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By A. F. Crawley

The density and viscosity of 1iquid thallium have been measured by absolute methods to temperatures of about 200° and 150°C, respectively, above the melting point. These new data reported, especially density data, do not closely confirm previous work. Density p, in g per cu Cm, is shown to vary linearly with temperaluve t, in °C, according to the equation p = 11.658 - 1.439 X l0-3t. The viscosity data obey the well-known Andrade equation nv1/3 = A exp C/vT , the constants A and C for thallium having values of 2.19 x A and 79.648, respectively. This paper reports some new data for the density and viscosity .of liquid thallium. Measurements of these fundamental physical properties were undertaken as part of a continuing research program at the Mines Branch, Department of Energy, Mines and Resources, Ottawa. Canada. A literature search has revealed that data are so scarce that there could not be a consensus on the true values of the density and viscosity of liquid thallium. To be more specific, there exists only one set of viscosity data' and only two acceptable sets of density data,273 one of which is limited in scope.3 In Liquid Metals Handbook,3 another density study is reported but indications of impurities in the thallium render the results suspect. In this situation, further careful experimentation was required to realize the true density and viscosity of thallium. EXPERIMENTAL METHODS Density. Densities were determined using a graphite pycnometer. The technique and its accuracy have been discussed in earlier papers.4'5 It is considered that experimental data can be obtained which are accurate within +0.05 pct, all sources of random and systematic errors having been evaluated. Density results for thallium were identical whether measured under an atmosphere of argon or a vacuum of 5 x 10-6 torr and, for the most part, the argon atmosphere was used. Viscosity. Viscosity measurements were made in an oscillational viscosimeter by an absolute method—the liquid metal being held in a closed graphite cylinder. Design and operation of the apparatus, constructed in this laboratory, have previously been discussed.6 For thallium, runs were made under a vacuum of about 2 x 10-6 torr. To evaluate viscosity coefficients from the various experimental parameters, the mathematical analysis of Roscoe7 was used. Measurements of the necessary parameters and the accuracy of these measurements have also been discussed.6 The cylinder dimensions were corrected for the anisotropic expansion of graphite, as discussed for density measurements.4,5 It is well-known that thallium oxidizes rapidly and hence a newly machined surface quickly tarnishes in air. The oxide film, however. is nonadherent and is easily removed by rubbing or by solution in water. Hence, immediately before use, both density and viscosity charges were immersed in water, wiped dry, and quickly transferred to the apparatus which was then rapidly evacuated. Specimens removed after determinations were only slightly tarnished and there was no other evidence that tarnishing affected the results. For example, the sharpness of the specimen edges from the containing vessels indicated complete filling by the liquid metal. Thallium of 99.999 pct purity was used in this investigation. Because of its high toxicity care was exercised in handling this material. For example, the melting procedure to prepare machinable ingots was carried out in an open, well-ventilated area, while protective gloves were always worn when handling the solid metal. RESULTS AND DISCUSSION Density. Measurements were made over a tempera-ture range of about 200°C above the melting point. The results are listed in Table I and plotted in Fig. 1. From the graph it is evident that the relation between density and temperature is linear. Such a relation has been observed before in this program for other metals and alloys475 and elsewhere by other workers. A least-squares analysis of experimental data gives the equation: pT1 = 11.658 - 1.439 x 10-3t where p = density in g per cu cm and t = temperature in "C. In Fig. 1, together with the present results, the data of Schneider and Heymer2 in the corresponding temperature range have also been plotted. Evidently, the two sets of data do not agree well, the results of Schneider and Heymer being about 0.6 pct higher. Viscosity. Viscosity data were obtained from the melting point, 303.5°C, up to 457.5"C. The data are listed in Table I and in Fig. 2 the plot of these results demonstrates a smooth curvilinear relation between

