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By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

By David R. Poirier

THE activity of carbon in Fe-C-Cr liquid solutions has been measured by Richardson and Dennis,1 Fuwa and chipman,2 and Goto et aL3 Fuwa and Chipman2 have presented their data along with data of Richardson and Dennis1 and utilized an interaction parameter. However, the interaction parameter is only valid for dilute solutions of carbon, because, as indicated, the same interaction parameter does not apply to more concentrated solutions of carbon (i.e., the effect of chromium on the saturation of graphite in liquid iron). Ohtani4 has attempted to account for the effect of carbon concentration on the interaction parameter; however even his analysis does not apply to the saturation data. Also, the effect of temperature on interaction parameters must be taken into account. Therefore, in any process where the concentration of carbon and/or the temperature changes (such as solidification), the use of an interaction parameter is not adequate to know the activity of carbon. The purpose of this communication is to make use of the existing data on the effect of chromium on the activity of carbon in liquid iron solutions in such a way that the activity can be described as a function of both composition and temperature. The method is an extension of Rist and chipman's5 analysis for the binary Fe-C solutions. As in Rist and Chipman's analysis, the activity coefficient is assumed to obey the relation: log y1 = at(l -X1)2 + It [1]

Jan 1, 1969

By Ben B. Cox

Oil produced in Iraq for export during 1938 was 31,354,090 bbl., or a daily average of 85,901 bbl; This is an increase of 182,614 bbl., or 0.5 per cent over 1937. All oil exported was produced from the Kirkuk field. The Khanaqin Oil Company, Ltd., a subsidiary of the Anglo-Iranian Oil Company, Ltd., continued to supply local market requirements from its Naft Khaneh field in the Transferred Territories. Slightly more than 32,000,000 bbl. was produced in Iraq, a small part of which was used in field operations. During the year 12 wells were completed and 9 wells were drilling at the end of the year. Of the completions, 5 were producers and 1 was an oil-water level observation well in proved fields, and 6 were listed as failures. Basrah Concession The outstanding event of the year was the granting, by the Kingdom of Iraq, of a 75-year concession embracing approximately 89,000 sq. miles to the Basrah Petroleum Company, Ltd., a British company with French and American participation. The concession covers all parts of the Kingdom, its territorial waters, islands, submerged lands, and its interest in the Neutral Zone separating Iraq and Saudi Arabia that

Jan 1, 1939

By Ben B. Cox

Oil produced in Iraq for export during 1938 was 31,354,090 bbl., or a daily average of 85,901 bbl; This is an increase of 182,614 bbl., or 0.5 per cent over 1937. All oil exported was produced from the Kirkuk field. The Khanaqin Oil Company, Ltd., a subsidiary of the Anglo-Iranian Oil Company, Ltd., continued to supply local market requirements from its Naft Khaneh field in the Transferred Territories. Slightly more than 32,000,000 bbl. was produced in Iraq, a small part of which was used in field operations. During the year 12 wells were completed and 9 wells were drilling at the end of the year. Of the completions, 5 were producers and 1 was an oil-water level observation well in proved fields, and 6 were listed as failures. Basrah Concession The outstanding event of the year was the granting, by the Kingdom of Iraq, of a 75-year concession embracing approximately 89,000 sq. miles to the Basrah Petroleum Company, Ltd., a British company with French and American participation. The concession covers all parts of the Kingdom, its territorial waters, islands, submerged lands, and its interest in the Neutral Zone separating Iraq and Saudi Arabia that

