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By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By J. W. Furness

Before attempting any discussion of the importance of tariff enactments as applied to exhaustible resources, certain basic factors should be emphasized. First, it must be remembered that minerals differ from organic substances in that they are irreplaceable, and when once taken from the earth's crust enter into uses which ultimately dissipate them, so . that they cannot be recovered for future use. A second factor entering into the problem is the unequal distribution of the mineral deposits of the world. No industrial nation has within its political confines a sufficient quantity of all the minerals necessary for the maintenance and advancement of present civilization; hence international exchange of these commodities is inevitable. As minerals are essential to modern industry, the supply available to any given nation constitutes a factor which limits its ambition to advance industrially. A nation which has this ambition endeavors to secure not only a supply of minerals sufficient for its current needs, but also sources which will assure it expansion. Should mineral raw materials be withheld from such a nation by enactment, it seems inevitable that every effort will be made to obtain them, and that, should the nation deem itself sufficiently powerful, its ultimate recourse will be force. Thus the importance of tariff enactments, not only from the standpoint of industrial prosperity but from the standpoint of international peace, can be appreciated.

Jan 1, 1932

By W. R. Ingalls

THE present administration has made sincere and effective efforts to reduce the expense of the Federal Government, but it has reached a point beyond which it seems impossible, or anyway extraordi-narily difficult, to go. This is ascribable to the large part of the budget that is represented as war expense. There is no doubt that this spells high taxation for many years to come. Nevertheless, although a large part of the taxation will be attributable to the war, the paying out of the proceeds of that taxation by the government will not be war expense, except in minor part, as will be hereinafter made clear. It will be useful to explain the economic meaning of this situation, for it has bear-ings upon several open questions, such as a bonus to the ex-soldiers, the foreign debt accounts, etc. The expense of the war on the part of the American people was in the main paid concurrently with its prose-cution. This was necessary. Warfare is not conducted with money, but with materials and labor. Except for such previous production as was represented by stocks of goods, the requirements had to be supplied by coincident production. With the end of 1918 our war expense ceased, save for such production, e.g., of ships, that was allowed to run on unchecked, and the indemnities that had to be paid for cancelled contracts. When those matters have been settled we shall be done, barring one important thing. Of course, our war expense began to contract right after the armistice and shrunk rapidly with the demobilization of the troops in 1919. If we had not been able to obtain all needful material from our own sources and had been constrained to borrow it from foreign countries, incurring a foreign debt, we should have been in the quite different posi-tion of having to repay that material, or its equivalent, during subsequent years. The European countries had to come to us for such supplies. This outlines the fundamental difference between their present situations and ours. We were therefore compelled not only to furnish materials and man-power for our own warfare but also much for the Allies.

Jan 3, 1923

By George Macready

TRINIDAD, British West Indies, is an island near the north coast of South America, situated between latitudes 10° and 11° N:, and. opposite the numerous outlets of the Orinoco River Delta. It is separated from Venezuela by the Gulf of Paria (salt, water) and straits over 5 mi. (8 km.) wide. The area of the island is approximately 1750 sq. mi. (453,- . 250 hectares) and the population is approximately 400,000. The climate is tropical with an annual rainfall of from 45 to 60 in. (114 to 152 cm.). The oil fields consist of several units, or fields, located in the southern half of the island. Approximately 90 per cent. of the total production has been yielded by fields situated within 7 mi: (11.3 km.) of the famous asphalt lake and on the southwest peninsula. The most important producing fields, or units, are the following, which are shown on the accompanying map: Brighton, or Pitch Lake Field, operated by the Trinidad Lake Petroleum Co., Ltd., is situated beside the famous Pitch Lake; it, even encroaches on the lake. Vessigny Field, operated by the Trinidad Lake Petroleum Co., Ltd., is situated 2 mi. (3.2 km.) south of Pitch Lake. Lot One Field, operated by the Petroleum Development Co., Ltd., the United British Oilfields of Trinidad, Ltd., and Stollmeyer, Ltd., is situated 3 mi. south of Pitch Lake upon Lot One of Morne 1'Enfer Forest Reserve and adjoining properties. Parry Lands Field, operated by the United British Oilfields of Trinidad, Ltd., and the Petroleum Development Co., Ltd., is situated 3;2 mi. south of Pitch Lake on Lot Three of Morne l'Enfer Forest Reserve and adjoining properties. Point Fortin Field, operated by the United British Oilfields of Trinidad, Ltd., is situated at Point Fortin, 6 mi. southwest of Pitch Lake. Fyzabad Field, operated by Trinidad Leaseholds, Ltd., is situated several miles southwest of Fyzabad Village and 6 mi. south-southeast of Pitch Lake. Barracpore Field, operated by Trinidad Leaseholds, Ltd., is situated several miles south of. San Fernando and 15 mi. (24.14 km.) east of Pitch Lake.

