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By M. S. Smani, P. Blazy, J. M. Cases

Investigations on the beneficiation of sedimentary Moroccan phosphate ores are reported in four separate parts. The first discusses electrochemical phenomena at the solid-aqueous solution interface for minerals of the apatite group. In the second part, the electrochemical properties of the calcareous gangue associated with the phosphate ore are investigated. The flotation of calcite and phosphate oölites, using both anionic and cationic collectors, is discussed in the third part. It is shown that selective recovery could be obtained for precise concentrations of collectors and pH ranges. Results of work aimed at optimizing depression of phosphate oölites during inverse flotation of the carbonate gangue with sodium oleate are reported in Part 4.

Jan 1, 1976

By William E. Ford, Edward Salisbury Dana

A. Anhydrous Carbonates The Anhydrous Carbonates include two distinct isomorphous groups, the CALCITE GROUP and the ARAGONITE GROUP. The metallic elements

Jan 1, 1922

By CHARLES DORRANGE

INTRODUCTION. CULM is a general term used in the anthracite regions for many years to denote a mixture of coal, bony coal and impurities which is sent to the refuse-banks. Thus, 35 years ago culm contained the pea and buckwheat sizes of anthracite; but to-day, and as mentioned in this paper, culm is used specifically to denote the material which passes through the smallest screen in the anthracite-breaker. The smallest size of commercial anthracite is known as No. 3 buckwheat, barley, or bird's-eye coal, and is ordinarily made through a round-punched plate having openings 3/16 in. in diameter, and over a round-punched plate with opening 3/32 in. or 1/16 in. in diameter. Thus culm will consist of coal, bony coal, slate, gravel, iron pyrite, etc., ranging in size from ? 3/32 in. down to dust. Other local terms for culm are " slush," " silt," and " dirt." The first experiments towards the utilization of anthracite culm by briquetting, and the first briquetting-work done in this country, were in 1872 at Port Richmond Piers, Philadelphia, Pa., by E. F., Loiseau.1 Clay was used as a binder and the finished briquette was water-proofed with shellac, etc. Excessive cost was given as the reason for discontinuing work at this plant. The Delaware k Hudson Co., in 1876, built a plant at Rondout, N. Y., which operated until 1880. Gas-tar was used as a binder, and anthracite screenings were briquetted for engine fuel. Excessive cost, poor results in firing, and the tendency of the fuel to cut the boiler-flues were given as the reasons for discontinuing the manufacture. The next plant was built by E. F. Loiseau about 1878, at Nesquehoning, Pa., near the No. 1 or Nesquehoning colliery

Sep 1, 1911

By A. R. Troiano, E. A. Steigerwald, F. W. Schaller

The initiation of localized cracking in hydrogenated high strength steel was dependent on the developmeni of a critical hydrogen conceniration and relatively insensitive to the magnitude of the applied stress. The stress was believed to influence the deluyed failure process by providing the means for grouping the hydrogen. On the basis of an assumed distribution law the observed changes in the lower critical stress as a function of notch acuity, yield strength, and temperature were predictable over a significant range of these variables. THE phenomenological characteristics of delayed failure in high-strength steel have been comprehensively investigated and the behavior has been attributed to the strong embrittling action of hydrogen.1-3 Delayed failure or, as it is also termed, static fatigue, is the most sensitive means of detecting hydrogen embrittlement since it allows the maximum time for hydrogen diffusion during a test.3 The nature of delayed failure cail be aptly described by four parameters which are schematically depicted in Fig. 1. The upper critical stress corresponds to the rupture stress in a conventional notch tensile test. The lower critical stress or static fatigue limit is the stress below which no delayed failure will occur. The incubation period is the time required for the formation of the first crack and the fourth parameter is the failure time. An increase in hydrogen content, notch acuity, or strength level of the material increases the susceptibility for delayed failure by decreasing the lower critical stress, the incubation period, and the time to failure.lY3 A decrease in test temperature prolongs the incubation period in accordance with the lower diffusion rate of hydrogen, and also de-

Jan 1, 1961

By J. Charles Miller

THE expansion of facilities for rapid transportation of perishables by train, truck and airplane has necessitated consideration of refrigerants of a minimum weight and volume per pound of cooling and has stimulated the use of solid carbon dioxide commercially. The gas probably has not had wide application in the past in air-cooling equipment for mines, theaters or buildings, owing to its thermodynamic properties, as will be deduced from examination of Table 2. However, consumption of the liquid in carbonating beverages remains a dominant factor. In addition to these uses, carbon dioxide is employed to a limited degree as an explo-sive in the liquid form, as a freezing agent in plumbing, in laboratories for low-temperature work, and in the manufacture of golf balls.

