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By F. E. Wood, H. W. Young, A. W. Buell

This paper summarizes the results of laboratory tests conducted to determine the properties of the paraffin or rod-wax encountered in the Salt Creek field, Wyoming. It also describes field tests and methods employed to cope with the paraffin problem. The conclusions to bo drawn from the laboratory work are: 1. Samples of Salt Creek paraffin range in consistency from soft lo hard, the melting points varying from 120" to 156" V. 2. Masses of soft paraffin are soluble to an appreciable extent in crude oil and its liquid fractions at temperatures somewhat below the melting point of the paraffin. Hard paraffin is very slightly soluble. under these conditions. 3. Agitation apparently increases the amount of paraffin that will go into solution. 4. Paraffin congeals from solutions upon cooling to the point of saturation ation, which is in all cnscs below thc melting point of the paraffin. 5. Crutltl oil is tlie most effective. of all the solvents for holding paraffin in solution. 6. Pressure alone does not appreciably affect the solubility of paraffin in crude oil nor does it aid materially in holding paraffin in solution when the temperature is reduced. 7. Natural gas in solution under pressure does not appreciably increase the solubility of paraffin in crude oil, hut is effective in holding paraffin in solution when the temperature is reduced. 8. A foreign body introduced into a solution of paraffin in oil is imrnediately coated with paraffin if the temperature of the solution is at or below the melting point of the paraffin, and the object is considerably cooler than the solution. It may not be entirely correct to ray that paraffin is taken into solution; it is impossible that the paraffin may be in suspension rather than in solution.

Jan 1, 1928

By David C. Grant, Erich W. Tiepel

In situ mining is a process for recovering uranium from relatively small or low grade ore bodies. The process involves passing a lixiviant and oxidant, typically NH4HC03 and H202, through a uraniumcontaining ore body. As the solution progresses through the ore body, the uranium is oxidized from the plus four to the soluble plus six state. The bicarbonate complexed uranium laden solution is removed from the ore body and the uranium recovered in an above-ground processing plant. During the leach process lixiviant cations may be sorbed on the ore host, if the host contains exchangeable clay minerals. This report examines the implications of this clay interaction on ground-water quality, the various available in situ mining restoration methods, laboratory procedures for simulation and development of those methods, and the results of using the restoration methods in the field. Various restoration methods, including ground-water sweeping, clean water recycle, and chemical restoration are presented and discussed. The use of ore characterization, agitation leach tests, and column tests to study cation sorption and desorption, and thus, to identify and evaluate restoration methods is discussed. Ore characteristics identify the clay type and clay content, which allows the estimation of the magnitude of the cation sorption by that ore. The chemical effects of clay exchange and of chemical restoration can be examined using agitation leach experiments and packed ore column tests which also provide information on the physical effects. The agitation leach test is a relatively rapid means of determining the sorption and desorption characteristics of an ore. Unlike agitation leach tests, column tests can be used to assess the influence of solutions on permeability, on precipitation problems, and on other chemical changes. The effectiveness of using restoration methods, which were developed and tested in the laboratory, are examined by presenting field restoration data from several mining sites.

Jan 1, 1979

By C. F. Quest, T. S. Washburn

The steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more comprehensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collection of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combination of tables and an equation. The latter include work by Campbel12,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Teosile etrength = 41500 + 770C + 1000P + yMn [1 y was a variable depending on the carbon and manganese content of the steel and was listed in tables. Webster investigated acid Bessemer steel and developed the equation: Tensile strength = 38000 + 800C + xTP+ yMn [2]

Jan 1, 1940

By R. S. Dean, A. B. Hersberger

Although it is obvious that in any flotation process we must have a froth, in recent years the development of collecting reagents has caused the possibilities of better frothing agents to be overlooked. Some investigators have even gone so far as to say that the number of satisfactory frothing agents was sufficient. A little consideration will show, however, that the reagents available in the past were far from ideal frothers. The properties of an ideal frother for flotation work may be set down as follows: 1. It must form in low concentrations a copious but not too persistent froth. 2. It must be insensitive to hydrogen-ion concentration of the pulp; that is, it must froth equally well in an acid or alkaline medium. 3. It must be insensitive to salts, even in high concentration. 4. It must be absolutely noncollecting to both sulfides and nonsulfides. 5. Its frothing properties must not be affected by collecting reagents, including soap, the most generally used nonsulfide collector. 6. It must readily emulsify and disperse any insoluble collecting agent that is likely to be used. Clearly the existing frothers do not qualify. Pine oil, for example, is an acceptable frother for many purposes but if used in soap flotation a delicate balance between pine oil and soap must be struck because, as pointed out by Coghill1, these two reagents are incompatible in certain concentrations. The objections to soap itself as a frother are obvious, and the cresols and their substitution products all have some collecting power and very little emulsifying power. The mechanism of frothing in flotation was early explained on the basis of the Harkins-Langmuir theory of oriented molecules.2 These investigators showed that if an organic compound having an unsym-metrical molecule (in which one end of the molecule contained water-

Jan 1, 1939

By James Norman, E. W. Gieseke

Spodumene is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content, it might be a desirable constituent of glass batches. The use of spodumene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components. The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manganese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li²O on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston,S the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3The methods described in the second publication3 did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted. Study of Method of Flotation Separation Most of the work on concentration of spodumene was done with rock from near King's Mountain, North Carolina. Rock from two

