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By W. F. Brace, James D. Byerlee

Although prediction of failure of rocks may be ultimately possible without knowing in detail how failure occurs, understanding of this process is certainly of fundamental interest in rock mechanics. Of the various failure mechanisms, probably brittle fracture is of greatest interest. Recent reviews have brought this subject nearly up to date (Hock,1 Price,2 and Jaeger 3) and here, we summarize certain recent developments. As our understanding of brittle fracture is derived almost solely from laboratory studies this will amount to a review of certain laboratory experiments. New studies in four areas are pertinent; these concern 1) the volume changes which accompany brittle fracture, 2) the propagation of cracks in compression, 3) certain frictional characteristics of rocks and minerals at high pressure, and 4) the law of effective stress for crystalline rocks. Our objective here is less to present an entirely consistent, complete picture of how a rock fractures than it is to emphasize gaps in our understanding and, thus, suggest areas that need further study. Progress is still painfully slow in this field and perhaps this approach will stimulate new work. OBSERVATIONS Although the behavior of large rock masses is most often the concern in rock mechanics, the number of large-scale experimental tests is still vanishingly small. Our experimental observations arc, by and large, still made on small, relatively flaw-free, rock samples. Here also we report the behavior of small samples.

Jan 1, 1967

By Walter Harvey Weed

INTRODUCTION. IN a previous paper upon the enrichment of mineral veins by later metallic sulphides,† the writer has shown that certain masses of rich ores, such as are found in many mines, either near the water-line or as bonanzas in depth, are of secondary origin, and are due to a leaching of lean ore and the concentration of the material by reaction between the solution and the unaltered ore below. The geological and mineralogical evidence is believed to form an adequate basis for a chemical and physical explanation of the phenomenon. In the present paper the writer will give a brief synopsis of this theory, and will apply it more particularly to deposits of the precious metals, laying special emphasis upon the dependence of such enrichments upon the presence of iron sulphide (as pyrite, etc.) in the primary ore, and upon structural features which control the circulation of the enriching solutions below the water-level. It is believed that many, though not all, of the bonanzas and pay-shoots of rich sulphide ores, especially those carrying gold and silver, which are encountered in ore-deposits, are of such secondary origin. Apparently it is essential that the occurrence and structural relations of such ore-masses should be understood, as the success of the mine is often dependent upon the finding and extraction of these ores. A legitimate deduction, too, is that such ore-deposits decrease in value with depth. As my own studies have been mainly in Montana, my illustrations must be drawn from the ore-deposits of this and adjacent States, with such as I have noted in hurried visits elsewhere. The literature of ore-deposits doubtless affords also

Jan 1, 1902

By R. A. Wagstaff

The method of charging a reverberatory furnace has changed many times since smelting was introduced in this country from the old smelters of Swansea, England. The cause of the latest change at the Garfield plant has been the excessive fineness of the charge due to fine grinding in the concentration of the crude copper ores. The many desirable features of deep-bath smelting as now used at Garfield have been proved. The old method of dropping the charge through holes in the arch (known as center-feed method) causes excessive dusting which makes heavy slag and flue-dust losses, also rapid deterioration of the silica brickwork of the furnace through fusion with the iron oxides from the dust. The purpose of this paper is to describe a gun feeder that was designed to overcome the disadvantages of the older methods of center feeding and still maintain the good features of deep-bath smelting with the hot finer charge. A gun feeder was designed to introduce the finely divided hot calcines under the moving gas stream of the combustion zone and still have them spread in a uniform blanket over the highly heated matte bath. The temperature of the furnace was so great that it was impossible to maintain a stationary feeder, so a movable feeder was designed that could be introduced into the highly heated zone and be withdrawn after the charge had been dropped. It was necessary to protect the nozzle of the gun with a water-cooled coil. Many different types of protected nozzles were tried, such as air jackets, water jackets and heat-resisting steel alloys, but none proved satisfactory. The angle of inclination of the feeder was found to be an important factor in spreading the charge evenly over the surface of the bath. An angle of 34" to 37" was found to be the most advantageous. To allow a continuous flow of ore from the charge car to the point of discharge inside the furnace, the feeder was made with telescopic connections. The pipe leading from the car is stationary and forms the inside part of the telescope. The outside section of the telescope is movable, and is