Jan 1, 1936

By Richard Akerman

At the International Sessions of the Iron and Steel Institute of Great Britain, the American Institute of Mining Engineers and the Verein Deutscher EisenhUttenleute, held in Allegheny City, Pa., in October, 1890, Sir James Kitson, then President of the Iron and Steel Institute, presented an account by Sir Henry Bessemer of the origin of the process which bears his name.? The paper graplhically told how, after the first successes immediately following the first reports given at Cheltenham of the new process, there rapidly succceded such obstacles and difficulties in its practical application, that the whole matter was nearly abandoned in 1858. Suddenly, however, the situation changed, so that at length it became possible

Jan 1, 1894

To THE BOARD OF DIRECTORS AND MEMBERS OF THE AMERICAN INSTITUTE OF MINING AND METALLURGICAL ENGINEERS. GENTLEMEN Like every other significant activity in the United States today, the work of the Institute has been affected by and adjusted to the prosecution of war against Germany, .Japan and their satellites. As the elaborate engines and materiel of modern mobile warfare are made, for the most part, of metals and other minerals; and are powered by mineral fuels, the industries -represented by the A.I.M.E. are of primary and vital importance. Of some 29 critical materials officially listed by the War Production Board, 24 are minerals. An alternate for one of the others, rated as a nonmineral, is to be made principally from petroleum. This alludes, of course, to rubber. The procurement of tremendous quantities of such raw materials and the effective processing, fabrication, and utilization of them depend on members of those branches of the engineering profession represented by the A.I.M.E.

Jan 1, 1943

By H. C. Chang, N. J. Grant

Creep of very coarse grained, high purity aluminum was studied at 400° to 1100°F with an initial stress range of 50 to 1200 psi. The process of boundary sliding and migration was studied. The driving force of boundary migration under creep conditions is shown to be a combination of strain energy migrationand surface energy. A theory is presented regarding the strainenergyrole the grain boundaries play under creep conditions. From this thetheory intercrystalline failure of commercial alloys can be explained. Also from this theory an optimum grain size should exist for good high temperature properties of high purity materials. IN the investigation of the creep of very coarse grained, high purity aluminum previously reported,' the cyclic nature of the process of grain boundary sliding and migration has been established by microscopic observation of the actual creep process as well as metallographically. It was also substantiated by measuring localized strains across the grain boundaries. In addition, it was shown how extensive subgrain and fold formation may result from boundary sliding and how the slid grain boundary may become sharply wavy as a result of subgrain formation. Since the publication of those results, additional information on the process of grain boundary sliding and migration has been obtained. It is the purpose of this paper to report on the direction and driving force of boundary sliding and migration, the effect of grain size, and the effect of temperature. Finally the effect of decreasing purity (alloys 2s and 3s) on the process of boundary sliding and migration is noted. From these results, an explanation is presented for the intercrystalline failure of alloys under creep conditions. The effects of grain size on the creep properties of impure and high purity materials are discussed in the same light. The experimental procedures and technique have been presented elsewhere.' It is only necessary to state how the 2s and 3s aluminum specimens are prepared. Machined specimens were first annealed at 600°F for about 12 hr. In order to produce a large grain size the specimens were then stretched 3 to 8 pct. The specimens were marked with reference marks, electropolished, annealed at 900°F for 24 hr and at 1150°F for 12 hr, and repolished. The grain size of 2s aluminum produced by this treatment is comparable to that of high purity aluminum in the direction of its width of the specimen, i.e., there are 2 to 4 grains across the width of the specimen. However, the grains of 2s aluminum are 3 to 10 times longer in the direction of the specimen axis. On the other hand, the grain size of coarse grained 3s aluminum ranges from 10 to 20 grains across the width of the specimen due to the treatment just outlined and therefore is much smaller than that of both high purity and 2s aluminum. As in 2s aluminum, the grains are about 3 to 10 times longer in the direction of the specimen axis than in the direction of the width of the specimen. The arrangements of the grains in 2s and 3s aluminum were generally irregular; therefore it was difficult to follow the course of the grain boundaries. Results Method of Presentation: In order to show the arrangement of the grains, especially the direction and positions of the grain boundaries, traces of the grain boundaries on the four surfaces of the specimens were unfolded and mapped out after macroetching. Figs. 1 and 2 show the structural development drawings of specimens P-3 and P-8 respectively. The two flat surfaces (of which the front one faces the microscope) and the round-edged surfaces will be called the "front surface" and "back surface" and

