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By N. Mungan

Laboratory water floods were performed in oil-wet and waterwet alundum and Torpedo cores, displacing a refined oil with n-hexylamine or Triton X-100 solution. Also, some floods were performed in which a sucrose solution was displaced with n-butyl alcohol. The Purpose ot the tests was to see if the oil recotlery could be increased and to examine what role the inter-facial tension reduction and wettability change play in the recovery mechanism. it was found that the chromatographic transport of amine was influenced by core wettability. In oil-wet cores, the rate of advance of the amine band could be predicted from equilibrium chromato-graphy, while in water-wet cores the amine band moved faster than predicted, indicating a non-equilibrium process. By reducing the interfacial tension to 1.1 dyne/ cm, oil recovery was increased. More oil was recovered from Dri-filmed cores than from water-wet cores. Reversing the wettability of the porous media from oil-wet condition also resulted in some additional oil recovery. Neutral wettability floods did not increase oil recovery. INTRODUCTION Interfacial forces in petroleum reservoirs are responsible for retention of large quantities of residual oil. Increasing exploration costs have created an incentive to attempt recovery of this residual oil by new and novel processes. One novel process involves changing the interfacial forces by introducing a chemical into the reservoir during water flooding. Recently, several investigators have carried out laboratory displacement tests using amines. lt3.4 The amines adsorbed onto initially water-wet core surfaces, changing them to oil wet. Additional oil was recovered when the cores were flooded in a manner reversing the. wettability from oil-wet conditions. In all these studies, the wettability reversal was considered responsible for increased oil recoveries although it was noted that amines also reduced oil-water interfacial tension. In the present study, displacement experiments were performed in water-wet and Dri-filmed cores. The purpose was to separate the effects of lowering the interfacial tension from changing the wettability. LABORATORY STUDY All experimental data given in this paper have been obtained at a temperature of 70F + 1 and prevailing atmospheric pressure. FLUIDS AND MATERIALS The oil used in these experiments* was washed with H2S04 and passed through two 100-200 mesh silica-gel beds to remove unsaturates and surface active impurities. Normal hexylamine** of practical purity was used, and the alundum cores*** were composed of nearly pure A1203. Fused quartz (SiOi) and Lucalox (A12 )t plates were used in the contact angle measurements. DISPLACEMENT TESTS Displacement tests were performed in alundum and Torpedo cores. Before displacement runs, cores were acidized with 0.1 normal HCI, flushed with distilled water and fired at 1,200F to make them water wet. This procedure also reduced water sensitivity of the Torpedo cores. Oil-wet cores were prepared from water-wet cores by flowing several pore volumes of 1 per cent by weight Dri-film SC-87 solution in heptane through the cores, flushing the cores with nitrogen, evacuating, and finally heating the cores at 300F for 4 or 5 hours. Between floods, cores were cleaned by conventional procedures and treated again as above.

Jan 1, 1965

THE following employment items are made available to AIME members on a nonprofit basis by the Engineering Societies Personnel Service, Inc., operating in cooperation with the Four Founder Societies. Local offices of the Personnel Service are at 8 W. 40th St., New York 18; 100 Farnsworth Ave., Detroit; 57 Post St., San Francisco; 84 E. Randolph St., Chicago 1. Applicants should address all mail to the proper key numbers in care of the New York office and include 6c in stamps for forwarding and returning application. The applicant agrees, if placed in a position by means of the Service, to pay the placement fee listed by the Service. AIME members may secure a weekly bulletin of positions available for $3.50 a quarter, $12 a year. MEN AVAILABLE Project Manager or Construction Engineer, 48, married. Twenty-five years' experience on mine, mill and smelter construction work, design and operation, U. S. and Mexico. Speak Spanish. Now employed; available 30 days notice. Prefer U. S. or Mexico. M-698-489-E-1-San Francisco. Mining Geologist, 53, single. Eleven years' intensive field experience giving a completely practical competence for the smallest or largest of areas; plus the highest possible grade of academic background and independent research qualifying for top rating. Available in thirty days or less. Any location acceptable. M-699-3611-E-7-San Francisco.

Jan 1, 1952

By AIME AIME

A METALLURGICAL research building is to be erected for the Armour Research Foundation at the Illinois Institute of Technology. It will be located at the corner of Federal and 34th Sts., Chicago, and fully equipped will cost $250,000. It will provide the Middle West with the largest and most complete of facilities for the conduct of developmental and industrial research in this field. The new building will be constructed around an existing foundry and metallurgical research building which has become too small to carry on and service the many research projects contracted for by the Foundation, having to do with steel, alloys, and nonferrous metals. After two bays of the new unit have been completed, the old unit will be torn down and the new one completed.

