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Discussion of the paper of Blarney Stevens, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1285 to 1303. F. L. GRAMMER,Leesburg, Va. (communication to the Secretary*):¬ Mr. Stevens refers to an explanation of parallel jointing by W. 0. Crosby, which I noted when reading one of his excellent text books. It seemed to me earthquakes were not a satisfactory explanation, and I looked up several authorities; but I never realized how small the usual amplitudes were until Mr. Stevens presented his paper. Several letters to the U. S. Geodetic Survey showed me there were very few records of tidal movements of earth crust in the United States. Altitude and latitude would be influencing factors; but this diurnal movement must exceed earthquake amplitudes, besides being more nearly universal. My inquiries brought the answer that the major directions of jointing had not been extensively tabulated. If major directions of jointing were recorded-with notes as to angle with mountain chain, or North Star, and distance between joints, with nature of rock and maximum and minimum tidal up-heaval-some interesting relations might be made manifest.

Jan 11, 1913

By N. A. Gokcen, John Chipman

SILICON is the most commonly used deoxidizer and an important alloying element in steelmak-ing; hence a detailed study of this element in liquid iron containing oxygen is of considerable interest. The equilibrium between silicon and oxygen in liquid iron has been studied by a number of investigators but generally with inconclusive or incomplete results. The variation of the activity coefficients of silicon and oxygen with composition is entirely unknown. Published investigations deal with the reaction of dissolved oxygen with silicon in liquid iron and the results are expressed in terms of a deoxidation product. For consistency and convenience in comparison of the published information, the deoxidation product as referred to the following reaction is expressed in terms of the percentage by weight of silicon and oxygen in the melt in equilibrium with solid silica: SiO (s) = Si + 2 O; K'l = [% Si] [% 012 [I] Theoretical attempts to calculate the deoxidation constant for silicon in liquid iron from the free energies of various reactions yielded results which were invariably lower than the experimental values. Thus, the deoxidation "constants" calculated by McCance,1,2 Feild,3 Schenck, and Chipman were of the order of 10, which is below the experimental values by a factor of more than 10. Experiments of Herty and coworkers" in the laboratory and steel plant resulted in an average deoxidation constant of 0.82x10 ' at about 1600°C. The technique employed in their investigation was crude and the reported temperature was quite uncertain. The concentration of silicon was obtained by subtracting silicon in the inclusions from the total. Since at least some of the inclusions resulting from chilling must represent a fraction of the silicon in solution at high temperatures, such a subtraction is not justifiable. Results of Schenck4 for K'1 from acid open-hearth plant data yielded a value of 2.8x10-5, which was later revised as 1.24x10 at 1600°C. Similarly Schenck and Bruggemann7 obtained 1.76x10-5 at 1600OC. The discrepancies and errors involved in the acid open-hearth plant data as compared with the results of more reliable laboratory techniques were attributed by these authors to the lack of equilibrium and the impurities in liquid metal and slag, and are sufficiently discussed elsewhere." Korber and Oelsen" investigated the relation between dissolved oxygen and silicon in liquid iron covered with silica-saturated slags containing varying concentrations of MnO and FeO. The deoxidation products obtained by their method scatter considerably, and their chosen average values of 1.34x10, 3.6x10-5, and 10.6x10-5 1550°, 1600°, and 1650°C, respectively, represent the best experimental results which were available until quite recently. Darken's10 plant data from a steel bath agree approximately with their data at 1575° to 1625°C. Zapffe and Sims" investigated the reaction of H2O and H2 with liquid iron containing less than 1 pct Si and obtained deoxidation products varying by a factor of more than 20. Inadequate gas-metal contact and lack of stirring in the metal bath should require a longer period of time than the 1 to 5.5 hr which they allowed for the attainment of equilibrium. Furthermore, their oxygen analyses were incomplete and irregular and confined to a few unsatisfactory preliminary samples. Their results did indeed indicate that the activity coefficient of oxygen is decreased by the presence of silicon, although they made no such simple statement. They chose to attempt to account for their anomalous data by the unlikely hypothesis that SiO is dissolved in the melt. Hilty and Crafts" investigated the reaction of liquid iron with acid slags under an atmosphere of argon, making careful determinations of silicon and oxygen contents at several temperatures. Despite erroneous interpretation of the data at very low silicon concentrations, their data represent the most dependable information on this equilibrium that has been published. In the range 0.1 to 1.0 pct Si, their data yield the following values for the deoxidation product: 1.6x10-5, 3.0x10- ', and 5.3x10 at 1550°, 1600°, and 1650°C, respectively. The purpose of the work described herein was to study the equilibrium represented by eq 1 as well as the following reactions, all in the presence of solid silica: SiO2 (s) + 2H2 (g) = Si + 2H2O (g);