Jan 1, 1954

By AIME AIME

MONDAY evening a reception, supper and bridge in honor of the guests of the Woman's Auxiliary was given by the New York Section in the Engineering Woman's Club. After supper, tables were made up for bridge. Some tried jig-saw puzzles, while others merely visited. On Tuesday morning the annual business meeting was called to order by President Bassett. Mrs. Bassett read a note from Mrs. Hoover regretting her inability to be present, and then gave her welcome and message: It gives me much pleasure to welcome you in this annual meeting, and I hope you will be able to come next year, and those who are not able to come this year I hope will be here next year.

Jan 1, 1933

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By W. Chubb

FOR the past several years there has been considerable interest in the development of zirconium and zirconium alloys for application in nuclear reactors. In a portion of the development work being conducted, attention has been given to the development of high-strength zirconium alloys. One of the most outstanding alloys developed in the course of this work is Zr-4 wt pct Sn-1.6 wt pct Mo.' Fabrication and Test Methods Over 50 ingots of zirconium containing either tin and molybdenum or both have been evaluated in the process of selection of an optimum composition. Most of these were prepared as 20-g are-melted buttons; a few were prepared by induction melting. All ingots were prepared by the me of Foote Mineral

Jan 1, 1958

By Irwin Roman

NUMEROUS results and formulas have been published for analyzing seismic records, but most of them apply only to large-scale phenomena such as are encountered in studying earthquakes. In a few cases,1 formulas have been published for some of the simpler structures. In the present paper, an attempt will be made to analyze several types of struc-tures without using methods more advanced than those of a first course in calculus. In, tracing a disturbance through a medium, it is almost always possible to base the analysis on Fermat's Principle of Extreme Time, which states that waves of displacement travel between points in such a manner as to make the time of travel an extremum with respect to all neighboring paths. In the simpler cases, comprising most of those used in optics or geophysical prospecting, this time is a minimum and the principle is often referred to as the Principle of Least Time. Within a homogeneous medium, having a uniform speed of transmission of the disturbance in all directions and throughout the medium, the paths are straight and are refracted at the interfaces in accordance with the Snell law of refraction, which states that the ratio of the sine of the angle, made by the ray with the normal to the interface, to the speed of trans-mission is the same on both sides of the interface. Thus, in any medium composed of homogeneous sections, this same ratio has a constant value at all points. In particular, if all interfaces are horizontal, it is apparent that the angles of incidence are the angles made by the ray with the vertical direction. Furthermore, the incident ray, the refracted ray and the normal to the interface are all in the same plane at each refraction;