Jan 9, 1920

By C. A. Rowland, M. D. Flavel

There are seven basic comminution circuits that can be used to prepare beneficiation feed from the product of a primary crusher. This paper gives a comparison of these circuits based on average process and economical data. The paper is principally devoted to a discussion of the test work required to obtain the process data needed to evaluate each circuit. The results of the test work in conjunction with geographic and economic factors can be used to narrow down the choice of possible circuits to one, two, or three before making a detailed engineering study.

Jan 1, 1985

By Hans-Jürgen Schaller, Horst A. Brodowsky

Activity coefficients of boron in palladium were determined at concentrations up to PdB0.23 by reducing B2O3 between 870" and 1050°C in a controlled H2-H2stream and measuring the resulting weight gain. The deviations from ideal behavior closely resemble those of the system Pd-H and are interpreted in terms of three principles: 1) The solute atoms occupy octahedral interstitial positions. 2) They donate their valence electrons to the 4 d and 5s bands of palladium, raising its Fermi energy. 3) The lattice strain energy is lower for two nearesl -neighbor interstitial particles than for two farther separate ones. SOLID solutions of hydrogen in palladium are a useful subject for studying thermodynamic aspects of the formation of alloys and of nonstoichiometric systems.1-3 The activity of hydrogen is readily measurable to a high degree of accuracy,4'5 even at low temperatures where the deviations from ideal behavior are more pronounced, and its simple structure facilitates an interpretation of these deviations in terms of a detailed model. Two effects are discussed to account for the non-ideal properties:3 An "electronic" effect, connected with the rise of the Fermi energy, as electrons of the interstitial hydrogen atoms enter the electron gas of the metal, and an "elastic" effect, due to an interaction of the regions of strain around each interstitial atom. The electronic effect is based on the idea that the lowest energy levels of the dissolved hydrogen atoms are higher than the Fermi energy, so that the electron will not occupy a localized state but enter into the electron band of the metal.6 The elastic effect is based on the observation that dissolved hydrogen distorts and expands the palladium lattice. The hypothesis is put forward that the elastic strain energy is lower for two adjacent dilatational centers than for two separate ones; i.e., they attract each other. The resulting pair interaction can be used to calculate an elastic contribution to the thermodynamic excess functions by means of one of the statistical methods. This model permitted a detailed description of the solution properties of hydrogen in palladium3 and in palladium alloys.798 An extension of the approach to describe the excess functions of substitutional palladium alloys is possible.9 In order to further test and refine the model, an investigation of other interstitial alloys was started. Palladium dissolves considerable amounts of boron in homogeneous solid solution.10 The palladium lattice expands linearly up to nB = 0.23 (nB = B/Pd atomic ratio), the highest concentration studied." The expan- sion, extrapolated for 1 mole of interstitial per mole of palladium, is 17 pct of the lattice constant of pure palladium vs 5.7 pct in the case of hydrogen.12 The fact that the lattice expands rather than contracts is a strong indication that interstitial positions are occupied. According to neutron diffraction experiments, hydrogen occupies the octahedral sites of the fcc lattice.13 Unfortunately, this direct evidence is not available for the Pb-B system, mainly because of the high-reaction cross section of boron with thermal neutrons. However, by way of analogy and on the grounds of the rather close similarities between the two systems to be reported here, it seems safe to attribute octahedral positions to the dissolved boron, too. At higher boron contents, compounds of stoichiomet-ric compositions are reported such as Pd3B, which has the structure of cementite,14 so that a close structural relationship seems to exist with the system r Fe-C. In their study of hydrogen absorption in Pb-B alloys, Sieverts and Briining noted that alloys with an atomic ratio of about nB = 0.16 are no longer homogeneous15 This observation was confirmed in an extensive X-ray investigation.11,16 The phase boundaries of two miscibility gaps were established. One two-phase region was stable below a transition temperature of about 315°C and extended from nB = 0.015 to 0.178. The other one extended from nB = 0.021 to 0.114 slightly above the transition temperature and had an apex at nB = 0.065 and 410°C. All phases involved have the fcc structure of pure palladium with lattice expansions proportional to their boron contents. The occurrence of miscibility gaps, i.e., the coexistence of dilute and concentrated phases, points to an energy of attraction between the dissolved particles, in the Pb-B system as well as in the Pd-H system. The filling up of the electron bands seems to be analogous, too, in the two systems, as indicated by the hydrogen absorption capacit15,17,18 and by the suscepti bility of Pd-B alloys.l8 In both types of experiments, boron acts as an electron donor. A chemical method was used to measure the activity of boron in palladium. Boron trioxide was reduced in a moist hydrogen stream: B2O3 + 3H2 = 2B + 3H3O [l] At known activities or partial pressures of boron trioxide, hydrogen, and water, the activity of boron could be calculated from the law of mass action. The equilibrium concentration of boron corresponding to this activity was determined as the weight gain of the sample. EXPERIMENTAL The samples consisted of small pieces of foil of 0.1 mm thickness and about 100 mg weight. The palladium was supplied by DEGUSSA, Germany, and stated to be