Jan 1, 1942

[Admissions: B. M. Gottlieb, Chairman Edmond F. Egan K. Marshall Fagin John S. Fuller Edward E. Monteith T. A. Pollard Howard J. Ritts, Jr. Kenneth W. Robbins Harold E. Wright Advertising and Exhibits: Bernard F. Klein, Chairman Bob Diggs Brown R. E. Howard H. M. Krause, Jr. R. G. Parker Mrs. Evelyn R. Robertson]

Jan 1, 1961

By Douglas Ashmead

In his paper Mr. Braley makes no mention of the bacteriological aspects of the problem. It is now quite well established that certain bacteria play a major role in formation of acid mine waters, and it is a simple matter in the laboratory to show that under sterile conditions the rate of acid production from a pyrites suspension is only about one quarter of that obtained from a similar suspension inoculated with drainage from a mine producing an acidic pit water. Under sterile conditions the oxidation is due to direct chemical action and, from the evidence just given and from much other evidence, this increase under nonsterile conditions is due to certain bacteria. Experiments recently completed, and shortly to be published, have shown that this bacteriological oxidation can be prevented by the maintenance of pH conditions above 4. It was found that to raise this pH above 4 at the beginning of the experiments was not sufficient but that, due to the continuing chemical oxidation, alkali had to be added daily to maintain the pH conditions above 4. The amount of alkali added, however, over a fixed period, was only about one quarter of the alkaline equivalent of the acid produced when pH conditions were not controlled over an equal period. The opinion expressed by Mr. Braley that sodium hydroxide has little or no effect on the rate of oxidation of pyrites is not substantiated by the above experiments. The writer does not claim that these results show a practical solution to the problems, especially in abandoned workings, but feels that the application of an alkaline coating, such as lime wash, to exposed accessible workings might be well worth trying. S. A. Braley (author's reply)—In 1919 Powell and Parrl suggested that bacteria, or some catalytic agent, hastened the oxidation of pyritic or marcastic sulfur in coal. Carpenter and Herndon (1933)' attributed the action of Thiobacillus thiooxidans. Colmer and Hinkle (1947)3 observed an organism similar to T. thiooxidans and another organism that oxidized iron. Leathen and Braley 9rst discovered this organism in 1947 in a sample of water from the overflow of the Bradenville mine (Westmoreland County, Pennsylvania). They characterized the organism in 1954" and gave it the name Ferrobacillus ferrooxidans. Although Temple and Colmer (1951)' had suggested the name Thiobacillus ferrooxidans, since they claimed it oxidized both ferrous iron and thiosulfate, we have found that pure cultures of the organism do not oxidize thiosulfate, hence the name F. ferrooxidans. In 1955 Ashmead7 isolated an organism, similar to the one called Thiobacillus ferrooxidans by Temple and Hinkle, from acid mine water in Scotland. It is probable that this organism was F. ferrooxidans. In 1954 Bryner, Beck, Davis, and Wilsonh reported microorganisms in effluents from copper mine refuse. These organisms appeared to be similar but were not in pure culture. In view of this history of bacterial investigation of acid mine water and our own ten years of experience, we do not agree with Mr. Ashmead that bacteria play a major role in acid formation. We do not find that any of these bacteria will directly oxidize pyritic material. They do, however, augment the chemical formation of sulfuric acid by atmospheric oxidation. In two papers in 1953% eathen, Braley, and McIntyre discuss the role of bacteria in acid formation and postulate the mechanism through which they operate. Mr. Ashmead in his discussion of my paper has assumed that this work was carried on in the presence of acid mine water in which bacteria would be present. This was not the case. Strictly sterile conditions were not maintained, but the organisms present in mine drainages were definitely absent in these experiments. We believe that we have demonstrated that alkalis do not inhibit the chemical oxidation of pyritic material. This is also indicated by Mr. Ashmead's discussion in which he says that alkali must be added daily due to the continuing chemical oxidation. It is interesting to note that Mr. Ashmead finds that maintenance of pH above 4.00 decreases the activity of the bacteria. We have found also that a decrease in pH below 2.8 also inhibits its activity. Table XIII of published data'" illustrates the decrease in activity with increased acidity, although pH values are not given. These values are in comparison with uninoculated controls and show the marked increase in acidity up to 22 weeks but a decline at 29 weeks, at which time the experiment was terminated. It is probable that after a longer period only chemical oxidation would have continued. From our studiesv we have postulated that the iron oxidizing bacterium (Ferrobacillus ferrooxidans) oxidizes the ferrous iron, resulting from chemical oxidation, to ferric iron. The ferric iron then aids the atmospheric oxidation of the sulfuritic material and is itself reduced to ferrous iron, which in turn acts as food for the autotrophic bacteria. Study of the physiologic properties of F. ferrooxidans shows that its preferred pH is about 3.00 and its activity decreases with variation in either direction. It is extremely inactive above pH 4.00 and below 2.5. This inactivity above 4.00 is indicated by Mr. Ashmead's observations. These properties of F. ferrooxidans then correlate perfectly with our hypothesis. Ferrous iron is oxidized very slowly by atmospheric oxygen in highly acid sohtion and since the bacteria become inactive, acid is formed only by atmospheric oxidation. At a pH of 4.00 or above iron is more readily oxidized by atmospheric oxygen, but the bacterial activity is decreased. However, with a pH above 4.00 the ferric iron is removed from the field of activity since its soluble sulfate hy-drolyzes and precipitates the iron as ferric hydroxide or a basic sulfate. As we have shown in the paper under discussion, the alkali does not inhibit the chemical oxidation, and thus the acid formation continues. This