Jan 1, 1934

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By G. J. Borbely, E. A. Devuyst, V. A. Ettel

Introduction Of the techniques reported for cyanide removal from effluents, alkaline chlorination is the most common (Fisher and Wasser, 1969; Reidt, 1969). Shortcomings with this technique are the high reagent costs, chlorine contamination, and potential formation of cyanogen chloride. Chemical oxidation methods are also not suitable to remove cyanide from effluents containing sulphides in suspension, such as flotation tailings. An inexpensive method for removing cyanide, combined cyanide and related species from waste waters has been developed in Inco laboratories. The method is based on the use of sulfur dioxide (or a sulfite), lime, and air as the reagents. The decomposition reactions of cyanide, combined cyanide, and related species are catalyzed by copper in solution. Complete removal of cyanide species, most of which are oxidized to cyanate, is obtained by treating copper containing cyanide effluents with sulfur dioxide-air mistures while maintaining the pH between 6 and 10 with addition of lime. The new approach can also be applied to selective destruction of cyanide and combined cyanide in effluents containing sulphides in suspension, such as pyrrhotite. Again, a sufficient amount of dissolved copper must be present or added. Metals and precious metals present in the effluents are recovered as hydroxides by adjusting the pH of the treated effluents to about 9-10. Using the new method, the anionic species are removed in the following order: Free CN- > Complex CN- > Thiocyanate The above removal sequence is unusual as oxidants such as chlorine and ozone oxidize thiocyanate preferentially over the combined cyanide.

Jan 1, 1985

GENTLEMEN Herewith are transmitted reports from the Treasurer and of the principal standing committees of the Institute. To these special reports members are referred for details as to the year's work. Despite the unfavorable business conditions obtaining throughout the year, the Institute was able to carry on its various activities without curtailment and without drawing on the surplus accumulated through previous years. In fact, small additions were made to the Life, Member¬ship and various other funds. It is highly desirable that such additions should continue to be made, especially to the Life Membership fund, for reasons reported last year. At present, money must be used from current receipts in order to enable the Institute to fulfill its obligations to those who on joining the organization commuted their dues by a single payment. In addition, with the passage of years the number increases of those who have paid dues forty years or more and who, by reason of age or dis¬ability, are unable longer to practise their profession. These men have supported the Institute through their active professional life and it would be a pity to lose them as members through resignation or for failure to keep up their dues. In accordance with the By-laws the Board has authority to advance such members, on application, to the Honor Roll of Senior Members and to relieve them from further payment of dues. It has been the policy of the Board to do this liberally, but to keep up this, as well as to meet other obligations, it is necessary for money to be provided. It has been estimated by the Treasurer that nearly $50,000 additional should be placed in the Life Membership fund as soon as possi¬ble to meet these obligations without using current income and to that end it is necessary, not only to avoid running behind currently but to earn, if possible, some surplus each year. The small amount transferred to the Life Membership fund from surplus this year was, as a matter of fact, made possible by certain members paying personally bills that were properly chargeable to the Treasury. Such generosity is common among those active in Institute work and probably no year would have closed with a surplus except for it.

Jan 1, 1923

By Gilbert E. Doan

IN a technical civilization, that is. one whose major difference from past civilizations is its enormous development of technology, in transportation, communication, labor saving, centralized control, and mass production, it is natural that the most critical problems should be those that arise out of technologic advances; it is natural also that a. man who understands these advances should be chosen as the leader to meet these problems. This was done in the selection of Herbert Hoover as President of the United States. Mr. Hoover was a good, and perhaps a great President. But he was not a great politician and that ensured his defeat when a crisis came.

Jan 1, 1939

By AIME AIME

S ULFURIC acid made in the United States during the last four years has averaged approximately 7,000,000 tons of 50" B6 acid a year. This is double the production of the year 1913. About 66 per cent of the acid is made from sulfur, 16 per cent from pyrite, 13 per cent at copper, lead, and zinc smelters, and the remainder from miscellaneous sources it her the chamber process or the contact process, (at some plants both) is used. In 1923, the contact process accounted for nearly 30 per cent of all the sulfuric acid made in this country and since then it has been increasingly employed. It was first introduced here in 1898, and has always .proved less expensive than the chamber process for the manufacture of .acid of high concentration and purity, but the latter produces acid of low strength suitable for many industries.

