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By T. Egleston

ALTHOUGH the success of metallurgical operations depends so largely on the possibility of finding proper refractory materials, which enter so prominently into the cost of their operations, it can hardly be said that our knowledge of them is in a very satisfactory condition, or even that we know very much about them, beyond a few facts which have been gathered through their use. Experience, as a general thing, is an excellent master, but the requirements of * This article was written at the suggestion of the Committee of the Institute on Refractory Materials, with a view of calling attention to the anomalies and difficulties of the subject. It was hoped that its discussion would eventually lead to the appointment of a Commission, by the great metallurgical interests of the United States, to investigate the whole subject, since it is believed that a better and cheaper artificial product can be made than any now in use, and that many other important incidental results would be accomplished by such an investigation.

Jan 1, 1876

By Freeman Bishop

The tight electric power supply is one of the most dramatic problems facing the mining industry in 1971. This is caused by rising demands for energy. Clean-fuel and air-pollution controls have contributed to the problems of producing energy from sulfur oil and coal. Coking coal has become scarce. One stimulating development is that coal is no longer the cinder in the mining industry's eye. In fact, it may be the favorite candidate as a base for fuel within a few years. Synthetic gas from coal is the watchword. In dedicating a multi-million- dollar project aimed at converting coal into oil and gas, Hollis M. Dole, Assistant Secretary of the Interior, recently made it clear that coal, which has been taking a back seat to nuclear fission research and study grants, is now coming into its own. Conversion pilot plants are being activated in all parts of the nation.

Jan 1, 1970

Jan 1, 1923

By R. Bakish, M. A. Badiali, N. W. Kirshenbaum

One pound of ultra pul-e molybdenum has been produced containing both metallic and nonmetallic impuvities close to or less than the limits of detection. various purification methods were investigated; althouglz the use of move than one purification step was consideved, it was found that a single, caefully-controlled sublimation of MoCl5 yielded a highly puvified product without prior treatment or recourse to repeated sublimation. Hydrogen reduction of MoC1, to metal was attempted at atmospheric pressure; however, reduced pressure was necessary to obtain substantial yields. The tubular deposits of metal were consolidated into bulk fovm by electron beam melting undev high vacuum yielding a very low gas content. Boblems involved in monitoring the puvity of these materials and analytical results obtained are also presented. THE pronounced effect of even trace amounts of impurities upon fundamental properties of materials is well known to metallurgists and solid-state physicists. Consequently, groups interested in basic studies of metals have in recent years immensely stimulated the preparation and production of numerous ultra-pure metals. Increased demand by scientists for these high purity materials has necessitated development of facilities to prepare them in significant quantities; the procedures reported here were devised to produce significant quantities of ultra-pure molybdenum. Previous work performed in the field of vapor phase purification and hydrogen reduction of several other refractory metal chlorides had demonstrated valuable techniques applicable to molybdenum.' Various purification and reduction steps were individually investigated. Those procedures which showed the most favorable results with respect both to attainment of high purity and to ease of operation were then incorporated in the process utilized to produce the metal.' STARTING MATERIALS It is well known that because of differences in volatility, chlorides may be separated by fractional distillation. It was presumed that distillation of molybdenum pentachloride offered a simple and straightforward method of purification due to its relatively low boiling point. Alternatively, sublimation of the solid chloride also appeared feasible since MoC15 has both a reasonably narrow temperature range in which it exists as a liquid (a property typical of refractory metal chlorides) and a low enthalpy of sublimation. Pertinent thermochemical data of MoC15 are given in Table I. It should be noted that this compound must be handled with care as it is extremely hygroscopic. Anhydrous MoC15 was obtained from the A Metal Climax Co. METHODS OF PURIFYING MOLYBDENUM PENTACHLORIDE Distillation. It was expected that distillation methods, while affording an efficient purification, would prove simple to control and would have a higher production rate than sublimation processes. Also considered was the possibility of effecting a high degree of purification by using both these volatilization methods in conjunction—possibly a distillation followed by sublimation of the solidified condensate. Distillation of MoC15 was investigated using a single stage distillation column packed with chemically resistant glass beads. Heating coils were wound around the column and collection tube (condenser). As-received MoCl5 was charged into a flask connected with the column using a side loading arm under an argon flow. After the column and condenser were brought to about 270" and 210°C, respectively, the apparatus was lowered until the flask was fully immersed in a constant temperature fused salt bath maintained at about 285 °C. Distillation was continued for about 10 or 15 min until 50 to 70 g of distillate had been collected. Analyses of these distillations indicated that several elements, e.g., Cu, Fe, Ni, Cr, and Mg, were lowered in quantity although not all were removed to the same extent. The occurrence of Na, B, Si, and A1 in the distillates appeared to be due to contamination, possibly from corrosion of the pyrex glass. An improved distillation system of larger capacity and longer distilling column was built. Improvements were effected in lowering the amounts of such impurities as B, Mn, Ni, Na, Mg, Cr, Cu, and Fe. These studies were pursued concomitantly with efforts to purify by sublimation; it was subsequently found that although improvements in purity were obtained by distillation, sublimation processes were simpler to control and effected a high degree of purity.