Jan 1, 1953

By P. M. Robinson, J. S. LI. Leach

The heats of solution oj' indiurrr, tin, lend, nrzd tellurium have been calculated from the measured heat effects when mechanical mixtres of indium and telLuium tin and tellurium, and lead and tellurium were added to liquid bismuth. The results are in good agreement xith publislzed values.s for the separate sollction of each eleltzent in bismuth. The heats oj solution of cadmium and tellurium calculated from the rneasuved heat effects on adding trechanical mixtures of these elements do not ugree zc,itl the published values jbv the separate solution of each element. It is shown that at 623°K Ile interaction between cadmium and tellurium dissolved in liquid bismuth is strong enough to led lo preciPitation of solid CdTc. The heats oj- jor-mation of CdTe at 273" nd 623°K (1)-c crilculated fi-or the measured heat ejlfecls. The calcnlaled az'erage deviation from the Kopp-l\'ez?,zunrz rule fov solid CdTe is less than 0.06 cat per g-atom- C over this lertzperalure range. Tlze importance 0.f these oDserl.ations to the determination of heals of formation hy metal solution calorimetry is considered. LIQUID metal solution calorimetry is a convenient method for determining the heats of formation of solid compounds. In this technique the heat of formation is the difference between the measured heat effects on dissolution of the compounds and of mechanical mixtures of the components in the liquid metal.' The heat of solution of the mechanical mixture may be calculated from the measured heat effect. At infinite dilution of the solutes, this heat of solution is equal to the sum of the heats of solution of the separate components. If the heat of solution of one of the components is known, the value for the other can be derived; if both are known, they may be used to check the accuracy of the calorimetric technique. The heats of formation of the tellurides of cadmium, indium, tin, and lead have recently been measured by metal solution alorimetr. The heats of solution of indium, tin, lead, and tellurium at infinite dilution in liquid bismuth at 623"K, calculated from the measured heat effects on solution of the mechanical mixtures, are in good agreement with the published values. The heats of solution of cadmium and of tellurium calculated from the measured heat effect on solution in bismuth at 623'K of mechanical mixtures of cadmium and tellurium, however, do not agree with values estimated from the literature. 1) EXPERIMENTAL PROCEDURE AND RESULTS The Heats of Solution of Indium, Tin, Lead, and Tellurium in Bismuth. The heat effects were measured when mechanical mixtures corresponding to the compounds In,Te, InTe, In2Te3, In2Te5, SnTe, and PbTe were dissolved in bismuth. The calorimetric procedure and the method of calculation have been described elsewhere.' The heats of solution of the mechanical mixtures were obtained by subtracting the change in heat content per gram-atom of the sample between the addition temperature (273°K) and the bath temperature (623"K), (H623°K - H273°K)S, from the measured heat effects. The calorimeter was calibrated with pure bismuth. The reported values of the measured heat effects are based on (HGoK - ^273oK)Bi = 4.96 kcal per g-atom.3 The measured heat effects are found to be linear functions of the solute concentrations of the bath in the dilute solution range. The values, extrapolated to infinite dilution, are listed in Table I, together with the heats of solution of the mechanical mixtures calculated using the published values of (H 623°K - H273°k)s for indium, tin, lead,3 and tellrium. All the error limits quoted in this work represent the spread of values obtained. The heats of solution in liquid bismuth at 623°K of mechanical mixtures of indium and tellurium in four different proportions were determined. Values of the heats of solution of the two components were then calculated from the resulting four simultaneous equations: The heats of solution at infinite dilution of tin and lead in liquid bismuth at 623°K were calculated from the heats of solution of the mechanical mixtures of tin and tellurium and of lead and tellurium using the heat of solution of tellurium calculated above. These values of the heats of solution are listed in Table I1 together with some published values for comparison.

Jan 1, 1967

By R. A. Oriani

The partial molal volume of hydrogen is one of the parameters that describe the elastic interaction between the solute and the stress fields about inclusions, dislocations, and cracks. As such the partial molal volume is probably of importance in the elucidation of phenomena such as hydrogen embrittlement and hydrogen yield point. A knowledge of this quantity would also be helpful in thinking about the state of dissolved hydrogen in iron. However, because of the very low lattice solubility of hydrogen in iron the usual ways of determining the lattice expansion are not practicable. It is therefore of interest to apply the thermodynamics of stressed bodies to two sets of measurements of the effect of elastic stress upon the permeability of hydrogen in order to deduce a value of the partial molal volume, VH, of hydrogen dissolved in a iron. Beck ..' and previously de Kazinczy, observed that a uniaxial tensile stress increases the permeability of hydrogen in iron and in various steels. Beck et 01. employed Armco iron and A.I.S.I. 4340 steel, whereas de Kazinczy used a steel the composition of which was 0.13 C, 0.23 Si, 0.46 Mn, 0.006 P, and 0.038 S. Upon releasing the stress the permeability increment disappeared if the stress was below the elastic limit. Both investigators employed cathodic charging to introduce the hydrogen. de Kazinczy measured the permeation through a thin-walled tube by collecting the gas, whereas Beck et al. measured the permeation through sheets of various thicknesses by a very sensitive electrochemical technique. Both investigators measured the steady-state permeation at constant rate of hydrogen ion discharge, and Beck measured in addition the hydrogen diffusivity by a time-lag technique which is independent of the boundary conditions. Beck et al. and de Kazinczy found a linear relationship between log (J,/Jo) and the stress, where Ju/Jo is the ratio of the flux of hydrogen when the metal is under uniaxial tensile stress, a, to the flux under zero stress, for the same temperature and charging current. Beck et al. found in addition that the diffusivity of hydrogen is not changed by stress. Both investigators concluded that the observed change in permeability is due to an increase in hydrogen concentration, and furthermore that the increase in concentration is due directly to the thermodynamic effect of stress upon concentration. Accepting this assessment of the situation for reasons given below, one may use the equation3j4 in order to evaluate I/H, the partial molal volume of hydrogen. This equation is valid for the domain of a/E «¦ 1 (where E is the Young's modulus) and under the assumption that hydrogen expands the lattice isotrop-ically. From the data of Beck el al, one calculates V7H - 2.0 cu cm per g-atom, and from those of de Kazinczy one obtains 1.8 cu cm per g-atom. That the increase of concentration with stress is indeed of thermodynamic origin is attested to by the facts that the experimental results conform to the thermodynamic relation, Eq. [I], and that the results are the same whether a pure iron1 or each of two different steels172 is used. Neither of these facts wou1.d necessarily be expected if the effect of stress were, rather, to increase the ratio kn/k, of the kinetic factors of the following competing reactions: H(ads) — H (dissolved) Such a change of kinetics at the surface could be an alternative explanation of the effect of stress on the permeability. Although this writer does not deem this explanation to be the correct one for the reasons given above, it must be admitted that unambiguous proof that the phenomenon has a thermodynamic origin does not yet exist. Two kinds of experiments may be suggested. One is to plate a variety of metals on the input surface of the steel and repeat the stress experiment at a variety of hydrogen charging currents. The other is to employ somewhat thicker specimens in order to be able to apply uniaxial compressive stress. Eq. [I] shows that ln(c,/c,) depends on the sign of the stress, but it is difficult to see a physical basis for which k2/kl would depend on the sign of a. The present value of V^ in a iron agrees with phragmen's5 estimate, which he based on comparisons with the lattice expansion by hydrogen of titanium, zir-