Jan 1, 1929

By Robert E. Green, Edmund G. Henneke

The velocities of the three possible modes of elastic wave propagation have been calculated for single-crystal copper at 1-deg intervals throughout the standard stereographic triangle. The results are presented as isospeed contours. The deviations between the direction of maximum energy flux and specimen axes are presented as arrows drawn on stereographic projections. The orientation factors associated with dislocation motion on the primary slip system only and also on all twelve slip systems have been calculated for all three elastic waves. The orientation factors associated with a longitudinal standing wave resonant specimen have also been calculated. The results of these calculatians are compared with earlier calculations on aluminum crystals and the relevance of these results to ultrasonic attenuation measurements is discussed. GREEN and inton' have recently outlined a procedure for determining the orientation factors for dislocation damping in single crystals. The stress field associated with a given mode of elastic wave propagation is resolved on the slip systems in which it is assumed the dislocations are vibrating due to this stress field. Since, at room temperature, slip has been observed on a limited number of systems in fcc and hcp metal crystals, it is assumed that these systems are the appropriate ones to use for the resolving process. This procedure has been applied to aluminum crystals by Hinton and hreen' and to zinc crystals by Henneke and Green.3 In the present paper the modes of elastic wave propagation have been calculated for copper crystals possessing orientations at 1-deg intervals throughout the standard stereographic triangle. The deviation of the energy flux vectors from the specimen axis have been calculated for each mode. The stress field associated with each mode has been resolved on the (111)(110) slip systems in order to determine the orientation factors for dislocation damping. MODES OF ELASTIC WAVE PROPAGATION For any direction in a linear homogeneous aniso-tropic material three elastic modes can be propagated. In general, each of these modes has both longitudinal and transverse particle displacements associated with it and thus are not "pure" modes. However, there is always one component which is greatest in either a longitudinal or transverse direction and hence the mode may be referred to as quasi-longitudinal or quasi-transverse, accordingly. For certain axes of high symmetry pure modes may be propagated. The phenomenon of refraction of the energy flux vector is also exhibited by elastic wave propagation in ani-

