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By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By M. R. J. Wyllie

The relationship between the electromotive force (E.M.F.) across a shale barrier and the concentrations of sodium chloride solutions on either side has been investigated. It is shown that the action of a shale barrier is analogous to a glass membrane separating two acid solutions of different hydrogen ion concentrations. The shale behaves as a sodium electrode and is responsive to the activities of the sodium ions in the two solutions in such a way that the potential can be calculated by means of the Nernst equation. This conclusion is confirmed by laboratory experiments. In a borehole the total E.M.F. of a shale cell is the algebraic sum of the ~otential across the shale and a boundary potential. The relationship between total E.M.F. and the resistivity ratio of two sodium chloride solutions is indicated for a number of formation temperatures. The E.M.F. thus predicted is then compared with the .elf potential read from an electric log and good agreement is demonstrated. Based on both the self potential and resistivity curves of the electrical log. a method is given for calculating connate water content in a bed having in-tergranular porosity and containing both connate water and hydrocarbons. INTRODUCTION The first paper on electrical well logging by C. and M. Schlumberger and E. G. Leonardon in 1934' attributed the self potential curve principally to streaming potentials, i.e. to electroki-netic effects. Almost immediately great difficulties were encountered in reconciling many of the curves they obtained with this interpretation. and a ~econd paper' by the same authors soon appeared. In this second paper self potentials were attributed to the combined effects of streaming potentials and electrochemical potentials, the electrochemical potential being considered the result mainly of the interaction of fluids of differing salt concentrations, i.e. a boundary potential, and partly of potentials set up at the faces of impermeable materials. Some experiments involving a gray clay for the impermeable material were quated. The Schlumbergers and Leonardon deduced from the equation for a simple boundary ~otential that the electrochemical potential, as opposed to the electrokinetic potential, could be expressed in the form E=Klog- .......1 pe where K is a constant, pm the mud resistivity. p, the resistivity of the connate water in a porous bed. However, no general expression for the constant K was obtained. Although the literature between 1934 and 1943 contains a number of quotations of their results, the valuable work of the Schlumbergers and Leonardon was not extended so that the electrochemical potential has been generally attributed wholly to boundary potentials between the mud in the borehole and the connate waters in porous formations. Unfortunately, however, the fundamental premise of all these papers, that a boundary potential can give rise to current flow in a borehole, is thermodynamically untenable. As will be shown. the fact that the electrochemical potential can be fairly accurately express as E = K log pm/pc, a form in which a boundary potential may also be written, is partly fortuitous. The boundary potential is indeed an integral part of the expression for the electrochemical potential in a horehole, but in magnitude it represents only about 20% of the total potential. In 1943 an important step in the elucidation of electrochemical potentials was made by Mounce and Rust3 who showed that if a wall of shale separated two compartments which contained saline solutions of different concentrations, and if the two solutions were themselves brought into contact in the pores of a porous inert membrane (such as unglazed porcelain) a current flowed through the shale and saline solutions. The direction of positive current was from the shale into the more dilute solution. The paper of Mounce and Rust, while repeating some of the observations of the Schlumbergers and Leonardon, seems to be the first to show that the shale was the seat of a genuine electrochemical effect capable of causing current flow. In the same paper Mounce and Rust pointed out the similarity between the fundamental conditions of their experiment and the conditions which existed when a bed of shale in the ground was simultaneously in contact with a porous sand containing saline connate water and mud fluid of salinity different from that of the water in the sand. Since it is now generally recognized that the S.P. curve measures ohmic potential changes in the mud fluid in the well bore resulting from changes in current flow, it is apparent that currents having their origin in the electrochemical interaction of mud filtrate and connate waters with shale beds are a very important portion of the total S.P. The work of Mounce and Rusta and others appears to indicate that, in general, the electrochemical portion of a particular kick on a S.P. curve far exceeds any electrokinetic potentials resulting either from streaming potentials or Dorn effects. The Dorn effect, or sedimentation potential. arises when small particles are allowed to fall through certain fluids under the influence of gravity. a difference of potential being observe? between two electrodes placed at different levels in the stream of falling particles. The Dorn effect is unlikely to affect seriously the S.P. curve as now measured. A successful analysis of the electrochemical aspects of the S.P. log should

Jan 1, 1949

By F. N. Rhines

I. An Outline of the Theory of the Sintering of Pure Metal Powders SINTERING may be defined as the process by which powders bond themselves into coherent bodies, usually, although not necessarily, under the influence of pressure and elevated temperature. For the sake of clarity and simplicity, the present survey will exclude from consideration the sintering of mixed or alloyed powders, with attendant complications, but at the risk of overlooking information of general applicability. Sintering in the presence of a liquid phase is thus automatically eliminated. The sintering of alloys involves much additional subject matter and deserves separate consideration. Since the literature of the subject is extensive and widely scattered, it will not be feasible to consider the contributions individually. Instead, the subject matter will be classified according to experimental observations and theory, and will be presented in summary form. It should be noted that the appended list of references does not constitute a complete bibliography; it includes only those works quoted below. More extensive bibliographies are included in several of the references; see particularly references 7, q, 28, 34, 38, 50, 52, 54 a "Bibliography on Powder Metallurgy" published by the Library of Congress and a pamphlet published by the Metals Disintegrating Co. entitled "The Field of Powder Metallurgy and Bibliography." II. Summary of Experimental Observations The following classified list is composed of general statements of established fact derived from the experimental results reported in the published literature. A few contested observations are included, because of their potential importance; these are labeled as such. Any satisfactory and complete theory must be capable of explaining all of the uncontested facts. Obviously, some important facts may be missing from this list and these may hold the key to the correct explanation of the sintering process, but the possible lack of such material should not deter attempts to understand the subject on the basis of what is available here. A. The Initial Bond at Room Temperature a. To a limited extent uncompressed powders and massive metals adhere at room temperature.28 Clean tin powder forms a weak "cake" on standing at room temperature, the strength increasing with time. Clean gold surfaces adhere on light contact,"' as do those of many other substances, including nickel." b. Upon compression the strength of the bond is increased progressively.28 There is a limit of pressure

