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By Yves Dardel

INTRODUCTION SINCE the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts,2 then Baukloh and Oesterlen,3 during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreau,4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per 100 g of metal. Winterhager,5 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitz6 as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhauser8 extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per 100 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per 100 g, while that of the usual apparatus was only about 0.2 cm3 per 100 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. [ ] Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of Eborall and Ransley, as well as the earlier apparatus,

Jan 1, 1948

By J. L. Huitt

Some of the problems associated with the acid treatment of oil wells are related to the control of the composition of formation treating acid. One test usually made at the well site is the determination of the acid concentration. Heretofore, the concentration of the acid delivered to the well site usually has been interpreted from a hydrometer measurement of the specific gravity of the acid solution. Experience has shown that this indirect measurement of acid concentration can give erroneous results. More reliable results are, of course, obtainable by the titration method; however, this method is not easily adapted to well-site testing. To overcome these objections, a device was developed for use in the field which permits determination of the concentration of treating acid both quickly and accurately at the time of the acid treatment. Its purpose was three-fold, namely, to determine: (1) the concentration of the fresh treating acid, (2) the concentration of the spent acid returning from the well, and (3) the solubility of formation samples in treating acid. The device was designed to operate on the principle of the stoichiometric relation between the calcium carbonate—hydrochloric acid reaction and the carbon dioxide gas resulting from the reaction. By confining the carbon dioxide gas within a reaction cell of the type shown in Fig. 1, the pressure inside the cell is increased. Since the pressure is an indication of the quantity of carbon dioxide gas produced, it may be used to estimate the concentration of the acid, provided an excess of calcium carbonate is used. From information on the volume of the reaction cell, the volume of acid used, and the pressure and temperature of the gas after the completion of the reaction, the concentration of the treating acid may be computed. The reaction cell is essentially a pressure vessel equipped with a pressure gage, temperature indicator. pressure release valve, and a special sample holder. Plastic and metal construction makes the cell both rugged and acid-resistant. The sample holder is so designed that a sample of calcium carbonate (or sample of carbonate rock) can be dropped into the acid