Jan 1, 1970

By J. Chipman, T. Fuwa

The effects of various elements on the activity coefficient of carbon in liquid iron have been studied by two experimental methods: 1) equilibration with controlled mixtures of CO and CO2; 2) the solubility of graphite in the melt. Activity coefficient of C is increased by Al, Co, Cu, Ni, P, Si, S, and Srz. It is decreased by Cr, Cb, Mn, Mo, W, and V. THE thermodynamic properties of the iron-carbon binary system have now been fairly well established, although some uncertainty remains with respect to the exact location of some of the phase boundaries. The activity of carbon in ferrite and in austenite has been measured in the classic researches of R. P. smith' while similar measurements by Richardson and ~ennis, and by Rist and chipman3 have established the values of the activity of carbon in liquid iron up to 1760°C. On the other hand, our knowledge of the effects of alloying elements on the activity of carbon in dilute solutions is restricted to Smith's experiments on systems Fe-C-Mn and Fe-C-Si in the austenitic range and to some more recent experiments of schwarzman4 in the a range. In addition there have been a number of determinations of the effects of various elements on the solubility of graphite in liquid iron, and from these the corresponding effect in saturated solution may be obtained. The purpose of the present study was to extend the investigation of the liquid system to include the effects of alloying elements upon the activity coefficient of carbon, principally in dilute solutions. Equilibrium measurements were made on the reaction C + co, = 2 CO (g) The prepared mixture of CO and CO,, diluted with argon, flowed over the surface of the liquid metal which, after several hours' exposure to the gas, was quenched and anqlyzed. As in the earlier experiments, the principal experimental difficulty was in the deposition of carbon on the parts of the furnace at temperatures slightly below that of the metal bath. In order to minimize this difficulty, the ratio (Pco)2 /PCo2 was restricted to values not much higher than 100 atm, and correspondingly the carbon concentration in the metal seldom exceeded 0.30 pct. EXPERIMENTAL METHODS The method and apparatus were essentially the same as used by Rist and Chipman.3 The gaseous mixture consisting of highly purified CO, CO,, and argon, each controlled by a flowmeter, was led into the furnace and passed over the surface of the liquid-iron melt which was heated and stirred by high-frequency induction. One slight modification was made in that a molybdenum susceptor was placed outside the crucible for the sake of uniformity of temperature and to combat the tendency of carbon to precipitate on the crucible wall. Pure alumina crucibles approximately 25 mm ID were used. The charge consisting of about 30 g was made up of electrolytic iron, the alloying element to be added, and enough graphite to supply slightly more or less than the anticipated equilibrium carbon concentration. All metals used were of high purity. Metallic chromium, columbium, and vanadium were from special lots supplied by the Electro Metallurgical Co. Tin, copper, molybdenum, tungsten, cobalt, and nickel were of purest commercial grades. The electrolytic iron, after being cut to the proper size for charging, was prereduced by hydrogen at 850° to 1000°C to remove surface oxidation. The oxygen content of the reduced material was 0.002 pct. This treatment made it easy to control the carbon content of the initial melt. The charge was melted under the gas mixture to be used for the entire run. In some earlier melts the charge was melted under a stream of argon, but in this case some alumina was reduced from the crucible, and the aluminum thus absorbed in the melt was subsequently oxidized with the formation of a solid film of alumina on the surface of the melt. AS another safeguard against film formation, overheating of the bath was carefully avoided. All runs were made at a temperature of 1560°C. Under experimental conditions a charge of pure iron picked up 0.17 pct C in 3 hr and 0.23 pct C in 6 hr under an atmosphere for which the equilibrium concentration of carbon is 0.27. It is clear that the time required to reach equilibrium from an initially carbon-free melt would be very great. For this reason each experiment was started with a melt of known carbon concentration not far above or below the expected equilibrium value, and each melt was held at temperature for a period of at least 5 hr. Under such circumstances it was possible to chart the approach to equilibrium from both high-carbon and low-carbon materials. Temperature was controlled by frequent optical observation and adjustment and the metls were timed in such a way that the final 2 hr occurred during a time when electric power was steady; for example, 2 to 4 pm or after 11 pm. In melts containine volatile metals such as copper, tin, and mangane\e the time of holding was decreased somewhat in