Jan 1, 1969

By W. G. Sinclair

The North Texas district incorporated in this paper corresponds with the Railroad Commission's District No. 9, and includes the counties of Archer, Baylor, Clay, Cooke, Foard, Hardeman, Jack, Knox, Montague, Wichita, Wilbarger, and Young.† Table I,Oil and Gas Production in North Texas District, has been changed to conform with the nomenclature of pools designated by the Commission in order to facilitate compilation of the data, since most of the companies operating in the area are coming more and more to recognize one central authority in the matter of naming each new oil pool. No effort is being made to discuss the structural characteristics of the region, since it is generally known by oil men that most of the oil and gas comes from Pennsyl-vanian, with some of less importance from the Mississippian and Ordovician. Development during 1944 There were 1550 wells drilled during 1944, an increase of 450. Of this number, 677 were completed as oil wells, and 11 as gassers. Production increased 1,505,025 bbl., making the year's total 43,172,005 bbl. of oil having an average gravity of 40". Development generally, however, was somewhat disappointing. The 47 new pools, extensions, or new pay horizons in old fields, had a combined initial production of only 19,146 bbl. It is estimated that these wells added approximately 10,000,000 bbl. to the reserves. The largest single addition to the reserves was in the Caddo conglomerate in the Hildreth pool, Montague County. During the year, 66 wells were completed as the result of three extensions, I to 136 miles west, northwest and north of the field. Young, Archer, and Clay were the most active counties. Eleven new potential - oil fields were developed in Young County, nine in Archer and nine in Clay. Outlook for 1945 In spite of the fact that exploration as a whole was disappointing in 1944, prospects for increased development are bright for 1945. At the close of last year, 2.1 geophysical crews were operating in the district, which, together with the Ohio Oil Company's No. I W. R. Ross, a wildcat Strawn discovery in King County, 1 1/2 miles beyond the west boundary of district 9, stimulated a lease play extending over four counties. Two of them, viz., Foard and Knox, are in the area incorporated in this report. Acknowledgments The writer is indebted to Mr. C. W. Hanley, Zone Agent of the North Texas District, and Mr. William M. Lourcey, head of the Land, Leasing and Scouting Department for the Gulf Oil Corporation, both of Fort Worth, Texas, for permission to prepare this paper.

Jan 1, 1945

By R. I. Jaffee, E. S. Bartlett, D. N. Williams

The oxidation resistance and fabricability of molybdenum powder-metallurgy alloys containing up to 20 wt pct nickel in the form of a fine dispersion were studied. The effects of dispersion distribution and of amount and type (pure nickel or nickel compounds) of additive were considered. A definite improvement in oxidation resistance was observed, but the amount of improvement fell far short of requirements for an oxidation-resistant alloy. Fabricability by hot-rolling was limited. INVESTIGATIONS at Ohio State university1 and Battelle Memorial institute2 have indicated that the attainment of a truly oxidation-resistant molybdenum-base alloy for high-temperature service, with the coincident retention of high-temperature strength and toughness, will be a difficult, if not impossible, feat. Among the most promising alloy systems studied was the molybdenum-nickel system shown in Fig. 1. Alloys in this system show good oxidation resistance at temperatures well above the normal melting point of molybdenum trioxide because of the regenerative formation of protective nickel-molyb-date (NiMoO4) on the surface of the alloy during exposure at high temperatures. Unfortunately, the required alloy content to obtain oxidation resistant molybdenum-nickel alloys far exceeds the limits of the narrow terminal solid-solution boundary, and closely approaches the peri-tectic composition involving the brittle intermetal-lic compound, MoNi. Because of the peritectic reaction, fusion alloys are characteristically brittle, since the MoNi phase, being the last to form, tends to occur as a continuous grain-boundary network around each molybdenum grain. An added problem with this system is that the protective nickel-molybdate layer formed at high temperatures is unstable, undergoing one or more allotropic modifications upon cooling. The volume changes associated with this modification during cooling are such as to cause violent expulsion of the protective molybdate coating from the surface of the piece. This is, of course, quite detrimental in material exposed to cyclic temperature during service. The research reported here resulted from an attempt to overcome the aforementioned problems associated with the molybdenum-nickel alloys primarily by controlling the amount, size, and location of the MoNi phase. By using powder-metallurgy techniques of alloy preparation and sintering the blended molybdenum-nickel powder mixtures at a temperature below the peritectic reaction temperature, molybdenum-nickel alloys with a randomly dispersed MoNi phase were produced. MATERIALS The molybdenum powder used in the preparation of alloys for this study was commercial hydrogen reduced, minus 325-mesh (Tyler) material. Master alloys, by which nickel was added, consisted of elemental carbonyl nickel powder (12 average particle size), an alloy of 50 wt pct Ni-50 wt pct Cr, and compounds of MoNi, Ni,Si, and Ni2B. The nickel-chromium powder was prepared by filing a vacuum-arc-melted ingot, separating impurities magnetically, and screening to minus 200-mesh. The MoNi powder was prepared by pulverizing a hydrogen-sintered powder-metallurgy compact to minus 325-mesh material. Further sizing of this powder for study of effects of dispersion distribution was accomplished by air classification of the minus 325-mesh powder. The Ni2Si and Ni2B powders were prepared by crushing vacuum-sintered powder-metallurgy compacts to minus 200-mesh material. EXPERIMENTAL PROCEDURE Specimen Preparation—The general procedure followed in the preparation of alloys for testing is described as follows: 1) Blending. Either hand-blending of the powders in a ceramic mortar and pestle for X 1/2 or mechanical blending was used. Hand-blending seemed preferable for optimum homogeneity. 2) Compacting. Most of the blended powders were pressed to green compacts at pressures of 15 tons per sq in. in a single-action die, although some were pressed at 80 tons per sq in. A 1 X 11/4 X 1/4-in. green compact was the standard size for oxidation test material, and 7 X 1/2 X 1/4-in. compacts were used for fabricability test specimens. 3) Sintering. All green compacts were sinteredat