Jan 1, 1942

By T. F. Witherbee

In a paper read at the Lake Superior meeting, August, 1580, an account was given of the successful use of Rendrock. and Monaky powder upon a .scaffold- and salamander in the furnace. On April 5th, 1881,' the same trouble called for like treatment, which, though not so immediately successful, was on the whole more instructive than the first trial, and points, I trust, to a reasonably sure remedy for all such difficulties. Up to December 4th, 1880, foundry and mill iron were made from Old Bed and Sew Bed magnetite, and Kearney red hematite, when a return was made to Bessemer iron, from an inferior quality of New Bed ore as compared with that used during first blast. January lath, 1881, New Bed, Chateangay, and East-shaft, a newly-opened Bessemer deposit of Messrs. Witherbee, Sherman $ Co., were first used, and continued up to February 13th, on a fuel charge of 80 per cent. anthracite and 20 per cent. coke, the product on the three ores being about 10 tons more per day than on New Bed alone. From this time until March 11th all coal was used, and New Bed, Chateaugay, and East-shaft ores, up to February 224 and from that date Chateaugay and New Bed, the product falling off 9,8, tons per day as a result of not using coke. It is fair, however, to state that the furnace was not in good condition during this period, being over-burdened, and the New Bed ore was, temporarily, uncommonly poor, for reasons of no particular interest here. It required to properly flux it at least 140 per cent. of limestone; and 101 per ent. was actually used. March 11th, all Chateaugay ore aid 80

Jan 1, 1882

By T. F. Witherbee

IN a paper read at the Lake Superior meeting, August, 1880, an account was given of the successful use of Rendrock and Monaky powder upon a scaffoldn and salamander in the furnace. On April 5th, 1881, the same trouble called for like treatment, which, though not so immediately. successful, was on the whole more instructive than the first trial, and points, I trust, to a reasonably sure remedy for all such difficulties. Up to December 4th, 1880, foundry and mill iron were made from Old Bed and New Bed magnetite, and Kearneyy red hematite, when a return was made to Bessemer iron, from an inferior quality of New Bed ore as compared with that used during first blast. January 18th, 1881, New Bed, Chateangay, and East-shaft, a newly-opened Bessemer deposit of Messrs. Witherbee, Sherman & Co., were first used, and continued up to February 13th, on a fuel charge of 80 per cent. anthracite and 20 per cent. coke, the product on the three ores being about 10 tons more per day than on New Bed alone. From this time until March 11th all coal was used, and New Bed, Chateangay, and East-shaft ores, up to February 22d, and from that date Chateangay and New Bed, the product falling off 9 6/10 tons per day as a result of not using coke. It is fair, however, to state that the furnace was not in good condition during' this period, being over-burdened, and the New Bed ore was, temporarily, uncommonly poor, for reasons of no particular interest here.. It required to properly flux it at least 140 per cent. of limestone; and 101 per cent was actually used. March 11th, all Chateangay ore and 80

Jan 1, 1882

By James Norman, E. W. Gieseke

Spodumene is a lithium-bearing pyroxene, and is an important source of lithium compounds. Because of its high alumina and lithia content, it might be a desirable constituent of glass batches. The use of spodumene in ceramics will undoubtedly increase, as it has been shown that a mixture of the proper proportions of this mineral with soda feldspar and potash feldspar has a much lower maturing temperature upon firing than has any one of the three components. The mineral spodumene seldom occurs as pure mineral, but ordinarily with feldspars, mica and quartz. All spodumene-bearing rocks tested contained these minerals as gangue. Small amounts of iron and manganese oxides also were present, usually as stains on the silicate grains. Mica associated with the spodumene carried a considerable amount of lithia. This was discovered in flotation tailings, which, although virtually free of spodumene grains when examined microscopically, showed 0.4 to 0.5 per cent Li²O on chemical analysis. The lithia content of micas picked from the North Carolina spodumene rock was variable. Some samples contained little lithia, others more than 3 per cent. In 1938, under the supervision of Oliver C. Ralston,S the Bureau of Mines, in cooperation with the Tennessee Mineral Products Corporation, undertook to study the beneficiation of North Carolina spodumene by froth flotation. The Bureau had previously published investigations on the beneficiation of spodumene.2,3The methods described in the second publication3 did not give good results with badly weathered spodumene rock, so that more thorough investigation of the subject was warranted. Study of Method of Flotation Separation Most of the work on concentration of spodumene was done with rock from near King's Mountain, North Carolina. Rock from two