Jan 1, 1939

By D. M. Collingwood

The year 1928 has been marked by scattered but considerable wildcat drilling considering the overproduction prevalent in the oil industry. This wildcatting has resulted in the discovery of oil in one interior salt dome, several small fields producing from serpentine, Taylor marl, and Austin chalk, and two new fields producing from the Edwards limestone, one of which in the Bruner or Salt Flat area of Caldwell County promises to be of major importance if not quite as large as the Luling field. Fig. 1 shows production by fields for 1928, compared in the case of the older fields, with that for 1927. New Production From Salt Domes Boggy Creek Dome This salt dome was discovered in 1927 by core drilling and deep tests recommended on the evidence of surface geology. A large block of acreage controlled by the Humble Oil & Refining Co. covers the dome. Since the discovery of the deep-lying salt plug and oil on the flank of this dome in 1927, development has proceeded slowly. Since most of the acreage is controlled in a large block by one company there has been no intensive competitive drilling. Approximately 8 producers and 16 dry holes have been drilled. Production is from the eastern equivalent of the Woodbine and Eagleford horizons of the Mexia district, and has been found extending in a northeast-southnlest direction across the River Neches on the southeast flank of the dome. One of the best wells, the T. H. Jones No. 2, had an initial production of 90 bbl. per hr., and others have made from 100 bbl. per day to 50 bbl. per hr., but production of the better wells has either been shut in or choked down to less than 2000 bbl. per day. At the end of the year the daily average, production was about 2500 bbl. from 8 wells. Considerable gas pressure is present and one well, the Elliot Clark No. 2, drilled in 1927, was shut in with an estimated wet gas production of over 5,000,000 cubic feet.

Jan 1, 1929

By I. E. Puddington

The property of surface tension in liquids is said to have been known to Leonardo de Vinci in about 1500. Approximately'300 years later Thomas Young and others provided the ground rules relating surface tension to the wetting of solids and to the pressure drop across curved surfaces. In retrospect it seems remarkable that more than 100 additonal years were required for substantial technological use to be made of the-information. Thus super critical and freeze drying to avoid shrinkage of finely divided solids have only seen industrial use since the 1930's and doubtless additional possible applications will be equally slow in finding concurrence of conditions to make them attractive economically. The use of a second liquid phase that preferentially wets ,a suspended solid as a flocculant for that solid was pointed out in 1943 (1). Combining this phenomenon with mechanical energy to alter the morphology of the flocs or with surface chemistry to utilize it in the selective flocculation in mixed solids required more than an additional decade. A major stimulant in advancing surface energy based technology 'of suspensions was the report by D. I. Stock in 1952 (2) that mechanical agitation of a dry suspension of barium sulphate in benzene produced dense microspheres of the solid with highly desirable sedimentation characteristics. Investigation of this observation revealed that it resulted from small quantities of water in the system and mechanistically the phenomenon was identical with that reported in 1943.withthe addition of mechanical packing (3). Here then was a base from which to separate more efficiently suspended solids, to make small spheres from powders, to separate selected components from mixtures of finely divided solids or to break emulsions. Each of these possible branches of technology has been slow in developing on other than an experimental scale although considerable

Jan 1, 1979

By Ronald E. Versaw

Environmental legislation, both existing and proposed, requires that mills, tailings dams, evaporation ponds, and related processing facilities be located, constructed, and operated within stringent guidelines. An early step in planning a new processing facility is performing a site selection study in which topographic, hydrologic, geotechnical, and environmental parameters are evaluated for several alternate sites. Once a site is selected, then an environmental report, including a description of the proposed action, alternatives, baseline surveys, and discussions of potential environmental impacts, mitigation measures and monitoring programs is required. The federal legislation, siting studies, and environmental studies (along with the implications of these as they affect design) are discussed. In addition, costs for performing these studies and implementing control of effluents are discussed.