Jan 1, 1969

By H. W. Reinhardt, J. W. Dally

A dynamic photoelastic analysis of stress waves interacting with a free surface is described. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb N,). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. The mechanics of rock breakage by means of explosives has received considerable treatment by many investigators including Duvall, Obert, Broberg, Rinehart, and Langefors1-11 over the past two decades. Indeed in more recent years several texts12-15 have been written on the topic, treating a wide variety of subjects which are logically related to the modern technique of rock blasting. In rock blasting the chemical energy of a concentrated explosive contained in a relatively small diameter borehole is utilized to fragment the rock. The explosive is transformed into a gas with enormous pressures which exceed 10-5 bars18 This high pressure shatters the rock in the area adjacent to the borehole and produces dilatational and distortional stress waves which propagate radially away from the borehole. The state of stress associated with these outgoing waves produces a system of cracks which extend for a few feet from the borehole. The breakage produced in this manner is limited as the dynamic stress in the pulse attenuates markedly with distance. In the absence of a free surface, the stress wave propagates away from the source without further fracture. With a free face of rock near the drill hole, another mode of breakage occurs which is due to scabbing failure of the layer of rock adjacent to the free face. These scabbing failures are produced by the reflection of the incident waves and the conversion of compressive stresses into tensile stresses sufficiently large to fracture the rock. The detailed nature of the interaction of the stress waves with the free surface is complex and difficult to treat analytically. However, dynamic photoelasticity offers an experimental approach which gives a fullfield visual display of propagating stress waves and the reflection process. Applications of static photoelasticity to solution of problems related to mining technology have become relatively common (see, for instance, Refs. 17 and 18) with a plastic model loaded to produce a state of stress representative of that occurring in the workings of a mine. The application of dynamic photoelasticity is ex tremely limited. Tandanand and Hartman19 have used a multiple spark camera to study fracture in glass and plastic plates impacted by a chisel-shaped tool. This paper describes a dynamic photoelastic analysis of stress waves interacting with a free surface. The free surface is that of a bench with a fixed bottom so common in quarry applications. The stress waves are generated by line charges of lead azide (Pb-N6). Four models of identical geometry are investigated with the direction of detonation of the line charge varied between the four models. Dynamic photoelastic patterns are recorded and analyzed to indicate which method of detonating the line charge produced the largest magnitude of tension at the free surface. Experimental Procedure The model illustrated in [Fig. 1] was fabricated from a sheet of Columbia Resin CR-39 to represent a bench with a fixed bottom. Properties of the CR-39 pertaining to these dynamic experiments are listed in [Table 1]. Scribe lines on 1-in. centers are used to identify locations along the bench face. The bench height was 8 in., the burden was 3 in., and the overall dimensions of the sheet, 16 and 18 in., were large enough to eliminate reflections from nonessential boundaries during the period of observation of the dynamic event. To simulate a charge in a borehole, a groove 0.062 in. wide and 0.080 in. deep groove was cut into the sheet from one side. The lower end of the groove was 1 in. or 1/3 the burden distance below the bottom of the bench. The upper end of the groove was 3 in. or one times the burden distance below the upper level of the bench. The groove was packed with 60 mg of Pb No per in. of length, and ignited with a bridge wire detonator. Four different ignition procedures were used to examine the effects of detonation direction on the stress wave interaction with the free face of the bench. In Test 1 the line charge was ignited at the top and the line charge detonated downward. In Test 2 the line charge was ignited at the bottom and the charge burned upward. In Test 3 the charge was ignited in the center with the top half burning upward and the bottom half burning downward. Finally in Test 4 the line charge was ignited at both ends simultaneously. Sixteen high-speed photographs of the photoelastic fringe patterns representing the stress wave propagation were recorded for each of the tests. A Cranz-Schardin multiple spark gap camera 20,21 was operated at framing rates which were systematically varied from 110,000 to 250,000 frames per sec during each test.

Jan 1, 1972

By C. R. Kuzell

The Editor desires to call attention to the charts in the paper of the above title which were published in the August Bulletin on pages 2190 and 2191. It was impracticable to include in the Bulletin. charts of sufficient size to be used as working diagrams for the direct determination of operating values, but the Institute is prepared to furnish copies of these charts on a large-size scale, at a moderate cost, to those who desire to have them for this purpose. CORRECTIONS Page 2185, line 3. For "is accessory apparatus" read "in accessory. apparatus." Page 2188. Substitute for lines 11 and 12: Nitrogen, oxygen, carbon monoxide, Cp = 6.50 + 0.0010T Hydrogen, Cp = 6.50 + 0.0009T

Jan 9, 1914

By H. E. Ellis, O. L. Patterson, Granville Dutton

A large-scale water-injection program for the Holt Bryant reservoir of the Delhi field has been established by means of the new automatic multi-pool analyzer. The objectives of this program were to increase reservoir pressure and eliminate a cross-dip gradient of 200 psi. Pressure increases during the first 15 months of operation have allowed for increased oil production rates of 2,600 BID or 25 per cent. To determine the required water injection it was necessary to predict natural water influx ram. Elimination of the pressure gradients required the water-injection program to account for the fluid migration and pressure interaction between segments of the reservoir. An integral part of the ana1ysis included the determination of in-place volumes of oil and gas. The operation of the automatic multi-pool analyzer in determining the water-injection program is described. New features of the analyzer inc1ude an automatic maferial balance analog and a leart-squares computer for determination of unknown reservoir properties. Operational procedures are sufficiently simple to allow direct use by reservoir engineers on a routine basis. The rapidity and accuracy with which problems may be solved permit repeated ana1yses as a check upon reservoir performance. INTRODUCTION This paper describes the use of a new analog com- puter in determining the optimum injection program for a complex reservoir. The Holt-Bryant (Fig. 1) is the major reservoir in the Delhi field of Louisiana. Production is from the Tuscaloosa at subsea depths of 2,970 to 3,286 ft. The sand dips to the south and southwest from three to five degrees. The reservoir is approximately 12 miles long and varies in width from 1/2 to 2 miles. Various calculations have placed the initial volume of oil in-place in the wide range of 275 to 355 million STB. Two small gas caps were initially present in the reservoir. The Holt-Bryant reservoir was discovered in Dec.. 1944, and was fully developed with 188 producing wells by 1948. After development was completed, an east-west pressure gradient began to establish itself. This