Jan 1, 1946

By G. Bhat, J. F. Libsch

lsoembrittlement curves depicting the influence of time and temperature in the range 800' to 1260°F (425' to 680°C) on the development of embrittlement in a commercial chromium alloy steel and a commercial molybdenum alloy steel are presented. Two distinct regions of embrittlement occur in the chromium alloy steel: I—at 800' to 1000°F (425' to 540°C) and 2—in the region just below the lower critical temperature. Embrittlement is most pronounced at 800' to 1000°F, decreasing very rapidly with increasing temperature above this region, only to increase again as the lower critical temperature is approached. The data suggest two distinct modes of embrittlement with possible superposition of the two modes at extended embrittling times in the temperature range 1100° to 1150°F (590' to 620°C). While the molybdenum alloy steel shows little susceptibility to embrittlement at 800' to 1000°F (425' to 540°C), considerable embrittlement may occur just below the lower critical temperature. THE subject of temper embrittlement in alloy steels has received considerable attention in the last few years. Points of view on the mechanism of embrittlement differ, however, resulting in part from the incompleteness of the data developed and in part from the speculation regarding the susceptibility of plain carbon steel to temper embrittlement. Libsch, Powers, and Bhat1 carried out short-time embrittling treatments on an AISI 1050 steel and demonstrated that hardened plain carbon steels are quite susceptible to embrittlement when tempered in the range from 850°F (455°C) to the lower critical temperature. The isoembrittlement diagram,' representing the embrittling characteristics of this steel, is reproduced in Fig. 1. It is evident from the shape of the curves shown that embrittlement in plain carbon steel increases progressively with both temperature and time in the embrittling range. A comparison of the isoembrittlement diagram for AISI 1050 steel with that presented by Jaffe and Buffum' for an SAE 3140 steel shows that up to 930°F (500°C) the isoembrittlement characteristics of the plain carbon steel are similar to those of SAE 3140 steel, although the embrittlement is much more severe in the latter steel. Above 930°F (500°C), the rate of embrittlement in the plain carbon steel increases continuously with increasing temperature; whereas, in the SAE 3140 steel, the embrittlement rapidly decreases. The influence of alloying elements upon embrittlement during tempering thus appears to cause a decrease in embrittlement above the region of maximum embrittlement, i.e., 850" to 1000°F. The question naturally arises as to what effect individual alloying elements have upon the embrittling characteristics of the plain carbon steel. Current knowledge on the influence of alloying elements on temper brittleness may be found in the review papers of Hollomon" and Woodfine. Hollo-mon," from the results of other investigators, has shown that, in general, the amount of embrittlement increases with increasing alloy content (except for molybdenum and possibly tungsten and columbium). Jaffe and Buffum," by a comparison of the embrittlement in a plain carbon steel with that of a SAE 3140 steel postulated that the presence of alloying elements in moderate amounts tends to retard the development of temper brittleness. It is difficult to determine what effect chromium has upon temper brittleness, since most of the information available has been based on the combined effect of other elements with chromium, particularly nickel and manganese. However, Wilten, and recently Jolivet and Vidal,' Vida1, and Woodfine have reported that chromium steels are temper brittle, that the embrittlement is reversible with a maximum rate of embrittlement at approximately 975°F (525"C)," and that the susceptibility increases with increasing amounts of chromium. Taber, Thorlin, and Wallacel" have found a large embrittling effect with increasing chromium content in a medium C-Mn-Ni steel. But Hultgren and Chang," from their experiments conducted on synthetically prepared ternary Fe-C-Cr alloys, could not conclude that these alloys are susceptible to temper embrittlement. However, on addition of manganese or phosphorus, these Fe-C-Cr alloys became susceptible, from which fact they concluded that the embrittlement developed in chromium-bearing Fe-C alloys is due chiefly to the presence of these elements. Considerable data are available to show that molybdenum decreases the susceptibility of steel to temper embrittlement. However, its effectiveness in preventing or decreasing embrittlement appears limited to its presence in small amounts. Vidal" has shown that a plain 2 pct Mo steel was susceptible. Hultgren and Chang" also have shown that molybdenum additions in excess of 2 pct to synthetically prepared Ni-Cr steels did not prevent embrittlement. Jolivet and Vidal' and Lea and Arnold found that molybdenum reduced temper brittleness. Lea and Arnold further stated that molybdenum decreased the rate of embrittlement rather than the total amount of embrittlement, whereas Preece and Carter" have shown that the presence of molybdenum greatly reduces the equilibrium extent of the change at a given temperature but does not appear to influence the rate of embrittlement. There appears to be very little information as to how molybdenum by itself affects the temper brittleness susceptibility of a plain carbon steel.

Jan 1, 1956

By F. E. Bash

Previous to the war, this country depended on Europe for its supply of a number of alloys of great importance in the manufacture of electrical apparatus and equipment. When this source was cut off shortly after the beginning of hostilities and the small stocks in the United States were exhausted, either inferior substitutes had to be used or the manufacture of the apparatus suspended. Since electrical equipment was of primary importance in the prosecution of the war, the substitutes had to be used until the composition and processes of manufacture of the alloys could be determined. Included among these alloys was one generally known as manganin, which is composed chiefly of copper and manganese and which, beside having a low-temperature coefficient of resistance, has a low thermal electromotive force against copper. These qualities make it valuable for the manufacture of electrical instruments and machines in which it is used in the shape of wire, rod, and strip. As a result of these circumstances, an investigation was started to determine how manganin could be made on a commercial basis so that a product of uniform quality and the necessary electrical characteristics could be produced. The object was to procure an alloy with temperature coefficient of resistance not greater than 1 X 1X per " C. and a thermal e.m.f. against copper no greater than that of the imported material. It is characteristic of manganin that the temperature-resistance curve is not a straight line but has a peak, which varies in position with different samples; it is most desirable, however, to have it at a temperature of 25' C. if possible. The coefficients of manganin from all records available ranged from a large negative to a large positive value. The composition as reported by different authorities is given in Table I. Prof. Matthew A. Hunter, of Rensselaer Polytechnic Institute, made up a number of small melts of manganin in a graphite crucible and the one that he reported as having the best cocfficient gave the following analysis: Copper, 83.6 per cent.; nickel 2.5 per cent.; manganese, 13.6 per cent.; iron, 0.3 per cent. An analysis of a sample of German manganin gave the following: Copper, 82.6 per cent.; nickel, 3.8 pcr cent.; manganese, 12.8 per cent.; iron 0.7 per cent.