Jan 1, 1960

By Ed Van Eeckhout

As part of a U.S. Bureau of Mines-sponsored project on the utilization of "stiff" backfill to minimize potential rock burst hazards, a finite element study was undertaken to predict stresses and displacements around a stope mined up from the 5400 level of the Sunshine mine, Kellogg, Idaho. This stope was to be backfilled using a high-modulus fill. In preparation for that configuration, certain instrumentation was installed near the 5400 level to monitor stress changes. Due to untenable economics, only 2 cuts of the stope were ever made. This paper presents the results of the instrument readings taken during the first cut and compares them with the numerical predictions, as well as presents the modeling results of closure and fill stresses in the stope if it had been mined.

Jan 1, 1984

By Basil Prescott

A thorough knowledge of the peculiarities of this type of orebody is necessary in sampling these limestone replacement deposits. Oxidized ores are often overestimated because of error in determining specific gravity and actual cross-section of the orebody, and sulfide ores are often underestimated because it is difficult to scatter the samples so that they will accurately represent the area under consideration. This paper describes various methods of sampling and cites factors that enter into the estimation of these deposits. IN THE science of evolution of the species, there is a law which, simply stated, avers that the history of the individual repeats the history of the race. Similarly, if unassisted by the experience of others, each successful engineer would perfect and develop his methods and technique from the rough grab sample up to the carefully taken, recorded and studied samples and observations which now determine and decide the expenditure of the large sums required for modern mining. Hence real progress results from the interchange of experience, as in that way the entire experience of the profession can be made available to every engineer. The literature of this subject is already voluminous, but some progress has been made in the gathering of data and in their compilation or presentation.

Jan 3, 1924

By Jean Howard

ThE formation of the (100) [001) texture in 3-1/4 pct Si-Fe strip was first reported by Assmus ef a1.l in 1957. Since then much experimental work has been carried out with a view to establishing the mechanism involved. The papers cited above state that the (100) [001] texture was developed in strip rolled from material melted and cast in vacuum. (The impurity content of the ingot is reported as 0.005 pct.) The present note records that similar results can be obtained in material processed by powder metallurgy. A processing schedule is described.which enables the texture to be formed in strip up to 0.010 in. thick, but there seems no reason why this should not be achieved in thicker strip, provided that large grains are developed after sintering. The materials were prepared from Carbonyl Iron Powder Grade MCP (particle size 5 to 30 p) of the International Nickel Co. (Mond) Ltd. The powder contains about 0.15 pct 0, 0.01 pct C, 0.004 pct N, <0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni— that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The silicon powder was 99.9 pct purity, or material of transistor quality (ground in pestle and mortar). The mixed powders (3-1/4 pct Si to 96-3/4 pct Fe) are heated in hydrogen at 350" and 650°C to deoxidize the iron before sintering loose at temperatures between 1350" and 1460°C (depending upon the ultimate thickness of strip required) for up to 24 hr. The object of the high-temperature sinter is to develop a large grain size at this stage. Alternatively, the loose sintering can be done at a lower temperature followed by rolling or pressing and then annealing at temperatures between 1350" and 1460°C. Both methods produce large grains, which remain large throughout the process. The compact is then hot-rolled to approximately 1/8 in. with high-temperature interstage anneals if necessary. This step is taken to avoid intercrystalline cracking which would occur if the material of such large grain size were cold-worked. The bar is then annealed at 1050°C and reduced to its final thickness by approximately 50-pct reductions and 1050°C interstage anneals. Throughout the process the dew point of the hydrogen furnace atmosphere is maintained at about -40°C. Samples were annealed in hydrogen at various temperatures and times. Secondary recrystalliza-tion to (100) [001] was developed on the thinner material (i.e., up to 0.002 in.) by annealing in hydrogen at 1050" to 1200°C with a dew point of - 40°C or in vacuum (10-5 Torr) at 1050°C. With the thicker materials (i.e., up to 0.010 in.) the best results were obtained by annealing in hydrogen at 1200°C with a dew point of - 55°C. Complete secondary recrystal-lization to (100) [001] textures was obtained. Above these temperatures secondary recrystallization to (110) [001] tended to develop. The final annealing of samples was normally carried out with the samples placed between recrystal-lized alumina plates, but some experiments were performed with the samples suspended so that their surfaces were not in contact with anything except hydrogen, and these were equally successful in developing secondary crystals. An approximate determination of the proportion of material (before secondary recrystallization took place) having crystals with the (100) or (110) planes in or near the rolling plane showed that 11 pct of the sample had (100) and 16 pct (110). The method used for the determination is described below. A sample was annealed at a temperature just below the secondary recrystallization temperature and etched to reveal the (100) planes. The approximate area covered by crystals having (100) or (110) in or very near the surface was measured on the screen of a Vickers projection microscope. This was repeated for twenty positions chosen at random and a mean of the results calculated. The main hindrance to developing the secondary crystals in the thicker materials was the difficulty of obtaining a large enough initial primary grain size before secondary recrystallization. This was overcome by increasing the particle size of the silicon powder used. During the course of the work, it had been observed that the larger the grain size after sintering the more likely it was that the material would be successful in developing secondary crystals at a later stage. An experiment was therefore carried out to determine whether the material with the larger grain was more successful in developing secondary crystals due to the large grain produced at the sintering state per se or whether it was due to the greater reduction of silica brought about when the sintering temperature was raised in order to increase the grain size. A comparison was made between two compacts, one of which was made with silicon powder of 60 to 100 mesh, the other with silicon powder which was finer than 200 mesh. F?r this experiment, use was made of a phenomenon previously observed that the larger the particle size of the silicon powder employed in making a compact, the larger is the grain size of the compact. The silicon powder was ground