Jan 1, 1957

By W. J. PRIESTLEY

WHEN during the war the Navy Department decided to build an armor-plate and gun-forging plant of its own at South Charleston, W. Va., one of the most important units of the equipment proposed was a 14,000 gross ton forging-press to be used for forging, bending, and rectifying battleship armor-plate and making hol¬low forgings for large caliber guns. A press suitable for doing this kind of work was put into operation in the fall of 1921 and was operated successfully on armor-plate and large forgings until the closing down of the ordnance plant following the Limitation of Armament Conference held in Washington, February, 1922. PURPOSE OF THE PRESS There are three methods by which armor-plate can be made, namely, hammering, forging, and rolling the ingot. Each method produces a different result in the mechanical working of the steel. The hammer was eliminated as impractical from an operating standpoint. The first armor-plate made in this country was worked under a hammer at the Bethlehem Steel Co., between the years 1891 and 1893, but was superseded by forging when the large press was completed in 1893. Harry T. Morris of the Bethlehem Steel Co. informs me that the 1.25-ton steam hammer began operations in 1891 and was in operation for about two years. The Carnegie Steel Co. and the Midvale Steel and Ordnance Steel Co. also forged armor-plate. Certain European manufacturers rolled the plates from large slab ingots, after removing the sink-head and giving the body of the ingot a light pass under a hydraulic press. While rolling accomplished more mechanical work on the surface of an armor plate, forging, on the other hand, resulted in a greater amount of work in the interior of the plate. Either type of equipment involved an enormous expendi¬ture, so it was deemed advisable to adopt the method which would make it possible to use the equipment for more than one purpose. Since g large rolling-mill could be used only for the single operation of rolling armor-plate, a press was decided on, for the reason that it might be designed so as to forge armor, as well as bend and rectify it, and also be used in the forging of ingots for large caliber guns, both in the form of hollow forgings and also solid shafts.