Jan 1, 1956

By Larry Kaufman, Joan B. Berkowitz-Mattuck, Edward V. Claugherty

The oxidation characteristics of hafnium and zirconiunr diboride were measured between 1200 and 2200&apos;K by a thermal- conductivity method which continuously ttzeasures the rate of reaction of oxygen with the diboride and by a metallographic air oridation method zuhich provides a measure of the total arr7ount of bovide conuerted to oxide for a given time interval. The oxidized specimens obtained from the tl~eritaal-coi~ductitrity method were also examined by quantitatire metal-lographic procedares. The significant results obtained in this investigation reveal that metal-rich compositions of lzafi~iutil diboride proride the most oxidation-resistatzt material up to 2000°K; hafnium diboride is tmre oxidation- resistant titan zirconium diboride at all tempevatures examined; the morphology of the oxide formed on H/B2 and Llie temperature coefficient qi. the oxidation rate constants change at the temperature of ttze monoclinic to tetragonal phase transition] in HfO2; the oxidation of neither HfB2 nor ZrB2, results iN catastrophic Jazlure at lorc. oxygen pressures; and pvefevetztial gvaLti boundary oxidation was not obsevued for either HfBi or ZYB, A comprehensive study of the high-temperature characteristics of refractory transition-metal di-borides is currently in progress. This program has included investigation of the physical, thermal, and thermodynamic properties of TiB2, ZrB2, HfB2, NbB2, and TaB2. In addition, aspects of the synthesis and fabrication of such materials have been studied. In view of the diverse nature of this research, a number of other laboratories have actively participated and contributed specific capabilities for analysis and characterization of these materials. As a consequence, an extensive description of the relevant properties of these compounds has emerged which is central in evaluating their high-temperature (1200" to 2500°K) performance. To date, information on thermodynamic stability, specific heat, and vaporization characteristics,1 hot hardness and electrical resistivity,1, 3 therma1 expansion:&apos;4 and thermal conductivity 1, 5 has been presented. This information has been generated on materials of the highest purity (98.5 to 99.9 wt pct Me + B) and density currently available. Samples fabricated by zone melting6 and high-pressure hot pressing"3&apos;7 techniques have been used to generate suitable specimens for all of the aforementioned studies. dation characteristics of the most oxidation-resistant of these materials, hafnium and zirconium diboride, is presented and a description of the synthesis and the experimental procedures used to prepare and characterize specimens is given. The high-temperature range under consideration (1200" to 2200°K) and the known dependence of oxidation characteristics on sample chemistry, density, and oxidation conditions required a close coupling of the synthesis, fabrication, and evaluation procedures.8 This was accomplished by continual surveillance of chemical composition of starting materials before and after specimen fabrication and by evaluation of density, phase constitution, and microstructural features prior to and after oxidation exposure. I) PROCUREMENT AND CHARACTERIZATION OF STARTING MATERIALS In view of the current state of the art in fabricating refractory boride materials, the methods used in preparing samples for the present study are given in detail as follows: starting materials were purchased in high-purity powder form and fabricated by high-pressure hot pressing into 0.40 by 1.00 in. bars from which oxidation specimens were obtained. The hafnium diboride used in this study was purchased from Wah Chang Corp.; the zirconium diboride from U.S. Borax and Chemical Co. These powders were routinely characterized by quantitative chemical analyses for metal, boron, carbon, oxygen, nitrogen, and iron, by qualitative emission-spectrographic analysis for trace impurities, by X-ray procedures for extraneous phase identification, and by powder densitometry for comparison with X-ray (theoretical) density. Hafnium and zirconium metal and elemental boron were also purchased as high-purity powders and characterized for impurities by emission-spectrographic analyses. The hafnium diboride was procured in three shipments which were designated as HfBl.g7(1), HfB1.88(2A), and HfB2.12(2). The indicated stoichiometry is based on the atomic ratio of total boron to total hafnium; the number in parentheses identifies the shipment number. Shipment 1 was 5 1b, shipment 2A, 1 1b, and shipment 2, 8 1b. The zirconium diboride was procured as a 20-1b shipment and designated as ZrB1.89(1). A small quantity of purified zirconium diboride was also supplied and designated ZrB1, 9(P). The averaged results for chemical analyses which were generally performed according to the procedures set forth in the compilation by KrieGe9 are presented in Table I. Qualitative spectrographic analyses indicated that Ca, Cr, Ti, Si, Zr (in H~B~), and A1 were present at levels between 0.01 and 0.10 wt pct. Other metallic elements were found to be less than 0.01 wt pct. Since it is virtually impossible to purchase these materials in the desired quantities (5 to 20 lb) as single-phase compounds it is necessary to obtain

Jan 1, 1968

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.&apos; It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.&apos; It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By A. N. Mitinsky

Discussion of the paper of A. N. MITINSKY, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1697 to 1705. LAWFORD H. FRY, Burnham, Pa. (communication to the Secretary*). -The author assumes that the proportional limit and the elastic limit are coincident or very nearly so, and then further assumes that the stress corresponding to these two points is the least stress which if repeated will cause failure. The point is extremely interesting and it is to be regretted that the author did not quote experimental data to show the relation between the limit of repeated stress and the other properties of the material. The author&apos;s suggestion that a steel of poor quality may have a normal value for the yield point and tensile strength (see Fig. 2) and an abnormally low elastic limit, and that this will correspond to a low resistance to repeated stress, may account for a number of failures of axles in which the tensile tests show normal physical properties. If so and if a determination of the proportional limit would have eliminated the material before it was put into service, this determination will merit most earnest attention. It appears, however, that considerable further research is necessary before any definite conclusion as to the quality of a steel can be drawn from its proportional limit. Mr. Mitinsky&apos;s paper is extremely interesting and if it stimulates thought and work along the lines indicated, it may prove of considerable practical benefit. H. V. WILLE, Philadelphia, Pa.-The paper discusses the difference between the proportional limit, or elastic limit, and the yield point, and refers to the fact that much harm results from confusion of the terms yield point and elastic limit. Similar confusion has arisen in this country; the American-Society for Testing Materials does not even consider the elastic limit and proportional limit to be identical and recently adopted the following definitions:

Jan 12, 1915

By A. J. Shaler, J. Prieto Isaza, John Wulff

TANTALUM metal has a number of unique properties which give it widespread application in modern technology and in research. In electronic apparatus involving high temperatures in vacuo some of the refractory metals become brittle. Tantalum retains its ductility at elevated temperatures, and this property, together with its low vapor pressure and its ability to absorb gases, make it important in this field. Its chemical inertness in the presence of acids, halogens, and other corrosive media, makes it useful in chemical apparatus and in neuro and orthopedic surgical applications. As an addition to tungsten carbide in steel-cutting grades of cemented-carbide tools, the carbides of tantalum and of its sister element columbium have found considerable use. The present-day method1 of manufacturing tantalum is to sinter a powder compact of the metal in vacuo. Because tantalum- columbium alloys are difficult to work and since tantalum ores almost always contain columbium, the two metals must be separated chemically, the products of the separation being generally in the form of potassium tantalum fluoride and potassium columbium oxyfluoride. These salts are used in fused-salt electrolytic baths from which coarse metallic powder is deposited as a sponge at the cathode. Finer powder can be made from the coarse product or from tantalum scrap by first submitting it to an embrittling heat treatment in hydrogen and then crushing it. The fine hydrogen- containing powder may subsequently be degassed in vacuo at a high temperature. Prompted by the success of others2,3 in the magnesium reduction of titanium and zirconium halides, one of the authors under- took4 an investigation of the thermo- chemistry of the reaction between solid magnesium and gaseous tantalum penta-chloride, a subject which had not previously been studied. He found that the heat of formation of tantalum pentachloride is approximately 364,250 cal per mol at temperatures lower than the melting point of magnesium. A value of 83 units was found for the standard entropy at these temperatures. With these values, it was shown that magnesium and tantalum pentachloride are capable of reacting exothermically at temperatures less than the melting point of magnesium, and that no great violence is to be expected when these substances are heated together. The exothermic nature of the reaction indicated that the process should be efficient and should not require much externally applied energy. Tantalum pentachloride is not commonlv made commercially, and any process using it therefore involves the subsidiary problem of producing and handling this substance. A series of experiments was carried out in which dried chlorine saturated with carbon tetrachloride was passed over heated tantalum, either in the metallic state or combined

Jan 1, 1947

By Paul M. Tyler

The term "milling" as applied to nonmetallic minerals often refers merely to pulverizing without preliminary beneficiation. As applied to dimension stone, it embraces all the gteps involved in shaping and giving the desired finish to blocks. Processes such as sawing, planing, rubbing and polishing seem far removed from milling as the term is used in ore dressing, nevertheless they involve the element of concentration, for only 25 to 50 per cent of the gross quarry output may leave the mill as finished products after imperfect stone has been culled and the rough blocks trimmed. On the other hand, numerous nonmetallic minerals have to be concentrated in much the same manner as low-grade ores. Engineers and machinery manufacturers have begun to recognize more clearly the opportunities awaiting them in the nonmetallic field and have brought with them the methods and equipment developed in metal-mining camps, occasionally with little modification. General Economic Considerations Approximately one-half of the total value of the mineral production of the United States represents mineral fuels, and the other half is about equally divided between metals and nonmetals, the nonmetals recently having become relatively more important. In terms of volume the domestic output of nonmetallic minerals other than fuels is more than 10 times the annual output of metals. Considered on the basis of industrial utility and general commercial and military significance, moreover, the flow of nonmetallic mineral products is quite as needful to our national integrity and well-being as is that of metals, fuels, or other basic materials. Despite their importance individually and as a group, the nonmetallic mineral industries differ so widely in essential characters and economic environment that producers thereof have been slow to develop a community of interest among themselves or with the metal-mining fraternity. A spirit of change is in the air, rule-of-thumb methods soon may be relegated to limbo, and new methods—especially time-tested ideas borrowed from ore-dressing practice—are being introduced. A faithful record of plant practice in certain of these fields, however, must register