Jan 1, 1921

By William Hague, Robert H. Bedford

The objects of this paper are: 1. To give cost data on drilling obtained at the North Star mine in California; 2. To describe the methods of testing drills employed there, giving the results of shop tests, and the correlated data obtained underground; 3. To demonstrate that these tests form a satisfactory basis upon which to judge rock drills. The rock at this mine is either close-grained diabase in the upper levels, or tough grano-diorite in the lower levels. The vein, which has an average dip of 23", consists of about 5 ft. of " formation" lying between walls of unaltered country rock. Of the 5 ft., solid quartz and stringers make up 18 in. of pay ore. The formation, which consists of but slightly altered country rock, is almost as hard as the unaltered walls. From 4 to 44 ft. is sent to the mill. One-third of the holes are drilled in the quartz; two-thirds in the formation. The holes are about 4 1/2 ft. deep and break on the average of 1.15 tons per hole. The average number of holes per stope drill shift is at present 5.65. The number of drill shifts throughout the mine in 1913 was 18,679, and the cost of labor for drilling, power, supplies, upkeep of machines and air lines, tool sharpening, and distribution, amounted to 33 per cent. of total mining expense. To do this work there are in commission 43 No. 12A, three No. 17V and eight No. 16V Waugh stopers, three Jackhamers, two Waugh pluggers, and 17 No. 8 and two NO. 7 water Leyners. For the past three years a record has been kept of the repairs on each machine and number of shifts operated by it. The figures given in Tables I and II for the cost of repairs per drill shift have been taken from this record. The underground air pressure is about 90 lb. The air consumption per drill shift was measured by aerometers. The leakage of pipe lines between compressor and meter is not included. From the number of pieces of steel sharpened for each type of drill during the year the average used per drill shift has been ascertained. For other supplies the figures given represent a year's average.

Jan 1, 1915

By Gifford E. White

Explanations of the basic procedure for making earth-conductivity studies by the Eltran method have already appeared in several placeS. 1,2,3 In its essentials, this method consists of applying step functions of voltage to one pair of earth grounds and measuring the transient potential resulting at a separate pair of ground points. As previously pointed out,' the transient potential resulting from a suddenly applied steady voltage is the indicia1 transfer function of Carson1 6 which has been extensively studied in network theory. The discussion here, with one special exception, will ignore the problem of how the physical configuration of the earth affects the transient response voltage; it appears that this phase of the problem has been solved in only a few special cases having any direct bearing on the prospecting problem. Entirely distinct from the potential-theory aspect of the conductivity problem is the interesting material that can be had from studying the well-known network relations between cause and effect in linear circuits, and thus deducing criteria for the application of the several experimental methods available. To do this, only one assumption need be made about the nature of the earth. The earth is to be considered a linear conductor within the tolerance of ordinary measurements. The discussion will be restricted to collinear electrode configuration like that of Fig. I, since this is the only type of spread practical for use with driving currents that vary with time. Here one pair of grounds carries the driving current, and in line with these and external to them is a RECORDING Fair of potential probes. The problem will be to consider the relation between the different voltages appearing between the potential circuit terminals when various types of driving voltage sources are inserted in the current circuit. Suppose that the grounding points G, and G2 make good contact with the earth, and that a battery of sufficient voltage to produce one ampere of direct current is introduced into the current circuit by the closing of a switch. The potential transient response to such a voltage can be measured by taking an oscillogram at the potential Directors terminals, giving the time function that has been called A(l).4 This time function has been solved for analytically in the case of a homogeneous earth,"' and the

Jan 1, 1946

By Gifford E. White

Explanations of the basic procedure for making earth-conductivity studies by the Eltran method have already appeared in several placeS. 1,2,3 In its essentials, this method consists of applying step functions of voltage to one pair of earth grounds and measuring the transient potential resulting at a separate pair of ground points. As previously pointed out,' the transient potential resulting from a suddenly applied steady voltage is the indicia1 transfer function of Carson1 6 which has been extensively studied in network theory. The discussion here, with one special exception, will ignore the problem of how the physical configuration of the earth affects the transient response voltage; it appears that this phase of the problem has been solved in only a few special cases having any direct bearing on the prospecting problem. Entirely distinct from the potential-theory aspect of the conductivity problem is the interesting material that can be had from studying the well-known network relations between cause and effect in linear circuits, and thus deducing criteria for the application of the several experimental methods available. To do this, only one assumption need be made about the nature of the earth. The earth is to be considered a linear conductor within the tolerance of ordinary measurements. The discussion will be restricted to collinear electrode configuration like that of Fig. I, since this is the only type of spread practical for use with driving currents that vary with time. Here one pair of grounds carries the driving current, and in line with these and external to them is a RECORDING Fair of potential probes. The problem will be to consider the relation between the different voltages appearing between the potential circuit terminals when various types of driving voltage sources are inserted in the current circuit. Suppose that the grounding points G, and G2 make good contact with the earth, and that a battery of sufficient voltage to produce one ampere of direct current is introduced into the current circuit by the closing of a switch. The potential transient response to such a voltage can be measured by taking an oscillogram at the potential Directors terminals, giving the time function that has been called A(l).4 This time function has been solved for analytically in the case of a homogeneous earth,"' and the