Jan 1, 1978

By H. O. Hofman

(Canal Zone Meeting, November, 19]0.) THE sudden decease, April 1, 1910, in Chicago, of Dr. Franklin R. Carpenter was a shock to his- many friends. He died in his sixty-second year, of heart paralysis. To most fellow-members of the Institute who have followed the progress of the. last twenty-five years in the mining and treatment of non-ferrous ores, the work of Dr. Carpenter in that line is familiar ; but very few, even of those who knew him well in the later years, are acquainted with his earlier struggles to satisfy an inborn hunger for knowledge. The story of his life resembles that of the pioneer who opens up new country; overcoming hardships with indomitable courage, meeting doubts and difficulties with an alert and open mind, and exercising in the face of reverses an unconquerable perseverance. It seems appropriate to place on record in the Transactions a brief outline of the life and work of this eminent engineer. During the past 15 years of his life Dr. Carpenter was much interested in genealogy. In the pursuit of this study as an avocation, he traced his own ancestry to the time when ?Hugh," called "le Charpentier" on account of the dexterity with which he had swung his battle-axe as a crusader, settled in Sussex on lands received from William the Conqueror. The Carpenters came to this country with William Penn. A prominent member of the family was Joshua Carpenter, the founder of Christ Church, Philadelphia. Dr. Carpenter's branch of -the family moved from Pennsylvania into that part of Virginia which is now West Virginia, where his grandfather settled in Harrison county, while the grand-uncle went further west, and built the first iron-furnace at Hanging Rock, Lawrence county, Ohio. In fact, since early times, the Carpenters appear to have been iron-masters. Franklin R.. Carpenter was born, Nov. 5, 1848, in Parkers-

Aug 1, 1910

By R. Maddin

IN analyzing the relation between the orientation of new grains and that of the deformed matrix of axially extended and recrystallized single crystals of face-centered cubic metals, a two-stage rotation process" is generally used where the first rotation is made in order to account for an "adjustment of orientation to the environment of strain."&apos; It has been argued that in spite of the difference of orientation, which may amount to as much as 12" (in a brass),&apos; between the octahedral plane as observed in the parent lattice and in the recrystallized grain, it is believed to be a common plane in the sense that it constituted the nucleus in the parent strained crystal from which the new grain grew.&apos; A possible source of the deviation in orientations of a common pole in the new grain and that of the deformed single crystal matrix from which it has grown may be found in the distribution of strain resulting from the plastic deformation. It might be expected in view of the incongruent nature of shear&apos; that the perfection of the octahedral plane along which glide has occurred is disrupted and that this disruption constitutes the strain from which nuclei of new grains can grow during recrystallization. Evidence for the existence of strain along glide planes was first detected by Taylor" in 1927 and substantiated by Collins and Mathewson&apos; in 1940. In their investigations, however, the deformed single crystalline specimens (aluminum) were cut mechanically along the glide planes followed by mechanical polishing. X-ray exposures (glancing angle) of only 8 min with filtered radiation were used. It was later shown&apos; that this type of surface preparation did not remove with all certainty the mechanically disturbed surface. It was felt that a re-investigation of this phenomenon using more refined techniques might reveal a more correct extent of the strain resulting from the deformation which might correlate the deviation of the common pole of the recrystallized grain with the acting slip plane of the matrix crystal. In accordance with these thoughts, a single crystal of a brass (70/30 nominal composition) M in. in diam x 5 in. long, tapered as in previous experiments,&apos; was extended and carefully documented with respect to elongation and shear. Disks about % in. thick paralle&apos;l to the primary slip planes were cut from the specimen by means of an etch cutter." These disks represented volumes of the specimen which had been extended 0, 5, 10, 15, and 20 pct. Copper Ka monochromatic radiation was obtained by reflecting 35,000 v copper radiation from the c-cleavage face of a pentaerythritol crystal. The monochromatic radiation was collimated and led on to the disk set at the proper 0 angle for reflection from the primary (111) planes. The monochromatic beam was aligned in a plane containing the active slip direction. Following a 10 hr exposure at the theoretical Bragg angle, the disk was reset at 0 + 1°, 0 — 1", 0 + 2", 0 — 2", etc., until no Bragg reflection was obtained. The disk was then rotated 90" about its polar axis, and the same X-ray procedure was used. The results are shown in Table I. It may be seen from the results in Table I that the plastic deformation (20 pct elongation) produces fragments of the glide plane which are rotated or tilted as much as 25 " from the normal position on a purely block slip model. In addition to the large variation in 0 angle in the slip direction, there is a variation in 0 as much as 20" in the direction at right angles to the direction of slip, i.e., <110>. In view of the results shown, it may now be argued that the strain distribution finds its origin in the incongruent nature of the slip process.&apos; The use of the two-stage rotation process seems valid in attempting to explain the relation between the orientation of recrystallized grains and the matrix from which they have grown. Acknowledgment This work was sponsored by the ONR under Contract Number N6 onr 234-21 ONR 031-383. The author would like to thank N. K. Chen for reading and correcting the manuscript. References &apos;R. Maddin, C. H. Mathewson, and W. R. Hibbard, Jr.: The Origin of Annealing Twins. Trans. AIME (1949) 185, p. 655; Journal of Metals (September 1949). &apos;J. A. Collins and C. H. Mathewson: Plastic Deformation and Recrystallization of Aluminum Single Crystals. Trans. AIME (1940) 137, p. 150. eN. K. Chen and C. H. Mathewson: Recrystallization of Aluminum Single Crystals After Plastic Extension. Unpublished. 4 C. H. Mathewson: Structural Premises of Strain Hardening and Recrystallization. Trans. A.S.M. (1944) 38. :&apos;C. H. Mathewson: Critical Shear Stress and Incongruent Shear in Plastic Deformation. Trans. Conn. Acad. of Arts and Science, (1951) 38, p. 213. "G. I. Taylor: Resistance to Shear in Metal Crystals, Cohesion and Related Problems. Faraday Soc. (1927) 121. &apos;R. Maddin and W. R. Hibbard, Jr.: Some Observations in the Structure of Alpha Brass After Cutting and Polishing. Trans. AIME (1949) 185, p. 700; Journal of Metals (October 1949). &apos;R. Maddin and W. R. Asher: Apparatus for Cutting Metals Strain-Free. Review of Scientific Instruments (1950) 21, p. 881.