Jan 1, 1933

By Henry F. Adams, Guy H. Ruggles

IN this paper the authors aim to chronicle the experience and salient points brought out in changing flotation reagents at a concentrator which had probably been using a mininium amount of oil at a minimum cost per ton, to a more complicated system requiring a partial chemical control. The original oils were coal tar and pine oil. The new reagents are lime, xanthate and pine oil. It was found that there were no insurmountable difficulties and eventually the cost of the new reagents per ton of ore proved to be very little more than that of the old. LIME PLANT When the question of handling lime came up there were two propositions open: (1) to handle the lime dry; (2) to handle it wet in the form of an emulsion. Granting that a dry lime feeder would function properly, delivering lime uniformly, the chief objection was the dust that would be raised when these feeders were being charged or operated, as the only possible location was on a gallery beneath which men were working. With this objection the handling of lime as an emulsion seemed to be the better scheme. The lime plant which was first installed was for experimental work on one section. This was gradually changed and developed until it was of sufficient size to accommodate 20 sections. The various changes will not be discussed and the following description deals only with the fully developed plant. Crude as it is, and perhaps somewhat expensive to operate, the lime-handling plant has been quite successful. Much has been learned which will pave the way for a better installation in the future. Burnt lime is received loose in standard gage box cars. This is the product of the kilns and has had no screening or sorting. A grab sample is taken from each car as it is unloaded. An average of the analyses of samples from 44 cars gave the following: [ ]

Jan 1, 1928

By David P. Hale

THE Cartersville barite district is near Cartersville, Ga., in the southeastern part of Bartow County, about 43 miles northeast of Atlanta. The area over which active mining is being done extends about six miles in a northeasterly direction and is about three miles wide. Barite production in Georgia began about 1907,1but the existence of the mineral was known much earlier. At present four companies are operating washing plants and three other plants are operating on leases from those companies. The chief impurities in the ores are silica and iron oxide. The silica is easily washed and jigged out and gives little trouble. Any gravity separation between the iron and the barite is generally poor, owing to the slight difference in specific gravity. Two operators have turned to magnetic separation as the solution to the problem and have made remarkable improvements in the finished product. By very close sizing prior to jigging, the separation between iron and barite has been greatly improved. In some localities manganese occasionally appears as an impurity, but is fairly easy to eliminate by gravity methods. A considerable percentage of iron and silica is eliminated by being broken free in crushing. Until methods for the recovery of fine ore were introduced a minimum of crushing was done, but modern methods allow more than formerly. The depression years brought about the need for increased recovery of ore handled on the part of the producers and a demand for a higher grade of product on the part of the buyers. Improvements in milling and mining practice have had a far greater effect, however, than merely the production of a better grade of ore with greater recovery. They have opened for mining large areas that a few years ago were considered noncommercial deposits because of their inaccessibility and their high iron content. It is no exaggeration to say that the new methods have more than doubled present known reserves of barite ore of economic value.

Jan 1, 1938

By Martin E. Chenevert

The early work of Terzaghi1 showed that the true stress state of a rock can be expressed by the principle of effective stress. This principle states that effective stress is equal to total applied stress minus the pore pressure. Since the introduction of this principle, a great effort has been made to measure the pore pressure of rocks so that the true stress state can be determined. For clean, permeable sandstones, it is usually found that the effective stress principle can easily be applied. Direct measurement of the pore pressure is achieved with a hydraulic pressure device and the effective stress state thereby computed. However, for fine-grained rocks which contain large amounts of clay (referred to herein as shales), pore pressure measurements are usually quite difficult because of the adsorptive forces of the clay platelets, which produce negative internal pressures. No suitable device is known for measuring internal pressures of dry shales; the effective stress approach is therefore not feasible and data are usually presented in another form. As an example, data from compressive strength tests are presented as a function of rock wetness, rather than effective confining stress. The work of Belopoloskii2 and Colback and Wiid3 are examples of such data. It was pointed out by Lambe and Whitman4 that a better way must be found to express the effective stress of argillaceous rocks. The information presented herein is an attempt to fill that need. Various authors have been able to measure moderate negative pore pressures (0-240 psi) within rather wet, argillaceous rocks by means of various pore pressure devices. In 1961 Lambe5 resented information which shows that pore pressures in argillaceous rocks are indeed negative ; he presented values of suction pressure as low as - 14 psi. Likewise,

Jan 1, 1970

With one shaft almost completed and another shaft being sunk, the scope of the Saskatchewan potash area is beginning to come into focus. Some 18 companies have reportedly leased more than four million acres to explore potash possibilities. PCA, farthest along, is located about 15 miles southeast of Saskatoon, and IMC has its project underway near Esterhazy in the eastern edge of the province. U. S. Borax and Chemical Corp. is also reported exploring the area. The field lies in the middle Devonian geological formation which was probed by oil companies along the 200-mile area across the province. Extensive examination began after World War II and deep drilling was started a few years later.