Jan 1, 1946

By R. G. Wayland

SINCE the installation at Kropfmuehl, Bavaria, of a modern flotation concentrator in 1938, the flake and fine graphite from the Passau area can now be delivered in about any normal specified carbon content of any size range up to a flake averaging about 0.7 mm. The graphite finds a wide German and export market for crucible manufacture, pencil leads, dry cells and other uses. A controversy over the origin of the graphite deposits is being resolved in favor of syngenesis rather than epigenesis. The syngenetic theory is newly supported by the yet unpublished work of Hartmann of the Bavarian Geological Survey. Development work and exploration for graphite in the area may be changed in direction as the syngenetic theory is accepted. Crystalline graphite is produced in the area east of Passau near the junction of Germany, Austria and Czechoslovakia, as shown in Fig. 1. This is the only graphite area of importance in Germany, and Gra-phitwerk Kropfmuehl AG is the only operating firm in the area. The plant and mine are located at Kropfmuehl near Hauzenberg, Kreis Wegscheid, about 10 miles east of Passau. A narrow gage railway from the mine connects with the German Railway at Schaibing Bahnhof. The Pfaffenreuth mines date from about 1730. Until the early 20th century mining operations were carried out in a haphazard fashion. During World War I graphite mining and milling was increased, since it had to cover almost all of the crucible needs of the Central Powers. Between the wars some 11 mines were operated by two large and several small companies, but under the Nazis these were consolidated by 1938 into the Kropfmuehl enterprise. Kropfmuehl built a modern flotation mill to treat its own ores and small amounts of custom ores and tailings from the area. Since Graphitwerk Kropfmuehl AG was an I.G. Farbenindustry subsidiary, it has been under Military Government Property Control and probably will be sold to private German capital. Geology The country rock of the graphite area is part of the "kristallines Grundgebirge," the series of old gneissic and schistose rocks that constitutes the bed rock of most of the Bohemian basin and rims the Sudeten-land. The gneissic rocks of the graphite area are considered to have been metamorphosed during the Carboniferous period. They are bordered on the north by granite stocks and penetrated by numerous smaller granite and pegmatitic intrusive rocks, as shown in Fig. 1. The gneiss is classed as a micaceous, coarse-grained cordierite gneiss by most investigators. It is much metamorphosed by the granite, particularly in the north near the larger granite bodies. Interbedded in the gneiss are the graphite seams and lenses, and also beds and lenses of crystalline limestone containing disseminated graphite in noncommercial quantities. The gneiss, together with the included graphite and limestone seams and lenses, is cut and displaced by a number of granite sills of medium to fine grain and by a large number of diorite lamprophyre dikes and a few syenite-pegmatite dikes. The lamprophyre dikes are of various mineral compositions and textures, but many are banded and richly impregnated with pyrite; while the syenite-pegmatite dikes are coarse-grained with good crystals of titanite, pyroxene, uralite and other green amphiboles. Most investigators and the miners speak only of diorite and granite dikes cutting the graphite seams. The diorite dikes are later than the granite and some of the faulting, as is evident from Figs. 1 and 2. Individual graphite seams and lenses may be mined for thicknesses of several feet up to several scores of feet, and for distances of several hundred feet. The aggregate thickness of a series of some 20 seams of graphite, limestone and interbedded gneiss at Kropfmuehl is stratigraphically about 450 ft. Laterally, the graphite in a seam may pinch out or grade into crystalline limestone. Graphite crystals also are found disseminated in the gneiss itself, although in unmineable concentrations. The faults that cut the graphite seams carry graphite for some feet or tens of feet away from the seams, apparently mechanically. Similarily, the graphite lenses themselves often contain mechanically introduced inclusions of wall rock, probably from flowage during folding. Graphite crystals make up 10 to 30 pct of the fresh, mineable graphite lenses at Kropfmuehl, averaging about 20 to 25 pct after hand-sorting by the miners. In weathered lenses, the graphite concentration is said to be as high as 50 pct. The associated primary and hydrothermal minerals are dom-inantly feldspar and calcite, plus quartz, pyrrhotite, pyrite, biotite and occasional garnet, hornblende, sphalerite and galena. Associated secondary minerals include kaolin, nontronite, mangano-oxide-silicates (mog), adularia and chlorite. The superimposed suite of siliceous cementation minerals present consist largely of opal, chloropal, chalcedony, jasper, and hyalite. The kaolin is of special interest since it too was mined as early as 1730 and was used in the well-known Nymphenburg porcelain from 1756 on. The kaolin is derived from the gneiss and the syenite pegmatites. The crystals of graphite vary in size within a given seam, but in seams more than a mile away from the granite on the north the average crystal-linity is less coarse, lowering the commercial value. The lenses in the Kropfmuehl-Pfaffenreuth area are the most developed, and are the only ones with deep workings now accessible. Other similar crystalline graphite lenses are known from older workings at Habersdorf, Oberoetzdorf, Ficht, Diendorf, and

Jan 1, 1952

By Lendall P. Warriner, Blandford C. Burgess

Jasper County lies just north of the geographical center of Georgia, bounded on the west and north by the Ocmulgee River. The county seat, Monticello, is approximately 65 miles east-southeast of Atlanta and 40 miles north of Macon. It is served by the Macon-Athens branch of the Central of Georgia Railway Co. and by five paved highways converging from adjoining county seats. Farming and lumbering are the principal local occupations. About half the county is covered with pine and mixed hardwoods; a large part of the forested land is owned by the Soil Conservation Service of the Department of Agriculture in its Piedmont Land Utilization Project. The topography is one of gently rolling field and forest with occasional hills rising 100 ft or more above the creek beds. Though annual rainfall is in the neighborhood of 60 in., most of it falls in torrential downpours of short duration which tend rapidly to erode the red soil and convert the country roads to greasy tracks of red mud. History The pegmatites of Jasper County produced a small amount of mica in World War I. In World War 11, our Government's search for this strategic mineral brought to Georgia B. C. Burgess, then Southern Manager of Colonial Mica Corp., subdivision of Metals Reserve Corp., who noted on State Highway 83 the presence of pegmatitic material used as road metal. In 1944, after severing his Government connection and returning to private practice, Mr. Burgess investigated the source of the pegmatitic material noted on his previous visit and discovered that graphic granite pegmatite had been mined for the road metal. He secured mineral leases from the Soil Conservation Service and from private owners and began preliminary development work. By 1946 he had uncovered enough pegmatite to warrant an enterprise to undertake economic development of the feldspar. In March 1947, he conveyed his leases and interest to Appalachian Minerals Co., remaining with it as Vice President and General Manager. This company has carried on additional development, removing overburden by bulldozer and drilling the pegmatites uncovered. A modern and efficient feldspar grinding plant to produce 20 mesh feldspar for the glass industry was completed and placed in operation May 1, 1948. Geology GENERAL GEOLOGY OF ROCK TYPES OTHER THAN PEGMATITE Jasper County lies within the Appalachian Crystalline Complex and approximately 40 miles north of the "Fall Line," where the Upper Cretace-