Jan 1, 1959

By AIME AIME

THE annual session for the election of officers and transaction of other official business of the Institute, which must be held, in accordance with the By-Laws, in New York on the third Tuesday in February, was the only session scheduled for the morning of Feb. 19. Many members gathered in the auditorium at 10 o'clock, and President George Otis Smith presided. He said that his report was best set forth in the reports of the other officers and committees, which were avail-able in printed form. Productive activity had characterized the Institute's year and a number of new ventures had been successful. He felt that he had "rattled around" in the office of president, as he had traveled some 39,000 miles during the year in visiting the various Sections, having visited everyone that had held a meeting during his term of office. He spoke of the educational effect on a president of these broad contacts and suggested that a three-year course would be even more enlightening than one.

Jan 1, 1929

By P. Barnes

Some statements have already been made to the Institute in reference to the cost of other departments of the above-named works, and some details have been given in tabular form.* For the purpose of the present paper it may be sufficient to say that this converting works is made up of three buildings, a cupolahouse, an engine-house, and a converting-house. The machinery and fixtures comprise two blowing-engines, two pressure-pumps, two five-ton converters, five hydraulic cranes, three pig-iron cupolas, four spiegel cupolas, two lifts for the cupolas, together with the usual arrangements of smaller parts. Every effort was made in the construction to combine efficiency of operation with durability, and the general course of the operation of the works during two and a half years seems to warrant the belief that the large outlay has been fully justified. * In the accompanying tabular statement all items on vouchers less than ten dollars, and all freight items have been omitted.