Jan 1, 1935

By E. A. Gulbransen, J. W. Hickman

INTRODUCTION DURING the past two decades considerable progress has been made in the art of manufacturing heater alloys. The conventional iron-chromium-nickel alloys have been improved by the addition of small quantities of other elements. Up to the present time, to our knowledge, there has not appeared a systematic study of these alloys where the newer tools of investigation have been brought to bear on the problem. It is not yet clear what roles the additional elements play in increasing life time in usage. As a first approximation one might guess that elements such as manganese, silicon, zirconium, calcium and aluminum would aid in the formation of a protective film on the alloy surface, thus retarding the oxidation rate and increasing lifetime. If these additional elements do form protective oxides in the outer surface of the oxide film, it may be possible to identify them by means of reflection electron diffraction. It is also possible that the additional elements may not diffuse to the surface but may remain at the interface between the oxide and the metal. Then, too, the major elements in the alloys undoubtedly form oxides which are stratified on the surface. If the minor elements concentrate in a layer in contact with the substrate where they undergo oxidation and if this oxide film offers resistance to the diffusion of iron, chromium and nickel ions, then the lifetime of the heater element might be expected to increase. It is also possible that preferential reduction in the diffusion rates of the several ions may occur to such a degree that oxides may form in the body of the film and on the outer surface which are different from those that would normally form if the additional elements were not present. The use of transmisson electron diffraction may aid us in interpreting these phenomena. Up to the present time all of the factors which influence the lifetime of a given heater element are not definitely known. Among these are: (I) The rate of oxidation of the alloy. This may be dependent upon the composition and the physical state of the alloy. (2) The stability of the structure of the coating which forms. Transitions from one structure to another or solid phase reactions resulting in a change of composition may occur. The tendency of the film to adhere to the substrate when heated and cooled successively will be important. (3) The evaporation of various constituents from the alloy such as the removal of carbon by oxygen in a decarburization reaction. With these possibilities in view, an electron diffraction study of the oxides occurring on six different nickel-chromium alloys was undertaken with the hope that the results of this study could be correlated with oxidation rate studies as determined by means of the vacuum microbalance method1 and with

Jan 1, 1948

By Gunnar Thaning, Borje Bjorkvall

At LKAB Central Division for Metallurgical Research at Malmberget, Sweden, fired pellets are examined in respect to mechanical and reduction properties. The paper deals with descriptions of the test methods. It also involves the rationale for the choice of these tests. Their correlation to the blast furnace operation will be examined. The mechanical tests used are the ISO-tumbler test and the cold compression strength test. Concerning the metallurgical properties, experiments have shown that some superbasic pellets in particular have different disintegration properties in different temperature ranges. Pellets which have favorable reduction properties when tested under isothermal reduction at high temperature may disintegrate to a large extent under low temperature reduction. This is also valid for some types of acid pellets. Consequently, it was found to be necessary to determine the reduction strength both at high and low temperatures. In the low temperature range, the disintegration is measured by tumbling the pellets in soft reducing conditions at 600°C in a modified Linder test equipment. The high temperature reduction strength is determined under load in the Burghardt-Grebe equipment. However, in order to get more information of the high temperature strength, LKAB intends to introduce a softening test. The tendency of high temperature disintegration will also turn up in the swelling test. The swelling properties are examined according to a procedure developed at LKAB. In this test the pellets are subjected to free swelling without mutual contact. The reducibility of the pellets is recorded in the swelling test.

Jan 1, 1974

By F. L. Wolf, G. E. Alderson

The reclaiming of nietallics from slag and sweepings is of vital interest to every brass-foundry man, but the first cost and interest on the investment often make it prohibitive for the small foundry to enjoy the benefits of a complete concentrating unit. However, the cost of such an installation and the cost of operation are often exaggerated to such an extent that foundries dispose of their copper-bearing refuse at a great loss. This paper gives the actual costs and the returns obtained in the reclaiming plant used at the Ohio Brass Co. This plant is divided into two sections—the preliminary treatment and concentrating departments. In the former occur the screening, crushing, and hand-picking operations whereby rnost of the non-valuable and heavy metallic constituents are removed. The concentrating equipment consists of an elevator, bins, jigs, ball-mill, arid table. Preliminary Treatment The preliminary treatment varies, depending on whether the material is slag, foundry-floor sweepings, or brass casting-floor sweepings. Material of the first class is produced from the operation of six Steele-Harvey and six Schwartz furnaces; the second class represents sweepings from an average of thirty-five. molding floors per day: and the last is collected around the sprue cutters and knockout bench. Treatment of Slag The slag, analyzing 30 to 40 per cent. copper, is passed over a 3-mesh yard screen (Tyler standard mesh) stretched on an inclined rectangular frame supported by adjustable legs and equipped with a hopper which directs the undersize into a barrow. The fine product, running about 20 per cent. copper and representing 20 to 25 per cent. of the total slag, goes direct to a storage bin for concentrator frrd. The oversize is charged into a No. 2 Hill cinder crusher, which takes 175 to 200 11,. to a charge and crushes two charges per hour through &apos;a No. 4 riddle. It