Jan 1, 1963

By P. A. Young

The historical background of on-strand cooling is given, together with a resume of recent practical developments. Laboratory test procedures are then considered in detail, for both productivity and quality parameters, with particular reference to the design of the Ravenscraig No 3 machine (Scotland). A heat transfer model is presented for a porous sinter with propagating cracks. The influence of cooling/sintering area ratio, sinter strength, granulometry, return fines, coke consumption and FeO levels are examined in relation to economics. A detailed comparison of capital and running costs for two different strands, designed for identical duties, but with off or on-strand cooling, is then given.

Jan 1, 1977

By W. B. Agocs

In August 1954 a low altitude test geophysical survey was made in the Green Pond area of Morris County, New Jersey, with a Gulf Research and Development Co. Model I1 total magnetic field variation magnetometer mounted in a Sikorsky S-55 helicopter. The test was made in this area to compare the results of a high precision, very low altitude magnetometer survey with an existing ground magnetic survey in this area having known magnetite concentrations, so that the method could be used in areas of difficult access for the detailing of airborne magnetometer anomalies of interest in place of ground surveys. The load capacity of the Sikorsky S-55 permitted installation of a recording scintillation counter so that a radioactivity survey would be made simultaneously with the magnetometer survey.

Nov 1, 1955

By W. C. MENDENHALL

THE problem of maintaining the mining industry is two-fold; finding new supplies in the face of increasing difficulties, and making such advances in the arts of extraction and preparation as to use supplies of lower grade. Progress in mining and reduction methods and in transportation makes ore today of that which was waste yesterday. These are the fields of the metallurgists and the transportation engineers. The geologists and mining engineers must work together on the problem of ore finding. As the old prospector fades from the scene, men with equal hardihood and patience and equal power to meet the physical obstacles which confront the seeker after ore, must take his place, armed with all that has been learned from human experience about the causes, the controlling conditions, the indications, and hiding places of the metals. Such a seeker is dealing with some of the most complex and obscure of natural phenomena. In nature's laboratory, tremendous forces are at work. Tempera-

