETIC INSTRUMENTS The principle underlying the majority of magnetic intensity variom-eters is a comparison of the force to be measured with another force of known magnitude. The known force may be (a) of a magnetic nature, such as magnetic fields produced by magnets or coils, or (b) of a mechan-ical nature, such as (1) the elastic forces of wires, or (2) the force of gravity, such as employed in bifilar magnetometers and magnetic balances. In instruments of such type, usually a magnetic system is employed, free to move about either a horizontal or vertical axis, on some sort of a suspension. If the earth's magnetic field alone were present, such a system would adjust itself into the direction of the field or that of its components. Owing to the simultaneous action of the comparison force, however, the magnetic needle assumes a position that differs from the direction of the magnetic force; for all such instruments, the angle of deflection a is given by tan a = F/X, where F is the known and X the unknown earth magnetic force component. In other words, the magnetic system merely serves as an "indicator" for the position of balance of the two forces. Considering the matter from this point of view, it is not immediately obvious why the temperature of such a magnetic system should modify the results. In magnetic instruments, we may distinguish two different effects of temperature: (1) a magnetic effect and (2) a mechanical effect. The first is due to the fact that the magnetic moment of a magnet drops with an increase in temperature. This drop is characterized by the temperature coefficient of the magnetic moment µ (see equation 1). The second effect is due to the change in the .torsion of suspension wires with temperature or to the expansion of lever arms of masses acting on magnetic balances.

Jan 1, 1932

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

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

Jan 1, 1970

By R. J. Schaefer, M. E. Glicksman

Direct, in situ observation of metallic alloys during solidification reveals that in some systems crystal multiplication occurs by means of a dendrite remelt-ing process, without the necessity of independent nu-cleation events. The solidification is observed on optically clean surfaces of supercooled molten alloys. In one system (Sn-3 wt pct Bi) , a fine-grained equi-axed structure is produced by the complete disintegration, via remelting, of transient initial dendrites. In contrast, several other metallic systems show little or no evidence of remelting activity. The behavior of these metallic systems is consistent with that expected on the basis of published observations of dendrite remelting in transparent organic alloy systems. It is concluded that dendrite remelting is an important crystal multiplication process in some metallic alloys, but is velatively unimportant in some other alloys. The detachment of dendrite branches from the primary stem by a remelting process has been observed by Jackson, Hunt, Uhlmann, and seward1 during the solidification of some transparent organic alloy systems. The branches released by this remelting process can drift free of the primary stem and serve as seeds for the formation of numerous independent crystals. This proliferation of new crystals does not require repeated independent nucleation events, but only modification of the initial solidification structure. The mechanism of dendrite remelting, as described by Jackson et a1.1 and by Tiller and O''Hara,2 is dependent on the transport of both heat and solute and is, therefore, expected to operate only in alloys, and not in pure substances. It was found in the transparent organic alloy systems that remelting occurred primarily in the constricted regions near the base of dendrite branches, where the branches had grown through the solute-rich liquid layer surrounding the primary dendrite stem. It was suggested that impure solid had formed in these constricted regions at a relatively low temperature and had later become unstable as further solidification of purer material raised the temperature. Jackson et al. proposed that the equiaxed zone of metal alloy castings originates from a similar remelting process, and they demonstrated the operation of this mechanism in "ingots" poured from saturated salt solutions. Although these substances were especially selected to show solidification behavior similar to that of metals,3 the remelting mechanism has, until now, been subject to the objection that its operation has not been directly observed in a metallic system. Considering the fact that thermal properties such as diffusivity may differ by as much as two or three orders of magnitude between metals and organic compounds, this objection was considered to be possibly serious. A method has now been developed by which it is possible to make direct optical observations of metals during solidification. This method has revealed transient solidification processes which would not be detected by metallographic examination of totally solidified specimens. In particular, a grain-refinement process in a metallic alloy has been observed to be a direct consequence of the total disintegration of an initial dendritic structure. The influence of an initial, transient solidification structure on the final solidification structure is demonstrated here for the first time in a metallic system. I) EXPERIMENTAL The technique of using a transparent flux to maintain an optically clean metal surface during solidification has been described by us elsewhere.* The

Jan 1, 1968

By Arthur Knapp

No oil territory in the world has been so rich in large producing wells, in a comparatively small area, as the Baku field. Particularly is this true of the Bibi Eibat field, which formerly produced millions of "poods," of " gusher," or as it is called in Russia, " fountain " oil. The Bibi Eibat and Balachany fields have been exhausted of gas and ruined by water, but the Surachany and Benegadi fields are still fountain territories and many outlying districts that have only been prospected produce rich fountains. The method of controlling fountains, or gushers, is the result of growth, along with the Russian system of drilling, where large diameters and riveted casing have been in vogue. The screw casing is seldom used except to exclude water. Formerly the method of finishing wells and the condition of the casing at the top of the well would not permit the use of gates, manifolds, and connections as is standard elsewhere. The life of the flowing wells is very short, particularly those 10 in. (25 cm.) or more in diameter, which produce large quantities of sand and often flow for but a few days and are then a complete loss. More than 1,000,000 poods in 24 hr. have been claimed in several instances, but in no case was the flow for more than a few days. The oil sands of this district are free uncemented sands and vary in thickness from paper thin to a maximum of 10 ft. (3 m.). The sands are interlaid with strata of soft clay. In spite of this, the practice has been to drill into such sands and produce from the open hole without screen or liners. Sometimes the casing is set below the oil sand but in this case holes from 2 ½ to 3 in. in diameter are drilled opposite the oil sand, which would not have the effect of a screen.

Jan 1, 1920

Jan 1, 1925