Jan 1, 1950

By Nicholas J. Grant, Ulf Kalling, John Chipman

THE operation of a blast furnace is dependent to an important extent upon the sulphur content of materials charged and the desired limit of sulphur in the product. It has long been known that the blast furnace is the most efficient tool for desulphurization in common use and that this efficiency is associated with the strongly reducing conditions of the hearth and is enhanced by increased basicity and fluidity of the slag. The chemical reactions of desulphurization may be studied from the viewpoint of the ratio of the process or of the final equilibrium conditions. Both kinds of studies contribute to an understanding of the process and both are included here. A simple measure of the desulphurization power of a slag is given by the ratio: Pct sulphur in slag (Pet S) Pct sulphur in metal [Pct S] This ratio was used by Holbrook and Joseph',' to measure relative desulphurizing powers under controlled laboratory conditions. It was also used by Hatch and Chipman3 as a measure of the equilibrium distribution. For the latter purpose it would be preferable to employ thermodynamic activities rather than percentages, but until very recently this has been impossible for lack of data. Now, thanks to the work of Morris and Williams and Morris and Buehl," the effects of carbon and silicon upon the activity of sulphur in the metal are known. The confirmation of this work and its extension to include the effects of other elements by Sherman and Chipman and by Rosenqvist and Cox' make it possible to calculate the activity of sulphur in pig iron of any composition. Hence it is now possible to use data on the equilibrium distribution of sulphur to find its activity in the liquid slag and to approach an ultimate solution of the thermodynamic aspects of the problem. The rate of transfer of sulphur from metal to slag is the problem of major industrial importance and indeed the principal need for equilibrium data has been as a necessary adjunct to the kinetic studies. The rate of approach to equilibrium under laboratory conditions seems slow compared to the requirements of industrial practice, and it is clear that further laboratory studies of rates are needed. In the research reported below, the items which were investigated were the following: I—The role of mechanical stirring on the approach to equilibrium. 2—The role of MgO in desulphurization as compared to CaO. 3—The role of MnO in desulphurization. 4— The limiting reactions which constitute the slow steps in desulphurization. Experimental Procedure The experimental set-up and procedure previously described by Hatch and Chipman" were essentially followed with several small modifications. The graphite crucible containing the slag and metal charge was altered to provide considerably more active stirring and mixing of the slag and metal in the carbon monoxide atmosphere. For this purpose the crucible was machined to provide two deep cylindrical wells which were interconnected at top and bottom as shown in Fig. 1. A graphite screw with a flat thread and of shallow pitch (4 threads per in.) spinning at 600 to 800 rpm was used to lift the slag and metal over the partition between the two wells and throw them over into the second well, where the metal settled through the slag into the reservoir at the bottom. It was possible to see actual particles of slag and metal being thrown over the partition. In this respect, the stirring was more vigorous than used in the work of Hatch and Chipman. A charge of 400 g of wash metal was first melted, and 20 g of FeS was then added to yield a bath containing 1.65 pct S. Immediately 400 g of slag (as pure mixed oxides) was added and fused. The slag was generally fused in 1 hr * 10 min. Within 30 to 45 min after melting, the temperature was adjusted to 1525"C, and the first slag and metal samples were taken. The slag was picked up on the end of a cold Armco iron rod, whereas the metal was sucked into a silica tube. The wash metal composition was (in percent): 4.29 C; 0.022 S; 0.021 P; 0.38 Si. The slags used were of four fixed starting compositions covering a wide range of acid-base ratios shown in Table I. Deliberate variations in MgO were made in these slags to check the role of MgO in blast-furnace desulphurization. Changes due to additions and reactions were followed by analysis of samples. Additions of Mn and MnO were made to most of the heats to note the role of Mn and MnO on desulphurization. Three heats (62 through 64) were made in an open pot induction crucible (graphite) using a

Jan 1, 1952

El Indio, eighty percent -owned by Compania Minera an Jose Inc., a subsidiary of St. Joe Minerals, and twenty percent-owned by private Chilean investors, will open their new flotation and Carbon -In -Pulp plant near La Serena, 480 km (300 miles) north of Santiago, Chile, in early 1981. The underground mine, at an altitude of 4,270 m (14,000 ft), will produce about 1,270 mt per day (1,400 st per day) of ore containing about 2. 2570 Cu, and gold and silver to the extent of 16 and 254 g per mt (0.47 and 7.4 oz per st) respectively. While construction of the plant was underway, development ore, containing some 1,400 kg (45,000 oz) of gold, was shipped to the United States for recovery in a copper smelter. At El Indio the underground ore is rail-hauled to the mill a short distance from the portal where it is crushed, ground, and floated to produce a copper concentrate containing both gold and silver. The crushing plant also crushes waste for use as mine backfill. Approximately 92% of the copper and 60% of the gold and silver are recovered in the flotation concentrate. Flotation tailings, at a grade of 19 g Au and 116 g Ag per mt (3.4 oz Au and 0.55 oz Ag per st), are cyanided for 72 hours in six Pachucas with auxiliary air lifts for pulp transfer. Lime, cyanide, lead nitrate, and a phosphate are also fed to the cyanidation Pachucas. After cyanidation, the pulp is treated in four air lift Carbon-In-Pulp tanks equipped with external vibrating screens for carbon advance. Loaded carbon is stripped in two pressure vessels in parallel. Pressure stripping must be used because of the high altitude. Stripped carbon is dewatered in a spiral classifier before being reactivated in a rotary kiln and returned to the C. I. P. circuit. Pregnant solution is then sent to four banks of four Zadra cells for gold and silver recovery on steel wool. Zadra cell cathodes.are washed with the slimes being captured in a plate and frame filter. The filter cake and the washed cathodes are then dried on an infrared dryer and smelted in two stages to bullion bars. Published reports indicate that the total investment for this unique operation was in the neighborhood of $80 million.