Jan 1, 1967

By Lewis E. Dr. Young

MINING engineers in the United States understand that mining conditions in the British coalfields are much more difficult than in most of the mines now being operated in the United States. We realize also that in the near future we must face some of these same difficult problems. Early Mechanization The progress made in mechanical loading in the United States is the result of a long struggle in many coalfields to mine with power tools safely and to increase output per man-shift. Attempts to use power to loosen coal and to transport broken coal in the U. S. may be said to date from the Stanly Header, or Entry-Driver brought from England in 1888. The principle of this boring machine was used in the McKinlay Entry-Driver, almost continuously used in the U. S. since 1920. Since 1888 experimental loaders, scrapers, and conveyors were installed with more or less success. Beginning in 1918, considerable progress was made with mobile loaders, and in 1920 the first wage agreement for the operation of mechanical loaders was made in Indiana. In 1923 the Pocahontas Fuel Co. loaded nearly 1 million tons of coal using 23 Coloders. Labor Policy The United Mine Workers of America have never officially opposed the Mechanization movement. On December 10, 1945, in a statement before the House of Representatives Labor Committee, John L. Lewis said, regarding the policy of the United Mine Workers of America: "We have welcomed progress; we have welcomed machines. We have told our people that they had to accept that condition; that it was the process of progress, and that they would have to take their chances." Recent Development In 1951 about 71 pct of the tonnage mined underground was mechanically loaded. Over 4000 shuttle cars are in service and it is estimated that much more than half of the tonnage loaded underground is produced by trackless mining. In 1947 roof-bolting was introduced extensively and it is estimated that more than 2 ½ million bolts are now being used per month in about 600 mines. The use of roof bolts has permitted the more effective and safer use of loaders and shuttle-cars. Continuous Mining The McKinlay Entry-Driver could have been used for continuous mining, but for many years it was used only .for entry driving. In 1946 the Silver machine was developed in Colorado, and in 1947 this was acquired by the Joy Mfg. Co. and called the Joy Continuous Miner. Other types of combination mining-loading machines which eliminate drilling and blasting operations are the Marietta Miner, the Colmol, the Lee-Norse Miner, the Junior Miner, the Goodman and the Konnerth machines. There are several other types in the process of development. Probably by January 1953 there will be about 250 continuous miners in operation in the U. S. Payment of Mine Labor One of the most important problems in mechanizing was the establishing of rates of pay that would be attractive to the best men. Prior to the installation of mobile loaders the hand loaders and cutters have been paid by the ton. It was felt that a system of a day's pay should be established and that piece and tonnage rates should be abolished completely. Without exception, all coal loaded in mines equipped with mobile loaders is prepared and loaded by men paid an hourly rate. Trends in Mining Research There are two diverse approaches in coal production research; to try to design a mining machine to fit current methods, or to adapt mining practice to take advantage of proven machines. A great deal of credit must go to the mine operators who have been enterprising and dynamic enough to use available equipment intensively and to discard it as soon as an improved or new machine is available. Effect of Changing Markets Formerly there was an important demand for lump and prepared coal in the larger sizes for domestic use. The use of bituminous coal for house heating has decreased so that not more than 19 pct of the annual tonnage goes to retail trade, only 12 pct is used by the railroads, and much of the retail and most of the railroad coal is in stoker size. As a result of this decline in the market for coarse coal most of the large mining operations have crushers installed in the tipples or preparation plants. Mass production at the face requires increased preparation facilities. Another important trend is in connection with complete seam mining with mechanical loading. In many mines where the immediate roof is apt to fall with the coal no effort is made to separate roof material from coal prior to

Jan 1, 1952

By C. G. Albert

The clay particles of 2 microns or less required for modern paper coating are predominantly flat plates, lying smoothly on the sheet and producing a high gloss. Operating speeds of today's coating machines necessitate a clay composition of 60 and sometimes 70 pct solids as against the 35 to 40 pct required in the past. Since clays in suspension may solidify in flow, only those of intrinsically low viscosity can be used as high coating solids. THE literature of paper technology contains a number of articles having reference to developments in the field of coating and filler clays for use in paper manufacture. Much of this information has not been included in mining publications and has therefore not been readily available to all in the mineral industry. Recent developments in this field, including spray drying of clays, are presented here. U. S. Bureau of Mines figures for 1952 indicate that the paper industry consumes more than 50 pct of all kaolin produced and sold in the U. S. As most of the kaolin used by the industry comes from Georgia producers, the fraction of their output destined for paper use is thus appreciably higher than 50 pct. Small wonder that the kaolin industry, especially in Georgia, is highly sensitive to the quality requirements of paper mills and must respond promptly to technological developments in paper manufacturing. The paper industry itself is not the ultimate consumer. For the greater portion of the clay the end product is the printed page, and the demands of printing and publishing have sparked some of the technological advances in paper making which have, in turn, brought about methods employed in the kaolin industry. As compared with the product of 20 or 25 years ago, one of the most striking characteristics of the graphic arts today is the mass production of quality printing of fine pictorial work, much of it in full color. During this time periodicals with printing standards close to those of yesterday's slick-paper publications that were printed on a slow schedule and for a limited circulation have grown to the point where they go out to many millions of readers, often at weekly intervals. The complexity of technological improvements brought about by this increased circulation is probably not appreciated even by technical people, unless they have had reasonably close contact with the industry. The advance has come about through developments not only in the art of printing, but also in the field of paper making and even at the level of clay mining and processing. The smoothness required for faithful reproduction of the kind of printed matter under consideration is attained with a clay-coated paper. Since the distribution expense of the publication will depend to a great extent on its weight, the paper used must not be too heavy. This means a lower basis weight than was normal for conventional clay-coated papers some 25 years ago. And for this mass production market it becomes necessary to provide a paper having these and all the other required characteristics at a very moderate price—not the premium price conventional clay-coated papers formerly demanded. This challenge has been met by a new method of producing coated paper. In the past, application of clay coating to paper was a conversion operation, performed separately from the making of the base sheet. The newer development is called machine coating. Here application of the coating is an integral step in a continuous process by which wood pulp, clay, and other ingredients are manufactured into a sheet of coated paper. Many more problems are involved in this procedural change than are apparent at a casual glance. The coating operation, for example, must function at much higher linear speed than could be obtained with coating mechanisms previously employed. The application machinery developed to meet this requirement necessitated changes in composition of the coating color.* This created new requirements, summarized below, for the clay employed as coating pigment. In addition to smoothness, a relatively glossy printing surface is needed, and to a large measure it is the function of the coating clay to make possible the development of both these surface characteristics. Traditionally, pigments such as satin-white, prepared by reacting lime with paper-makers' alum, were used to assist in producing a high finish. However, economic considerations and others preclude large-scale use of such material in the new processes. In the 1930's Maloney' discovered that a certain particle size fraction of kaolin, consisting

