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By S. Pearson, L. Rotherham

Measurements have been made of the variation of internal friction with temperature for OFHC copper, and for a series of binary solid solutions of high purity copper with zinc, gallium, germanium, arsenic, and silicon, to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity. The apparatus used was of the torsional pendulum type developed by KeI1 modified so that the specimen and vibrating system could be maintained in a high vacuum. The activation energy for grain boundary relaxation in copper is 33,000 cal per mol. This is considerably less than the activation energy for self-diffusion, in disagreement with Ke's theory2 that the two activation energies should be the same. All the alloying elements increase the activation energy for grain boundary relaxation to approximately 44,000 cal per mol, increasing the grain boundary viscosity at a given temperature. The results are discussed in terms of theories of grain boundary slip put forward by MottQ and by Ke.+ Experiments have also been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. EXPERIMENTS described in this paper were designed to investigate the effect of alloying elements in substitutional solid solution on grain boundary viscosity, using the internal friction method developed by Kel for measuring grain boundary viscosity. It was considered desirable to make the system under investigation as simple as possible by making experiments on a comprehensive series of binary alloys of copper with the elements immediately following it in the periodic table, i.e., zinc, gallium, germanium, and arsenic. These elements are within the range of favorable size factor for solution in copper, and the systems have been extensively investigated by Hume-Rothery and his co-workers." Later, in order to study the effect of the relative size of the solvent and solute atoms, experiments were made on a series of Cu-Si alloys, since the apparent atomic diameter of silicon when in solution in copper—the diameter necessary to assign to the solute atoms to account for the lattice constant of the solid solutiona—is almost the same as that of the solvent atoms. Preliminary experiments were made to measure the variation of internal friction with temperature for pure copper. Ke made some experiments on copper," but found that the curves obtained were not reproducible in consecutive experiments. The copper was maintained in an argon atmosphere during the experiments but, although he took precautions to exclude oxygen, Ke came to the conclusion that the precautions were not entirely satisfactory, and that the lack of reproducibility must be due to absorption of oxygen by the copper. Experiments have therefore been made to investigate the effect of small amounts of oxygen on the variation of internal friction with temperature for copper. Previous Work Ke made extensive experiments on high purity aluminum and was able to show that the grain boundaries behave viscously at high temperatures. He found that the relative rate of movement of the grains could be expressed as Where v is the velocity of slip, A is the constant, u is the shear stress, H is the activation energy, R is the gas constant, and T is the absolute temperature. By assuming that the boundary layer was one atom thick, he obtained a value for the viscosity which, when extrapolated to the melting point, gave good agreement with the viscosity of the liquid metal at the melting point. Ke also made experiments on other high purity and commercial purity metals:, and on some alloys." " He came to the conclusion2 that the activation energy for grain boundary slip was the same as for self or volume diffusion and for steady state creep in single crystals. Rotherham, Smith, and Greenough" have shown recently that the activation energy for grain boundary slip is not the same as for self-diffusion in tin,