Jan 1, 1926

By C. H. Ma, J. S. Makris

This paper describes a modified X-ray diffraction microscope wzethod based on the general principles of Berg-Bawett's Method, Lang's Method, and Woosters1 Technique. This new method may be used for stationary or oscillatory photomacrographs, with both reflection and transmission techniques. In the stationary technique, a small point-source of a divergent X-ray beam of white radiation is used; in the oscillatory technique, a monochromatic divergent beam is employed. The chief advantages of the method described herein are that only approximate alignment of the Bragg angle -of-interest is needed during exposure, and that a large portion of a crystal-specimen surface can he irradiated. In recent years, the study of dislocations through X-ray diffraction microscope techniques has received considerable attention as concerns the per,fection of single crystals. Very promising results have appeared in the literature.'-' These techniques are very useful when the dislocation density of a crystal is near 105 per sq cm or lower. The principle of X-ray diffraction microscopy is based on the differential effect of X-ray primary extinction between the distorted parts and the perfect parts of a crystal. When an X-ray beam impinges on a set of planes of a crystal at the correct Bragg angle, diffraction of X-rays will occur with a 90-deg phase shift of the diffracted beam. This once-diffracted beam still forms the correct Bragg angle with the planes ahead of it, if the planes are not distorted. Thus, part of the strength of the once-diffracted beam is rediffracted and the beam continues to travel in the direction of the primary X-ray beam. This twice-diffracted beam not only takes away part of the strength of the once-diffracted beam, but also causes destructive interference with the primary beam because it now is exactly 180 deg out of phase with the primary beam. As the primary beam goes farther and farther into the crystal, its intensity is continuously weakened. Asa result, the ultimate X-ray diffraction power of a set of undistorted planes is largely extinguished. This phenomenon is called primary extinction.1,2'4 If the set of planes ahead of it is distorted, the once-diffracted beam will have less chance to be rediffracted, because it could not meet the exactly correct Bragg angle for rediffraction. If a part of the beam does rediffract, this twice-diffracted beam is not exactly 180 deg out of phase with the primary beam, and thus it causes less destructive interference. As a result, the registered X-ray diffraction power of the distorted part of a crystal appears stronger than that of the perfect part. Thus, point-by-point contrast of a diffraction image is theoretically possible from a crystal containing dislocations. Two most popular X-ray diffraction microscope techniques today are Berg-Barrett's Method and Lang's Method. Both of these techniques require a

Jan 1, 1964

Jan 1, 1936

By David S. Cahn

Pilot-plant and laboratory tests were made on blends of steel plant flue dust and portland cement to determine whether the flue dust could be pelletized for use as a source of iron in dry process cement manufacture. Strength and setting time results showed that an acceptable agglomerate can be made with a Type II portland cement binder. Abrasion-resistant and well-sized pellets were made in a horizontal drum, using a simulated closed circuit, with a binder content of 7.5% and a moisture content below 15%. Pellet quality was found to be relatively insensitive to changes in binder concentration above 5%. Simulations of stockpiling and weathering indicate that little difficulty would be encountered with use of the flue dust pellets in cement plants.

Jan 1, 1972

By F. F. McINTOSH

STEEL is a general name applied to the alloys of iron and carbon. These alloys always contain , other elements such as manganese, silicon, sulfur, and phosphorus. Manganese and silicon are usually considered to be alloying elements. Sulfur and phosphorus are regarded as impurities. Tradition has damned them both and, in addition to classifying them as impurities, has established the general impression that many of the ills of steels are the result of the presence of one or both of these elements. Metallurgists are inclined to question the soundness of this tradition. The fact that one blast-furnace plant is devoted entirely to the production of ferro-phosphorus which is used to rephosphorize basic open-hearth steel, and that sulfur is added to many heats of steel, indicates that these so- called impurities might also be classed as alloying elements, and that the tradition which damns them may not be altogether fair and well founded. A critical search through the technical literature on the effect of phosphorus on steel will disclose many references to its harmful effect. Most of these are general in character, but there has been a strong tendency to accept this traditional belief in the harmful effect of the element.

Jan 1, 1926

By AIME AIME

THE accompanying photograph: submitted by C. L. Bransford, assistant district manager of the Republic Steel Corp., in Birmingham. Ala., shows the remains of the old Tannehill blast furnaces, one of the first furnace plants in the South. They were built by Moses Stroup and operated during the Civil War period, when cannon balls were cast there. The record day's run of this furnace plant was said to be 30 tons of iron. The furnaces were fed by a water-wheel-operated bellows and used charcoal, a product of the neighboring forest. They were first owned and operated by the Pioneer Mining & Manufacturing Co., that later became the Republic Iron & Steel Cu., and subsequently the Republic Steel Corp. in that district.

Jan 1, 1936

Executive. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS, ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANE WAY, JR., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L. YOUNG, Chairman. KARL EILERS, JAMES GAYLEY.