Jan 1, 1957

The co-operation of the members of the Institute is earnestly sought by the Committee on Nominations, recently appointed by the Board of Directors, in its work of formulating a ticket for officers and places falling vacant in the Board of Directors in February, 1916. The Committee must present the official ticket of nominations to the Board of Directors at its October meeting. Members are, therefore, urged to send promptly their nominations for officers and Directors in order that the Committee may have an opportunity to give them full consideration. The officers to be elected at the annual meeting in February, 1916, are: One officer, known as Director and President. Two officers, known as Director and Vice-President. Five officers, known as Director. The officers of the Institute whose terms expire are as follows: President, William L. Saunders (not eligible for re-election). Past President, Charles F. Rand. Vice-Presidents, Thomas H. Leggett, District 0; Fred W. Denton, District 4.

Jan 9, 1915

By Samuel S. Wyer

Bethlehem Meeting, February, 1906 THE following abbreviations have been used in the text:¬ Am. MF. and Iron World. American Manufacturer and Iron World, Pittsburg, Pa. Can. Min. Rev. Canadian Mining Review, Ottawa, Can. Cass. Mag. Cassier's Magazine, New York, N. Y. Col. Eng. Colliery Engineer, London, Eng. Col. Guard. Colliery Guardian, London, Eng. Eng. and Min. Jour. Engineering and Mining Journal, New York, N. Y. Eng. News. Engineering News, New York, N. Y. Engr. Engineering, London, Eng. J. I. and S. I. Journal of the Iron and Steel Institute, Lon¬don, Eng. Jour. W Soc. of Engrs. Journal Western Society of Engineers, Chicago, Ill. Lond. Eng. The Engineer, London, Eng. Mines and Min. Mines and Minerals, Scranton, Pa. North of Eng. I. M. E. North of England Institute of Mining Engineers, Newcastle-on-Tyne, England. Oester Zeitsch f. Berg u. Hüt. Oesterrcichische Zeitschrift für Berg. und Hüttenwescn, Vienna, Austria. Pract. Engr. Practical Engineer, London, Eng. Proc. I. C. E. Proceedings Institution of Civil Engineers, London, Eng. Trans. A. I. M. E. Transactions American Institute of Mining Engineers, New York, N. Y. Trans. A. S. M. E. Transactions American Society Mechanical Engineers, New York, N Y Trans. Fed. I. M E. Transactions Federated Institute Mining Engineers, Newcastle-on-Tyne, England. Trans. I M E Transactions Institute Mining Engineers, Newcastle-on-Tyne, England.

Mar 1, 1906

By A. J. Lynch, N. W. Johnson, D. J. McKee

The behavior of nonsulfide gangue in chalcopyrite flotation circuits has been investigated. Plant and laboratory tests were conducted on five different ores. Linear relationships between the recovery rates of free nonsulfide gangue and water were observed. From pilot plant tests, there was evidence that the linear relationship was actually a linear approximation to a parabolic relationship. There was evidence that free nonsulfide gangue is transported from the pulp to the froth in the water and that the gangue is subjected to hydraulic classification in the froth column. A classification matrix has been proposed to define this behavior. This matrix is suitable for inclusion in a mathematical model of the process.