Jan 1, 1921

By Tell Ertl, Ernest E. Burgh

INTRODUCTION THE Bureau of Mines is operating an oil-shale mine 10 miles west of Rifle, Colo., as part of its Synthetic Liquid Fuels program. The purpose of operating this mine is twofold: First, to supply oil shale to an experimental processing plant; and second, to develop practices and select methods for mining oil shale on a commercial scale at the lowest practicable cost. The second purpose-that of finding out how to mine oil shale most cheaply-entails considerable mining research. Since the drilling of oil shale probably will be one of the major items of the mining cost, factors that influence drilling speeds were investigated. One phase of the drilling program was the development of a successful hard-surfaced rock-drill bit1 that can be used for drilling long holes in oil shale without changing bits. During that phase, drilling speeds were measured and drill cuttings were collected for assay and for screen sizing. When the cuttings from the individual tests were compared, a definite relationship was shown to exist between the drilling speed and the coarseness of the drill cuttings. PROCEDURE Measurement of Drilling Speeds All drilling in the tests was done with a Model UMB-D-99W Gardner-Denver wagon drill. Round-lugged drill steel, 1 ¼ in. in diameter was used in 6, 12, and 18 ft lengths with 2 1/8 -in. Timken H-type bits hard-faced with acetylene tube borium. The tests were made in the lower adit of the Bureau of Mines oil-shale mine; the grade of the oil shale drilled ranged from 18.6 to 42.7 gal per ton. During the experiments air pressure varied between 75 and 90 psi while water pressure remained fairly constant at 75 psi. All holes were drilled almost horizontally. Each drill hole was thoroughly cleaned of cuttings after being collared. The advance of the drill along the carriage was measured and recorded as the drilling speed in inches per minute. Method of Collecting Cuttings To facilitate the collection of cuttings, each drill hole was collared in a smooth, vertical portion of the oil-shale breast (Fig 1). A galvanized-steel sheet was fastened to the breast below the area in which the hole was to be drilled. The cuttings washed out of the drill hole by the drilling water were guided by the steel sheet into a wooden box. The cuttings that remained in the drill hole after the drill was withdrawn were scraped out and placed in the same box as the cuttings washed out of the hole. After the cuttings from a 1-min. drilling interval were collected, they were placed in flat metal pans. The fines were allowed to settle and the clear water was decanted. The cuttings then were dried in the sun.

Jan 1, 1947

Philip Argall, Denver Col. (communication to the Secretary): Dr. Raymond claims (Trans., xxiii., 560)) that my statement (p. 557) regarding the crystallization of iron "is beyond question incorrect." He says: "It is not even settled that vibration will crystallize iron under any conditions." While admitting that authorities differ on the possibility of cold crystallization of iron, I believe it is a settled and undisputed fact that vibration in the presence of heat will crystallize iron. Bloxam and Huntington say :* " Vibration assists &apos;in converting fibrous metal (iron) back into a crystalline state when heated, a lower temperature sufficing than in the absence of vibration." Mr. A. F. Hill, summing up a very exhaustive review upon the crystallization of iron and steel, pronounces against crystallization, but only at temperatures below 900&apos; F. Mr. Howe, discussing ,the breakage of a 20-foot porter-bar with a crystalline fracture, suggests that it was attributable to heat, jointly with the jar. We see, then, that vibration of heated iron bars will induce crystallization and consequent change of structure. Referring to my statement, I wish to point out, that I was discussing the vibration of stamps arid should have said, "vibration under all such conditions," etc. That is, vibration attended with sharp blows, such as a stamp-stem is subjected to, will crystallize iron; yet I believe that intense vibration under any condition will