Jan 4, 1913

By M. V. Nevitt

In the systems Ti-Mn-O, Ti-Fe-O, Ti-Co-O, and Ti-Ni-O the bounda.r-ies of the Ti2Ni-type phases were determined at one or more temperatures and the variation of the lattice parameter with oxygen content was determined. Densities were calculated from the lattice parameters and compared with measured density values. The: results indicate that the occurrence of the phase in these systesms can be correlated qualitatively with valency electron concentration, and that the role of oxygen is that of an electron acceptor. The lower limit of oxygen solubility appears to be determined by the valencies of Mn, Fe, Co, and Ni, while the maximum oxygen concentration coincides with the filling of the 16 (c) positions of the O 7h - Fd 3m space group. THE suggestion has been made by several investigators'" that the phases having the cubic E9,-type structure, and known as 17-carbide-type, double-carbide-type and Ti,Ni-type, are members of a family of electron compounds. This concept has been given additional support by recent work8 in which new isostructural phases involving second and third long period combinations were found, and which provided further evidence of the regularity of occurrence of the phase in terms of periodic table relationships. In this laboratory attention has been focused on the isomorphs containing titanium, zirconium, or hafnium, and the role that oxygen plays in their occurrence. In some binary systems Ti,Nitype* phases occur having the formula A,B where A is the titanium group element. Based on previous workq and the present investigation, oxygen is known to be soluble in two of these binary phases, Ti,Co and Ti2Ni. It is probable that oxygen is also soluble in the other phases of this kind. In other binary systems the Ti,Ni-type phase does not occur, but does occur in the corresponding ternary systems with oxygen .3-5 The experiments described here were performed to determine whether the occurrence and composition of certain of the Ti,Ni-type phases could be related to an electronic effect and whether oxygen's stabilizing role is exerted through an influence on the electron: atom ratio. The ternary systems Ti-Mn-O, Ti-Fe-O, n-Co-O, and Ti-Ni-O were selected for study for two reasons: First, several schemes have been proposed for first long period elements which, although not in quantitative agreement, show a generally consistent trend for the variation of valency with atomic number. Although for a transition metal the term valency is difficult to define and is generally not a constant number which can be applied to all alloys, it is usually assumed to be an index of the number of electrons per atom involved in metallic cohesion. Second, the determination of the Ti2Ni-type phase boundaries was facilitated by the fact that the phase relations in several of these ternary systems have been investigated by other workers."' EXPERIMENTAL PROCEDURE___________________ The alloys were prepared by arc melting crystal-bar titanium, reagent grade TiO, and electrolytic manganese, iron, cobalt, and nickel. Each button was remelted at least three times. The metals had a minimum purity of 99.9 pct except the nickel whose purity was 99.4 pct, the major impurity in this instance being cobalt. The preparation of the manganese alloys was attended by the customary difficulties associated with the vaporization of manganese. The technique used in this case was to add approximately 10 pct extra manganese to the original charge and to continue remelting the button until the final weight was in agreement with its intended weight. At least three alloys in each system were analyzed chemically and the results, even for the manganese alloys, were in good agreement with the intended compositions. A few additional alloys in the Ti-Mn-O system were prepared by the sintering of mixed powders in evacuated quartz tubes followed in some cases by arc melting. For annealing, the alloys were wrapped in molybdenum foil and placed in fused silica tubes containing zirconium chips. The fused silica tubes were evacuated at room temperature to a pressure of 1 x l0-6 mm of Hg and sealed. These capsules were then annealed for 72 hr at an external pressure of 5 x 10-5 mm of Hg in a vacuum furnace whose temperature could be controlled to + 1°C. The success of this procedure in avoiding significant oxygen or nitrogen pickup was indicated by the bright, ductile condition of the molybdenum foil and by the complete absence of a microscopic reaction layer on the specimens. This method did not permit rapid quenching of the specimens but in no case did metal-lographic examination indicate that a solid-state transformation had occurred on cooling. Metallo-

Jan 1, 1961

By A. V. UDELL

OF all the metals that have from time to time been called the "Wonder Metal," mercury, often called quicksilver, is probably the most deserving of this designation. A wonder metal it must have been to those workers of an earlier day who named it after that Latin god of commerce and gain, characterized as the fleet messenger of the gods and the conductor of souls to the lower world. The word mercury has been used to indicate a carrier of tidings, a bearer of news, a nimble or clever person, a hawker, and a skillful thief. All of these attributes, and more, are recognizable in this metal, the technical terminology of which is "Hydragyrum," meaning water-silver, and from which the chemical symbol "Hg" is derived. Fickle in its occurrence in nature, simple in its metallurgy, illusive in captivity, it serves man in life or death, in war or peace, in commerce, science and arts, in mining, agriculture, and forestry with a versatility found in no other element.