Jan 1, 1926

By George E. Cole

While many parts of Canada's pre-Cambrian shield are well served by railway, it is frequently necessary for prospecting purposes to proceed farther into areas inaccessible by rail. To such areas in summer the canoe was at one time the accepted means of travel for the prospector while the dog team was much used in winter. Although summer travel was much improved by the development of the outboard motor, the lack of facilities for cheap transportation has been a serious hindrance to the employment of capital in opening up the distant fields. The pre-Cambrian surface of Manitoba, like that of Ontario, is hummocky, with rounded hills and ridges of rock alternating with basinlike depressions and valleys occupied by lakes and rivers Or by many low-lying portions covered with muskeg' Routes to the mines have not usually been direct or easy and seasonal vagaries have presented problems in themselves. In summer, water transportation may be the cheapest method for the longer distances but it is not every water route that will satisfy the conditions of loading freight on to a boat or scow and of conveying it without interruption to its destination. By its location, a mine may require a large program of boat transportation in summer Over part of its route, to be followed by winter freighting for the remainder. In order to carry on development and produc- tion over a long period, it may be necessary to haul large quantities of supplies during the winter. This seasonal problem, particularly for the out-of-the-way properties, is SO important and demanding as to make it a major operation in the life of the mine. The -use of the tractor during winter months for heavy machinery and bulk supplies, and the use of the airplane throughout the year for the transportation of personnel and for emergency requirements, have greatly improved transportation to places that are inaccessible by rail. Canada has pioneered in both these methods. Development oF Transportation Twenty-two years have seen a marked change in transportation methods in Canada's mining country. Horse-drawn sleighs have given way to the tractor and that to some extent has been supplanted by the airplane. One of the earliest ventures involving transportation of considerable magnitude was that of the Mandy mine, on Schist at in northern Manitoba. According to accounts of early mining activities in Manitoba, the Mandy mine, beginning December 1916, had 3300 tons of ore hauled 40 miles by sleigh to Saskatchewan River and in summer this was conveyed by barge to The Pas, 130 miles, and then by railroad to Trail, British Columbia, 1200 miles. The mine shipped 6000 tons of ore in 1918 and 15,000 tons in 1919. In winter of the latter year, as many as 300 teams of horses were used on the 40-mile stretch to

Jan 1, 1943

By George E. Cole

While many parts of Canada's pre-Cambrian shield are well served by railway, it is frequently necessary for prospecting purposes to proceed farther into areas inaccessible by rail. To such areas in summer the canoe was at one time the accepted means of travel for the prospector while the dog team was much used in winter. Although summer travel was much improved by the development of the outboard motor, the lack of facilities for cheap transportation has been a serious hindrance to the employment of capital in opening up the distant fields. The pre-Cambrian surface of Manitoba, like that of Ontario, is hummocky, with rounded hills and ridges of rock alternating with basinlike depressions and valleys occupied by lakes and rivers Or by many low-lying portions covered with muskeg' Routes to the mines have not usually been direct or easy and seasonal vagaries have presented problems in themselves. In summer, water transportation may be the cheapest method for the longer distances but it is not every water route that will satisfy the conditions of loading freight on to a boat or scow and of conveying it without interruption to its destination. By its location, a mine may require a large program of boat transportation in summer Over part of its route, to be followed by winter freighting for the remainder. In order to carry on development and produc- tion over a long period, it may be necessary to haul large quantities of supplies during the winter. This seasonal problem, particularly for the out-of-the-way properties, is SO important and demanding as to make it a major operation in the life of the mine. The -use of the tractor during winter months for heavy machinery and bulk supplies, and the use of the airplane throughout the year for the transportation of personnel and for emergency requirements, have greatly improved transportation to places that are inaccessible by rail. Canada has pioneered in both these methods. Development oF Transportation Twenty-two years have seen a marked change in transportation methods in Canada's mining country. Horse-drawn sleighs have given way to the tractor and that to some extent has been supplanted by the airplane. One of the earliest ventures involving transportation of considerable magnitude was that of the Mandy mine, on Schist at in northern Manitoba. According to accounts of early mining activities in Manitoba, the Mandy mine, beginning December 1916, had 3300 tons of ore hauled 40 miles by sleigh to Saskatchewan River and in summer this was conveyed by barge to The Pas, 130 miles, and then by railroad to Trail, British Columbia, 1200 miles. The mine shipped 6000 tons of ore in 1918 and 15,000 tons in 1919. In winter of the latter year, as many as 300 teams of horses were used on the 40-mile stretch to