Jan 1, 1956

By S. J. McCarroll

Fig. 1—The belt shown at right carries filter cake to mixing station over calciner. Crude ore conveyors appear in right background. THE Three Kids mine, some six miles east of Henderson, Nev., is in a typical southwest desert area, with high dry summer heat and cool to cold winter seasons. The manganese deposit was located during World War I.' During this period 15,000 to 20,000 tons of ore assaying up to 41 pct manganese were shipped. Interest in the deposit was not revived until the middle thirties, when experiments on the ore were initiated. Test work indicated possible recovery of only 70 pct by flotation, but in 1941 additional work was done at the Boulder City pilot plant of the U. S. Bureau of Mines and also by M. A. Hanna Co. As a result, the Manganese Ore Co. was formed and a plant utilizing the SO2 process was constructed. Numerous operation difficulties ensued, and the plant. was closed when the manganese situation in the country eased. In 1949 Hewitt S. West initiated negotiations to acquire the plant. In 1951 Manganese, Inc., was formed and contract entered into with the General Services Administration to supply 27 million units of metallurgical grade manganese in the form of nodules to the national stockpile. A second contract was made to upgrade 285,000 tons of stockpile ore. Test work was undertaken by the Southwestern Engineering Co. and likewise by the Boulder City pilot plant at the U. S. Bureau of Mines. Results obtained indicated the commercial feasibility of the flotation process. Construction of the plant, which is shown in Figs. 1 and 2, was started in June 1951, and operations on a break-in basis began in September 1952. Apart from the usual starting difficulties two major disasters caused serious setbacks, one a kiln failure in February 1953, and the other a fire that destroyed the flotation building in June of the same year. The nodulizing section of the plant resumed operation in November, and the flotation section in January 1954. The ore minerals are chiefly wad,* with minor amounts of psilomelane, and occur in sedimentary beds of volcanic tuff. The ore is overlain with beds of gypsum which outcrop or may be covered with surface gravel. Intermediate beds of red and white tuff occur frequently with lenses of red and green jasper and stringers of gypsum and calcite. Small amounts of iron are present; lead content averages about 1.0 pct and minute amounts of copper and zinc are found. Barite, celestite, and bentonite are present. Since these are made up of minute asicular crystals, moisture content is very high, averaging about 18 pct. Ore reserves have been estimated at 3 million tons averaging 18 pct Mn2 and up to 5 million tons after grade is dropped to 10 pct Mn. A good part of the orebody was stripped of overburden by the previous operating company . Approximately 50 pct of the ore, representing more than 60 pct of the manganese, can be mined by open-cut methods. A system for underground min- . ing has not yet been decided on. Open-cut mining with benches of 20 ft has proved satisfactory. Although the ore is soft and appears dry and dusty it has a certain resilience, probably due to the porosity and moisture which makes drilling and fragmentation difficult. Wagon drills have been abandoned in favor of the Joy 225-A rotary drill which will put down a 43/4 -in. hole at the rate of 2 ft per min. Holes are spaced in a pattern with 8 to 9-ft centers. Forty percent powder has been used, but better breaking to 2-ft size is obtained with low velocity bag powder of 30 pct strength. Loading is done with one 21/2-yd shovel, and cleanup follows with one D-7 bulldozer. The ore is hauled with Euclid trucks about 1000 ft from the pit to a blending pile, where the daily mine production is spread in layers by bulldozing until approximately one month's mill feed is accumulated. A new pile is then started and mill feed is drawn from the first pile by one 13/4-yd shovel and Euclid trucks, with a haul of approximately 500 ft. Mining is performed by an independent contractor with engineering and supervision by the company staff. Early test work indicated that the manganese could be floated with soap, a wetting agent, and fuel oil to give a recovery of better than 75 pct with a grade of 43 pct Mn. The concentrate when nodulized with coke would upgrade to 46 pct Mn or over, and the lead volatilized to 0.6 pct residual.

Jan 1, 1955

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,' and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,' the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,' who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By H. J. Levinstein, H. J. Guggenheim, C. D. Capio

An optical incestigation of the phase transformations in RbFeF, has been conducted. Details of the ferromagwetic phase transition and the metamagnetic state are disczrssed. The three-dimensional magnetic domain structure existing in bulk crystals of RbFeF3 is described, as well as the effect of the magnitude and direction of the applied magnetic field on the domain struclure. The strong magnetoelastic interaction in RbFeF, is demonstrated. The results of the direct observation of the role of dislocation subboundaries and slip bands as nucleation sites and as pinning sites for magnetic domain walls are reported. THE perovskite compound RbFeF, has recently been shown to exhibit three magnetic states.''' Above 102°K it is paramagnetic, between 102" and 87°K it is antiferromagnetic. and below 87°K it is ferromagnetic (i.e., exhibiting remanence) with a modification of the magnetization occurring at 40°K. The changes in magnetic structure at 102o, 87°. and 40°K are accompanied by shear transformations to successively lower crystal symmetry classes.3 At 102°K a second-order phase transformation to a tetragonal crystal structure occurs. The c/o ratio increases with decreasing temperature to a value of 1.0034 at 87°K where the crystal undergoes another shear transformation to an ortho-rhombic crystal structure. The magnetic modification at 40 K is also accompanied by a shear transformation to a lower crystal symmetry. RbFeF3 is unique in that in the ferromagnetic state it is transparent in the bulk to visible light, has a low saturation magnetization, a large magnetic rotation. and has good optical properties.' All these features make it an ideal material for the investigation of magnetic domain structures in bulk crystals. In addition a dislocation etch has been developed which reveals the point of emergence of dislocations with the (100) surfaces of RbFeF3,5 making it possible to determine the dislocation arrays in the material. As a result domain wall dislocation interactions can be observed in the bulk crystal. In this paper we report on 1) the crystallography of the phase transformations in RbFeF3. 2) the domain configurations as a function of magnetic field and crystal orientation. 3) the interaction of dislocations and magnetic domain walls in RbFeF,. EXPERIMENTAL PROCEDURE Since the temperature range of interest is below room temperature the dewar shown in Fig. 1 was employed. It was designed to fit on the stage of a Leitz panphot metallograph, and permitted examination of the sample at a magnification up to 150 times. The dewar consists of a double-walled glass cylinder bent into an L shape. The space between the walls is evacuated. The viewing wirldows were made of four optically flat quartz discs aligned parallel to each other and sealed to the sides of the concentric cylinders. The specimens were mounted in a holder attached to a flexible plastic shaft. Various holder designs were employed depending upon the type of observations to be made. For studies of the phase transformation between the antiferromagnetic and ferromagnetic state the holder shown in Fig. 2(d) was employed. This holder permitted accurate temperature control at 82" to 88°K by balancing the heat input from the carbon resistance heater against the heat loss to a heat sink immersed in liquid N2. Magnetic field studies were conducted by employing the holders shown in Figs. 2(a) and (b). The holder shown in Fig. 2(n) has a solenoid imbedded in it. such that the magnetic field direction is in the same direction as the incident light. The magnetic field provided by the holder in Fig. 2(b) is perpendicular to the incident light direction. The holder in Fig. 2(r) was employed when observations of the specimen were desired while an elastic bending stress was applied to the sample. The stress was applied to the sample by pulling a wire from outside of the dewar. The wire was attached to a lever pivoted on the holder. which caused the knife edge of the lever to push against the sample. The crystal growth and the sample preparation were described previously.' PHASE TRANSFORMATIONS The first phase transformation in this system is from the cubic perovskite structure to n tetragonal