Jan 5, 1958

By W. F. Campbell

One of the deepest coal operations today is the Springhill No. 2 mine of Cumberland Railway & Coal Co., subsidiary of Dominion Coal Co. Ltd. Mining is now conducted at a slope distance of 14,000 ft, with 4400 vertical ft of cover. The record of Springhill No. 2 can be said to contain the history of bumps in the Province of Nova Scotia. The Springhill coal field forms part of the Cumberland field of Carboniferous age. There are seven mineable fields in the area, numbered in the order they were discovered. Mining has been carried on in all but the No. 4 and 5 seams, but present operations are confined to the No. 2. Fig. 1 shows a vertical section through the seams. Opened in 1873, No. 2 mine was first worked from parallel slopes driven from the outcrop of No. 2 seam down to the 7700 level. As the mine went deeper, a two-place auxiliary slope was driven from the 6900 level to the present workings. A transfer level at the 7800 connects the main haulage with the auxiliary haulage slope. The No. 2 mine plan is shown in Figs. 2 and 3. The seam is bituminous, averaging 8.5 to 9 ft thick. There is a well defined parting 14 to 16 in. from the roof, and this roof coal is harder than the rest of the seam. Average pitch at the outcrop is 30°; at the 6500 level, 20°; at the 7900 level, 16°; and at the 13,800 level, 10°. Immediate roof and floor strata consist of beds of variable thicknesses of shales, grading to arenaceous shales to shaly sandstones to sandstones. A characteristic of the strata is the appearance and disappearance of sandstone bands, of considerable thickness, over distances of several hundred feet. MINE HISTORY Entrance to No. 2 mine is obtained by three parallel slopes, separated by 100-ft pillars except in the upper portion of the mine where the pillars are smaller. Main haulage levels were originally driven 600 ft apart for room and pillar extraction. A parallel drainage and intake airway was driven below each haulage level and a parallel return airway (counter level) above. Pillars 80 to 100 ft wide separated these two servicing entries from the center haulage level. Inclines up to 700 ft apart were driven off the levels up pitch to the upper levels, and at 40-ft centers level rooms 12 ft wide were driven off each side of the inclines, separated by crosscuts every 50 to 100 ft. The rooms were driven up to 350 ft or until they were holed into the room from the adjoining incline—a plan followed until the level reached its boundary. When the entire area between two levels had been divided into pillars, the pillars were extracted from the boundary back to the slope pillars. As depth of cover increased, mining conditions required larger pillars, and at the 3300 level, where NECESSARY PRECAUTIONS FOR MINING AT DEPTH In Room and Pillar Extraction: 1) Pillars must not be too small. 2) Pillar size must be uniform. 3) Extraction lines must be kept as straight and as uniform as possible. If they are irregular they should be brought back into line slowly. 4) Peninsulas of coal surrounded by gob must be avoided. 5) Pillars should not be disturbed after they have been formed. If it is necessary to increase the width of an opening, stripping or ribbing should be done gradually over a long distance. If increased width of openings is necessary at certain locations and can be anticipated, the openings should be widened during development. 6) Under no conditions should small pillars be left in the gob that would interfere with caving. In Long wall Operations: 1) Pillars formed during development for retreating longwalls should be uniform in size and shape. 2) Pillars should not be split after development, but if pillar splitting does become necessary it should not be carried out within the zone influenced by the working faces. 3) Width of levels should not be increased after the levels have been developed. If it does become necessary to widen a level it must be done gradually over a long distance by stripping or ribbing the coal ribs. 4) Extraction lines should remain uniform. If several walls are worked together—one behind the other—a uniform distance must be maintained between them and the wall faces must be kept as straight as possible. If the walls do get out of line, they must be brought back into line gradually to allow for a gradual change in the stress distribution over the area. 5) Stumps of coal, roof supports, etc. must not be allowed to remain in the gob to interfere with caving. 6) Midwalls should be built as rigidly as possible and properly maintained.