Jan 1, 1943

By E. P. Abrahamson II

The effect of transition element binary solid-solution additions upon the recrystallization temperature of vanadium has been investigated. Cr, Fe, Co, Ni, Mo, Ru, Rh, Os, and IY lower the recrystallization temperature, while Ti, Mn, Zr, Cb, Pd, Hf, Ta, W, Re, and Pt raise it. The majority of elements have their greatest effect in less than 0.15 at. pet. Both the rate of change of recrystallization temperature with atomic percent solute and the limit of initial linearity are found to Correlate with the free atom grozdnd state outer electron configuration of the sollte element. THE work of Abrahamson and Grant1 and Abraham-son and Blakeney2 has shown that the solute's elec- tron configuration appears to be a prime determinant of both brittle-to-ductile transition and recrystallization temperature in dilute binary alloys. It has also been shown by Abrahamson3 that the limit of linearity, i.e., the limit of initial linear change of recrystallization temperature with atomic percent solute, is also a function of the electron configuration of the solute in iron base alloys. Because of the systematic nature of the solute electron configuration correlation, it is to be expected that some systematic variation might be observed upon changing the solvent. Thus, this study of recrystallization in vanadium base alloys is the first of a series aimed at defining the role played by the electron configuration of solute in determining the recrystallization characteristics of dilute transitional alloys. PROCEDURE All alloys were made using 99.8 pct V containing 0.011 C, 0.024 N, 0.08 0, 0.006 H, 0.035 Ta, and

Jan 1, 1962

By Clyde Orr

INTRODUCTION Cracks, crevices, holes, and fissures -- here collectively termed pores -- occur in all manner of substances in sizes from those evident to the unaided eye to those well below electron microscopic levels of detection. Naturally occurring materials having varying degrees of porosity are represented by wood, rock, soil, and mineral formations. Man-made materials that are porous include ceramics, sintered metals, catalysts, adsorbents, filters, and various compacted objects. The extent of their porosity greatly influences the hardness, rigidity, integrity, and general usefulness of such materials, and assessing both their pore volume and size is becoming increasingly necessary. Means by which this pore information can be obtained is the subject here. No attempt will be made to include all techniques and variations of them that have been suggested, but, hopefully, those of most general applicability will be described in sufficient detail to enable a potential user to judge their merit for a particular need. The results of pore measurements are made useful by relating them through other tests to performance criteria such as weatherability, water penetration, frost damage, oil recovery, strength, or thermal or electrical conductivity. These tests, of course, are outside the bounds for inclusion here. A pore is variously defined in dictionaries as "a minute opening", "a small interstice admitting passage of liquid", and "an interspace between particles". Clearly any object through which it is possible to find a continuous path from one side to the other either for a liquid or a gas must be regarded as porous. Passageways are not necessary for porosity to exist, however. There are so-called blind

Jan 1, 1980

By G. R. Gardner, D. H. Davis

INCREASING realization of the importance of dust control, and the recommendations of various agencies, have led the mining industry to become actively concerned with this problem. The background and necessity for adequate dust-suppression measures have been discussed in a number of publications, including those of the U. S. Bureau of Mines, and the use of spray water to reduce dust at the face and on roadways has been recommended. The problem resolves itself into obtaining adequate dust reduction at a reasonable cost. Inasmuch as the term "adequate dust suppression" has never been clearly defined, nor have permissible limits of dustiness (in terms of dust count) been established, it is apparent that any method selected may be required to meet additional demands. Until the industry has been given some indication of permissible limits of dustiness, no permanent solution is possible. Progress will be somewhat handicapped until such information is available. In addition, dust reduction must be obtained without the addition of any excessive moisture to the coal, since consideration must often be given to: I. Quality standards, particularly reduction in heat value. 2. Handling characteristics, particularly in regard to unloading from railroad cars and bins. 3. Application of dry methods of coal cleaning. 4. Necessity for fine screening within specified limits of oversize and undersize. Little detailed information is available as to the advantages and disadvantages of the several methods of water distribution, the location and protection of sprays, operating data on pressure, quantity of water, and so forth, and results obtained. In 1940 an investigation was undertaken to determine and evaluate the principal factors involved. This paper constitutes a progress report on this work and cannot in any way be regarded as complete on any one of the several phases. CLASSIFICATION OF DUST SOURCES The various sources of underground dust may be classified as primary or secondary. A primary source is one associated with appreciable degradation of size, that is, where the greater part of the actual fines capable of becoming air-borne dust are produced. A secondary source may be considered as one in which the greater part of the fines have been produced at some previous operation and are in such condition that they can be dispersed as air-borne dust. These conceptions appear to be of practical significance, as experience indicates that when dust is controlled at the primary sources the importance of secondary sources is minimized. For these reasons, investigations to date have been concerned principally with the primary sources of dust, and this paper is concerned particularly with one of these-namely, undercutting. In accord with the foregoing definitions, the sources to which the following opera-