Jan 1, 1957

By W. B. Braden

This paper presents a suitable method for predicting gas-free oil viscosities at temperatures up to 500F knowing only the API gravity of the oil at 60F and the viscosity of the oil measured at any relatively low temperature. The API pravity and the one viscosity value are used as parameters to determine the slope of a straight line on the ASTM slanaord viscosity-temperature chart. Then, knowing the slope of the line and one point on the line, the vrscosities at higher temperatures can be determined. The line slope correlations were developed at I00 and 210F since viscosity data are frequently measured at these temperatures. A procedure is given for predicting line slopes from measurements at other tetnperatures. A nomogram is furnished for solving the relationship. The correlation has been evaluated at temperatures up to 5OOF for oils varyzng in gravity from 10 to 33 " API. The correiution is applicable only to Newtonian fluids. Comparison at 500F of true viscosities and those predicted from values at 100F shows an average deviation of 3.0 per cent (maximum deviation of 6.0 per cent). Predictions from the values at 21 0F for the same oils how an average deviation of 1.5 per cent (maximum deviation of 3.4 per cent). INTRODUCTION Correlations have been developed by Beal' and by Chew and Connally' for predicting viscosities of gas-saturated oils at reservoir conditions. Each of these correlations requires a knowledge of the solution gas-oil ratio and the viscosity of the gas-free oil at the reservoir temperature. For temperatures below 350F, measurements of the gas-free oil viscosities can be made easily using commercially available equipment. In thermal recovery processes, however, reservoir temperatures well in excess of 350F are encountered. Viscosity measurements at such conditions are more difficult and time consuming and require modification of existing equipment or the construction of new equipment. Measurements are further complicated by the difficulty of handling highly viscous oils associated with thermal recovery processes. Therefore, it is desirable to have a correlation which allows accurate prediction of viscosities at high temperatures. A commonly used technique for predicting viscosities at high temperatures is to measure the viscosities at two lower temperatures, plot the values on ASTM standard viscosity-temperature charts and extrapolate to the temperatures desired. If either of the values is slightly in error, the extrapolated value can be significantly in error. To justify an extrapolation, three points are actually necessary. This procedure can consume much time, particularly with heavy oils. Considering the cost of viscosity measurements, it would be desirable to eliminate the need for direct measurements by having correlations which would allow viscosity predictions from other physical or chemical properties. Beal1 investigated the possibility of correlating viscosity with oil gravity at temperatures from 100 to 220F. While showing that a general relationship exists, he also found significant deviations. It is possible that correlations will be developed based on oil composition as more information becomes available. While not eliminating the need for viscosity rneasurements, the method presented herein requires that only one viscosity measurement be made. The API gravity must also be known. The theory is based on the fact that the viscosity of paraffins (high gravity) changes less with temperature than does the viscosity of naph-thenes or aromatics (low gravity). The gravity. therefore, is used as a parameter to determine the slope of a straight line on the ASTM standard viscosity-temperature charts. The correlation is applicable only to Newtonian oils, and deviations due to thermal decomposition and nonhomo-geneity cannot be predicted. Oils containing additives have not been evaluated. PROCEDURE Fifteen oils were used in developing the correlation; eight were crudes and seven were processed oils. Oil gravities varied from 9.9" API (naphthene base) to 32.7' API (paraffin base). The temperature range studied was 81 to 516F. Each oil used had a minimum of three viscosity measurements and each plotted essentially as a straight line on the ASTM charts. In all, 91 viscosity measurements were used in the correlation. Saybolt, rolling ball and capillary tube viscometers were used for the measurements. Viscosity data for Samples 1, 2, 4, 7, 10, 11 and 14 were obtained in Texaco, Inc. laboratories. The data for Samples 3, 5, 6, 8, 9, 12 and 15 were from Fortsch and Wilson,3 and data for Sample 13 were from Dean and Lane.' All data points used in the correlation are plotted in Fig. 1. It is seen that some of the viscosity values deviated slightly from the straight-line plots at the higher temperatures. Properties of the oils after exposure to the

Jan 1, 1967

By Renato G. Bautista, Gary A. Beetner, Anthony L. Frey

The flow of material in a pump mixer-settler extractor was studied photographically and visually by injecting dye into the equipment and following its advance through the various sections of the equipment. Volumetric measure of the flow was obtained from analysis of the photographs. The organic portion of the settling chamber, the fluid surrounding the pump mixer, and the pump mixer itself were found to be operating in plug flow. The aqueous portion of the settling chamber was found to be partially mixed. Significant dynamic effect was noted due to density changes in the feed streams. The quantitative and qualitative observations made of the flow within a single stage should be of value in predicting the flow patterns in all similar equipment, including opaque and liquid metal solvent extraction systems.

Jan 1, 1973

By Louis D. Huntoon

The Porcupine gold area, located on the Hudson Bay slope of northern Ontario, has produced over $100,000,000 in gold and has paid more than $28,000,000 in dividends, since the first real production in 1912. The character of the ore has been studied by the geologists of the Bureau of Mines of Ontario, the geological staffs of the operating mines, and engineers commissioned to examine properties there. What information the Government has is free to everybody; the geological staffs of the several properties also give to the visiting engineer what information regarding ore deposition they possess, and the author wishes to express his indebtedness to the geologists of the Ontario Bureau of Mines and the staffs of the operating mines for their free discussion of geological questions. This paper is based on the examination of several properties, various petrographic reports, not only on specimens from Porcupine but from elsewhere in northern Ontario, and interviews with Government and mine staff geologists. The petrographic work has been done by Prof. R. J. Colony, of Columbia University. Geological History The geological history of the district may be summarized as follows: The outpouring of great floods of lava accompanied by beds of tuff, flow following flow; the contacts of different flows can be seen in various parts of the camp. This period mas followed by an uplift and the production of the Temiskaming sediments by erosion. Later, dynamic action turned the sediments and underlying lavas on edge; this was followed by the intrusion of igneous rocks—in the Porcupine area the quartz porphyry, which is of such great importance in connection with the gold deposits. Doctor Burrows says: "The intrusions of quartz porphyry have in some way influenced the deposition or location of the gold but it is not likely the porphyry has been the source of the gold-bearing solutions." This statement of Doctor Burrows I indorse. The formation of non-gold bearing quartz veins followed the intrusion of the porphyry. These veins occur along or near the contact of