Jan 1, 1895

By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By W. A. Ver Wiebe

Under the impetus of new demands caused by the war, the oil and gas industries of Kansas established new records during the year 1942. In all, 1513 test wells were drilled, which is somewhat of a drop from the figure of 2113 for 1941. The 1513 tests yielded 800 new oil wells, 85 new gas wells, and 628 dry holes. Thus there was an increase in two categories, the gas wells and the dry holes. Considering that last year only 592 dry holes were completed out of a much larger total, the figure of 628 dry holes causes some concern among local operators. The increase in unsuccessful tests illustrates once more the fact that each year it is becoming harder to find the remaining oil pools. When the figures are broken down, it appears that western Kansas accounted for 1177 tests, of which 689 were oil wells, 33 gas wells, and 455 dry holes. The total potential daily initial production uncovered by the successful wells amounted to 753,178 bbl. of oil and 619,734,000 cu. it. of gas. The figures for new initial production indicate a substantial drop from last year&apos;s figure of 1,691,000 bbl., and the figures on gas are slightly higher. In 1941 the new gas as based on a daily potential was 508,000,-000 cu. ft. In eastern Kansas, 336 wells were drilled. Among these in were oil wells, accounting for a daily initial potential production of 16,199 bbl. The new gas wells numbered 52 and added 253,725,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 173 in number, were dry. It is interesting and perhaps significant that about half (630) of the wells drilled in western Kansas were drilled by the independent operators. Among the large companies, the Cities Service Oil Co. drilled 163 wells; the Stanolind Oil and Gas Co., 52; the Skelly Oil Co., 39; the Continental Oil Co., 48; and the Shell Petroleum Co., 21 wells. In eastern Kansas the independent operators drilled 297 out of the total of 336 wells. Among the major oil companies the Cities Service Oil Co. drilled 19; the Phillips Petroleum Co. 7; and the Sinclair-Prairie Oil Co., 6 wells. The figures based on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas almost one half of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 547 wells in western Kansas, of which 379 were successful in finding either oil or gas. It thus appears that the major companies fared better than the independents. In eastern Kansas the major companies drilled 39 wells, of which 29 were successful in finding commercial quantities of oil or of gas. No less than 329 wildcat test holes were put down in western Kansas and 105 in eastern Kansas, or 434 in all, during 1942. Considerably more than half of these were drilled by independent operators; 223 in western and 99 in eastern Kansas. An exploratory hole 56 mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, about 80 per cent of wildcat wells were failures. In western Kansas only 20 per cent found either oil or gas. The failures were about equally distributed among the major

Jan 1, 1943

By W. A. Ver Wiebe

Under the impetus of new demands caused by the war, the oil and gas industries of Kansas established new records during the year 1942. In all, 1513 test wells were drilled, which is somewhat of a drop from the figure of 2113 for 1941. The 1513 tests yielded 800 new oil wells, 85 new gas wells, and 628 dry holes. Thus there was an increase in two categories, the gas wells and the dry holes. Considering that last year only 592 dry holes were completed out of a much larger total, the figure of 628 dry holes causes some concern among local operators. The increase in unsuccessful tests illustrates once more the fact that each year it is becoming harder to find the remaining oil pools. When the figures are broken down, it appears that western Kansas accounted for 1177 tests, of which 689 were oil wells, 33 gas wells, and 455 dry holes. The total potential daily initial production uncovered by the successful wells amounted to 753,178 bbl. of oil and 619,734,000 cu. it. of gas. The figures for new initial production indicate a substantial drop from last year&apos;s figure of 1,691,000 bbl., and the figures on gas are slightly higher. In 1941 the new gas as based on a daily potential was 508,000,-000 cu. ft. In eastern Kansas, 336 wells were drilled. Among these in were oil wells, accounting for a daily initial potential production of 16,199 bbl. The new gas wells numbered 52 and added 253,725,000 cu. ft. per day to the gas potential production of the state. The remaining tests, 173 in number, were dry. It is interesting and perhaps significant that about half (630) of the wells drilled in western Kansas were drilled by the independent operators. Among the large companies, the Cities Service Oil Co. drilled 163 wells; the Stanolind Oil and Gas Co., 52; the Skelly Oil Co., 39; the Continental Oil Co., 48; and the Shell Petroleum Co., 21 wells. In eastern Kansas the independent operators drilled 297 out of the total of 336 wells. Among the major oil companies the Cities Service Oil Co. drilled 19; the Phillips Petroleum Co. 7; and the Sinclair-Prairie Oil Co., 6 wells. The figures based on relative percentages of dry holes to successful oil or gas wells are revealing. In western Kansas almost one half of all wells drilled by the independent operators were dry holes. The major oil companies drilled approximately 547 wells in western Kansas, of which 379 were successful in finding either oil or gas. It thus appears that the major companies fared better than the independents. In eastern Kansas the major companies drilled 39 wells, of which 29 were successful in finding commercial quantities of oil or of gas. No less than 329 wildcat test holes were put down in western Kansas and 105 in eastern Kansas, or 434 in all, during 1942. Considerably more than half of these were drilled by independent operators; 223 in western and 99 in eastern Kansas. An exploratory hole 56 mile or more from production is regarded as a wildcat well in Kansas. On a percentage basis, about 80 per cent of wildcat wells were failures. In western Kansas only 20 per cent found either oil or gas. The failures were about equally distributed among the major