Jan 1, 1942

By Foster Fraas

MOST commercial electrostatic separators utilize the electrical property of conductivity, but although based on the same principles, they are constructed in a variety of forms, a common one being the simple roll type. Some information obtained during an investigation of that type of separator, and which indirectly is applicable to other types, is presented here. NUMERICAL RELATIONSHIP In Fig. I material discharged from hopper 6 is fed onto grounded rotating roll 2. Electrode 3 is at a high electrical potential with respect to roll 2, and any conductive particle in contact with roll 2 therefore acquires an electrical charge of such polarity that, when present in the electrical field, the force on it is in the direction of electrode 3. A detailed description of the charging by conductance as utilized in electrostatic separators may be found in a previous publication.1 As a result of this force, the path of the projected particle is changed in increasing amounts in the direction toward region C as the magnitude of the charge is increased. With the dividing edge 4 the projected particles may be divided into two fractions -those in region C designated as "deflected" or " deflectant " and those in region B designated as "residue." When material is passed over the roll only once, a complete separation is seldom obtained, therefore most commercial separators contain several roll-separator units in [ ] series, and some practical machines use as many as 12. In this paper a "pass" means the passage of material over a single-roll unit. The procedure is to repass either residue B with a low potential on electrode 3 or deflectant C with a high potential on 3. Most electrostatic separations follow a flowsheet of roughing and cleaning either the concentrate or the tailing, on both. In a specific instance, a dry, heated mixture of wet cleaned chromite and garnet from an

Jan 1, 1942

By A. J. Weinig

The Liberty Bell cyanide precipitate is unique in that it is apt to vary widely in composition in the course of very short periods of time, and a method of refining and melting that would prove highly satisfactory at one cleanup would yield7almost a hopeless "mess" at a second. Table I gives a general conception of the wide range in grade and composition of those raw precipitates. It is evident that no one standard flux could be expected to produce a high-grade bullion with such a widely variable precipitate, and that any method of treatment with acid requires most careful consideration. Refining by Acids Naturally, our first efforts to improve our precipitates were directed along the lines of acid treatment. Table II embodies the results of careful sampling and analysis of one cleanup at the time when wet refining reached its maximum development at this mill. We have now discarded all methods of wet refining, successfully replacing them by a more scientific method of flux calculation described herein, but it is believed that a general description of this wet refining is warranted as it throws some interesting side lights on acid refining in general. Table I.—Range of Composition of Raw Precipitates Per Cent. Gold and silver.................................... 25.0 to 75 Zinc.............................................. 18.0to 30 Lead............................................. 0.5 to 52 Copper........................................... 0.5 to 20 Silica............................................ 1.0 to 5 Calcium oxide...................................... 4.0 to 8 Sulphur.......................................... 0.5 to 8 Column A gives the analysis of the raw precipitate; column B, that of the precipitate after heating with steam, with frequent addition of hydrochloric acid until a point was reached where the batch had a strong tend-

Jan 1, 1917

IN this survey of the progressive development of education for the mineral industries throughout the United States, the review of the history of each school has usually been completed wherever it is first mentioned, but the history of the schools in the cities of the eastern seaboard was not carried beyond 1870. It is necessary now to cover what happened during the period of approximately the last quarter of the nineteenth century in several of the schools in the east. PHILADELPHIA Of Philadelphia, it has been related in chapter 4 that the Polytechnic College of Pennsylvania began offering a curriculum leading to the B.S. in mining in 1853; that the school did not prosper, and finally closed about 1890. The establishment of a Department of Mining, Arts, and Manufactures at the University of Pennsylvania in 1855-56 was also mentioned, but its history was not carried beyond 1860. In 1859 J. Peter Lesley was appointed professor of mining in the University of Pennsylvania. The son of a cabinetmaker, born in Philadelphia Sept. 17, 1819, he had taken his A.B. degree at the University of Pennsylvania in 1838 and then secured a position on the Geological Survey of Pennsylvania under H. D. Rogers. When the Survey was discontinued, in 1841, he went to Princeton to study theology, was ordained a Presbyterian minister and followed that career until 1853, when the Pennsylvania Geological Survey was again started and he rejoined its staff. He published "A Manual of Coal and its Topography" in 1856, and studied at the École des Mines, Paris, in 1850-57. He published an 800-page "Iron Manufactures Guide" the year that he was appointed to the staff at the University of Pennsylvania. In 1863-64 a College of Agriculture, Mines, Arts and the Mechanic Arts was established, but it was not a separate school