Jan 1, 1879

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By T. Kilner, A. Plumtree

DURING an investigation of electro-deposited silver structures, samples were prepared for metallographic examination by cold mounting in plastic, grinding on successive grades of emery paper down to 3/0, and chemically polishing by swabbing using the chromic acid solution described by Gilpin and Worzala.1 Attempts to etch these samples using the standard solutions described for silver (e.g., 5 pet KCN-5 pet Na2S2O8, H2O2-NH4OH, and various potassium dichro-mate solutions) all failed to give good results due to staining of the samples and to rapid etching. The staining was caused by the chromic acid polishing solution being trapped in small fissures between the sample and the mounting plastic, and also in small fissures in the sample itself. To overcome these difficulties, an etchant was developed which prevented staining at the same time as it slowly etched the sample. This resulted in a very clean, crisply etched surface as shown in Figs. 1 and 2. This etch consisted of 10 ml of orthophosphoric acid, 10 ml of distilled water, and 2 drops of the polishing solution noted above,' which is made by mixing 100 ml of saturated CrO3 solution, 45 ml of 10 pet HC1 solution, and 800 ml of distilled water. The etching procedure involved taking the final polished sample, either immersing or swabbing in the etchant for a period of 1 to 2 min, rinsing as quickly as possible in distilled water, alcohol, and ethyl ether in that order, and then immediately drying. This etch is easily controlled due to its slow rate of etching, and produces samples with clean, sharp surfaces. Pits due to overetching produced varying contrast effects when viewed under polarized light, and are therefore obviously useful for revealing many structural details within the sample. Another effect of overetching was to produce a height varia-

Jan 1, 1968

By Frank T. Sisco

The discovery of phosphorous is usually credited to the German alchemist Brand, in 1669, and the element was rediscovered the next year by Boyle in England. IT was more than 100 years later, however, before its presence was detected in high-carbon iron produced in early blast furnaces. In 1781 the German chemist Meyer published the results of his investigation on the ?white earth? that he had found in cast iron made from bog ores. This white earth was metallic in appearance, it was extremely brittle, it was readily fusible, and it was not attracted by magnet. Meyer noted that cast iron containing this white earth was more fusible than other cast iron, and he was sure that he had discovered a new metal ? for which he proposed the name Wassereisen, or the Latin term Hydrosiderum. Two years later the distinguished Swedish Chemist Bergmann made the same discovery, finding a ?white calx? in cast iron, which he also mistakenly considered to be a new metal, and for which he proposed the Siderum.

Jan 1, 1944

JOHN.B. HASTINGS, Los Angeles, Cal. (written discussion).-This paper reminds me that when I had an option on a Nevada mine, where the only orebodies assayed $4 gold, I went to San Francisco to learn the cost of putting broken ore in a 25-ft, vein on the mine cars, and sought Mr. Alfred Wartenweiler, who said "There is not a mine in California that can tell what it costs to move ore in the stopes." When building small mills in the mountains, and with only 30 or 40 employees, by entering in a log at night the work performed by each man, I have been able to plot the costs with the accuracy shown in this paper, and very good discipline it is. Cost of new construction and repairs is carefully kept by most companies, and is compiled after completion; probably the outlay of labor and material in pieces of work sufficiently important to call for blueprints is estimated beforehand, but numberless odd jobs of construction and repairs are so itemized. . Might it not be worth while, at a large plant, to have these smaller daily tasks described in advance in a central repair office, and then let inspectors look over the job, report time and material needed, and enter it in sufficient detail in proper ledgers, the men then being sent to accomplish it, and reporting when finished? The forecasts would soon be made quickly and correctly and would give the head mechanic, carpenter, and electrician easy supervision of their men, and the results could be seen at a glance by the managers.

Jan 4, 1918

By Wallace Pratt

INTRODUCTION IRON-ORE deposits in the Philippine Islands became the subject of official record as early as 1664. Undoubtedly iron ore was known and recognized by the Filipinos long before the earliest Spanish records. It is even possible that the Filipino practice of smelting iron ore is, like the native copper smelting, older than the Spanish conquest of the islands. The first records have to do with the magnetite-hematite ores near the towns of Santa Inez and Bosoboso in Rizal Province, from 15 to 20 miles east of Manila. The magnetite-hematite ores of Bulacan were exploited in 1783. Similar ores near the town of Mambulao in Camarines Province yielded a number of specimens to be exhibited in Spain in 1834. With the exception, then, of the lateritic iron ores on the eastern coast of northern Surigao, the true nature of which was not recognized until 1914, the important iron-ore deposits of the Philippines had all been discovered before the islands came under the dominion of the United States. Indeed, in the Spanish documents relating to the history of iron mining are statements which, if their accuracy be not questioned, leave us in the Philippines today with much less iron ore than the Spaniards found. To quote, for example, a report submitted to the Superior Government in Spain in 1835 by one of its emissaries, Don Lorenzo Calvo: "The Philippine Islands, most excellent Sir, possess iron and exhibit it in nearly every known mineralogical combination, and in such abundance that the cordillera of the island of Luzon, from Montufar Point in San Bernardino Straits to Cape Bojeador, is composed of no other mineral than iron, its ranges, of the third order, being in content and structure totally iron of the best quality, the more valuable in that its combinations are such as to facilitate its fusion and to render its reduction to metal simple."