Jan 1, 1943

By A. G. Weber, K. H. Coats, M. H. Terhune, R. L. Nielsen

Two computer-oriented techniques for simulating the three-dimensional flow behavior of two fluid phases in petroleum reservoirs were developed. Under the first technique the flow equations are solved to model three-dimensional flow in a reservoir. The second technique was developed for modeling flow in three-dimensional media that have sufficiently high permeability in the vertical direction so that vertical flow is not seriously restricted. Since this latter technique is a modified two-dimensional meal analysis, suitably structured three-dimensional reservoirs can be simulated at considerably lower computational expenses than is required using the three-dimensional analysis. A quantitative criterion is provided for determining when vertical communication is good enough to permit use of the modified two-dimensional areal analysis. The equations solved by both techniques treat both fluids as compressible, and, for gas-oil applications, provide for the evolution of dissolved gas. Accounted for are the effects of relative permeability, capillary pressure and gravity in addition to reservoir geomety and rock heterogeneity. Calculations are compared with laboratory waterflood data to indicate the validity of the analyses. Other results were calculated with both techniques which show the equivalence of the two solutions for reservoirs satisfying the vertical communication criterion. INTRODUCTION Obtaining the maximum profits from oil and gas reservoirs during all stages of depletion is the fundamental charge to the reservoir engineering profession. In recent years much quantitative assistance in evaluating field development programs has been provided by computerized techniques for predicting reservoir flow behavior. Because of the spatially distributed and dynamic nature of producing operations, automatic optimization procedures, such as those now in use for planning refining operations, are not now available for planning reservoir development. However, present mathematical simulation techniques do furnish powerful means for making case studies to help in planning primary recovery operations and in selecting and timing supplemental recovery operations. A number of methods have been reported which simulate the flow of one, two or three fluid phases within porous media of one or two effective spatial dimensions>-4 However, applying computer analyses to actual reservoirs have been limited mostly to two-dimensional areal or cross-sectional flow studies for two immiscible reservoir fluids. To obtain a three-dimensional picture of reservoir performance using such two-dimensional techniques, it has been necessary to interpret the calculations by combining somehow the results from essentially independent areal and cross-sectional studies. To the authors&apos; knowledge, the only other three-dimensional computational procedure, in addition to those presented here, was developed by Peaceman and Rachford8 to simulate the behavior of a laboratory waterflood. Two computational techniques which may be used to simulate three-dimensional flow of two fluid phases are described in this paper. The first method, called the "three-dimensional analysis", employs a fully three-dimensional mathematical model that treats simultaneously both the areal and cross-sectional aspects of reservoir flow. The second method, called the vertical equilibrium (VE) analysis", is applicable

By Renato G. Bautista, Theodore D. Tiemann

A kinetic study of the hydrogen reduction of taconite from the Wisconsin Gogebic range was made over the temperature range from 500° to 1000°C on eleven size fractions from 4 to 150 mesh. Two stages of reduction were observed, a rapid initial reaction followed by a slower reaction presumably taking place at an internal receding FexO-Fe interface. Calculated mean activation energies for the two reactions were 7800 and 14,600 cal per mole respectively. In recent years there has been an increased interest in the direct reduction of iron oxide ores to metallic iron by means of gaseous reducing agents such as hydrogen and carbon monoxide.1,2 These investigations have been motivated by the desire to develop a process that will by-pass the blast furnace in the production of steel. The majority of these processes have been developed to produce metallic iron by direct reduction from high-grade iron oxide ores.3"5 Very little work has been done on the low-grade siliceous iron oxide ores.6"8 The work reported here is directed principally towards the fundamental aspect of the reduction reactions of siliceous iron oxide ores, since the practical aspects of the gaseous reductant process were discussed previously. The ore used in the investigation was obtained originally from the United States Bureau of Mines10 trench sample of the Yale member of the Wisconsin Gogebic range iron formation. The Yale taconite has an average analysis of 28.2 pct Fe and approximately 50 pct SiO2. Chemically, these nonmagnetic taconites contain on the average about 53 pct silica and 30 pct Fe. An average analysis calculated fron the USBM10 figures for a composite of the five members (Norrie, Plymouth, Pence, Pabst, and ale) of the iron formation is given in Table I. Mineralogically, based on previous X-ray diffraction and other studies, the principal minerals are hematite (Fe2O3), geothite (Fe2O3.H2O), and quartz (SiO2). Minor amounts of iron containing silicates, siderite (FeCO3) and magnetite (FeO. Fe2O3) are present.10,11 The iron minerals and the quartz are finely disseminated requiring extremely fine grinding for liberation. For the experimental work, the ore sample was screened into a number of size fractions, the analyses and densities of which are given in Table II. EXPERIMENTAL PROCEDURE The reduction experiments were carried out in a 24 in. by 2 in. ID nichrome-wound vertical-tube furnace mounted on a stand. A 1 1/2 in. OD zirconium-oxide combustion tube was used inside the furnace to contain the atmosphere. To the top of this combustion tube was joined a pyrex ground-glass joint to which was attached a glass bulb with a small (1.0 mm) opening at the center, and with two outlets controlled with a stopcock on each side. A pyrex-glass joint with connections to three stopcock joints for introducing hydrogen, nitrogen, and mixtures of hydrogen and nitrogen gas was joined to the tapered bottom of the combustion tube. The sized ore fractions were contained in a 1 in. diameter by 1 1/2 in. 150-mesh nickel screen basket. The basket was suspended in the furnace from a balance by means of a supporting nickel wire which hung freely inside the combustion tube. The furnace temperature was controlled by a Leeds and Northrup Speedomax Type G controller, connected to a chromel-alumel thermocouple placed