Jan 1, 1942

By Thomas Leonard Watson

I. Historical. Barite has been mined for many years in various parts of Virginia, probably the earliest mining-operations being in Prince William county, within 600 ft. of the Fauquier county line, about 4 miles south of east from Catlett, a station on the Southern Railway. It is claimed that the mineral was mined here as early as 1845. Mining-operations in Campbell and Pittsylvania counties in the Piedmont region, and near Marion in Smyth county, in the southwest Virginia Valley region, were begun about 30 years ago. The mining and milling of barite on a commercial scale in Tazewell and Russell counties are more recent, and commenced about 15 years ago. II. Geographical and Geological Distribution. Barite occurs in many counties in the State, as shown in Fig. 1, but the industry has been confined to only a few of them. Its occurrence is noted in two of the three major divisions of the State—namely, the Piedmont region east of the Blue Ridge, and the Paleozoic area west of the Blue Ridge. In the Piedmont region the mineral has been mined in the following counties: Bedford, Campbell, Louisa, Prince William, and Pittsylvania. In the region west of the Blue Ridge, composed of Paleozoic sediments, barite has been mined in Montgomery, Russell, Smyth, and Tazewell counties. Of the counties mentioned, Bedford, Campbell, and Pittsylvania of the Piedmont region, and Russell, Smyth, and Tazewell of the Valley region, have been the principal producers. In 1906, operations were confined to five counties—Bedford, Louisa, Pittsylvania, Russell, and Tazewell—but in the first two counties named there was no production, the work being solely development.

Jan 1, 1908

By Walter H. Bruckner, George B. Clark

Since the end of World War 11 interest has been increasing in the use of shaped charges in the mining industry and in other industries using explosives for blasting purposes. Shaped charges employ the principle known as the "Munroe effect," which was discovered by Charles E. Munroe more than 50 years ago (in 1888). Details of their design have been explained elsewhere.1,2,3 Fig I shows the essential features of design of two types of shaped charges (with conical and hemispherical cavities) and a schematic sketch of their action upon detonation. The following discussion deals with the behavior of the metal in the cavity liners when they are subjected to intense Pressures exerted when the explosive charge is detonated. Among the conclusions reached in research on shaped explosive charges, the following have been established conceming cavity liners:1'2 I. The optimum wall thickness of a conical cavity liner is dependent upon the apex angle of the cone as well as On the base diameter of the charge. Acute apex angles require thinner walls for optimum perfonnance and more obtuse angles require thicker walls for the same base diameter. '. Cones were more effective in forming a penetrating jet when the walls were tapered; that is, the thickness of the wall of the cone increased from the apex down. 3. The physical and mechanical properties of metals have a marked effect upon their performance as cavity-liner material. Boiling point, ductility, malleability, ten-sile strength, and hardness are among the properties that influence the effectiveness of a metal used as a cavity liner. Lead, for example, makes a wide, flat crater in steel plates. Aluminum makes a deeper crater than lead, and an aluminum alloy having a high tensile strength makes a deeper hole, but slightly smaller in diameter. Cast iron makes a deep, narrow hole. These findings, together with the following analysis under Metallographic Survey of slug, offer solutions to many of the problems involved in solving the mechanism of the formation of Munroe jets. It has been fairly well established that cavity liners collapse in a manner similar to that indicated in Fig 2, Conical liners are known to collapse upon themselves while hemispherical liners are believed to turn inside out in the process of jet formation. The first has been definitely proved by recovery of collapsed portions of cones, while liners from partly detonated charges show that hemispheres may turn inside out. Fig 3 shows a sketch of a recovered slug from a 6-in. shaped charge using a 45" cone made of cast iron. (This size of charge drilled holes up to 3 ft in depth in solid granodiorite.)