Jan 2, 1916

By Gerhard Derge

The extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: i. The reaction C + FeO Fe + CO is rapid enough to make the correct sampling Of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautiol and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to Al2O3, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. z. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. Indirect Methods Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed the readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached is not well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the con- than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equiliblium relations may be used mole readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory mean, of determining oxygen for the calibration is felt keenly, For example, the statistical analysis of the relation between carbon and oxygen4.6 illustrates that even iia a single plant wide variations exist under llormal conditions of operation. Never. theless, this is one of the best methods now

Jan 1, 1943

By Gerhard Derge

The extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: i. The reaction C + FeO Fe + CO is rapid enough to make the correct sampling Of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautiol and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to Al2O3, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. z. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. Indirect Methods Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed the readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached is not well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the con- than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equiliblium relations may be used mole readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory mean, of determining oxygen for the calibration is felt keenly, For example, the statistical analysis of the relation between carbon and oxygen4.6 illustrates that even iia a single plant wide variations exist under llormal conditions of operation. Never. theless, this is one of the best methods now

Jan 1, 1943

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By T. C. Atchison, W. I. Duvall, D. E. Fogelson

Dr. Clark has given an excellent resum6 of the recent theoretical re- search work that has been done on the generation and propagation of stress waves in various types of media.1 Unfortunately the dynamic properties of rock do not fit the assumed properties of the idealized media. As a result, none of the theoretical solutions for the generation of stress waves by applied pressures to interior boundaries of the spherical or cylindrical cavity appear to be completely satisfactory to explain experimental data. This fact does not mean that the theoretical work is in error. It simply means that the appropriate dynamic properties of rock have not been taken into account in the present theoretical derivations. Because of the difficulty of theoretically accounting for the crushing and cracking that takes place when explosives are detonated in spherical or cylindrical cavities, it seems advisable that future theoretical studies should attempt to separate the generation of stress waves from the propagation of stress waves. Perhaps if these two problems are separated, we may be able to solve one of them satisfactorily so that theory and experimental data agree. Dr. Clark's resumé of the research work on scaling and crater formation by point charges is aimed at obtaining a basic understanding of the physical theory of rock breakage, wave generation, and wave propagation. A cursory reading of Dr. Clark's paper shows that there is very little information summarized that can be used by the practicing engineer in the field of blasting. When problems become too difficult to solve theoretically it is always helpful to take the empirical approach and collect experi-

Jan 1, 1967

By Orville R. Lyons

THE removal of moisture from coal has been a coal-preparation problem ever since the first wet-washing preparation plant was placed in operation. Today, when most of the coal produced in the United States is wetted at the working face when mined, or is cleaned by wet methods, the removal of moisture is a necessity for any one or a combination of the following reasons; (1) to avoid freezing difficulties during shipment, (2) to increase the B.t.u. content, (3) to effect savings in freight costs, and (4) to so improve the coal that it may be used for specific purposes-for instance, in the production of briquettes or the production of metallurgical coke-or so that it can be treated by dry cleaning methods. In general, the amount of water retained by coal particles varies with the size-consist of the coal. Fine coal has a larger surface area per unit weight than does coarse coal, so its capacity for retaining moisture is proportionately greater. The removal of moisture from coarse coal is relatively easy, while the removal of water from minus 10-mesh coal or finer is a major problem, usually requiring an individual solution at each preparation plant. As a result, a multitude of methods and a variety of equipment have been designed to solve both general and specific moisture-removal problems. Definitions In order that misunderstanding may be eliminated insofar as possible, it is necessary to define the terms to be used. The moisture content of any given increment of wet, washed coal is made up of two parts, inherent and surface moisture. Inherent moisture has been defined in various ways and as yet no standard definition has been agreed upon. However, in general, it is considered as the moisture that is present in the coal in the bed. The important point to remember is that coal with any amount of inherent moisture, whether 2 or 20 per cent, will appear dry if there is no surface moisture. Also important is the fact that inherent moisture can be removed, in part, by air drying at atmospheric temperatures. Surface moisture is that attached to the surface of the coal particles or that retained in cracks and fissures other than capillary openings in the coal substance. Essentially, insofar as the bituminous coal and anthracite indus-