Jan 1, 1964

By Leonard Obert

The structural stability of any mine or under- ground opening in rock is dependent on the stress field, that is, the state of stress in rock before mining, the stress distribution in the rock created by the opening, and the in situ strength of the rock. In the past mine design problems have been considered by assuming that the stress field is due only to the weight of the overlying rock, the stress around the opening can be calculated from elastic theory using laboratory-determined elastic constants, and the in situ strength of the rock can be determined from laboratory tests on small specimens. Solutions to hypothetical problems using this procedure are given in a report by Obert, Duvall, and Merrill.&apos; Because of the uncertainties of these assumptions, this method can give only a rough approximation to the solution of actual structural problems. Obviously, this approach to determining the stability of underground openings would be greatly improved if the rock stress could be measured in situ, and it is undoubtedly for this reason that in recent years many investigators have spent considerable effort on the development of procedures for measuring rock stress. In this report a method is described for determining in situ the absolute stress in rock. The method requires the measurement of the deformation of a borehole before and after the rock is stress-relieved. The magnitude and direction of the applied stresses are calculated from the borehole deformation and modulus of elasticity of the rock. Also, the results of absolute stress determination made in the walls and pillars of underground openings in five rock types are presented. From these results a number of conclusions are drawn regarding the accuracy and limitations of this method and the problem of stress measurements in general.