Jan 1, 1962

By J. T. Eash, N. B. Pilling

As a group, the alloys of iron, nickel and carbon are, in application, one of the most versatile of the ferrous alloy family, and while many investigations have been made of their properties and structure only a few attempts have been made to show the microstructural relation over a wide range of composition. It is necessary at once to be clear about the kind of structural relation with which we are concerned. The equilibrium diagram provides quantitative data regarding structural make-up and its variation with temperature, but equilibrium structures often are far different from the technologically significant ones. This is particularly true of steels and cast irons, and some of the most important components of their structure may have no place in the diagram of equilibrium. The fugitive phases that result from transformation are dealt with in a highly detailed and descriptive manner in the S-curves originated by Bain. The present effort lies in a still different field, which is to portray the relation between sweeping changes in composition and in resultant structure, under controlled but nonequilibrium conditions of thermal treatment. The Guillet1 diagram presented in 1903 was the initial attempt at such a correlation and frequent references to this diagram can be found in the literature even though later work has shown it to require considerable modification. Kase2 published in 1925 a diagram that was based upon observations of furnace-cooled melts. At low carbon contents this diagram agreed fairly well with experience in showing pearlite to exist in alloys containing up to 6 per cent nickel, and completely austenitic steels at 24 to 28 per cent nickel. At high carbon contents, however, irons were indicated as being martensitic at around 2 per cent nickel and austenitic at 12 per cent nickel; these interpretations are open to serious question. Based upon experience with steels and cast iron, Wickenden3 suggested a diagram that agreed fairly well with Kase&apos;s in the steel range but which presented a wide departure from it in the higher-carbon, high-nickel regions. In its broad picture, the Wickenden diagram is an approach to "practical" structures. [ ] Reference may be made at this point to the efforts of Marshy to construct an iron-nickel-carbon equilibrium diagram by the coordination of scattered data, which are described at length in the monograph cited. None of these preceding attempts has appeared to meet the need for an exposition of the structural sequence that is encoun-

Jan 1, 1942

By Victor G. Hills

CONTRARY to what seems to be the general impression, the island of Cyprus was not named for the metal copper, but the reverse was the case. The origin of the name is entirely lost. The ancient city Kition, the birthplace of Zeno, is supposed to be the same as Kittim mentioned in Gen. x, 4; Jeremiah ii, 10 and Ezekiel xxvii, 6, and Josephus states that this name seems to have been applied to the city and also to the island itself. Cyprus is 50 miles off the coast of Asia Minor. The mountains on the mainland are plainly visible across the sea from where I write six miles from the shore of Morphou bay. It is 200 miles from Joppa the port of Jerusalem, and 250 from Port Said. The shape of the island is like a lizard, the tail pointing directly toward the old city of Antioch near the northeastern corner of the Mediterranean. The island was once heavily timbered. Among the great trees the cedars were said to even excel the famous cedars of Lebanon. The Odyssey refers to it as the "sweet smelling island" and makes other references. But the continual wars of every race and age completely stripped it of its timber, and for centuries it has been woefully barren. There are two ranges of mountains. One borders the north coast and runs out in a slim rocky ridge forming the "tail." The other occupies the southwestern part of the island, the highest point being Mt. Troodes 6600 ft. high, sometimes called Mt. Olympus. Whether or not it be the Mt. Olympus, anyway right around there the ancient gods and godesses frequently "started things." These peaks are in plain sight 10 miles south from where I live.

Jan 1, 1926