Jan 1, 1941

By N. Plint, E. T. Pinkney

Copper segregation developments within the Anglo American Group are described with particular reference to the work of the TORCO Project Team. Some radical differences have been adopted in the mechan-ical approach as compared with methods used by previous workers. Most important among these are the following: (1) The heating unit is a fluidized-bed roaster. (2) A moving bed segregation chamber is used in which a packed bed of heated ore, to which reagents have been added, moves slowly downwards under gravity and is discharged at a controlled rate by means of a suitable valve mechanism. (3) The quantities of reagents used (sodium chloride and some form of carbon) are only a small fraction of those recommended by other investigators. (4) Retention times of only 2 min have been satisfactory for the complete segregation of many types of ore. Project TORCO is the code name given by Anglo American Corp. of South Africa, Ltd., to the investigation undertaken in Zambia to develop a plant capable of treating large tonnages of refractory copper-bearing ores by the segregation process. The process has now been under investigation for six years (1960-66) and during that period work has progressed from bench-scale laboratory tests through small-scale pilot-plant work to a 500-tpd commercial pilot unit. Test work has been carried out mainly on the ores of the Zambian Copperbelt and results have been encouraging. Recoveries on the order of 90% have been obtained on all Copperbelt ores tested with high concentrate grades. PRELIMINARY INVESTIGATION Laboratory scale segregation test work on Nchanga banded sandstone ore and oxidized ore from Kansan-shi was originally conducted by Professor Maurice Rey. SociCtC Miniere et Mktallurgique de Pefiarroya, in 1957. Both ores responded favorably to the process. In November, 1960, the consulting engineers of Anglo American Corp. of South Africa, Ltd., initiated preliminary investigations on the application of the segregation process to Copperbelt ores. In early laboratory work, samples were heated in a closed, externally heated tube furnace for one hour at temperatures ranging from 800 to 830°C. The free moisture content of the ore feed was 4% and reagent additions were 0.5% salt and 1.0% coal. Both salt and coal were pre-crushed to -48 mesh Tyler.* All samples except an ore from the Bancroft mine responded well to the process and recoveries of over 90% were obtained. The presence of dolomite was responsible for the relatively poor recoveries from the Bancroft ore, as tests on one of the other ores with additions of calcite or dolomite confirmed. Recoveries dropped from 94 to 45% Grades of all the rougher flotation concentrates produced were low at 10-15% copper. The laboratory investigation was then followed up on a pilot-plant scale. An attempt was made to carry out the segregation process in a coal-fired 5-ft-diam fluidized-bed roaster. The feed consisted of a banded sandstone from Nchanga to which 0.5% sodium chloride had been added. Reducing conditions were maintained in the roaster by the addition of coal in excess of that required for heating the feed. The excess coal and added salt constituted the segregation reagents and the temperature of the bed was held at approximately 750°C. Recoveries of copper and grades of concentrates were low. The reasons for lack of success were: (1) The reaction is a gaseous one and a fluidized-bed roaster is therefore unsuitable as a segregation unit. (2) Coal in excess of that required for heating was introduced into the fluidized bed and under these conditions some of the copper would be reduced in situ. The term "reduced in situ" is used here to describe any copper mineral reduced to the metallic state in its original site within the ore particles. If this copper is to be recovered by subsequent froth flotation it must first be liberated from the gangue by grinding or some other method which, in practice, is usually not feasible on ores of this type.

Jan 1, 1969

By C. C. Harris

The characteristics of some common size distribution equations are critically discussed. A generalized form of several well-known size distribution equations is obtained from a differential equation describing statistical distributions. The equation contains three parameters and can describe the major features of size distributions in the fine and the coarse size regions. A graphical method for its implementation is provided. The application of this and other equations to sets of data are compared both for the quality of fit and from a comminution kinetics viewpoint. If a narrow size range of a brittle material is broken sufficiently to obliterate the feed sizes, but not so severely that excessive secondary breakage occurs, a plot of cumulative fraction by weight undersize (Y) vs. sieve size (X) on a log log grid (sometimes called the Gates-Gaudin-Schuhmann plot)1-3 gives a straight line of slope ~ 1 over much of its range. On closer inspection, deviations in the extreme coarse range covering perhaps 10 to 30% of the total sample may be apparent (frequently, a change in slope from ~ 1 to a value different from unity) together with over-all slight irregular departures from a smooth line. One model of breakage postulates that the same fracture pattern persists throughout all size ranges.4 The fracture pattern is characterized by the slope of the line on a log log grid. Accordingly, a distribution of sizes broken in the manner specified earlier is expected to produce a size distribution having the same slope as that of a broken narrow size range. Additionally, the slight irregularities mentioned above should even out in the summation process, giving a smooth straight line of slope ~1 on a log log plot. This idealized state of affairs does not, however, describe the distribution of a multi-event process such as that for a tumbling mill product. On the average, these curves (plotted again log log) tend to have a slope in the fine region different from and usually less than unity,5 while the coarse size region curves with increasing slope for cases of mild reduction, and with decreasing slope when moderate or severe size reduction has occurred. In addition, there are usually slight irregular deviations from a smooth curve. Most curves display two distinct regions — fine and coarse — and a few curves show one or more intermediate regions. Feed size studies6,7 show an effect which theory is required to explain. For the same material, mill loading and other operating conditions, and the same time of grinding, plotting the dimensionless ratios Y vs. X/(feed size) does not reduce the size distribution data to the same curve. Y vs. X does not correlate the coarse region, but it can provide a crude correlation of the fine region which improves as size diminishes and as grinding time increases. The size distribution in the coarse region is somewhat more dependent on the feed size than is the distribution in the fine region wherein the degree of dependence diminishes as time proceeds; the distribution of sizes in the fine region are determined largely by the nature of the material and the comminution conditions. A comprehensive model of comminution must recognize that several different patterns or modes of breakage can occur in a mill; 5,8,9 that there can be some selection in that some size ranges are broken more than others; and that, while some particles may be the product of a single fracture event, or may even remain unbroken, others result from multiple rebreak-age. Thus, breakage in a tumbling mill is more complex than the Schuhmann4 model admits in that several different types of comminution micro-events* occur rather than just one type, and these events, though different in size scale, are of the same overall pattern as that which is visualized by the model. The concept of an average comminution micro-event has, therefore, a mathematical rather than a physical connotation, at least for tumbling milling. Equations with which to describe particle size distributions have been sought for over half a century.10-13 No equation presently in general use was first derived from an analysis of the statistical mechanics of breakage; whatever theoretical basis the existing