Jan 1, 1981

By H. E. Cline

Calculations of the formation and growth of faults caused by a variation in lumellar widths were made for a two-dimensioml three-plate problem. The angle between the a-ß boundary and the growth direction was allowed to vary and the time evolution was studied using a quasisteady state approach. At spacings smaller than a critical spacing given by X V = AO variations in the larrlellar widths grow in time to produce faults that coarsen the structure, while at spac-ings larger than this critical spacing, variations in the lamellar widths decay in time. If small plates are introduced into the structure they may grow only at large spacings to refine the structure. The time evolution and shape of faults were calculated for the three plate-problem and then the three dimensional problem and rod-like eutectic were qualitatively discussed. UNDERSTANDING of the mechanism by which the spacing of directionally solidified eutectics is determined may allow one to control their structure better. Steady state solutions for the growth of lamellar structures have been found for a range of lamellar spacings A and growth velocities V. To obtain a unique solution for the isothermal growth of pearlite, Zener1 assumed that growth occurs at a maximum velocity, while Tiller2 assumed that a eutectic alloy, grown under an imposed velocity, will choose a spacing corresponding to minimum undercooling. These assumptions are equivalent and have been referred to as "extremum growth". The extremum condition predicts the observed relation between velocity and spacing as given by V = constant [I] but does not provide a mechanism for changing the lamellar spacing. Jackson and Hunt3 calculated the interface shape by using solutions to the diffusion equation for a planar interface and a relation of the interface composition to the local curvature. If the spacing is much larger than the extremum spacing, the interface breaks down catastrophically to form forked plates. However, the catastrophic breakdown cannot account for the small adjustments in spacing that must occur in practice..3 Direct observations during the growth of organic eutectics4 and the Pb-Sn eutectic5 show that spacing changes occur by the formation of faults. A fault in a plate-like eutectic is the edge of a plate. Once the faults form, they may move to make small adjustments in the spacing.6,3 The motion of faults intersecting the growing interface was shown by an approximate analysis to give Eq. [I].6 A perfectly regular lamellar structure should be able to persist over a range of lamellar spacings. However, during growth small perturbations in the structure may occur. If the amplitude of the perturbation increases in time the structure is unstable, while if all possible perturbations decrease in time the structure is stable. In a previous paper7 variations in the shape of the solid-liquid interface were considered, while this paper considers only variations in lamellar widths while maintaining a macroscopically planar solid-liquid interface. Previously, theories of lamellar growth1"3 have artificially contrained the growth to give a regular periodic structure. To allow for a variation in spacing, the three phase intersections and groove angles were allowed to change with time as determined by assuming local equilibrium. THREE-PLATE PROBLEM Since the spacing changes in eutectics by local formation of faults,4'5 it is suggested that local variations in spacing are responsible. The interaction between neighboring plates will be greatest because they have the smallest diffusion distance. For simplicity, as a nearest neighbor approximation, a three-plate problem will be considered, as illustrated in Fig. 1. The structure consists of a periodic array in which all the plates are allowed to vary in width. As in steady state growth it is assumed that the average composition in the solid remains constant. A variation in plate widths, that maintains the composition in the solid, was introduced by making the first a-phase plate thinner by an amount A, keeping the width of the second B-phase plate constant, and increasing the width of the third a-phase plate. If the structure were not perturbed, as in the regular two-plate problem previously described,' then the groove angles at the three-phase junctions are the equilibrium angles, 0, and ? B, and the solid-solid boundary is normal to the interface. In the three-plate problem with a variation in plate widths the phase boundaries are assumed to be related to the three-phase junction by equilibrium angles, but the a/B boundaries may be rotated by an angle 0 from the growth direction. The angle H be-tween the tangent to the a/B boundary and the growth direction may vary during growth and determine the —> — — —.A_ Q-0 / 0 x, X2 Fig. 1—Schematic of the three-plate problem showing a variation in the spacing and the effect on the angles at the three phase intersections.

Jan 1, 1970

By R. Dawson Hall

The stresses in the simplest structures are often those we find most difficult to analyze. The most complex condition in mine stresses is found in simple tunnels where the roof, the sides, and the floor are a monolith. The functions of the parts are like the parts themselves not distinct and spccialized, and the problems to be solved are like those in a metal structure with riveted joints or a redundancy of bars. This difficulty explains perhaps why the condition has not been treated. But just because it cannot be discussed in its entirety is no reason why it should be treated as an action of parts with spccialized functions as a roof beam with supports and a foundation. The problern cannot be ignored on the ground that it is not of sufficient importance to warrant careful consideration, because conditions of complete monolithism, of which the tunnel is the type, are found materially unchanged in room-and-pillar and in longwall work. This unity between roof, sides, and floor, which to the coal miner is a difficult conception, really deserves a scientific appellation, and perhaps holoid (from holos, whole, and eidos, form) will serve the purpose as well as any other. In a simple tunnel the roof, the sides, and the floor form integral parts of one and the same structure, and the distortion of one cannot be conceived without a consequent strain in the others. Thus when the roof of the tunnel droops by reason of its weight, the upper parts of the sides are drawn in becausc they are integrally connected with the roof and must approach each other whenever, by the sagging of the roof, the distance between any two points in it is diminished. (See Fig. 1.) Thc sides in their turn operate on the floor of the holoid structure, producing a tensile stress. The writer has always been impressed with the value of soap as a means of illustrating the action of mine stresses. With that idea in mind' a cake of naphtha soap measuring 43/8 by 2¼ by 19i in. was taken and a tunnel was made through it 13/4 in. long, 21/2 in. wide and 1¼ in. high. (See Fig. 2.) A load was then placed at the mid-span of the tunnel. Eventually, the upper bar, or "roof," broke at the

Jan 1, 1916

By R. H. Sweetser

The Committee on Evaluation of Coal for Blast-furnace Coke reports progress in the working out of the problem of evaluation. There has been no full meeting of the Committee but there have been several conferences with two or more of the members present, and the different members have expressed themselves freely on the five points that have been under consideration since the meeting of the Committee in New York on Feb. 16, 1932. The need of a method of coal evaluation, not only of coking coals but all other kinds, is obvious. Under NRA it becomes imperative that coals of the same size from the same seam be priced according to their variations in quality, especially in reference to cleanliness in respect to freedom from extraneous ash-forming materials. In looking over the correspondence that has passed between members of our Committee, it is evident that much of the confusion and misunderstanding would disappear if we could realize that practically all of the variations in value of coal from the same seam of coal are due to variations in the amounts of extraneous materials that are contained in the coal as it passes over the scales for shipment. It is not now a question with our committee as to the differentials in value, or in prices, between different kinds of coking coals or between noncoking and coking coals; our present problem is to arrive at the method for determining the scale of values of the coal from a certain coal seam according to the increase or decrease of extraneous ash and moisture from a predetermined base line adopted for that particular coal. The five points mentioned above are the same as discussed at the meeting in February, 1932, except that the temperature for determining the moisture content has been changed from 212" F. to 221" F., at the suggestion of Dr. A. C. Fieldner. The points are: 1. It is proposed that the coal industry adopt as a base line for evaluating all coals the analysis of the coal as it passes over the neighing device that determines the tonnage of coal bought and sold. 2. It is proposed that the Committee on Evaluation of Coal for Blast-furnace Coke approve the adoption of the base line for Pittsburgh seam coal presented by F. A. Jordan at the annual meeting of A.I.M.E.