Jan 1, 1950

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By J. B. Cheatham

Applications of the mathematical theory of plasticity promises to lead to the solution of many drilling and rock mechanics problems. ,Because of mathematical considerations, the inelastic behavior of rock has frequently been represented by a perfectly plastic model in conjunction with a yield criteria of the Coulomb or Mohr type. The totality of all stress states for which a solid ceases to behave elastically can be represented as a limit surface in stress space. ,Probing of such limit surfaces indicates details of strain hardening which are not provided by the standard triaxial testing procedure. Probing tests of the limit surfaces have been performed on Cardova Cream limestone to provide data for extending plasticity theory to cover situations in which consolidation and strain hardening are present. Test results indicate that this highly porous limestone undergoes a permanent volume decrease when it is subjected to hydrostatic pressures in excess of 3,500 psi. A virgin sample tested under a confining pressure of 1,500 psi has a yield strength of 1,700 psi; however, if the sample is subjected to a consolidation pressure of 5,000 psi, before testing at 1,500 psi, the yield strength is raised to 2,300 psi. Thus, both consolidation and strain hardening are important considerations in describing the mechanical behavior of this limestone. Tests conducted with the axis of the core having different orientations indicate that this rock is also anisotropic. Portions of the initial and subsequent limit surfaces are determined for samples loaded either perpendicular or parallel to the bedding planes. INTRODUCTION Previous experimental work in rock mechanics indicates that no mathematically tractable constitutive theory is inclusive enough to describe the mechanical behavior exhibited by all types of rocks under all conditions of stress and temperature. Indeed, the type of deformation encountered in a single type of rock is known to depend upon the stress and temperature conditions in the rock during deformation.l-5 Certain rocks and minerals, notably those minerals composed of ionic salts, have been shown to exhibit plastic deformation when tested under conditions of high confining pressure.2 Since the mathematical theory of plasticity provides simplifications over the theory of elasticity in certain types of problems, such as those in which limit analysis can be applied, it is of interest to know under what conditions plasticity theory may be applied to rock mechanics problems. The following factors determine the nature of the deformation a particular specimen will undergo: (1) the microscopic structure of the rock, i.e., the structure visible under an optical microscope, including number of phases, porosity, distribution of phases, (2) the mineralogical structure of the solid phases, (3) the conditions of stress and the rate of change of stress and (4) the temperature. Extensive experiments on Yule marble, Carthage marble, Solenhofen limestone and other calcerous rocks indicate that these relatively nonporous rocks deform plastically under certain conditions of loading, and creep under other conditions of loading.l-3 This study is concerned with the behavior of Cordova Cream limestone (Austin chalk) which is also composed almost entirely of calcite and thus has the same mineralogical composition but, because of a rather large porosity, it possesses a different microscopic structure. This investigation was undertaken to learn if Cordova Cream limestone deforms plastically despite the embrittling effect of the pore spaces, and to provide data which can be used to determine whether the mathematical theory of plasticity can describe the mechanical behavior of Cordova Cream limestone. A brief discussion is given of some of the underlying principles of plasticity theory concerning stress space and limit surfaces. Strain hardening is defined and a discussion is given of how the mechanical behavior of a material can depend on the previous history of the loading. This is followed by a description of the experimental procedures