Jan 1, 1969

By Erwin L. Zodrow

A geological model of the modes of formation of magnetite and its distribution in the Smallwood iron-ore mine, Labrador, Newfoundland, is given, based on observation and geological mapping. This is called the conceptual model. If mathematical expressions plus probabilistic uncertainty are used to represent the conceptual model, then this is termed a mathematical model. The purpose of this paper is to test if there exists a correspondence between the conceptual model and two related mathematical models (called factor analysis). Details of the statistical technique are given. The results of factor analyses in relation to the magnetite formations in the Smallwood mine are discussed. Several practical mine applications are presented. The difficulty of maintaining quality control over ore mined from any deposit naturally depends on geological conditions; these are usually imperfectly known to concerned mining geologists. One geological condition that would greatly facilitate ore predictions is if a relationship between the observed ore particle distribution* and its mode of origin could be demonstrated. Such a casual interrelationship is normally sought through the application of well-defined geochemical principles of primary mineralization in given geological environments. However, the application of conventional tools of geological research, including geochemistry, to areas that have undergone repeated periods of geological deformation and metamorphism subsequent to primary mineralization becomes rather difficult. More important, the interpretation of such research results are nearly impossible on an objective basis. Mineral assemblages may have been reworked and changed due to tectonic influences to the extent that the present-day observable mineralogy and ore-particle distribution can effectively obscure the mode of origin of the ore. Quantitative measurements, based on petrological investigation of mineral assemblages, reflect the sum-total of all geological influences. Which of several influences had the most effect on existing ore particle distribution is difficult to assess, for these influences can neither be measured directly nor quantified by petro-logical logical or geochemical means. The present study is concerned with the magnetite distribution and its modes of origin within the Small- wood mine,' located in the southern extension of the Labrador geosyncline; see Fig. 1. This geosyncline is thought to have undergone at least two periods of geo-tonic tectonic deformation, separated in time, since the fer-rugenous rugenous sediments were deposited." Detailed geological observations and mappings (1 in. to 40 ft) have highlighted subtle, distinctive features of the magnetite distribution in the Smallwood mine: (1) The magnetite is generally concentrated in bands or layers within this ore body; these bands alternate with specularite-rich bands and quartz bands. The banded or layered nature is common in Precambrian iron-ore deposits, and this has been interpreted as a result of changes in depositional environments. (2) The grain size of the magnetite varies; near the contacts between the iron and quartz-carbonate formations, the magnetite occurs as well-crystallized octa-hedra. In areas of intense folding, magnetite is extremely fine grained and concentrated in bands and occurs in association with earthy manganese minerals. (3) Magnetite tends to be more highly concentrated near the geological contacts of the iron and quartz-carbonate formation in the northeast part of this mine, Figs. 2, 3, and 4. (4) Magnetite is also fine grained and tends to higher concentration near and parallel to fold axes; however, in this case, the ore is much softer than given in item 2. (5) Magnetite mineralization decreases along strike and away from the areas of intense folding, i.e., towards the approximate center of the mine, Fig. 3. How can these variations of magnetite be explained on a geological basis? We can postulate a conceptual model that the distribution of magnetite appears to be related to three basic geological influences: (1) geo-tectonics, i.e., concentrations of magnetite near geological contacts of the iron and quartz-carbonate formations, the fine-grained nature of magnetite and its higher concentrations near fold axes, and decrease of magnetite towards the approximate center of the mine; (2) secondary alterations, i.e., variation of grain size of magnetite near the iron and quartz-carbonate contacts, and in areas of intense folding where magnetite occurs together with earthy manganese minerals: (3) original

Jan 1, 1971

By L. H. Reiss, J. Groult, L. Montadert

Many fields, where the reservoir is composed of sandy layers, show great complexity because of the lack of continuity which results from a particular type of seditnentation. This complexity may be a factor of prime importance in studying reservoir drainage, especially in the displacement of oil by water or gas. This paper describes work done to study this heterogeneity and its influence in the exploitation of the fields of the lower Devonian sandy shale in the Fort Polignac Basin in Algeria. Two lines of research were followed. 1. On the border of the hasin, a detailed sedimentological study established rules for the distribution of the sandy zones, which furnished hypotheses necessary for devising a geologic model of the reservoir. A certain number of sandy zones were recognized and characterized by their sedimentation. 2. In the interior of the basin, production logs deterrnined the productivity profile. Study of these point data led to a description of the distribution of oil and gas phases in the reservoir so that the continuity of different zones between the wells could be deduced. These techniques were applied to the study of the lower Devonian sandy shale reservoir of Zarzaitine. The sedimentological study guiding the correlation work, with the aid of the conventional static data (logs and cores), led to the establishment of a useful geologic model of the reservoir. Production logs, thanks to the contribution of dynamic elements, permitted corrobora-tion of the model. In particular, the logs confirmed separation, as proposed by the sedimenfological study, of two comparable sandy groups by revealing the continuity of a thin impermeable layer, invisible on conventional logs. INTRODUCTION The heterogeneity of sandstone reservoirs considerably influences the distribution of fluids, as well as their displacement in the reservoir. Rational development of a field and maximum recovery of hydrocarbons are closely tied to an exact and precise knowledge of the intern architecture. We will try to show how it is possible I refine the knowledge of the reservoir by seeking qui different and varied sources of information. Productic geology, the group of techniques which leads to idei concerning reservoir architecture and its geometric descris tion, furnishes the framework of this undertaking. Of these techniques. those used so far are qui varied. Descriptive as well as quantitative, the technique partake as much of classical geology as of reservo science. They include (1) geologic studies of the enti basin, especially a stratigraphic and sedimentologic study of the reservoir member at its outcrop, detail1 observations of cores taken from wells and, finall oriented cores; (2) interpretation of geophysical dat (3) interpretation of electric logs, nuclear and sonic lo and dipmeters: (4) petrophysical study of the reserve on samples taken from wells; (5) reservoir dynamics (stu of the production history and, in particular, interpretati of production logs); and (6) analysis of the fluids a thermodynamic studies. This incomplete list could also include (1) study the migration of the fluids, (2) geochemistry (chemi characterization of the oils), (3) regional hydrodynamii and (4) injection and detection of tracers. If most of these techniques are classic, attention i nevertheless be called to applying two of the techniql in conjunction: the study of the reservoir member its outcrop and the study of dynamic distribution fluid phases in the reservoir through use of product logs, used in the study of the sandy shale reservoirs the lower Devonian of the Fort Polignac Basin, Alge in particular, their application to the study of the 2 zaitine field where they have led to a new and satisfact model of the reservoir will be described. THE ZARZAITlNE FIELD Situated in the interior of the Fort Polignac 8 about 150 kilometers (km) north of the lower Devol outcrop, the Zarzaitine Devonian oil field was discovc On Ian. 28, 19'' (Figs. 1 and l8). It is in the fern a monocline truncated by two perpendicular fault: great throw, with a downthrown section to the north\: Erosion at the top of the structure has caused one of it to disappear. It is a reservoir with a gas cap an m coefficient on the order of 1:5, open to the aql On the northeast, with the oil zone covering an Of 106 sq km and with initial oil reserves of 222 mi