Jan 1, 1970

By Ralph L. Erickson

The discovery of a Carlin-type gold deposit at Cortez, Nevada, in 1966 can be attributed directly to the use of geochemical exploration techniques. Most mineral deposits owe their discovery to geologic concepts, geologic analysis, and luck, but at Cortez, geochemistry as an exploration tool played the clearly dominant role in discovery. Of course, the economic significance of the discovery had to be determined by exploration and development drilling. The story of the discovery began in 1959 when field work was initiated on a new project, "Geochemical Halos Utah and Nevada," by R.L. Erickson and A. P. Marranzino for the US Geological Survey. The Cortez district was selected for geochemical work because it was an area with good geologic control where we could address the problem of how to prospect in barren outcrops for concealed ore deposits in potentially favorable structures (buried thrust zones) or favorable host rocks in the subsurface. Geologic mapping of the Cortez 15-min quadrangle, just being completed by Gilluly and Masursky (1965), showed that the quadrangle contained excellent exposures of both the upper and lower plates of the Roberts Mountains thrust fault, a major structural feature of north-central Nevada. Roberts (1960) had noted that a number of mining districts were associated with windows in the thrust. In 1959, Erickson and Marranzino did some reconnaissance rock sampling and spring-water sampling in the siliceous clastic rocks of the upper plate of the thrust. Results of this reconnaissance prompted a full-scale sampling program in 1960 in the upper plate rocks on the west flank of the Cortez window. Results of the investigation showed that anomalously high concentrations of metals occur in the upper plate rocks, and further, that the distribution of metals is fault controlled and shows a pronounced zoning pattern (central copper zone; intermediate zinc, copper, and lead zone; and outer arsenic zone). The anomalies were interpreted as primary leakage halos that originated from metal occurrences in the thrust zone or in carbonate rocks below the thrust and moved upward along normal faults that cut both upper and lower plate rocks. Erickson gave a talk about these anomalies in the summer of 1961 to the local AIME Section in Reno, Nevada; two short reports were published that year-" Geochemical Anomalies in the Upper Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1961) and "Hydrogeochemical Anomalies in Four Mile Canyon Near Cortez, Nevada" (Erickson and Marranzino, 1961). These releases prompted blanket staking in the area by several small companies. In 1963, geologic and geochemical mapping were started by the USGS in the lower plate carbonate rocks of the Cortez window west of the quartz monzonite stock at Mount Tenabo and north of the old townsite of Cortez. The results of the work showed anomalously high concentrations of arsenic, antimony, and tungsten in jasperoid, fracture filling, and shear zones in Silurian and Devonian carbonate rocks. The anomalous area was about 1.6 km (I mile) long and 300 m (1000 ft) wide. A brief report, "Geochemical Anomalies in the Lower Plate of the Roberts Thrust Near Cortez, Nevada" (Erickson et al., 1964a), was published in 1964. During this same time period, 1959-1964, several exploration or mining companies were active in the general area (chiefly mapping geology and acquiring property). In 1964, American Exploration and Mining Company (Amex) concluded that the entire Cortez district was worthy of an extensive exploration effort involving drilling as well as geologic, geophysical, and geochemical studies. To carry out the program, Amex formed a joint venture group with the Bunker Hill Company, Vernon Taylor, Jr., and Webb Resources. Their early efforts were directed to the upper plate rocks and to the lower levels of the old Cortez silver mine. The group also drilled some shallow rotary assessment holes adjacent to the area of the arsenic, antimony, tungsten anomaly in lower plate carbonate rocks described in Erickson et al. (1964a). Assay results from these holes offered little or no encouragement to the joint venture group. Splits of these drill samples were made available to the USGS. In order to enhance any metal content present in these rocks and to determine the mineral residence of any metals detected, heavy-mineral concentrates of each 3-m (10-ft) sam-