Jan 8, 1962

By M. A. Jones

Performance of a pilot flood in eastern Kansas indicates improved recovery and accelerated production resulting from mobility ratio control obtained by adding a high moleculur weight polymer to injected water. Ultimate pilot flood recovery of the 75-cp reservoir oil is anticipated to he 350 bbllacre-ft during the six-year flood life. Cumulative recovery to date totals 242 bbl/acre-ft after 30 months of injection. Reservoir parameters and flood performance are disc~rssed in detail to provide a case history relating to the feasibility of polymer flooding. INTRODUCTION The Vernon Polymer flood of the Brazos Oil & Gas Co., located in Sec. 2, 24 S., 16 E., Woodson County, Kans., was begun in late Oct., 1963. Injection of a 500 ppm solution of Pusher* polymer was initiated in a 15-acre pilot to determine feasibility of improving oil recovery by mobility ratio control. Performance to date and the anticipated recovery of 115,000 bbl from the 329 acre-ft pilot indicate efficient displacement of the viscous reservoir oil. Dependence of flood recovery on the displacing fluid-displaced oil mobility ratio has long been recognized. Displacement efficiency of the reservoir oil decreases with increasing mobility ratio. Therefore, economic reduction of this parameter is an attractive approach to improving oil recovery. particularly from viscous oil reservoirs where mobility ratios are often quite high. Waterflood mobility ratios can be controlled by dilute solutions of certain polymers&apos;; which provide a displacing fluid with considerably reduced mobility. Reservoir parameters and flood performance are emphasized in this paper to provide data relating to polymer flood applicability. THEORY The polymer used in the Vernon pilot exhibits the property of unusually high resistance to flow through porous media.&apos;.&apos; A small concentration in injected water effects a mobility reduction considerably beyond that predicted from increases in bulk viscosity as measured in a capillary or rotating cup viscosimeter. Water mobility in the subject flood is reduced by a factor of 7.55 with the addition of 500 ppm Pusher chemical to injected water while the bulk viscosity is increased from 1.03 to only 1.40 cp at 75F. The exact flow mechanism causing resistance to flow has not been established; however, it is observed only in tortuous flow systems and appears to be influenced by brine properties, rock properties and oil saturation. Consequently, mobility reduction is estimated from flow studies for a given sample of reservoir rock and is expressed in terms of a "resistance factor".&apos; This parameter is defined as the ratio of brine mobility to polymer solution mobility measured at residual oil saturation: RF= ?m/?p= (km/µm)/(kp/µp)M.......(1) where RF = resistance factor (dimensionless) k*. and A, = mobility of water and polymer solution, respectively k,,, and k,, = water and polymer permeability, respectively (darcies) µie and µp = viscosity of water and polymer, respectively (poise). Eq. 1 is similar to the expression commonly used to relate the relative mobility of the water bank at residual oil saturation to oil-bank mobility at irreducible water saturation: where M =mobility ratio of water to oil (dimension-less) A, = mobility of oil k, = permeability to oil (darcies) )i* = oil viscosity (poise). From Eqs. 1 and 2 it is apparent that the polymer-solution-to-oil-mobility ratio can be approximated by dividing the brine-to-oil ratio by the resistance factor RF: Mpn=M10/RF...........(3) where M,-, = mobility ratio of polymer solution to oil (dimensionless). This simplified presentation assumes no dilution of the polymer solution by connate water. Also, the presence of a connate water bank separating the polymer solution from the displaced oil is not considered. Displacement of oil by waterflooding is increasingly dominated by viscous forces as the viscosity of the oil displaced increases. When the oil mobility is less than that of the injected water, the oil-water interface is not a piston-like front.3,&apos; Instead, instabilities occur at the flood front in the form of viscous fingers which tend to penetrate the less mobile oil bank. The magnitude of these protrusions, or the degree of channeling, increases

Jan 1, 1967

Jan 1, 1879

It has been established that molybdenum sesquisulphide, not molybdenite, is in equilibrium with molybdenum metal and sulphur vapor in the vicinity of 1100°C. The S2 pressure for this system has been obtained using the Knudsen orifice method and the standard free energy for the dissociation of S2. THIS work was undertaken to help in determining the thermodynamic properties of the molybdenum sulphide which is in equilibrium with metallic molybdenum and sulphur vapor in the temperature range 1025" to 1150°C. From the results of MontoroL and of Parravano and Malquori&apos; molybdenite would be expected to be in equilibrium with molybdenum metal, while the results of Guichard indicate that a lower sulphide must be in equilibrium with the metal. Thus it was concluded that the problem warranted reconsideration, especially in view of the suspiciously low temperature independent term for the standard free-energy function for the reaction MoS² Mo + S,. The reaction was calculated and duly noted as being low by Richardson and Jeffes,&apos; using the data of Parravano and Malquori.&apos; Experimental Method The general method used in this investigation is that of the Knudsen orifice method for the determination of equilibrium pressure. The apparatus and technique are similar to those described for the determination of the vapor pressure of silver.% owever, a closed-end McDanel tube instead of fused silica was used to maintain the vacuum, a molybdenum effusion cell with a replaceable lid was employed instead of a silica cell, and a titanium getter maintained at run temperature was used to assure that no oxidation of the molybdenum or molybdenum sulphide was taking place. All runs were made at a residual pressure less than 10-5 mm Hg. The data are given in Table I. Runs 1 through 13 were obtained using molybdenite, analyzed 98.5 pct, from the Molybdenum Corp. of America. The remaining runs were done with a sample from the Climax Molybdenum Corp. which was their grade No. 3 and analyzed 59.87 pct Mo. The weight loss of the cell during heating up and cooling down was subtracted from the total weight loss of the cell during the run. Also, when the tem- perature was changed, the Knudsen cell was placed in the vacuum chamber and heated at temperature for several hours in order to allow the sulphide and the metal to adjust their compositions to the equilibrium values, to desorb or adsorb gases into or from the molybdenum cell itself, and to desorb any water from the molybdenum sulphide or molybdenum powder inside the cell. Water may have been adsorbed inside the cell because, after each run, the top of the cell was removed and the material in the cell was stirred to insure that a layer of molybdenum metal would not build up and obstruct the passage of sulphur vapor into the gas phase. It was established that the molybdenum cell alone decreased in weight an inappreciable amount when heated at the highest run temperature for long periods of time. There are two questions to be answered before the data in Table I can be used to calculate thermodynamic functions: 1—Which molybdenum sulphide is in equilibrium with molybdenum metal and sulphur vapor? 2—What sulphur species are present in the vapor phase? It can be assumed safely that no molybdenum is vaporized, since its vapor pressure is almost negligible at these temperatures. It will be shown subsequently that no sulphide of molybdenum is volatile. Question 1 was answered in the following way: The especially purified molybdenite, obtained from the suppliers mentioned previously, was charged