Jan 1, 1923

By Louis D. Huntoon

The Porcupine gold area, located on the Hudson Bay slope of northern Ontario, has produced over $100,000,000 in gold and has paid more than $28,000,000 in dividends, since the first real production in 1912. The character of the ore has been studied by the geologists of the Bureau of Mines of Ontario, the geological staffs of the operating mines, and engineers commissioned to examine properties there. What information the Government has is free to everybody; the geological staffs of the several properties also give to the visiting engineer what information regarding ore deposition they possess, and the author wishes to express his indebtedness to the geologists of the Ontario Bureau of Mines and the staffs of the operating mines for their free discussion of geological questions. This paper is based on the examination of several properties, various petrographic reports, not only on specimens from Porcupine but from elsewhere in northern Ontario, and interviews with Government and mine staff geologists. The petrographic work has been done by Prof. R. J. Colony, of Columbia University. Geological History The geological history of the district may be summarized as follows: The outpouring of great floods of lava accompanied by beds of tuff, flow following flow; the contacts of different flows can be seen in various parts of the camp. This period mas followed by an uplift and the production of the Temiskaming sediments by erosion. Later, dynamic action turned the sediments and underlying lavas on edge; this was followed by the intrusion of igneous rocks—in the Porcupine area the quartz porphyry, which is of such great importance in connection with the gold deposits. Doctor Burrows says: "The intrusions of quartz porphyry have in some way influenced the deposition or location of the gold but it is not likely the porphyry has been the source of the gold-bearing solutions." This statement of Doctor Burrows I indorse. The formation of non-gold bearing quartz veins followed the intrusion of the porphyry. These veins occur along or near the contact of

Jan 1, 1923

By James E. Mills

In the work of exploring certain gold-bearing gravels in the American Valley, Plumas Co., California, entrusted to my charge by Prof. A. Agassiz, of Cambridge, and Q. A. Shaw, Esq., of Boston, it became necessary to sink a shaft through loose materials containing in some layers large quantities of water, and I have been compelled to devise a new method which has proved successful and may be of service elsewhere.

Jan 1, 1885

By D. H. R. Price

This paper presents two tentative models of the use of a notional metal in a country like Britian, which have been developed using the System Dynamics modelling method. Computer simulations have been carried out using one of the models. These show the effect on the recycling of the notional metal of a wide range of possible future values of world market price and demand for the metal.

Jan 1, 1977

A New Process Builds An Industry

Jan 7, 1951

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today's most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By R. V. Wheeler

A matter of much concern at present to the coal-mining industry of Great Britain is the effect of the working of the Coal Mines Act, 1930. This Act, which received the Royal Assent on Aug. 1, 1930, contains five parts: (1) production, supply and sale of coal; (11) the reorganization of the coal-mining industry; (111) hours of work; (IV) the Coal Mines National Industrial Board; (V) general. The first three parts are of major interest and discussion can be confined to them. Part I.—Production, Supply and Sale of Coal Under Part I of the Coal Mines Act, 1930, provision is made for central and district schemes to regulate the production, supply and sale of coal by the fixation of standard tonnage, quota and minimum prices. By Nov. 1, 1930, all the district schemes came into force with the exception of that for Scotland, where the majority of the coal-owners did not see their way to accept the amendments to their draft scheme demanded by the Mines Department. A compulsory scheme for Scotland was thereupon prepared by the Mines Department and put into force on Nov. 24, 1930. It is administered by the coal-owners of the district. The essence of the schemes is the allocation of tonnage for each district by a Central Council, and the allocation of quota for each pit in a district by an Executive Board for that district. Up to Dec. 31, 1930, the various bodies of coal-owners engaged in administering the schemes were employed in work preliminary to their full operation. Standard tonnages had to be determined and coals had to be classified. In consequence, it was not found possible to put the regulation of output into force until Jan. 1, 1931. The determination of minimum prices proved to be an even longer process, and only in a few districts were minimum price schedules operative during the first quarter of this year. The working of the schemes during the March quarter, 1931, has been reviewed in an official publication by the Mines Department,' which can be summarized as follows:

Jan 1, 1932

ALABAMA. Aldrich.-Aldrich, W. F. Anniston.-Noble, A. E., 20th St. and Wilmer Ave. Auburn.-Brown, R. L., Box 0. Bessemer.-Abbott, C. E., T. C., I. & R.R. Co. Ferguson, V., U. S. C. I. Pipe & Fdy. Co. Williams, E. P., Tenn. C., I. & R. R. Co. Birmingham.-Aldricb, T. H. Aldrich, T. H., Jr., 406 Woodward Bldg. Allen, A. W., 1616 S. 14th Ave. Bowron, J., 1401 S, 20th St. Burbidge, T. A., Browu-Marx Bldg. Coxe, E. H., Tenn. C., I. & R. R. Co. Crawford, G. G., Tenn. C., 1. & R. R. Co. Crockard, F. H., Woodward Bldg. Dimmick, F. D., Dimmick Pipe Co. Ellis, E. E., 1515 Brown-Marx Bldg. Fairbairn, C. T., Woodward Bldg. Fies, M. H., 2316 Highland Ave. Hiller, E., 516 Brown-Marx Bldg. Hillman, M. P. G., 707 Empire Bldg. Ludwig, C. P., 12th Ave. and 12th St. McCormack, G. B., Lookout Mt. Iron Co. McCrery, C., Tenn. C., I. & R. R. Co. Moffett, C. A , 909 Brown-Marx Bldg. Peters, R.. Jr., Brown-Marx Bldg.

Jan 1, 1917

By P. R. Martin, R. B. Kelly

Drilling in Central Texas during 1933 was confined, for the most part, to the search for new serpentine plugs. Bastrop County led in this particular activity, with 50 completions during the 12 months' period, 12 of which were productive. Only one new field was opened in Central Texas during the year, it being known as "Hilbig" (Bastrop County) and was discovered by the Humble Oil & Refining Co. The finding of commercial production in the serpentine at 2500 ft. led to further search in this and surrounding counties, but without success. Bexar County actually provided the greatest amount of drilling but the activity was limited to shallow development from 400 to 2000 ft. The Edwards limestone pay, which has been such a factor in past years, received but slight attention during 1933. Unsuccessful exploration was carried on in Lee and Burleson counties. With the exception of Freestone County, the Woodbine sand area was given even less consideration. This county, because of its close proximity to Anderson and Leon counties, saw a very active leasing campaign and several important tests drilled. In Central Texas, 252 wells were completed in 1933, and of this number 52, or 21 per cent, were productive. Hilbig Field The discovery well, Humble Oil & Refining Company's Annie Hassler No. 1, was completed Feb. 16, 1933, for an initial production of 65 bbl. the first hour, through tubing and 1/2-in. choke. The production was found in serpentine at 2468 ft. and tested 37.2" A.P.I. gravity. Twelve producing wells were drilled during the year and served to indicate that not more than 300 acres would comprise the entire field. Daily production at the end of the year was 775 bbl., although the field potential was 18,240 bbl. daily through 1-in. choke. The field adapts itself to pressure maintenance, and this scientific handling is being undertaken by the Humble Oil & Refining Co. through one injection well. It is the only area in the district where work of this nature is under way. Proration of Oil The more stringent application of proration in 1933 did not affect materially the producing fields in Central Texas. This is accounted for

Jan 1, 1934

[PRESIDENT AND DIRECTOR * R. R. McNAUGHTON, '63, Trail, B. C., Canada PAST-PRESIDENT AND DIRECTOR * JOSEPH L. GILLSON, '62, Wilmington, Delaware PRESIDENT-ELECT AND DIRECTOR * LLOYD E. ELKINS, '64, Tulsa, Oklahoma VICE-PRESIDENTS AND DIRECTORS * JOHN S. BELL, '62, Houston, Texas * A. B. CUMMINS, '62, Bound Brook, New Jersey * WAYNE E. GLENN, '62, Houston, Texas * C. C. LONG, '62, Monaca, Pennsylvania * J. S. SMART, JR., '63, New York, New York * J. W. WOOMER, '62, Pittsburgh, Pennsylvania]