Jan 1, 1953

Sifto Salt Div. of Domtar Chemicals Ltd. has developed a new method for installing roof bolts in the high backs of its 1-million-tpy rock-salt mine at Goderich, Ontario, on the east shore of Lake Huron. The method teams a telescoping- boom hydraulic crane with a specially developed combination auger-drill and bolt-tightening ma- chine. One man, controlling all operations from a basket supported at the end of the crane&apos;s telescoping boom, installs an average of 100 5-ft roof bolts per shift, at heights to 45 ft. The mine has very long backs that are not as stable as might be expected. The result has been that roof scaling has occupied an unusually high percentage of the underground work force. About six years ago, company officials decided to go to 100% roof bolting of all backs as a safety measure. The present roof-bolting equipment is the result of a development program instituted at that time to find a faster and more economical method for doing the job.

Jan 9, 1967

By G. R. St. Pierre, R. D. Blackburn

Oxygen contents of&apos; liquid-iron alloys saturated with oxides are analyzed. Minimum points observed in particular Fe-X-O systems can be predicled by a simple extension of first-order interaction methods. If minimum oxygen content occurs at N; where r is the ratio of metal to oxygen in the oxide phase. RECENTLY, wisher&apos; reported on solubility measurements of A1203 in liquid iron at 1580°C which support the earlier work of d&apos;Entremont, Guernsey, and chipman2 and Gokcen and Chipman. Swisher&apos;s diagram is reproduced in Fig. l. Minimum points in oxide solubilities have also been found in the Fe-Cr-0 system,4 Fig. 2, and the Fe-Ti-0 system,&apos; Fig. 3. Minima positions can be used to confirm approximately the measured first-order interactions, &, cgr, and E&~, in liquid iron and to deduce compositions of components of constant activity in the oxide phases. Consider the solution of Alz03 in liquid iron: for which an equilibrium constant can be written as: differentiating Eq. [2] with respect to Na~, the atom fraction of &l in the metallic solution, and noting that If the activities of Al and 9 are expanded by a first-order interaction model, then:

Jan 1, 1969

By J. E. Coyne, L. E. Tanner, J. E. Boyd

In recent investigations of the isothermal transformations of the retained 0 phase in a titanium alloy having 13 pct V, 11 pct Cr, and 3 to 4 pct Al, there have been indications that the w transition phase is the initial decomposition product at temperatures below about 950°C (510 c).&apos; This metastable phase, found in a number of titanium-base alloys rich in stabilizing elements and known to have an adverse effect on their ductility and toughness, is not easily observed by the usual experimental techniques. Since wis coherent with the /3 matrix,495 distinct interphase boundaries are not revealed metallographically. However, in some cases, an etching effect (i-e., a "mottled" /3 surface) poorly resolved by light microscopy has been found to correspond with the presence of w.6 X-ray diffraction examination has generally been the most suc- cessful means for identifying this phase and crys-tallographic determinations have been made.4&apos;5 Dynamic elastic modulus7 and electrical resistivity measurementse have also aided in the identification of w. In the current study, the electron microscope was utilized to examine microstructures in aged Ti-13V-11Cr-3A1 that were unresolvable by light microscopy techniques. Using negative parlodion replicas (shadowed with chromium at 27 1/2 deg) examination was made of various transformation

Jan 1, 1962

By G. F. Comstock

The subject of transverse fissures in steel rails has been discussed very thoroughly in recent years from various points of view and the final opinions expressed may be roughly classified into two groups: That these fissures are the result merely of fatigue of the steel and are independent of the quality of the metal. That the quality of the metal and the mill practice must have something to do with them. The first point of view was most ably and logically presented by J. E. Howard,&apos; and in the discussion of this paper, as well as in several other preceding publications, Dr. P. H. Dudley, Consulting Engineer of the New York Central Lines, has strongly defended the other opinion.2 The steel makers of the country have naturally rallied under Mr. Howard&apos;s banner, hoping to place the entire blame for these failures upon the railroads with their high wheel-loads, hard steel, heavy traffic, and sometimes inferior road-bed; while the railroad men, on the other hand, have been busy accumulating statistics and records in the effort to find an actual reason in the rails themselves that would account for the seemingly haphazard occurrence of transverse fissures under varying conditions and at widely separated points. The view that these fissures were due merely to normal fatigue under alternating stresses seemed most reasonable to the writer until quite recently, because from work done in this laboratory, as well as the work of other investigators, of the problem, no structural differences, in the vast majority of cases, were found between metal at the nuclei of transverse fissures and metal at similar positions in the same rails or in other rails that had not developed fissures. Within the last year or two, however, since the method of etching polished sections for the microscope with a oupric chloride solution has been tried systematically on lengthwise sections, passing through the nuclei of transverse fissures, evidence

Jan 1, 1920

By T. F. Petty

During 1935 there were drilled in North Central Texas 1071 wells, of which 565 were dry holes, 469 were oil wells with an initial production of 43,766 bbl. and 37 were gas wells with an initial production of 129,332,000 cu. ft. Production has been 14,180,042 bbl., or a daily average of 38,849 bbl. In Table 1 are listed the various pools of the district. Most of the smaller pools are of minor importance and are merely productive spots. Numerous other similar spots might have been listed as pools but their production is included in other fields. There are a few flowing wells but practically all of the wells are being pumped. The estimated potential is about 50,000 bbl. and the allowable production is based on the Texas Marginal Well Law. In Table 2, wildcat wells that have resulted in the discovery of pools or important extensions to old pools or that have contributed to the geological information of the area are listed.

Jan 1, 1936

By T. F. Petty

During 1935 there were drilled in North Central Texas 1071 wells, of which 565 were dry holes, 469 were oil wells with an initial production of 43,766 bbl. and 37 were gas wells with an initial production of 129,332,000 cu. ft. Production has been 14,180,042 bbl., or a daily average of 38,849 bbl. In Table 1 are listed the various pools of the district. Most of the smaller pools are of minor importance and are merely productive spots. Numerous other similar spots might have been listed as pools but their production is included in other fields. There are a few flowing wells but practically all of the wells are being pumped. The estimated potential is about 50,000 bbl. and the allowable production is based on the Texas Marginal Well Law. In Table 2, wildcat wells that have resulted in the discovery of pools or important extensions to old pools or that have contributed to the geological information of the area are listed.