Jan 1, 1929

By Robert A. Rapp, Jan E. Verfurth

From the measurement of internal-oxidation band widths in Ag-In and Cu-A1 alloys, products for the solubility No and the diffusivity Do of oxygen in silver and apparent NODo products in copper have been obtained over a range of temperature. The NODO products for silver are in agreement with the product of the individually determined No and Do values of Eichenauer and Müller. Although interstitial diffusion of oxygen in silver is expected, the temperature-independent factor Do of the diffusion coefficient does not agree well with the theory of Wert and Zener. For Cu-A1 alloys internal oxidation does not follow the expression derived for ideal kinetics, since the apparent NODo product calculated from internal-oxidation measurements is a function of the alloy content in the specimen. Thus, unequivocal values for No or DO or even the product NODO in copper are not available from the literature. RELIABLE values for the saturation solubility NO and diffusivity DO of oxygen in fcc metals are lacking and difficult to determine, partially because internal-friction measurements are not applicable. Permeability experiments and Sieverts7-type adsorption -desorption methods3 have met with difficulty; however, Eichenauer and Müller4 have recently reported on the solubility and diffusivity of oxygen in silver as determined by the latter technique . Rhines, Johnson, and Anderson,5 and independently Meijering and Druyvesteyn,' introduced the possibility of deriving values for the product NODO in a metal from measurements of the widths of internal-oxidation zones (subscales) formed during the internal oxidation of alloys. In addition to these authors, several other investigators7-9 have made such measurements in various silver and copper alloys at various temperatures, mostly using me- chanically polished specimen surfaces. The purpose of this investigation was to determine over a range of temperature the calculated products NODO in silver and copper from systematic measurements of the widths of internally oxidized zones in Ag-In and Cu-A1 alloys, using specimens with electro-etched surfaces. Consider the internal oxidation of a dilute solid-solution alloy in which the base metal is not oxidized. If diffusion of oxygen is the rate-controlling step, then the depth 5 of the internal-oxidation zone is given by where y is a dimensionless parameter and t the oxidation time. Based on the solution of the diffusion equation, wagnerl0 has shown that under certain conditions several mathematical simplifications may be used in the evaluation of y, so that Eq. [I] may be expressed for the case that y « 1, and y(Do/DB) 1, where N(so)the is the equilibrium solubility (mole fraction) of oxygen in the solvent metal for the given oxidizing atmosphere, is the mole fraction of the solute metal in the bulk alloy, 4 is the diffusivity of the solute in the base metal, and v is the ratio of oxygen atoms to solute atoms in the precipitated oxide BO,. Rearranging Eq. [2] Maak' has derived an expression analogous to Eq. [3] for the case that an external-oxide scale, in addition to an internal-oxidation zone, is formed. For this combined external and internal oxidation for the case that 5/2 where 5 is the distance of the internal-oxidation front from the original external s.urface, and X is the distance of the external oxide/metal interface from the original external interface. The function F is defined by the expression

Jan 1, 1964

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

CHARLES KIRCHHOFF, Chairman. ALBERT SAUVEUR, Vice-Chairman. HERBERT M. BOYLSTON, Secretary, Abbot Bldg., Harvard Sq., Cambridge, Mass. John Birkinbine, J. E. Johnson, Jr., J. S. Unger, William H. Blauvelt, William Kelly, Felix A. Vogel, James Gayley, Richard Moldenke, Leonard Waldo, Henry D. Hibbard, Joseph W. Richards, William R. Walker, Henry M. Howe, C. F. W. Rys, William R. Webster, Robert W. Hunt, E. Gybbon Spilsbury, Frederick W. Wood. A. A. Stevenson, J. S. Unger and C. F. W. Rys have accepted membership on the Iron and Steel Committee. The Program Committee has held two meetings- in New York and has perfected the preliminary plans for the October meeting. The Committee will meet again in September. The following provisional program has been laid out by the Program Committee, but is subject to later additions and changes :