Jan 1, 1967

By J. E. Hilliard, J. W. Cahn

calculation has been made of the standard deviations to be expected in the measurement of volume fractions by areal analysis, lineal analysis and four point-counting Procedures. The effect of experimetztal errors is not included. Our conclusion is that a point count using a two-dimensional grid will be the most efficient method of volume fraction analvsis providing the grid spacing IS coarse enough. The predicted standard deviation for such an analysis is shown to he in good agreement with that determined experimentally. A metallurgist wishing to estimate a structural property by means of quantitative metallography is often faced with a choice between several different procedures. In such a case, he will naturally wish to know: a) Which procedure is the most efficient in the sense of requiring the least effort for a given precision? b) For a given procedure, what are the conditions for maximum efficiency? c) Under these conditions, how many measurements are required to attain a given precision? It is our aim in this paper to provide at least partial answers to these queries as they relate to the estimation of volume fractions from measurements on a random two-dimensional section of an opaque specimen. The commonly used techniques1,2 for volume-fraction analyses are based on one or more of the following principles: i) For an areal or Delesse3 analysis: That the areal fraction of a three-dimensional feature intercepted by a random plane provides an unbiased estimate of the volume fraction of that feature. ii) For a lineal or Rosiwal4 analysis: That the fractional intercept on a line passing at random through a two-or three-dimensional feature provides an unbiased estimate of, respectively, the areal or volume fraction of that feature. iii) For a point-count analysis: That the fractional number of randomly or regularly dispersed points falling within the boundaries of a two-dimensional feature on a plane, or within the boundaries of a three-dimensional feature in a volume, provides an unbiased estimate of, respectively, the areal or volume fraction of that feature. The absence of bias referred to in these principles does not, of course, imply that the results of an analysis will be free of error, but only that the expected result is equal to the true one. Application of the foregoing principles provide the following six possible experimental procedures: a) An Areal Analysis—This involves the measurement with a planimeter (or other means) of the area of a constitutent intercepted by the plane of polish b) A Two-Dimensional Random Point Count—Apos-sible experimental procedure for this analysis is to superimpose a sheet of transparent graph paper on a micrograph, and then use a table of random numbers to select coordinates for the points. c) A Two-Dimensiotuzl Systematic Point Count-Similar to b) except that the points are distributed in a prescribed manner, usually at the corners of a lattice superimposed on a micrograph or the screen of a projection microscope. d)A Lineal Analysis—A measurement of the fractional line length intercepted. It is usually performed by traversing the specimen under the cross hairs of a microscope and recording the distance travelled in each constituent. e) 4 One-Dimensional Random-Point Count— This could be performed by traversing the specimen with stops at random intervals to identify the constituent then present under the cross hairs. f) A One-Dimensionul Systematic Point Count— Similar to e) except that the traverse is stopped at prescribed (usually equal) intervals. It will be noted that the point-counting procedures b) and c) can be regarded as methods of estimating the areal fraction. Similarly, e) and f) are indirect methods of making a lineal analysis. All of the six procedures described above involve at least one stage of sampling. Thus, quite apart from any experimental errors, there will always be a statistical uncertainty associated with the final results. It is with the calculation of this uncertainty that we will be concerned. To avoid unnecessary repetition, the statistical relationships that will be used in the calculations are collected together in the appendix. For a fuller discussion reference should be made to one of the many textbooks5,6 on statistics. For symbols relating to the specimen structure we will follow as far as possible the terminology used by Smith and Guttman.7