Jan 1, 1934

By Robert Bedford

THE objects of this paper are: 1. To give cost data on drilling obtained at the North Star mine in California; 2. To describe the methods of testing drills employed there, giving the results of shop tests, and the correlated data obtained underground; 3. To demonstrate that these tests form a satisfactory basis upon which to judge rock drills. The rock at this mine is either close-grained diabase in the upper levels, or tough grano-diorite in the lower levels. The vein, which has an average dip of 23°, consists of about 5 ft. of "formation" lying between walls of unaltered country rock. Of the 5 ft., solid quartz and stringers make up 18 in. of pay ore. The formation, which consists of but slightly altered country rock, is almost as hard as the unaltered walls. From 4 to 42 ft. is sent to the mill. One-third of the holes are drilled in the quartz; two-thirds in the formation. The holes are about 42 ft. deep and break on the average of 1.15 tons per hole. The average number of holes per stope drill shift is at present 5.65. The number of drill shifts throughout the mine in 1913, was 18,679, and the cost of labor for drilling, power, supplies, upkeep of machines and air lines, tool sharpening, and distribution, amounted to 33 per cent. of total mining expense. To do this work there are in commission 43 No. 12A, three No. 17V and eight No. 16V Waugh stopers, three Jackhamers, two Waugh pluggers, and 17 No. 8 ,and two No. 7 water Leyners. For the past three years a record has been kept of the repairs on each machine and number of shifts operated by it. The figures given in Tables I and II for the cost of repairs per drill shift have been taken from this record. The underground air pressure is about 90 lb. The air consumption per drill shift was measured by, aerometers. The leakage of pipe lines between compressor and meter is not included. From the number of pieces of steel sharpened for each type of drill during the year the average used per drill shift has been ascertained. For other supplies the figures given represent a year's average.

Jan 8, 1914

By G. C. Gester

With the exception of exploration geological work that is being prosecuted in various parts of the mainland of Arabia, the only new developments in Arabia during 1934 were on Bahrein Island, which is in the southwestern portion of the Persian Gulf, approximately 25 miles from the mainland of Arabia. Here the Standard Oil Co. of California, through its wholly owned subsidiary, The Bahrein Petroleum Co., Limited, has continued to carry on a systematic drilling campaign and has constructed camps, pipe line and marine loading facilities. During 1934 eight wells have been completed at depths ranging from 2058 to 2253 ft. These wells have shown average initial productions ranging from 1500 to 5000 bbl., with one, No. 15, estimated as being capable of flowing as much as 11,000 bbl. per day. The oil is asphaltic in character and has a gravity range of from 32' to 34' A.P.I. The locating of all new wells has followed a plan of orderly development, with the ultimate object of obtaining efficiency of operation and maximum production. The wells are taking a penetration of 200 to 250 ft. of the lower or so-called Main productive zone. The upper oil zone, which is cased off, includes 300 to 400 ft. of alternating limestones, clays and shales and carries a heavier oil under lower pressures. The Main zone is similar lithologically to the upper zone. Micro-fauna collected from cores have shown that the oil occurs in formations of lower Eocene and Cretaceous age. Development to date has not progressed sufficiently so that either the maximum thickness of the oil-bearing horizons or the limits of the field can be determined. Something over 10,000 acres has been proven to date. Among other developments leading toward the marketing of oil from Bahrein during 1934 was the construction of a marine loading terminal. This included the laying of over 3 miles of 12-in. submarine pipe line from the small island of Sitra out into the harbor, terminating in 50 ft. of water; also the laying of more than 10 miles of gathering lines from the producing area to the terminal. Three crude oil working tanks with floating roofs were erected on Sitra Island, having a capacity of 250,000 bbl. A pumping plant was provided having a capacity of 5700 bbl. of oil per hour. This is housed in a dustproof building, as rather severe

Jan 1, 1935

By J. T. Brown

AS far as could be ascertained, no one had previously investigated the creep strength of silicon poly-crystals. Literature has appeared showing evidence for plastic deformation in silicon single crystals and whiskers.*1"6 Also the fact that germanium, a material of similar crystal structure to silicon undergoes plastic deformation under stress at temperatures above about 60 pct of its melting temperature, has been known for some time.2"4'7 This investigation was performed for the purpose of determining the strength and ductility of silicon polycrystals under creep conditions that would give fairly long times to rupture. PROCEDURE The silicon specimen blanks were obtained by first placing granulated transitor grade silicon (99.999 + pct pure) in a silica crucible. The crucible was surrounded by a graphite susceptor, and induction heating was used for melting the silicon in a vacuum furnace. Blank specimens were formed by freezing molten silicon onto a polycrystalline seed of silicon in a vacuum furnace. The seed was attached to a motor driven revolving rod. As silicon solidified, this rod was gradually withdrawn from the melt. A shape with a contracted center section was obtained by varying the rate of withdrawal from the melt. Specimens for the creep-rupture tests were ground from these "pulled" blanks. Creep-rupture tests were performed in spring loaded machines under constant load at 1800" and 2000° F. RESULTS AND DISCUSSION A test specimen which was sectioned longitudinally is shown in the photomacrograph in Fig. 1. Very little deformation has taken place in the portion of the specimen shown, however, slip lines from several slip systems within the same grain, and deformation band formation was seen. The elongated appearance of the grains is due to the method of growing the specimens. One of the most interesting aspects of the results obtained from the creep-rupture tests was the high strength and the accompanying large amount of ductility. The data obtained is listed in Table I which shows the stress to rupture in 100 hr at 2000°F is between 8000 and 9000 psi. This indicates that silicon's strength at 2000°F is about equal to that of the best commercial super-alloys. It is important to mention that silicon has less than 1/3 the density of iron-, nickel-, and cobalt-base alloys. The usual type alloys for high-temperature applications