Jan 1, 1961

By M. C. Udy, C. H. Lorig

THROUGH the years much interest has been centered in attempting to develop a direct method of iron-ore reduction, to replace or supplement the present indirect blast-furnace process. It would not be difficult to produce a list of more than 500 patents dealing with the direct production of iron and steel, but the few of this type of process that have proved successful do not produce in competition with the blast furnace; they produce special products. A survey of the literature reveals that the equilibrium conditions for the reduction reactions (iron oxides with carbon monoxide and with hydrogen) have been fairly well established but that data on the rate of reaction are discordant, although the general effects of the variables are known. This dissertation deals with the rate of reduction of a magnetite concentrate with hydrogen. The following variables have been studied: bed depth, gas velocity, particle size and temperature. The behavior of a single particle was also studied. LITERATURE Two general factors should he considered in a study of reduction of iron oxide: (1) equilibrium relations, and (2) rate of reaction. The first factor, equilibrium, has received the attention of many investigators and the equilibria Fe3O4-FeO-H2-H2O, Fe304-FeO-CO-CO2, FeO-Fe-H2-H2O, FeO-Fe-CO-CO2 are fairly well established. Of the second factor, the rate of reaction, much less is known. Data are comparatively scarce and there is very little concordance. The discordance probably results from the large number of variables influencing the reactions. However, the general effect of the variables is known. Among these variables are temperature, gas velocity, particle size, porosity, gas composition (distance from equilibrium), presence of impurities, greater or less prevalence of side reactions, and even design of the apparatus itself. Wetherill and Furnas1 published an excellent paper in 1934. They point out that any one or more of five processes (the chemical reaction, diffusion of the reactant through the gas film, diffusion of the reactant through the solid phase, diffusion of the reaction product through the solid phase, or diffusion of the reaction product through the gas film) may be the slow process, and thus the rate-controlling process. It is regretted that the work of these authors was limited to experiments at one temperature, and that the range of gas compositions was limited. Langmuir2 has shown that heterogeneous reactions take place at phase boundaries.

Jan 1, 1942

By D. Malhotra, R. M. Hoover

The effect of a surfactant, designated Syntex, on the wetting and spreading of hydrocarbon oil on molybdenite surfaces (faces) has been investigated experimentally through measurements of zeta potentials and factorially designed flotation tests. These studies indicate that Syntex has a positive effect in increasing molybdenite recovery in the rougher flotation circuit at the Climax mill. The analysis of experimental data using DLVO theory shows that the controlling factor in determining the magnitude of the repulsive energy barrier preventing oil from wetting and spreading on the molybdenite faces is the MoS2 zeta potential and the vapor oil droplet size. The role of Syntex in this case seems to be related to the decrease and stabilization of MoS2 zeta potential by Syntex adsorption and also to the emulsifying action of Syntex on vapor oil to provide a more favorable oil particle size.

Jan 1, 1976

By V. Koump, R. H. Tien

An approximate mathematical solution is found for the problem of unidimensional solidification of a slab of a binary alloy with time-dependent surface temperature. For the model considered, the solid skin does not form until the liquidus front has moved a certain distance. This distance depends on the rate of cooling and can be as large as half the thickness of the slab when the cooling rate is small. Assuming that the THE process of unidirectional solidification of binary alloys with constant surface temperature was analyzed by the present authors in a recent paper.' In the previous analyses, the surface temperature was considered to be lowered instantaneously, at the beginning of solidification, from its initial value to some surface temperature decreases linearly with time and that the solidus and the liquidus lines are straight, calculations are made of the temperature and concentration distributions, movements of the liquidus and the solidus fronts, as well as changes of temperature, solid fraction, and solute concentration of the liquid at the center of the slab. arbitrary temperature, lower than the solidus temperature. Although the solution of the problem for the case of constant surface temperature has some practical applications, instantaneous changes of temperature are physically impossible. Present theoretical study of the unidirectional solidification of a binary alloy is based on a more realistic model, i.e., in this case, the surface temperature of the slab decreases from its initial value continuously with solidification time. The model of solidification within the solid-liquid region is the same as the one described in the

Jan 1, 1969

By M. A. Mahtab

When characterizing orientations of rock joints in an engineering site with respect to mean values of the existing clusters or joint sets, a need may arise for a similarity test that allows grouping of observations from several adjacent sampling stations. Subjective judgment, though based on experience, may not produce realistic groupings in the data. A similarity test is developed in this paper for objective grouping of samples of joint orientations in engineering sites. The test is applied to the data from a large, geologically complex site of a potential open pit mine.