Jan 1, 1959

By Oscar Harder

IT is now just a quarter of a century since Fred W. Taylor§(23) pub-lished his classical paper On the Art of Cutting Metals, describing -his researches in which he, in cooperation with Maunsel White, had developed what is essentially the modern method of heat-treating high-speed steels. Regarding this research, Dr. Sauveur, (22) in his address on Steel Wizards, Past and Present, at the annual banquet of the American Society for Steel Treating in Philadelphia in 1920 said, "The discovery of high-speed steel, or if you prefer, of the treatment imparting high-speed properties to certain steels by Taylor and Maunsel White I am inclined to consider as our one epoch-making contribution to the metallurgy of steel." It was at about that same time (1900) that Taylor exhibited high-speed steels, heat-treated by the improved process, at the World's Exposition in Paris and attracted much attention by showing that the steels would operate at such feeds and speeds that the tips of the tools were visibly red hot. This observation must have started metallurgists to wondering regarding the relative hardness of the various steels at red-heat temperatures. Considerable work has indeed been done in an effort to measure the hardness of high-speed steels and. related materials in the red-heat range, using various methods. . The results, however, have been only partly satisfactory, owing to experimental difficulties. The present investigation had as its immediate inception an address by J. V. Emmons, of the Cleveland Twist Drill Co., to the Columbus Chapter of the American Society for Steel Treating in 1931, in which he deplored the fact that comparatively little was known with regard to the hardness of high-speed steels at elevated temperatures, in spite

Jan 1, 1933

By C. Scala, M. Gondouin

Published laboratory data have established that very significant streaming potentials can exist across mud cakes subjected to pressure differentials such as exist between a mud column and formation fluids. Since shale is similar in kind and in properties to a well-formed mud cake, it appeared possible that streaming potentials might also arise across shales. A practical consequence would be that the streaming potential contribution to the SP would be smaller than might otherwise be assumed since the SP is measured with respect to the "shale bare line". The resultant contribution would be the difference between the streaming potential across the shale and that across the mud cake. In order to investigate this possibility, a laboratory apparatus was devised for measuring streaming potentials under pressure conditions normally encountered in wells. Reported data on streaming potentids across mud cakes were verified. More important, appreciable streaming potentials were found across shale samples. As in the case of mud cakes, the shale potentials varied with the concentration and nature of the impregnating electrolyte. Dependence on pressure was In a different rela-tion than that for mud cakes, possibly because of the lower compressibility of shales. The differences in streaming potentials between the shales md mud cakes were generally small, although they might vary considerably in practice depending on the relative electro-kinetic properties of the particular shale-mud cuke combination. A "poorly eflective" shale with a "very eflec-tive mud cake" would produce the largest negative addition to the electrochemical component of the SP. Results of field experiments with pressurized wells were considered in the light of the laboratory results. INTRODUCTION Field experiments wherein the pressure of the mud column in a borehole was varied have often indicated the presence of a streaming potential, but its magnitude was not easily predictable and its sign sometimes changed from one formation to another in the same well.' In the interpretation of SP logs from standard surveys, nevertheless, the correct value of R,, is very frequently obtained, within the limits of field accuracy, using only the simple electrochemical expression of the SP provided that proper corrections are made for bed thickness, ion activity, etc.' Accordingly, it was apparent that the streaming potential component of the SP in a borehole was considerably more complex than commonly assumed and clarification was indeed necessary The close similarity in nature and constitution of a shale to a well-compacted mud cake suggested that a streaming potential might also exist across shales as pointed out by M. P. Tixier in 1953 and as recently emphasized by Wyllie." e practical consequence would be that the streaming potential across the mud cake would be canceled, at least in part, on electrical logs since the SP is recorded with respect to the shale potential as a base line. This appeared to be a plausible explanation for many of the effects observed but no supporting data were available. In 1955 preliminary experiments at low pressures were conducted in our laboratories which supported the hypothesis of the shale streaming potential and formed the basis for later studies at borehole pressures.* EARLY LOW PRESSURE EXPERIMENTS The early experiments were conducted primarily to determine the possibility of a streaming potential across shales. The shale used was a compact type designated as No. 7 from Reagan County, Tex. (Permian). Cut samples were saturated for over one month in .2 to 2.0-N NaCl solutions. In order to eliminate all electrode polarization effects, a dynamic method was used. A transient pressure of about 1 atm was applied across