Jan 1, 1949

[United States PAGE Alabama 242 Alaska 242 Arizona 1 242 Arkansas 243 California 243 Colorado 246 Connecticut 248 Delaware 248 District of Columbia 248 Florida 248 Georgia 249 Idaho 249 Illinois 249 Indiana 250 Iowa 250] [ ]

Jan 1, 1925

By AIME AIME

Air transport supplants the old methods. The 3-piece canoe fits in the plane and likewise makes possible not a bad division of labor over a 5-mile portage

Jan 1, 1933

A HIGHLY successful joint conference on coal-mine transportation was held at Pittsburgh on Oct. 20 by the Pittsburgh Section of the American Insti-tute of Mining and Metallurgical Engineers and Mining Section of the Engineers' Society of Western Pennsyl-vania. C. E. Lesher, executive vice-president of the Pittsburgh Coal Co., presided over 215 members and others in the morning and Graham Bright, sales en-gineer with the Mine Safety Appliances Co., presided over about 180 in the afternoon. There were four prepared papers and much discussion, as well as a good luncheon between the sessions. Mechanical loading in the Pittsburgh district was discussed by L. E. Young, production vice-president of the Pittsburgh Coal Co. More companies in this district are using loading machines, more types of machines are being tried, and more coal is being mined by them than heretofore. The draw-slate above the Pittsburgh seam is the main problem; but devices for supporting and moving draw-slate are being tested. Except in two mines, the slate is being taken down. The fundamentals of the machines are similar, but the electrical drive and other parts have been improved. The problem is to recover or move as much coal as possible without hand labor. Methods of cleaning coal must be improved to meet the new methods of loading. The Pittsburgh Coal Co. has ten Joy machines and others are under order, a Myers-Whaley machine, Jeffrey conveyors, and Eichoff conveyors. The last mentioned are used in entries and other conveyors in rooms. At Montour No. 10 mine, one Joy machine is worked in rooms and one in entries.

Jan 12, 1927

By V. D. Perry

Mineralized breccia pipes, because of their wide-spread occurrence and close structural relations to some of the world's great ore bodies, are objects of unusual interest for mining engineers and geologists. The literature contains many references to them, but it is questionable whether their genetic significance and economic importance have been sufficiently emphasized. The purpose here is to stress these features, relating them to the field facts, for the particular benefit of younger generations of geologists who, confronted with and sometimes confused by the growing flood of geochemical, geophysical, and other specialized research approaches, may be reassured that mappable field relations remain a foremost guide to a better understanding of ore deposits. A mineralized breccia pipe is a pre-mineral, breccia structure which has controlled the circulation and deposition of subsequently introduced mineralization. It is composed of relatively rotated angular or rounded rock fragments, set in a mineralized matrix. A pipe in plan outline may be circular, oval or approach polygonal form, with a steep to vertical axis proportionately much greater than its horizontal dimensions. The pipe is a steeply plunging, chimney-like mass of brecciated rock cemented with later minerals.

Jan 4, 1961

By David L. Sikarskie

The measurement of residual stress fields using X-ray diffraction techniques requires the removal of successive layers of material from the specimen. In the process of removing these layers, the underlying residual stress field is altered; hence, if the original stress field is desired, corrections must be made to the measured stresses. Although these corrections already exist for a number of cases, an alternate procedure is outlined herein whereby the corrections are presented in series form. This form is numerically more convenient within certain ranges of correction depths and in its simplicity gives additional insight into the factors affecting the corrections. It, further, readily permits determining the proper slice depth to remove and the effect on the correction of both specimen thickness and magnitude and form of the measured residual stress itself. ONE of the techniques currently being used to determine residual stress fields is X-ray diffraction. Since X-rays are diffracted essentially from the layers of atoms near the surface of the specimen, of the order of 0.0001 to 0.001 in. depending on conditions, the method can only determine stresses* in this very thin surface region. Therefore, if the residual stress field at some depth into the specimen is required it is necessary to remove successive layers of material taking measurements after each cut. In the process of removing a thin surface layer of stressed material, however, the over-all equilibrium of a cross section of the specimen is disturbed with the result that the internal residual stress which existed before the slice of material was removed is altered. This alteration of stress occurs after each slice and its effect is cumulative. Thus, if the original stress distribution is desired, corrections must be applied to the measured stresses. These corrections can be found by satisfying equilibrium on each new cross section. These corrections have been derived in detail for a number of cases, e.g., cylinders, bars, plates,' and also are given in Appendix VI of Ref. 2. In each of the above cases the correction terms require the evaluation of definite integrals of the measured residual stress distribution. In general, this is indeed the way one would proceed with the corrections. There are a number of instances, however, where the integrals can be replaced by a series form of correction which is considerably more convenient numerically and, also, gives added insight into the factors which influence the corrections. Such a form of the correction is particularly useful, for example, if one is interested in designing a test such that stress corrections will be small. Also, the question of what depth of slice to use in relation to both specimen thickness and residual stress distribution itself must invariably be answered. Questions of this type can be readily answered using a series form of correction. In addition, if the correct residual stress distribution is needed only for limited depths into the specimen the series correction provides numerical results which are equivalent to the integral correction. I) DERIVATION OF THE SERIES CORRECTION The problem to be considered here is that of a bar or plate,* i.e., either one or two dimensions of the specimen is large compared with the third. Also, the residual stress distributions considered depend only on z, see Fig. 1. In view of this it can be shown' that a stress correction, based on simple beam theory, satisfies all conditions of "elasticity theory" and hence is the correct (and only) solution. The integral form of the correction (this assumes that the measured residual stress is a piecewise continuous function) as given in Ref. 1 is:

Jan 1, 1968

By C. A. Stout, S. W. Nicksic

The materials that stubilize emulsions of some Southern California crude oils were isolated from the produced crude. These substances were separated into acidic and nonionic fractions by ion exchange chromatography. Each fraction was further broken into groups of homogeneous molecular weight composition by gel permeation chromatography. Both ionic character and molecular weight of the individual fractions are reflected in the properties of the original crude oil emulsion. Specifically, the more acidic and the higher molecular weight fractions appear to be the most effective stabilizers. INTRODUCTION The treatment of oilfield emulsions is a continuing problem for the oil industry. In almost all cases, these are water-in-oil emulsions. Much more is known about the formation and stabilization of oil-in-water (O/W) emulsions than of the water-in-oil (W/O) type. To understand W/O emulsions, more information is needed on the materials responsible for their formation and stabilization. This is especially true in the case of oilfield emulsions where the stabilizing materials are complex mixtures of large asphaltene-like molecules. To study the chemical and physical properties of these emulsion stabilizers, it is necessary first to separate them from crude oil. This separation was achieved in the case of two Southern California crude oils. The materials that were isolated appear at first to be little different from an asphaltene mixture. However, if a mixture of distilled water and mineral oil containing about 1 percent of the natural emulsion stabilizers is passed through a colloid mill, the W/O emulsion formed may be stored in the laboratory for many months without any sign of breaking. This could not be done using undifferentiated asphaltenes from the same wells, indicating that there is a real difference between these materials and ordinary asphaltenes. The colloid mill used to generate the emulsion was required because tile natural emulsion stabilizers had very little effect on oil-water interfacial tension. The one characteristic — complexity of composition — that emulsion stabilizers share with asphaltenes makes virtually impossible the exact structure determination of the components of the mixture. For this reason, it was decided to investigate first the influence of molecular weight on the ability of these materials to stabilize emulsions. The emulsion stabilizers were first separated into acidic and neutral fractions according to whether or not the material was retained on a weakly basic ion exchange column. The extraction procedure was not designed to remove basic components from tile oils, and no attempt to isolate such a fraction was made. Following this separation, selected fractions were analyzed by gel permeation chromatography. Gel permeation separates according to molecular size, largely independently of chemical or polar characteristics. A heterogeneous mixture is separated into a number of fractions having much more homogeneous molecular weight distribution. A number average molecular weight of each fraction is therefore close to the true molecular weight of the principal component of that fraction. The fraction weights, expressed as weight percent of the sample, and the number average molecular weight of a representative selection of the fractions, will be referred to in this paper as the molecular weight profile of the original sample. DESCRIPTION OF GEL PERMEATION ANALYSIS The first reported gel permeation analyses were for separating partially hydrolyzed protein molecules in an aqueous system using expanded starch granules. Most of the theoretical work on gel permeation has been done by biochemists.1 This theoretical treatment is still incomplete, but the

Jan 1, 1969