Jan 1, 1956

By J. Chipman, N. J. Grant, R. Rocca

Desulphurization of liquid iron by reducing slags of the electric-furnace type was studied from 65 heats. Variations were made in basicity over a wide range and in FeO up to about 5 pct for their effects on desulphurization. The role of FeO in desulphurization from the blast furnace, to the electric furnace, to the oxidizing conditions of the open hearth is shown to fit a relatively simple pattern of behavior. THE mechanism which controls the desulphurization of molten iron by basic slags has been the object of several investigations. In particular, equilibrium determinations have been made both in the field of basic open-hearth slags, which have a high iron-oxide concentration, and in the field of blast-furnace slags which have a very low iron-oxide concentration. In both cases the desulphurization ratio has been found to increase with increasing basicity of the slags; however, the mechanism of desulphurization differs in the two cases. In basic open-hearth slags desulphurization occurs mainly as a partition of iron sulphide:&apos; FeS * (FeS) and the desulphurization ratio is approximately independent of iron-oxide concentration in the slag. In blast-furnace slags the concentration of iron oxide is very low as a result of the highly reducing conditions in which they are formed. The controlling reaction for desulphurization is then:2,3 FeS + (CaO) <=* (CaS) + (FeO) The slags of the reducing stage in the electric furnace have an iron-oxide concentration which is intermediate between blast-furnace and open-hearth slags. The study of the mechanism of desulphurization for these slags has been the object of this investigation. The importance of low (FeO) in the slag for desulphurization was first verified by Bardenheuer and Geller,& who found that high desulphurization ratios were obtained in highly reduced slags. It was recognized" hat iron oxide in the slag becomes a controlling factor in desulphurization only at FeO concentrations approximately under 5 pct. A recent investigation conducted by Buehl,7 upon the suggestion of one of the authors, confirmed this opinion from the results obtained from a heat conducted in a small arc furnace. In the present investigation, slags of very high basicity, such as often are encountered in the basic electric furnace, could not be studied, but equilibrium data have been obtained for slags in a wide basicity range. The iron-oxide concentration in these slags ranged from 0.08 to 15 pct and was controlled by the addition of silicon to the metal. Other constituents of the slags were mainly CaO, MgO, SiO2, A120,, and CaF,. The experimental technique was essentially the same as that of previous investigations.1 8-lo In an open magnesia-lined induction furnace, 65 lb of Armco ingot iron was melted. An atmosphere of hydrogen was maintained over the melt for 1 hr to bring the carbon content down to approximately 0.010 pct maximum. The bath then was exposed to air for 25 min to remove hydrogen. The electrodes were put in place, and the furnace was operated from this point on in an atmosphere of nitrogen. A synthetic slag was added to which additions of silicon and iron sulphide were made. A rate study conducted at the beginning of this investigation had

Jan 1, 1952

By P. Davey Wheeler

San Francisco meeting, September, 1915) IN an article in the General Electric Review, January, 1915, reference was made to the X-ray examination of a steel casting 9/16 in. thick. Fig. 1 shows one of the radiographs thus obtained. All these radiographs showed plainly the tool marks on the surface of the casting. All but one showed peculiar markings the shape of which strongly suggested that they were indeed the pictures of holes in the interior. A circular piece, 1 in. in diameter, was punched from the casting at a point where the radiograph shown in Fig. 1 indicated that a blow-hole should be found. (Location of sample shown by circle in Fig. 1.) Fig. 2 is a photograph of the end of the punching, showing the .hole that was found. Since that article was written it has seemed desirable: (1) to obtain data from which the exposure necessary for any thickness of steel could be at once calculated; (2) to find the thickness of the smallest air inclusion which could be radiographed in a given thickness of steel; (3) to determine in what direction to hope for further progress; and (4) to develop the technique of, radiographing metals. In order to gain some preliminary data, several pieces of ½ -in(12.5mm.) boiler plate were obtained, 5 by 7 in. (12.5 by 17.5 cm.) in size. In one of these, holes were drilled in such a way that the axis of each hole was midway between the faces of the steel and parallel to those faces. The diameters of these holes were as follows: Hole number Diameter 1 1/4 in. = 6.3 mm 2 1/8 in. = 3.1 mm. 3 1/16 in. = 1.6 mm. 4 1/32 in. = 0.8 mm. 5 1/64 in. = 0.4 mm.