By B. E. Thompson, H. B. Fuqua

The area discussed herein, commonly known as the North Texas district, embraces the following 10 counties: Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita and Wilbarger. It is underlain by two major structural features. The northernmost portion of the district, including Coolie, Montague, northern Clay, Wichita, Wilbarger, Foard and Hardeman Counties, is underlain by the system of buried mountains known as the Red River uplift, which is parallel to and closely related to the Wichita-Amarillo uplift of Oklahoma and the Texas Panhandle. While the presence of a great majority of the numerous oil fields of the area is traceable to this feature, the production in Archer, southwestern Clay and southeastern Baylor Counties is due to the influence of what is known as the Cisco arch (so called because of its influence on Cisco deposition), the axis of which extends in a northwest-southeast direction across southwestern Wichita County into Archer County. Developments during 1938 Important discoveries in the district were considerably more numerous and of more economic importance than for several years. In addition to a number of small, relatively unimportant discoveries and to the usual local extensions to the various producing fields in the several counties, at least eight fields, most of them apparently of considerable areal extent and importance, were found. The Helmerich and Payne, Incorporated and Blackwell Oil and Gas Company No. 1 Wilson. 4 miles southeast of the town of Holliday, in north central Archer County, encountered a pay of Strawn age at a depth of 3841 to 3858 ft., and was completed for an initial production of 1952 bbl. T'his well opened a new deep pool in the K. M. A. producing zone 8 miles southeast of the K. M. A. production. Subsequently an additional deeper horizon, also of lowcr Strawn age, was discovered by wells that failed to yield commerecial oil from the horizon of the discovery well.

Jan 1, 1939

By H. B. Fuqua, B. E. Thompson

The area discussed herein, commonly known as the North Texas district, embraces the following 10 counties: Archer, Baylor, Clay, Cooke, Foard, Hardeman, Knox, Montague, Wichita and Wilbarger. It is underlain by two major structural features. The northernmost portion of the district, including Coolie, Montague, northern Clay, Wichita, Wilbarger, Foard and Hardeman Counties, is underlain by the system of buried mountains known as the Red River uplift, which is parallel to and closely related to the Wichita-Amarillo uplift of Oklahoma and the Texas Panhandle. While the presence of a great majority of the numerous oil fields of the area is traceable to this feature, the production in Archer, southwestern Clay and southeastern Baylor Counties is due to the influence of what is known as the Cisco arch (so called because of its influence on Cisco deposition), the axis of which extends in a northwest-southeast direction across southwestern Wichita County into Archer County. Developments during 1938 Important discoveries in the district were considerably more numerous and of more economic importance than for several years. In addition to a number of small, relatively unimportant discoveries and to the usual local extensions to the various producing fields in the several counties, at least eight fields, most of them apparently of considerable areal extent and importance, were found. The Helmerich and Payne, Incorporated and Blackwell Oil and Gas Company No. 1 Wilson. 4 miles southeast of the town of Holliday, in north central Archer County, encountered a pay of Strawn age at a depth of 3841 to 3858 ft., and was completed for an initial production of 1952 bbl. T'his well opened a new deep pool in the K. M. A. producing zone 8 miles southeast of the K. M. A. production. Subsequently an additional deeper horizon, also of lowcr Strawn age, was discovered by wells that failed to yield commerecial oil from the horizon of the discovery well.

Jan 1, 1939

By Edward Steidle

THAT veterans are crowding the colleges is no longer news; 78 per cent of the 1916-47 enrollment in mineral industries curricula in the United States were veterans, but the rapid comeback from an estimated 1262 total mineral industries students in 1944-45 to 11,422 in 1946-47 is almost astonishing. The figure, which includes 1008 graduate students, is a substantial increase over the previous top record of 9619 in 1938-39. A small part of the increase is caused by the larger number of women entering the field, of whom there were c 9 in 1916-47. Petroleum leads the curricula with 34.5 % of the enrollment, metallurgy is second with 28%, and mining is third with 18%. Table 1. shows all curricula offered and those accredited by ECPD. Using the Mississippi River as a dividing line, 31 colleges in the East and 27 in the West offer curricula in the mineral industries.

Jan 1, 1948