Jan 1, 1985

By F. Weinberg, E. H. McLaren

Dilute binary alloys have been solidified under controlled thermal conditions, and solute distributions, temperatures during freezing and melting, and the position and morphology of the solid-liquid interfaces have been examined. Binary Zn, Sn, and Pb based alloys were investigated with solute additions of AgU°, AU°, Sb'24, TlZo4, snH3, and Zns5. Approximately 150 cc of metal was used in each ingot. Appreciable solute segregation occurred in most of the ingots, depending on the solute concentrations, distribution coefficients. and freezing conditions of the alloys. Measurements were made of the general solute distribution by sectioning layers of material from the ingot circumference and counting the activity of each layer. Local segregation was detected by autoradiographic techniques. Freezing and melting curves for the same alloys were obtained by precision resistance thermometry. These curves are related to the corresponding measured solute distribution curves and those calculated from theoretical expressions. The position and morphology of solid-liquid interfaces during freezing were determined by both decanting and quenching techniques. The results indicate the manner in which freezing and remelting occurred under the conditions investigated. If an isomorphous dilute binary alloy is solidified or melted under equilibrium conditions, the concentration of solute in both solid and liquid would be uniform at all stages in the freezing process. The solute concentrations during freezing could be determined from the phase diagram of the alloy, and the freezing curves would have an alloy slope defined by the solidus and liquidus points. In practice, however, solidification under equilibrium conditions rarely, if ever, occurs, primarily because of low rates of diffusion in the solid and incomplete mixing in the liquid. As a result, the solute distribution and the shape of the freezing and melting curves obtained in a given system depends on a number of factors. These include, in addition to the extent of diffusion and mixing, the initial solute distribution and concentration, the distribution coefficient, the rate of freezing or melting, supercooling of the liquid, the morphology of the solid-liquid interface, and the effect of annealing. The purpose of the present investigation was to determine, experimentally, actual solute distributions and thermal curves for a series of dilute binary alloys, using tracer techniques to determine the solute distributions and precision resistance thermometry for the temperature measurements. In addition, observations were made of the positions and morphologies of the solid-liquid interfaces during freezing and remelting. The distribution of solute in a dilute alloy, assuming complete mixing in the liquid, and negligible diffusion in the solid, is given by1 where Co is the mean solute concentration of the alloy, C, is the solute concentration in the solidg is the fraction of the ingot solidified, and ko is the equilibrium solute distribution coefficient (assumed to be independent of concentration for dilute alloys). For the case of partial mixing, ko can be replaced by an effective distribution coefficient k. If solute transport in the liquid is assumed to be entirely due to diffusion, with negligible diffusion in the solid, then the solute distribution in the solid is given by Tiller et a1.' as where R is the rate of advance of the solid-liquid interface, D is the solute diffusion coefficient in the liquid, and x is the position of the interface from the start of freezing. The temperature at the interface TI is related to the solute concentration of the solid at the interface C, by the expression where Tm is the freezing temperature of the pure solvent and ml is the slope of the liquidus for the binary alloy being considered. Accordingly, by relating TL to the actual temperatures measured in the present experiments, solute distributions can be deduced from the temperature measurements. Using the above expressions, the measured solute distribution of a given alloy may be compared to the theoretical distributions, as well as to the distribution calculated from the observed freezing curve. EXPERIMENTAL The solvent materials used in making up the binary alloys were C. P. New Jersey zinc (99.999 pct), Vulcan Extra Pure Tin (99.999 pet), and Tadanac lead (99.998 pct). The solute elements were of 99.99 pct purity or better, and were activated in the

Jan 1, 1963

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By R. T. DeHoff, F. N. Rhines

The problem of determining the number of particles of a phase distributed randomly in unit volume c an opaque matrix from measurements made on random plane sections is closely investigated. A formalized derivation for the general case is presented. Applications of this formal result are made to specific types of aggregates dispersed in a matrix; circles, particles with flat circular ends, cylinders, and constant shape aggregates of ellipsoids of revolution. Quantitative measurements of the average geometric properties of these aggregates are developed. In 1953 R L. ullman' developed a technique for determining, from measurements made on random plane sections, the number per unit volume, Nv, of particles imbedded in an opaque matrix. Using meas urements previously developed for volume fraction, vV,' and surface area per unit volume, .SV,= he was able to determine average volume, average surface area, and average dimensions of particles, independent of size distribution, for spheres and circular disks,' as well as for uniformly sized cylinders of any axial ratio.4 The technique is mathematically rigorous for the cases studied. Recent studies of this problem have yielded rigorous solutions for the general case of cylinders, permitting evaluation of NV independent of size distribution and with all axial ratios intermixed. Generalization to shapes having flat, circular ends has been deduced. A solution has also been obtained for the ellipsoid of revolution, independent of size distribution, but requiring a constant axial ratio in the generating ellipses. In the following derivations, as in Fullman's work, it is assumed that the problem is purely a combination of geometry and probability theory,that is,eithe the particles to be measured are imbedded randomly in the matrix, or a sufficient number of random plane sections are taken to make the sample representative. A relationship exists between the number of par- ticles of a given size and shape that may be situated in unit volume (Ny) and the number of intersections a random plane can be expected to make with these particles (Na). It is the purpose of the following section to derive this relationship. The probability of Intersecting Convex Bodies. Consider a convex, closed surface, that is, one for which no two surface normals point in the same direction, situated at some arbitrary position and orientation in a cube of material that is one unit long at each edge. It is not necessary to assume that this surface is symmetrical. Let planes be constructed in the cube parallel to the top face and at random distances from it. Those planes which lie between the two planes which are just tangent to the top and bottom of the surface will intersect it. The probability that a plane will intersect the body may be defined as the limit of the fraction of planes that lie between the two tangent planes as the total number of planes constructed becomes infinite. This fraction, in the limit, is equal to the distance between the two tangent planes, DV, divided by the total length over which planes are constructed, which has been taken as unity. If the body is now rotated to a new orientation, applying the same argument, the probability of intersection is again numerically equal to the distance between tangent planes. Let DV ($, 0) be defined as the distance between tangent planes of a convex body as a function of orientation, Fig. 1. The probability, Pr, of intersecting the body with a randomly oriented and randomly positioned plane, is then equal to the average value of DV (0, $) over all possible orientations. It may be easily shown that for a system of spherical coordinates the probability of finding an orientation between Q and Q + de, $ and $ + d$ is (1/4n) sin $ dB d$, so that This relationship may be applied to each body in an aggregate of convex bodies. In particular, if the bodies in an aggregate are classified according to size and shape, and the ithsuch class is considered, Eq. 111 may be applied to this entire class, the probability of intersecting any body in this class being