Jan 1, 1936

By E. Horton Jones

CONTENTS I Page Introduction ....:......................... 3 Chapter I. Unit Costs. . ...................... 4 Chapter II. Comparative Costs ..................... 20 Chapter III. Composite Costs..................... 32 Chapter IV. Wage Scale....................... 36 Chapter V. Raw Material Prices................. 37 Chapter VI. Description oF Costs ................... 64 Introduction We have endeavored in the following "sheets" to give the unit construction costs derived from &apos;the building of the Arizona Copper Co.&apos;s new smelter, Clifton, Ariz., starting in February, 1912, and completing February, 1914.l In Chapter I—Unit Costs—are to be found the most elementary total unit costs which the accounts provide for. They are usable in the Clifton district. Here too are found the percentages to be added to an estimate for Engineering and General Expense. In Chapter II—Comparative Costs—these elementary costs have been classified, averaged and reported as labor and material unit costs. In such form the labor unit costs, when properly applied to similar conditions as these under which they were derived, are usable anywhere. The material unit costs are better disregarded for more accurate estimates and replaced by a newly priced bill of material. In Chapter III Composite Costs are given. They are unit costs built up from several elementary units, and likewise units of larger dimensions and simpler application, valuable for

Jan 1, 1915

By J. L. Rodda

A large amount of time has been devoted to the microscopical study of the copper-zinc alloys, emphasis naturally being placed upon the commercially important alloys of the system. Suitable methods are available for microscopically recognizing the two phases richest in copper, but none appear to have been developed for the positive identification of the other phases. This is, however, accomplished, for the phases normally encountered, by an electrolytic method described in the following pages. Five phases of the copper-zinc diagram (Fig. I) are considered for the purpose of this paper: the solid solution of zinc in copper, alpha (a); the intermediate phases, beta (ß), gamma (?), and epsilon (e); and the solid solution of copper in zinc, eta (11). Beta prime is not considered a separate

Jan 1, 1937

By F. Galasso, A. Paton

ThE recent emphasis on producing boron fibers by reacting boron trichloride and hydrogen on a hot tungsten wire has brought about a renewed interest in the tungsten boride phase diagram. The reaction of the boron with the tungsten core results in the formation of 6 WB, W2B5, and another tungsten boride phase, which was suspected of being the WB4 phase reported by Chrbtien and Helgorsky.1 While the powder-diffraction data for the boride in the fiber and those reported

Jan 1, 1967

By Max W. Ball

An intelligent discussion of the oil situation and its needs, whether from the standpoint of the prospector, the operator, the engineer, or the public administrative officer, must be founded upon a knowledge of the law under which oil lands are obtained. A consideration of new legislation must be prefaced by an understanding of the present law and its results. This paper undertakes to present no new remedy for the ills of the present situation, no new solution of the problems the oil business is facing. It attempts merely to summarize the present law, its provisions, its origin, its development, and its effects. The discussion does not pretend to be exhaustive from a legal standpoint. It aims to avoid legal intricacies which tend to. confuse rather than clarify. It seeks but to present the essentials of the existing situation. The title to government lands known to contain valuable deposits of petroleum may be acquired only under the terms of the placer law as embodied in Section 2329 et seq. of the Revised Statutes. As a preliminary to considering the desirability of this situation it is profitable to examine into its origin. Origin of the Law Congress has left no room for doubt as to the legal applicability of the placer law to oil lands. The Act of Feb.11, 1897(29 Stat., 526), provides: "that any person authorized to enter lands under the mining laws of the United States may enter and obtain patent to land containing petroleum or other mineral oils, and chiefly valuable therefor, under the provisions of the laws relating to placer mineral claims.&apos; . The immediate cause for the passage of this Act was stated in a brief report in the, House of Representatives (there was no debate in the Senate) to be a decision of the Department rendered Aug. 27, 1896 (Union Oil Co., 23 L. D., 223), directing the cancellation of an oil placer entry on the ground that land containing petroleum cannot be located and entered as a placer mine. The report of the Public Lands Committee of the House contains the following interesting statements Congressional Record, vol. xxix, p. 1409):