Jan 1, 1962

By G. Bruggeman, K. G. Kreider

Grain boundary dij]usion coefficienls were measured in tungsten between 1400° and 2200° C and can be expressed by the equation sq cm per sec This activation energy confirms some eavlier estimates made .from tungsten sintering experiments. Grain boundary diffusion was found to occur in sub-bozrndavies having -misorientations of less than 10 deg. The actiuation energy for this subboundavy diffusion is equal to that for dijjusion in incoherent grain boundaries with in the limits of error. This is shown to be consistent with the dislocation model of Low-angle boundaries wheve diffusion occlcvs along- the dislocation 'YPipes" comprising -tile boundary. RECENT investigations of the sintering of tungsten powders all report activation energies which are considerably less than the activation energy for tungsten volume diffusion. Kothari' reports a value of 100 * 5 kcal per mole, Hayden and Brophy' obtained 90 kcal per mole, and Vasilos and smith3 found 110.7 kcal per mole from their sintering studies. Since most determinations of the activation energy for volume diffu-sion4-' fall between 120 and 160 kcal per mole (the true value seems most likely to be nearer 150 kcal per mole), the conclusion is drawn that the mass transport leading to densification during sintering is accomplished by grain boundary diffusion. This interpretation is consistent with various diffusion models of the sintering process. 10-12 Vasilos and Smith calculate diffusion coefficients from their data which fit the equation D * 1.36 x 10* exp(-llO,700/HD However, no direct measurements of tungsten grain boundary diffusion have been made. Furthermore, considerable disagreement exists between the directly measured values of tungsten volume diffusion.'-' In order to corroborate the inferred results of the sintering experiments concerning grain boundary diffusion and to provide accurate diffusion data essential to the analysis of the kinetics of creep, oxidation, precipitation, and so forth, the present work was undertaken to measure self-diffusion in single-crystal and polycrystalline tungsten between 1400" and 2200°C. It is within this temperature range that tungsten sintering is done, the re crystallization of tungsten occurs, and the widest application of tungsten as a high-temperature material will probably be made. EXPERIMENTAL PROCEDURE Radioactive WlE5 was produced by irradiating tungstic acid in a neutron flux of 1.2 x 1012 neutrons per sq cm per sec for 36 hr. A 2-week waiting period was allowed for the decay of w"~ also produced by the irradiation. (w"~ has a half-life of 24 hr.) The half-life of the remaining isotope was determined to be 75 days confirming the presence of w lE5 and the absence of any undesired radionuclide. Specimens 4 in. in diam and $ in. thick were cut from polycrystalline swaged tungsten rods (recrystal-lized) and from Linde single-crystal rods. Chemical analyses of these materials appear in Table I. Actually upon closer examination, the single-crystal specimens were found to consist of several subgrains separated primarily by tilt boundaries in which the misor-ientation ranged from 3 to 10 deg. Thus, it was possible to measure boundary diffusion coefficients in these low-angle subboundaries as well as in the incoherent boundaries of the polycrystalline specimens. The two faces of each specimen were ground flat and parallel within 0.0001 in. The radioactive tungstic acid was dissolved in concentrated ammonium hydroxide, placed on the ground flat of the specimen, and evaporated to dryness. The oxide was then reduced in hydrogen at 1000°C resulting in a layer of wlE5 approximately 1 p thick. The diffusion anneals were performed in vacuum in a tantalum resistance furnace. Time at temperature ranged from 10 hr at 1400°C to 2 hr at 2200°C. The penetration profile was determined by measuring the residual activity after successive removal of surface layers by grinding on metallographic polishing paper. Extreme care was exercised to insure that sections were always taken normal to the diffusion direction; this was verified repeatedly by checking that front and back surfaces of the specimen remained parallel. The activity was measured with an end-window Geiger-Mueller counter. The sides and edges of the specimen were well-shielded to eliminate possible effects due to surface diffusion. The weight of the

Jan 1, 1968

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By Richard R. Zupp, David A. Stevenson