Jan 1, 1962

By N. Mungan, F. W. Smith, J. L. Thompson

Adsorption of polymers and transport, rheology and oil recovery efficiency of their solutions were studied in the laboratory to evaluate the use of polymers in waterflood-ing. While a tenfold mobility reduction was obtained with polymer concentrations as low as 0.05 per cent by weight, the mobility reduction depended on the type of polymer, molecular weight, salinity and pH of water, crude oil and capillary properties of the porous media. Choice of a suitable polymer and a workable concentration will have to be tailored for each application. Little reduction in the residual oil saturation can be expected from polymer flooding. Improvement in the volumetric sweep efficiency is possible hut the extent of the improvement can best be evaluated by properly designed field testing. Some aspects of the field use of polymer floods are discussed. INTRODUCTION Waterflooding is a simple, inexpensive secondary recovery method and is being used widely. Innumerable laboratory studies have been made to unravel the fundamentals of the displacement of oil by water and to find the ways of most efficient oil recovery. These studies and a great many field case histories have revealed that the prime cause of poor oil recovery is the inefficient and incomplete sweep of reservoir volume by the injected water. Sweep efficiency is affected by many factors of which the mobility ratio is an important one. Mobility ratio M is defined here as the ratio of water to oil mobilities: M = (k»/y,r)/(k,JJJJ........(1) In Eq. I, the permeabilities are the effective permeabilities and depend on fluid saturations and, hence, change during the different depletion stages in a flood. A wide practice is to use the effective water permeability at residual oil saturation and the effective oil permeability at interstitial water saturation in Eq. 1. If the mobility ratio is greater than one, the mobility ratio is unfavorable and water, being more mobile than oil, would finger through the oil zone resulting in poor oil recovery efficiency. If the mobility ratio is favorable (one or less) the displacement of oil by water occurs more or less in a pistonlike fashion. In some waterfloods. the mobility ratio is unfavorable and any additives by which the mobility of water can be decreased would favor more efficient oil recovery. The thing to bear in mind, however, is whether or not the improvement in oil recovery is sufficient to more than pay out the cost of the additives needed. For example, materials like sugars, alcohols and glycerine reduce water mobility by thickening the water, but the cost of material requirement precludes any field application. For an additive to be useful in water-flooding, it must bring about a large reduction in water mobility at low concentrations; it must be adsorbed only negligibly; and it must not completely plug up the formation. Some synthetic organic polymers have shown promise of meeting these requirements and have been used in the field.'-W owever, no in-depth studies of the rheological, adsorption and oil displacement characteristics of polymer solutions have been reported. The present work is a study of these properties. EXPERIMENTAL In this work, concentrations are given on a weight per volume basis; 0.5 per cent concentration means 0.5 gm of polymer is dissolved in enough water (or NaCl solution) to make 100 ml. A bactericide, usually 0.1 to 0.2 per cent by volume of 38 per cent formaldehyde solution, was used in the polymer solutions. The NaCl solution was 30,000 ppm. Some properties of the polymers studied are given in Table I. Physical properties of all cores used are in Table 2. Flow behavior of polymer solutions was studied by three consecutive flow tests in cores. First, water (or brine) was injected at constant rate of about 1 ft/D to obtain the water mobility. Then, filtered polymer solution (prepared in water or brine) was flowed through the core. Since the rate was constant, increase in the pressure drop across the core reflects decrease in the mobility. Finally, the core was flooded with water (or brine) to study recovery of mobility. The Alundum cores which were used in

Jan 1, 1967

By John D. Verhoeven

A technique has been developed for carrying out normal freezing experiments with a current density of 2000 amp per sq cut passing through the solid-liquid interface. The equation relating the effective distribution coefficient to the equilibrium distribution coefficient in electric field-aided solidification, originally developed by Huckc et al.,1 has been modified for the case of concentrated solutions. Preliminary experiments on the Sn-Bi system give qualitative agreement with the equation. The data are analyzed by a slightly novel use of the normal freeze equation which allows one to determine the effective distribution coefficient more easily. Very extensive mixing in the liquid was found at these high current densities and it is postulated that the mixing results from a vertical component of the magnetic Lorentz force generated by the electric current. In the search for techniques of obtaining ultrahigh-purity metals the inefficient but very effective technique of electrotransport has received little attention. Electrotransport is most effective in the liquid state and a natural application, therefore, is to apply an electric field across the liquid zone of a zone-melting experiment. The present investigation was undertaken to study the effect of an electric field upon solidification of metals, so that the usefulness of electrotransport in such solidification experiments as zone melting could be determined. In zone-melting and normal-freezing experiments it is difficult to achieve complete mixing in the liquid in the immediate vicinity of the solidifying interface. Consequently a solute build-up will occur at the interface in the portion of the liquid where complete mixing does not occur (an equilibrium distribution coefficient, ko, less than one, and unidirectional atom motion will be implied throughout). This local solute build-up produces a corresponding rise in the solute concentration in the solid so that the ratio of the solute concentration between the solid and the bulk liquid is larger than the equilibrium distribution coefficient. This ratio is defined as the effective distribution coefficient, k,. The differential equation describing the solidification process may be derived by applying the continuity equation to an expression for the net solute flux at the interface. The solution to this differential equation then allows one to determine the solute distribution in the liquid and the relationship between k0 and ke. One of the most useful solutions to this equation was first derived by Burton, Prim, and Slichter,' in which they assumed that a) the equilibrium distribution of solute was maintained on the plane of the interface, 11) the solute build-up ahead of the interface in the liquid disappeared at a distance 6 from the interface, and c) the solute distribution in the liquid was invariant with time. The following well-known relation between ko and ke was then obtained, where R is the rate of solidification and D the diffusion coefficient of the solute in the liquid. This equation appears to correlate the data from a number of different types of solidification experiments very well. Application of an electric field across the solid-liquid interface can produce an additional flow of solute atoms as a result of the electrotransport. When the polarity of the field is such as to direct the electrotransport flux away from the interface the solute build-up may be diminished, even to the point of producing a solute depletion and a consequent ke smaller than ko. The quantitative description of this process and the resulting form of Eq. [I] was first given by Hucke et al.1* and then inde- where E is the electric-field intensity and U is the differential mobility, i.e., the velocity of the solute atoms with respect to the solvent atoms per unit electric field. Both authors follow the method of Burton, Prim, and Slichter in their derivation, the only difference being the additional electrotransport term in the flux equation. It has been pointed out1,3 that Eq. [2] predicts the possibility of a noticeable increase in the purification of materials by solidification in an electric field. The validity of Eq. 121 has not been checked experimentally and it is possible that other factors' arising from the presence of an electric field across