Jan 1, 1915

By J. S. Billheimer, B. H. Sage, W. N. Lacey

A restricted ternary system made up of n-pentane, tetralin, and a purified bitumen was investigated at 70, 160, and 220 °F. Most of the experimental observations were at atmospheric pressure or at 200 psi." However, some experimental measurements were carried out at a pressure of approximately 8000 psi. It was found that the purified bitumen was precipitated from its solution or dispersion in tetralin by the addition of n-pentane and that the separation occurred at lower weight fractions of n-pentane at the lower temperatures. The bitumen-tetralin solutions show some colloidal characteristics at temperatures below 160 °F when near compositions at which the bitumen separates as a solid phase. At states remote from the phase boundaries and at temperatures above 160 °F these characteristics become less evident. Under these latter circumstances the mixtures tend to follow the behavior of true solutions, particularly in regard to the approach to heterogeneous equilibrium. An increase in pressure appears to increase the solubility of bitumen in tet-ralin-n-pentane solutions. This effect is more pronounced at temperatures above 160 °F than at lower temperatures. INTRODUCTION Asphaltic phases of plastic or solid nature have appeared in numerous instances during the recovery of petroleum from underground reservoirs. Such depositions occurring underground appear to have caused adverse production histories for particular wells or zones. Because of this field experience, it is desirable to understand the factors which influence the formation or separation of the asphaltic phases from petroleum. The problem is unusually complex because the number of true components involved is very large and the details of the phase behavior encountered are difficult to ascertain experimentally. The literature relating to asphalts, asphaltines, and bitumen is voluminous and widespread.&apos; Only those references which are directly pertinent to the work at hand are cited. The separation of an asphaltic phase, hereinafter called bitumen? from naturally occurring hydrocarbon mixtures has been the subject of several investigations.2&apos;3&apos;4&apos;5&apos;6 It has been found that as many as four phases4 may be produced from a crude oil by the solution of a natural gas and propane at a pressure of 1500 psi and a temperature of 70 °F. The separation of bitumen from such naturally occurring mixtures results in at least one liquid phase which is substantially free of high molecular weight components.³ The influence of the solution of lighter hydrocarbons on the separation of bitumen from a Santa Fe Springs crude oil has been investigated. The results indicate that in the case of the methane-crude oil system, the quantity of plastic or solid phase separated reaches a maximum between 0.14 and 0.19 weight fraction methane and then decreases until negligible at higher weight fractions of methane. Similiar behavior was encountered in the case of mixtures of ethane and crude oil. The decrease in the quantity of the solid phase with an increase in the weight fraction of the lighter component appears to result from the formation of an additional liquid phase6 in which the bitumen is relatively soluble. The formation of this additional phase probably occurs at a weight fraction of methane close to that at which the quantity of separated solid reaches a maximum. A comparison of the deposition of bitumen in the field with the separation of asphalts from lubrication oil has been made&apos; and apparently the phenomena are similar. The phase behavior of bitumen also appears to be comparable to that of coal tar."&apos; The chemical and physical characteristics of asphalts and bitumen have been the subject of extended investigations which have been reviewed in some detail by Katz.¹º The conclusion was reached that the dispersion of bitumen in a number of organic liquids was not entirely colloidal since it was impossible to isolate individual dispersed particles even with the electron microscope. However, the evidence appeared to indicate that at states close to phase boundaries the extent of the dispersion of the phases influenced the equilibrium to a greater extent than is encountered in many simpler systems. From earlier study of field samples it became apparent that the phase behavior of bitumen-hydrocarbon systems was unusually complex. It was difficult to characterize in detail the phase behavior involved in naturally occurring hydrocarbon systems, even after a relatively extended investigation. For this reason, the study of a somewhat simpler system which still behaved in a similar manner became desirable. Three major constituents were necessary as-follows: a bituminous solid, a liquid constituent which was a reasonably good solvent, and a constituent in which bitumen was largely insoluble. A sam-

Jan 1, 1949