Jan 1, 1984

By I. A. Lange, A. M. Richardson

Although methods for determining shaft lining thickness are well documented, little attention has been given to the design of station breakouts and other related shaft ground support structures. This paper discusses design of selected shaft structures for the Cathedral Bluffs project, a planned 54-kt/d (60,000-stpd) oil shale mine in western Colorado. Design philosophy and construction sequences used in the three completed 520-m (1700 ft) deep, 4.6-m (15 ft) to 10.4-m (34-ft) diameter shafts are described.

Jan 1, 1984

By N. Mungan

Laboratory imbibition and displacement experiments were performed using crude oil and cores drilled with water and preserved under anaerobic conditions. The purpose of these tests was to determine reservoir rock wettability and to find out if more oil could be recovered by use of NaOH solution than by conventional waterflooding. The preserved cores were found to be oil-wet. Contrary to work in the literature, these cores changed to water-wet upon contact with air. After exposure to air for a week, the cores yielded more oil by waterflooding than when preserved under exclusion of air. At reservoir temperature of 160F, flooding the preserved cores with 0.5N NaOH solution recovered more oil than an ordinary wa-terflood, and additional oil when following a waterflood. When the caustic solution was used from the beginning, all the extra oil was obtained before breakthrough; when the caustic followed a conventional waterflood, the extra oil was produced in the form of an oil bank ahead of the injected caustic. The increase in oil recovery resulted from wettability reversal. Also, use of caustic reduced the volume of injection required to flood out the cores. At room temperature, however, the caustic solution did not reverse the wettability and gave no additional oil recovery. Cores which had become water-wet by air exposure or caustic flooding were restored to their original oil-wet state when saturated with crude oil and allowed to equcilibrate at reservoir temperature for two weeks. Therefore, in the absence of preserved cores, it may be possible to restore weathered cores to their original wettability for use in laboratory floods. INTRODUCTION Waterflooding has been in use since 1865, and is by far the simplest of secondary recovery methods. Unfortunately, most waterfloods are inefficient in recovering oil, often leaving half or more of the original oil in place un-recovered. The low oil recovery generally results from low sweep efficiency and low displacement efficiency. Consequently, to increase oil recovery by waterflooding, sweep and displacement efficiencies should be improved. Sweep efficiency is primarily affected by reservoir heterogeneities and mobility ratio, while displacement efficiency is affected by the capillary forces between fluids and rock surfaces. For petroleum reservoirs, the capillary forces are expressed in terms of interfacial tension and wettability. If oil recovery is to be improved significantly in water- flooding, the capillary forces holding the oil in the raervoir porous matrix must be reduced or eliminated. One way to reduce capillary forces is to inject commercial surfactants ahead of the injection water into the reservoir. Laboratory tests of this method have shown no promise of an economical process yet, and no increase in oil recovery was obtained in the field trials which have been reported. Work is continuing in many companies to find surface-active agents which, in workable concentrations, can yield substantial added oil recovery. Another way to change capillary forces operating in petroleum reservoirs is by changing the pH of the injected water. Wagner et al.' showed that change in the pH sometimes activates the surface-active materials natural to some crudes and brings about gross wettability change. Since pH alteration can be obtained with cheap chemicals, such as hydrochloric acid or sodium hydroxide, the process shows promise of being economical in a field application. Pan American Oil Corp. reported oil recovery by use of caustic solution from a flooded-out reservoir.' Their test, conducted at a small additional cost, yielded results which were so sufficiently favorable and encouraging that the wettability reversal flood was expanded to portions of the field not previously flooded.13 It is important to bear in mind that changes in the pH of the water not only can reverse wettability but also can lower the interfacial tension between water and crude oil. Reisberg and Doscher4 have studied the pH dependency of the interfacial tension of Venture crude using sodium hydroxide solutions of various concentrations. Their data show that the interfacial tension was lowered from 23.0 to 0.02 dynes/cm by increasing the NaOH concentration from 0.005 to 0.5 per cent by weight. Thus, the use of NaOH may lead to additional oil recovery due to both wettability reversal and lowering of interfacial tension. Whether alteration of pH results in wettability reversal from oil-wet to water-wet and increases oil recovery depends on wetting properties of the reservoir rock and the crude. This necessitates delicate laboratory experiments, with suitable core and fluid samples from a field. Although many investigators have studied wettability reversal floods in the laboratory,1,2,5,6 these studies have been carried out with synthetic porous media, refined laboratory fluids and surface-active chemicals to simulate the process. The study presented in this paper is the first time that wettability reversal by pH alteration has been accomolished in laboratory core floods using carefully preserved natural cores, live crude and with experiments performed at reservoir pressure and temperature.

Jan 1, 1967

Jan 1, 1943