Jan 1, 1965

By F. S. Pettit

The oxidation of Ni-3 to 25 wt pd Al alloys has been studied in 0. 1 atm of oxygen at temperatures between 900° and 1300°C. These alloys have been found to oxidize by three different mechanisms which depend on the temperature of- oxidation and the alloy composition. Two of the three mechanisms do not permit a continuous layer of Al,0, to be formed on the alloy surface and the oxidation rates are greater than that for pure nickel. The third mechanism results in the formation of an external A1203 scale and lke oxidation rates are about three orders of magnitude smaller than those for pure nickel. The minimum amount of aluminum required for the formation of external scales of A L,0, has been determined. NICKEL-base alloys are currently the main source of materials for use at elevated temperatures in gas turbine engines. These alloys are usually coated to obtain oxidation resistance. Coatings on nickel-base alloys are frequently formed by reaction of the alloy with aluminum whereby alloyed nickel aluminides are formed. The alloyed nickel aluminides provide protection to the nickel base alloy because external scales of A1203 (alumina) are formed during oxidation and mass transport through A120, is slow in comparison to mass transport through most other oxides. In view of the protective properties of A1203, it is important to know how much aluminum is required in these alloys in order to form external scales of AlzO,. The present paper is concerned with the oxidation kinetics and the oxidation mechanisms of Ni-A1 alloys and the minimum amount of aluminum required in these alloys for the formation of external scales of Alz03. THEORETICAL CONSIDERATIONS When a Ni-A1 alloy is heated in oxygen at elevated temperatures, the following reactions can take place on the surface of the alloy where the oxide phases are assumed to be virtually pure: These oxide phases are in the form of nuclei scattered over the surface of the alloy and, in view of their rapid formation, they need not be in equilibrium with the alloy. As the oxidation process continues, equilibrium between the alloy surface and the oxide phases is approached and the stability of the oxide nuclei is determined by the composition of the alloy at the alloy/oxide interface because of the following reactions: 3NiA1204 + 2A1 (alloy) = 4AlzO3 + 3Ni (alloy) [41 4Ni0 + 2Al (alloy) = NiA120, + 3Ni (alloy) [ 5 1 Application of the mass-action law to Eqs. [4J and [5J yields the following equilibrium conditions for these reactions: where aA1 and aNi are the activities of aluminum and nickel, are the standard free energies of formation of NiO, A1203, and NA1204, respectively, R is the gas constant, and T is the absolute temperature. If the composition of the alloy at the alloy/oxide interface is such that (akl/ahi) is greater than the equilibrium values defined by Eqs. [6] and [7], then Reactions (41 and [5] will go to the right as written. Conversely, if the alloy composition is such that the activity ratio (aLl,/aki) at the alloy/oxide interface is less than the equilibrium values, then Reactions [4] and [5] will proceed to the left. The equilibrium activity ratios in Eqs. [6] and 171 can be calculated since values for the standard free energies of formation of the oxide phases are available. Standard free energies of formation for NiO and A1203 have been tabulated by Elliott and ~leiser.' The standard free energy of formation for NiA1204 can be obtained from the data of Tretjakow and Schmalzried.' The results of these calculations are tabulated in Table I. Table I shows that the following inequality is valid over the temperature interval 900" to 1300°C: (Reaction [5]) (Reaction [4]) « 1and therefore the aluminum activity for these compositions can be taken as equal to the square root of the activity ratios (i.e., aNi = 1). If equilibrium is estab-

Jan 1, 1968

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey' have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel'perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,' and Fletcher and Wilson' have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By R. O. Leach, O. W. Wagner

Because of unfavorable wetting conditions much residual oil is left when a porous material is Pushed by water. Methods suggested to change reservoir wetting to improve oil displncernrnt efficiency are generally expensitlr. The present 1aborator.y study was undertaken to gain an under.standinx of the factors which determine reservoir wettability, arid to find out if oil displacement efficiency might be improved by a wettahility change accomplished at low cost in on oil reservoir. Contact angle measurements were made on mineral surfaces using sevc.r~zl sets of reservoir oil and water samp1es. Results of the contact angle studies suggest that reservoir wetta-hility may he primarily determined by natural surface-active substances present in the reservoir fluids. The effect of changing sa1inity and pH of the water phase was studied. The re.suits suggest that gross changes in preferential wettability might be acc~o~npli.shed by injection of water containing simple chernicnls to alter pH or salinity in the reservoir. Such treatment could he much less expensive than injection of commercial surface-active agents. Waterflood tests have also been made using synthetic cores and oil and water having wening characteristics similar to those of reservoir fluids. Cores initially oil-wet were flooded in such a way that they were made prefermtial1y water-wct by the advancing flood water. This reversal in preferential wettability achieved greater oil displacement efficiency than when either oil-wet or water-wet conditions were maintained throughout the flood. For the systems studied, the higher the oil viscosity the greater the percentage improvement obtained over conventional waterflood recovery. This suggests that a flooding process making use of wettability-reversal may extend the oil viscosity range over which water flooding is attractive. Because a precise adjustment of reservoir wettability does not seem to be required, and because altering the pH or salinity in some reservoirs may be inexpensive, it appears that a waterflooding process employing wet-[ability-reversal could find .succesful field application. I NTRODUCTION The efficiency with which water will displace oil from a porous material is related to the nature of the capillary forces present. These in turn are controlled by the preferential wetting of the solid by the two fluids. Because of unfavorable wetting conditions, 30 per cent or more of the original oil in place may remain unrecovered in that portion of a reservoir flushed by water. This paper is concerned with the possibility of improving waterflood oil displacement efficiency by alterations in the wettability of the porous material. A laboratory study was made to gain a better understanding of the factors which control reservoir wettability, and to determine if the oil displacement efficiency could be improved by some inexpensive means of manipulating wettability of the porous medium. Contact angle measurements were made with several natural and synthetic oil, water and solid systems (1) to obtain a better understanding of how to duplicate reservoir wettability in the laboratory, and (2) to discover possible means for changing preferential wettability of natural reservoir systems. Flooding tests were also made in synthetic systems to determine if oil displacement efficiency could be improved by those wettability manipulations suggested by the contact angle measurements. Based on these studies a possible method for improving waterflood oil displacement efficiency is presented. This method involves causing an originally oil-wet porous material to become preferentially water-wet during the course of a water flood. The purpose of this paper is to present results of the laboratory studies. THEORY Rock surfaces in some oil reservoirs are believed to be covered with a firmly attached bituminous or other organic coating. Such surfaces would be preferentially oil-wet in the presence of both oil and water, regardless of composition of reservoir fluids. Other reservoirs are believed to contain rock surfaces not permanently coated with such materials, and which would be preferentially wet by water in the presence of water and oil free from surface-active substances. However, when the reservoir fluids do contain certain natural surface-active materials in sufficient quantity, rock surfaces acquire a degree of preferential oil wettability caused by adsorption of these natural surface-active materials on the solid. The equilibrium amount of these materials adsorbed per unit surface area is believed to depend upon their concentration in the bulk liquid phases.