By J. E. Strassner

Oilfield emulsions are stabilized primarily by film-forming asphaltenes and resins containing organic acids and bases. Adding inorganic acids and bases radically changes the physical properties of these films and their emulsion-stabilizing properties. Interfacial films show one of three different physical characteristics when retracted in pendent drop tests. These compressed films have rigid, soap-type or minimum film properties depending on the quantity of asphaltenes and resins in the crude oil and on the pH and composition of the brine. There exists for each crude oil-brine system an optimum pH range over which the adsorbed film exhibits minimum contracted filtn properties. In this range, intmfacial tension is high — frequently near its maximum value — indicating the absence of highly surface-active specier; crude oil-brine emulsions generally show minimum stability; and surfactant requirements for breaking these emulsions are significantly reduced — sometimes no surfactant is needed. About two-thirds of the world's crude oil is produced as emulsions that must be treated (demulsified) to be marketed.' Approximately three-fourths of all domestic crude oil produced must be treated. The percentage of crude requiring treatment increases as fields become older and more water is produced. Demulsification most frequently is attained through use of surfactants, heat and electric treaters. It is estimated that over 75 percent of all oilfield emulsions are broken by chemicals generally containing alkylene oxide condensates. Although acids and bases are known to affect emulsion stability:-' they rarely are used in the oil field except in batch treatment of the most severe emulsions. Nevertheless, pH adjustment by using acids or bases in demulsification has some advantages over other methods. Mainly, it is cheaper. Acids and bases frequently are cheaper to use than surfactants, or can appreciably reduce the amount of surfactant required for demulsification. Secondary advantages are that less oil is lost by emulsi-fication into the aqueous phase, and that less corrosion is encountered when the optimum pH is basic. Limitations to the use of pH include (1) use in brines containing high concentrations of reactive ions, (2) closer supervision for pH control than is required for surfactants and (3) need for corrosion protection when the optimum pH is sufficiently acidic. These factors indicate that the economics of pH con trol in demulsification will be maximized when relatively large treating facilities are needed, when relatively large surfactant concentrations are required to break an emulsion, when a relatively low concentration of the aqueous phase is emulsified in the oil and when the emulsified aqueous phase contains relatively low concentrations of reactive ions. Because there are no broad guide lines for using pH control in breaking oillield emulsions (and because the limited guides available are highly specific and frequently contradictory), this paper will attempt to clarify the principles involved in using acids and bases to break emulsions. These principles also should be useful in refinery separations and in other oilfield applications where stable or unstable petroleum emulsions are involved. Principles of Emulsion Stability Oilfield emulsions generally occur as water droplets dispersed in oil (w/o) and occasionally as oil droplets in water (o/w). These emulsion droplets are usually in the 0.1- to 10-micron range. However, more coarsely dispersed water droplets frequently are present in the emulsion. Pure hydrocarbons and water will not form stable emulsii except in extreme dilutions where the large distance brtween droplets inhibits coalescence. An emulsion breaks because interfacial tension acts to minimize the surface area of the dispersed drops by coalescence. However, emulsions can be stablized for long periods of time by the presence of a third phase that adsorbs at the oil-water interface and inhibits coalescence of the dispersed phase."' Emulsions generally are stabilized by (1) repulsive charges on the surfaces of the dispersed phase and (2) adsorbed films that, being preferentially wetted by the continuous phase, act as a physical barrier to inhibit contact between the dispersed droplets. Both these factors generally are important in stabilizing and in breaking o/w emulsions. However, repulsive charges are less effective in stabilizing w/o emulsions which generally are stabilized by adsorbed films.V or this reason the nature and importance of these films at oil-water interfaces were examined closely; as will be shown, pH changes were found to affect the films significantly, and this work led to laboratory tests of pH- adjustment in emulsion breaking. This paper will present evidence to show that emulsions are stabilized primarily by films that form around droplets

Jan 1, 1969