Jan 9, 1913

By H. J. Modi, P. L. De Bruyn

IN recent years interest has been aroused in flotation rate studies both from a technical and a more practical aspect. With increasing fineness of grind becoming a necessity in treatment of low grade ores, difference:; in flotation rates of various size ranges will assume importance in the evaluation of overall recovery results. Theoretical analysis of flotation kinetics was initiated by Schuhmann,' who sought to define flotation rate of a given mineral and specified size range in terms of certain physical variables of the flotation system. Using as a basis for his analysis the bubble-particle encounter hypothesis previously advanced by Gaudin,' Schuhmann writes for the rate of flotation (R,.) of particles of average size x, Rx = PcPa(x) V F. [1] In this relation Pc and Pa represent, respectively, the probability of collision between particle and gas bubble in a given time interval and the probability of adhesion of particle to the bubble after collision. Rigorously speaking, the term PC does not have the significance of a probability factor, since it depends on the time interval and therefore can be numerically greater than unity. The term c(x) expresses the concentration of particles of an average size x in the flotation cell in weight per unit volume of pulp, and V denotes the total volume of pulp in the cell. The product, P,c(x)V, defines the frequency of particle-bubble collisl.on, and when it is multiplied by P,, the number of collisions per unit time resulting in successful adherence is obtained. The factor, F, measures the froth stability and is introduced because after fruitful bubble-particle contact some particles may still riot reach the froth launder. Coalescence of bubbles in the froth column or too short a bubble life could account for this effect. Schuhmann also introduced the concept of "specific flotation rate" (Q) to allow for the relative abundance of different mineral species in the flotation pulp. The specific flotation rate, having the dimension of reciprocal time, is defined as Eq. 2: Qx =Rx/c(x)v [2] and it also follows from Eq. 1 that Qx = PcPaF. [31 The theoretical aspects of flotation kinetics were also considered by Sutherland,3 who tried to improve Eq. 1 by expressing the probability factors in terms of such physical variables as particle radius (x), bubble radius (X), velocity of bubble relative to particle (v), the number of bubbles per unit volume of pulp (N) and the induction period (A) necessary for air-mineral adhesion. According to Sutherland's treatment, the rate equation, Eq. 1, transforms to R, = [3pX x v N] [sech2 (3 v ?/4 X) ] ?c(x) V [4] where the first term in brackets on the right-hand

Jan 1, 1957

By Leonard Greenburg, William B. Harris, Gustäv Werner

HAULAGE in tunneling operations generally has been done with electric locomotives. As a rule, on short hauls the source of electricity is a storage battery mounted on the locomotive, which, of course, must be removed and recharged periodically. Where the distance from the recharging point to the tunnel face is very long, and where loads are heavy, trolley-driven locomotives are used. Diesel engines have been used in mining and tunneling operations in Europe for a number of years. The recent reports of studies in Belgium1 and by the Bureau of Mines in this country2-4 have indicated the potentialities of this form of power for haulage, mucking, bulldozing and many other underground operations. The hazards attending the use of Diesel engines in more or less closed spaces have long been known. The exhaust constituents that may create a harmful or objectionable environment are carbon monoxide, oxides of nitrogen and sulphur, carbon dioxide, aldehydes and smoke. Lack of precise information regarding the concentration of these gases and the ventilation requirements to reduce them to safe levels has to some extent suppressed their general acceptance in tunneling and mining work. Not until the work of the Bureau of Mines referred to above, and certain experience gained in the construction of the Delaware Aqueduct,‡ has there been available the requisite information regarding the conditions under which their use may be permitted. This paper concerns itself with the successful operation of Diesel engines underground in the construction of certain parts of the Delaware Aqueduct, and describes the conditions under which Diesel engines have been found to operate with a minimum production of noxious gases. The test data reported were obtained during the operation of Diesel engines over a period of two years.* STUDIES BY THE NEW YORK STATE DEPARTMENT OF LABOR Exhaustive tests were made by the Division of Industrial Hygiene, of the composition of the exhaust gases given off by a Diesel engine mounted on. a test block. These tests showed that certain quantities of the gases are discharged from the exhaust. On the basis of these figures, preliminary requirements of design and control

Jan 1, 1942

By Gerhard Derge, Harold Markus

The introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be dcscribed. For most of the additions, solutions containing 0.001 and 0.01 moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-l,ol~ate as follows: pH 0.1 M NaHC0............................................ 8.4 2 parts 0.1 M XaHCOr, 1 pa.rt 0.1 M NaZCO?................. 9.5 1 part 0.1 M NaHCOs, 2 parts 0.1 M iVa.,C03. ................ 10.0 0.1 M Na2C0............................................. 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves—sulphnte, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only -fuoridc, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also—phosphate, pcrborate, and chromate. Potential Measurements f The time-potential curves represntative of group 1 are shown in Fig. 1. These are the curves for 0.005 M sulphate ion and their similarity

Jan 1, 1939