An experimental method to determine the carbon activity in various solid solutions was developed. Samples of the solid solutions and an Fe-C reference sample were equilibrated with respect to carbon content by annealing them in a Hz-CHI gas mixture in a closed cell. The carbon content of each sample was determined, and the carbon activity was obtained from the carbon content of' the reference sample and well-established data for the dependence of the carbon activity on the carbon content in Fe-C alloys. The influence of vanadium on the activity of carbon in austenitic Fe-C-V alloys at 1000°C was determined by this technique. A general semiempirical correlation was developed to describe the dependence of the activity coefficient of- carbon on the composition of ternary austenitic iron-base alloys containing interstitial carbon and a substitutional solute. The correlation is particularly useful in predicting the partitioning of- carbon between various alloys. THE influence of substitutional solutes on the activity of interstitial solutes in metallic solid solutions is important in the theory of alloy phases. Solid solutions of particular interest are the fcc austenite phases of ternary Fe-C-Z systems, in which carbon is the interstitial solute and Z represents any substitutional solute. Carbon-activity data are also needed in these solid solutions to solve practical problems; the quantitative treatment of diffusion-controlled transformations' is an examvle. Experimental information is available for ternary austenitic solid solutions containing Mn,2 Si,2 and A16 as the substitutional solute. Because qualitative preliminary studies indicated that vanadium appreciably decreases the carbon activity,14 the present investigation was undertaken to determine the influence of vanadium on the activity of carbon in austenite. Although Flender and ever" measured carbon activity over a range of compositions in the Fe-C-V system, they were primarily interested in determining phase boundaries in the ternary system, so most of their measurements were outside the composition range for stability of single-phase austenite. Petrova and Shvartsman' also made limited measurements of the carbon activity in Fe-C-V alloys. The dependence of the carbon activity on the carbon content of an alloy may be determined by passing COCOz or H2-CH4 gas mixtures of carefully measured composition over the alloys, determining their equilibrium carbon content, and utilizing the relevant equilibrium relationships. smith16 used this technique with both CO-COZ and HZ-CH4 gas mixtures to determine the dependence of carbon activity on carbon content in pure Fe-C alloys. His data, which are in good agreement with those of some previous and subsequent investigators,6'17 but not with those of others,lfl'ao are usually considered to be the most reliable. Although the same method can be applied to Fe-C-Z alloys, it is difficult experimentally, because the appropriate gas mixtures are almost pure CO or Hz. A simpler technique is to simultaneously equilibrate the Fe-C-Z alloys and pure Fe-C alloys with the gas mixtures, and then use Smith's data to determine the carbon activity in the pure Fe-C alloy. A number of investigators have employed this technique. others Have used the partitioning of carbon at the interface of a diffusion couple prepared from an Fe-C alloy and a Fe-C-Z alloy. In the present study, a closed-cell method was developed by which carbon was selectively transferred via a gas medium between pure Fe-C alloys and Fe-C-V alloys which were not in physical contact. A similar method was developed independently by Heckler and winchel14 and used to study the Fe-C-Ni system. EXPERIMENTAL METHOD A schematic diagram of the experimental arrangement is shown in Fig. 1. In a typical experiment, a 5-g Fe-C sample was placed in one compartment of a quartz cell, and a 5-g Fe-V sample was placed in each of the other compartments. The cell was evacuated, outgassed, backfilled with approximately 125 Torr of hydrogen, and sealed. After being placed in a fur-

Jan 1, 1967

By H. M. Otte, A. L. Esquivel

A new leasl-squares method is Presented for determining lattice parameters of hexagonal or tetragonul structures. The method is adapted for use on electronic computers and involves a reiterative procedure. The correction factor employed raries linearly with the lattice parameter, a (determined from the Brag, angle). In contrast, Cohen's method and recent modifications of it use a correction factor that varies incersely as the squure of the lattice paramneter, a. While the recent modifications attempt to improve the precision of the extrapolated lattice parameter, a, (or-cu). by stressing the importance of the weighting factor. the present approach emphasizes the need for choosing the correct extrapolation function. A comparison between the present method (the Linear method) and Cohen's method indicates that the Linear method may be more appropriale in certain cases. through a priori no critertion appears to he available for making a chorce between the methods. The size of hexagonal and tetragonal crystal lattices is determined by two parameters, a, and c,. Although in principle the two lattice parameters can be determined independently from reflections for which h - k = 0 and 1 = 0, respectively, in practice this may be inconvenient (because of the angular positions at which these reflections may occur) or not easily possible (because of low intensity). Furthermore, if a high precision or accuracy is required, the limited number of reflections of this type available, particularly in the high-angle region, is not sufficient for the necessary corrections (mainly due to absorption) to be determined with accuracy. Several methods1-7,11-13 have been proposed employing all reflections, to obtain the optimum values, a. and co, either by a trial and error procedure or a least-squares fit. Of the latter method, cohen's5 is the best known one since it provides explicit expressions for the optimum a. and c,. However, Cohen's method is only strictly valid if an extrapolation function is used that varies linearly with l/a2 or lie2 (see Section 3), a requirement that does not appear to be generally appreciated. On the other hand, all the better known and more widely used A recent trial and error method was proposed by Massalski and King8,7 who computed extensive auxiliary tables of axial ratios vs the functions A = [(4/3)(h2 + hk +k2) + l2+(a/c)2] and C = A(c/a)2 used in computing a and c values from the observed Bragg angles. These values of a and c were then plotted against a function which permitted linear extrapolation. As a criteria; for the "optimum" values, Massalski and King rely upon a visual fitting of the line through points representing reflections of low 1-index points to compute the extrapolated value of ao and high 1-index reflections to obtain CO. The successive computations and graphical plotting required to reach the "optimum" value are quite lengthy and tedious even on a desk calculator and no quantitative assurance is obtained of having in fact selected the optimum value.* If the method of Massalski and King is used on an electronic computer, then their published tables become redundant and a least-squares fit becomes a natural selection for the choice of optimum values. Such an approach will be called the Linear method. For work now in progress on the effect of certain physical variables on the lattice parameters of hexagonal crystals, it has become essential to determine the confidence limits of small changes in the lattice parameters. Since extrapolation functions that varied linearly with a and c actually also appeared to vary linearly with l/a2 or l/c2 when tested against published as well as our data, a comparison of Cohen's method and the Linear method was considered desirable (Sections 3 and 4). For the latter method an electronic computer was required since a reiterative procedure to obtain the optimum ao and co values had to be employed. The purpose of this paper is to describe the principles of the Linear method, illustrate its application, and compare it with Cohen's method. 1) THE LINEAR METHOD The standard practice in obtaining the lattice parameters in the Debye-Scherrer method is to

Jan 1, 1965