Jan 8, 1915

By Paul Weir

BLEACHING clays have been used extensively in the oil-refining industries for a number of years. Their use in water purification is relatively recent and less extensive. They are frequently classified as (1) those naturally active and (2) those active after artificial activation with acid. Fuller&apos;s earths fall within the general group of bleaching clays and gradually the commercial term "fuller&apos;s earth" has been applied to natural clays originating, for the most part, in the south- eastern section of the United States. Bentonitic clays are usually classed as activable and are prevalent in the southwestern section of the United States. Bleaching clays vary considerably in chemical and physical properties throughout the country, or even in different parts of one deposit (Table 1). [ ] The fuller&apos;s earth type of clay is characterized by a lack of plasticity, relatively adsorbent, foliated structure, and does not swell to form a

Jan 1, 1939

By William Glenn

In their account of chromium, Roscoe and Schorlemmer (Treatise on Chemistry, London, 1879) state that "In 1762 Lehmann, in a letter to Buffon, de nova minerœ plumbi specie crystalline rubra, described a new mineral from Siberia, now termed crocoisite." In 1786 Lehmann analyzed it (Nicholson&apos;s Jour., Dee., 1798) and found that it contained chiefly lead, and that the " mineralizers " were arsenic and sulphur. It was next examined in 1189 by Macquart and Vauquelin, who stated that it contained an intimate mixture of iron, alumina, and lead peroxide. The account of their work was published over the name of Macquart. Vauquelin (Louis-Nicolas) was a Norman peasant, who had studied in the village school, and at the age of fourteen was a laboratory-boy in a pharmacy at Rouen. Later, he found his way to Paris, and in 1789 was assistant to Fourcroy, a pharmacist and a teacher of note. It was here that he met Macquart, with whom he did the work on Siberian red lead, and at this time his friend Cheradame taught him his Latin.

Jan 1, 1896

The American mining industry is vigorous today because it is young. At a time when the ore deposits of central Europe, for example, were being exploited actively, those of the United States were lying practically untouched. The founding fathers of our republic were not interested in mineral wealth because they were ignorant in such matters; their preoccupations were with defence against the Indians, the clearing of the forest, and the starting of agriculture in their new domains. They had no idea of establishing a mining industry. The Indians whom the American colonists dispossessed had no mines; they used only the metal that was to be found lying on the surface of the ground. Their arrows and spears were tipped with flint, which likewise called for little digging, if any. The native copper that glacial action had torn from the lodes of the Lake Superior region and had carried into the valleys of the Ohio and Mississippi was employed in the making of earrings, bracelets, knives, and scrapers. The same useful metal was found in many other places, in Virginia and Carolina, in Vermont and New Jersey, for example, but the Indians did not know how to melt it, much less how to smelt the ore, therefore they shaped it into tools and implements by hammering. Fortunately for them the hammering of the metal caused it to harden and therefore to become serviceable for implemental use. It is doubtful if they obtained the copper by actual mining, that is, by digging or excavating; it is true we find traces of such operations in the Keweenaw .peninsula of Michigan, but we have no

Jan 1, 1932

By Shawn T. Sorrell, Carl Hrovatic

Original by Carl Hrovatic and Shawn T. Sorrell Revised by Carl Hrovatic Land is a precious resource and should be treated as such by all members of our society. The soil covering this earth is only a very thin outer layer, varying in thickness from a few inches to a few feet and covering the rocks and minerals lying beneath the surface. The wise use of this valuable commodity is the responsibility of everyone. Many everyday activities disturb the earth&apos;s surface. Examples are highway construction, housing and commercial developments, agriculture, and various types of mining. This chapter discusses the relationships of the environment to land as it applies to surface operations in the coal industry. Mining by surface methods disturbs, for a brief period of time, thousands of acres of land annually. In addition, refuse piles, slurry ponds, abandoned mine structures, unprotected mine openings, and unsightly cleaning plants can also adversely affect land unless properly handled. ACTIVE SURFACE MINING OPERATIONS Mining by surface methods includes rock quarries; sand and gravel pits; huge open pits to extract iron, copper, phosphate, and other ores; and coal mining. Production of coal by surface methods is now approaching 408.2 Mt/a (450 million stpy), amounting to almost 60% of the total coal output. Surface coal mining can be classified into the following five broad categories : Open-pit mining is practiced where coalbeds are extremely thick, as in some western states, or where coalbeds are sharply pitching, as in the anthracite region of the eastern United States. A typical open-pit mine, with coalbeds of 3.05 to 30.5 m (10 to 100 ft) or more thickness and a

Jan 1, 1981