Jan 1, 1960

By H. R. Froning, R. O. Leach

In wertability alteration flooding, a chemical agent is rnoved through a reservoir by the flood water to increase oil recovery by decreasing the degree of wetting of the rock by the oil. Substantial amounts of the chemical may be lost during movement through the reservoir. The extent of the loss, and therefore the economics of the process, depends in some cases on factors which are difficult to reproduce in the laboratory. Therefore, a short-duration, low-cost field test method is needed to permit evaluation of chemical requirements under actual field conditions. This paper describes a small scale rest conducted at a single well for measuring chemical requirements, thereby giving a more reliable evaluation of this important factor in the applicability and economics of the process. In the rest a small wafer slug containing the chemical agent and a nonadsorbed tracer is displaced into the reservoir by a known volume of wafer. The well is then placed on producrion. Chemical loss per barrel of pore volume contacted is calculated from [he fractional recoveries of the agent tested and the nonadsorbed tracer. The method has been used to determine within the actual reservoirs the chemical requirements for both a sandstone and a dolomite reservoir. Several chemical agents are potentially available for wettability alteration flooding, although none is universally applicable. For some applications of the method, chemical costs per barrel of additional oil recovered can be substantially less than one dollar. INTRODUCTION Wettability alteration flooding provides a means of increasing oil recovery from reservoirs by decreasing the degree of wetting of the rock by the oil and increasing the displacement efficiency of the flood water. Earlier studies demonstrated a relationship between oil recovery during waterflooding and the degree of wetting of a rock surface by an oil. The application of wettability alteration flooding to the Harrisburg field of Nebraska provided a field test' of this recovery process. Subsequently, additional laboratory and field tests have developed additional procedures for evaluating wettability alteration flooding, and have indicated where the process may be applicable. Applicability of this process to specific reservoirs is determined by a progression of tests to determine sus- ceptibility of the reservoir to alteration of its wettability, to indicate the degree of recovery improvement and to estimate the amount of chemical required to process the reservoir. The economics of applying improved oil recovery processes depends not only upon the degree of improvement in oil recovery achievable by the process but also upon the process costs and the timing of the income and the investment. Emphasis in this paper is on the expenditure aspects of the process. The work reported in this paper indicates that the chemical investments required for wettability alteration flooding are substantial. For evaluating the economics of a potential flooding application it is imperative that a sound estimate of the chemical requirements be made for the reservoir. Generally, true reservoir conditions are not adequately simulated in laboratory chemical propagation tests. Because of wide well spacings, many years might be required to obtain chemical propagation data from conventional pilots or inter-well tests. Consequently, n short-duration, low-cost method is needed to determine chemical requirements in the field. The potential applicability of wettability alteration flooding is discussed, as well as the economics of wettability alteration with respect to the inherent and imposed restrictions on the timing of income and investments. DETERMINATION OF CHEMICAL REQUIREMENTS In the process of moving a chemical bank through reservoir rock, some of the chemical agent lags too far behind the flood front to be effective or is otherwise lost to the reservoir system. The extent to which these losses occur overshadows the reductions in chemical concentration due to diffusion and to mixing with the reservoir fluids. Experience indicates that almost without exception, chemicals which induce a wetting change undergo either sorption reactions or chemical reactions with mineral constituents of the pore surfaces. Other reactions may occur between the added chemical and the reservoir oil and water. Even in limiting consideration to reactions of the relatively inexpensive inorganic salts, bases and acids, the reactions may be exceedingly complex. Reservoir pore surfaces consist of more than silica in sandstone reservoirs, and more than calcite or dolomite in carbonate reservoirs. Many mineral species are present, each exhibiting specific tendencies to react with an injected chemical. The reactions which occur can consume enough of the agent to have an important effect on economics. These reactions can cause a change in pH of the chemical bank, or may remove some of the active chemical by precipitation, adsorption or reaction to form a new chemical which may or may not be effective in

By Yoichi Ishida, Ching-Yao Cheng, John E. Dorn

Tile creep behavior of a iron was investigated over the range of temperatures from 375° to 1150°K. Apparent activation energies for creep, obtained by the effect of sudden changes in temperature on the creep rate, revealed the presence of- four distinguishable regions. The creep behavior of a iron in Regions II (480° to 774°K) and 111 (775° to 1045°K) was found to correlate well with a model where the creep rate is controlled by the nonconsevualive motion. of jogged screw dislocations. An anomalous increase in the apparent activation energy fur creep in Region III was found to be in harmony with the known decrease in the free activation energy for self-diffusion over the Curie transformation range. Furthermore, the creep rates in Regions II and III were found to increase with stress due not only to the effect of stress on the activation energy but also to an increase in density of mobile dislocations. The evidence suggests that pipe diffusion along moving dislocations could be a significant factor over the lower temperatures of Region II. ALTHOUGH the creep properties of iron and steel have been of interest to metallurgists for some time and an extensive literature is now available, most of the published information has not produced much toward understanding the fundamental dislocation processes controlling the creep behavior of these materials. Whereas the activation energy for high-temperature creep of metals usually agrees well with that for self-diffusion, Sherby, Orr, and Dorn1 deduced from the data of Tapsell -and c1enshaw2 that the activation energy for creep of Armco iron is about 78,000 cal per mole and more recently Lytton and sherby3 reviewed the data of Jenkins and Mellor4 and found an activation energy for creep of a iron of 80,000 cal per mole. Both values are substantially greater than the activation energy for self-diffusion in a iron. Because of the limited data suitable for purposes of identifying the controlling dislocation mechanisms of creep and the unusually high activation energies for creep quoted above, it was considered desirable to reinvestigate in detail the creep of a iron by more reliable techniques which would provide sufficient data for determination of the creep mechanisms. EXPERIMENTAL TECHNIQUE Creep specimens were prepared from 3/8 by 4 in. iron bar stock of the following composition by weight percent: 0.001 C, 0.0120 0, 0.001 N, 0.004 S, and 0.003 P. The as-received bars were cold-rolled to a thickness of 0.100 in., annealed under argon for 30 min at 1113°K, cold-rolled to a final thickness of 0.063 in., and machined into tensile specimens having gage section 0.250 in. wide and 1.70 in. long. Finally they were recrystallized under argon at 1113°K. Specimens to be crept above 1060°K were recrystallized at 1173°K. Both recrystallization treatments gave the same reproducible equiaxed ASTM No. 4 grain size. Creep testing was conducted in machines fitted with Andrade-Chalmers arms that maintained a constant stress to within ±0.2 pct of the reported values. Deformation over the specimen gage section was sensed with a linear differential transformer and recorded auto-graphically as a function of time. The strains deduced from these measurements were sensitive to ±5 x 10-5. During creep the specimens were contained in an argon-filled chamber which was immersed in a temperature-controlled molten tin bath. Creep temperatures, as measured by thermocouples attached to the specimen, were maintained to within ±10.25°K of the reported values. For activation-energy determinations rapid changes in temperature of about 12°K were obtained within 30 sec by direct resistance heating of the creep specimen, and maintained to ±1°K of the reported values. Observations of structural details of specimens before and after creep tests were made by electrolytic polishing and etching in acqueous ammonium persulfate. EXPERIMENTAL RESULTS A typical example of the determination of apparent activation energies, Q, by the effect of small changes in temperature is illustrated in Fig. 1. Q is defined by

Jan 1, 1967