Jan 1, 1975

S. F. EMMONS, Washington, D. C.: Papers of Collins, Vogt, DeLaunay, etc.-Mr. Collins tells us about facts in the veins of Cornwall that suggest secondary sulphide-enrichment is highly interesting; and I am free to confess that I have not studied the literature of that region as fully as I should have done. Nevertheless, even if it had been as familiar to me as it is to Mr. Collins, I should probably have hesitated to draw theoretical conclusions without having seen the mines myself; for the personal equation and the point of view of the observer play, perhaps, a larger part in the study of ore-deposits than in that of any other natural phenomena. One important purpose of my paper, and its publication at the time of the Washington meeting, was to call forth remarks from other geologists upon deposits with which they were personally familiar, or to lead them to re-examine such deposits with the idea of secondary enrichment in mind. Mr. Collins's remarks on Rio Tinto, which he has the advantage of personally knowing, are also interesting. With regard, however, to his suggestion-advanced as an apparent argument against our theory-that the re-precipitation of copper from cupric sulphate solution by pyrite can hardly take place there, since it would upset the commercial process, I would remark that, while he is undoubtedly right as to the fact, it does not militate against the reduction and re-precipitation of cupric sulphate in veins; since on the surface, as at Rio Tinto, there is free access of air, and consequently an excess of ferric sulphate, whereas in depth the ferric sulphate would have been mostly reduced to ferrous sulphate, and (there being no excess of acid to hold it in solution) the small amount of copper in the presence of an excess of iron sulphide would be precipitated either as sulphide or as native copper. To Professor Vogt's analogous remarks, that in his experience sulphuric acid is formed only in subordinate amount in the attack of sulphides by ferric sulphate, I would say that Dr.

Jan 1, 1902

By E. S. Machlin

An extension of the thermodynamic theory has been made for the case of irreversible growth processes occurring by the motion of an interface. The theory is applicable to such diverse phenomena as diffusion, growth in recrystallization, continuous grain growth, growth of carbides, etc., growth of eutectoid products, growth in solidification, recovery, "slipless" flow, etc. THE publication of a recent book1 has served to focus attention on a very powerful means of treating certain irreversible processes. This method which has been formally described as the thermodynamic theory of irreversible processes is applicable to processes which involve an approach to equilibrium and for which the deviations from equilibrium are small. The irreversible processes can be classified into three groups: chemical reactions, transport processes (diffusion, heat and electrical flows), and relaxation phenomena involving a degradation of internal energy to more stable states. The limits of applicability of the theory can be precisely defined1,2 for each type of irreversible process. For example, in a chemical reaction at constant temperature and pressure, the Gibbs free energy released per mol in the process should be less than the thermal energy, RT. Another type of irreversible process, which sometimes involves a combination of the first two of the above-mentioned groups, is treated in this paper. This process is one characterized by the motion of an interface separating two regions having different values of free energy and may be briefly described as a growth process. Prigogine2 and Herring3 have treated special cases of this type of process. Previous conscious applications of the theory in metallurgy have been limited to the field of diffusion, one of the transport processes. Darken,4 Bardeen,5 Prigogine2 and others have made significant contributions in this respect. Some other applications of the theory are described in this paper. The Theory The thermodynamic theory of irreversible processes is based on the work of Onsager,6 DeDonder,7 Prigogine2 and others. A resume of the theory has been given by Prigogine2 and DeGroot.1 A brief description of the theory follows, although for a complete understanding the reader is urged to read the references. It is first assumed that the change in entropy, even for a system removed from equilibrium, is given by dS = [dU + pdV - Si µi, dn, - Sk Pk dxk]T-1 Using this expression, the irreversible entropy production in the system is calculated by subtracting the contribution to the change in entropy of the system by transfer of heat, work, or matter from the surroundings. Thus, for example, the irreversible entropy production of a system at constant temperature and pressure is given by dtS = — — dG (DeDonder7) Now it has been shown by Prigogine,2 DeDonder,7 and DeGroot1 that the rate of irreversible entropy production diS/dt, when calculated in the manner suggested, can be written as a sum of products of conjugate forces XK and fluxes Jk, i.e., d,s/ = Sk Jk Xk [I-1] dt The assumption is next made that a linear relation exists between a given flux and the forces, obtained from Eq. I-1, i.e., Ji = Sk Lik Xk (i = 1, 2, . . . n) [I-2] Generally, there is a degree of freedom in choice of the fluxes and forces. However, for all the choices consistent with Eq. I-1 the Onsager8 relations, based on the principle of microscopic reversibility, namely, Lik = Lki, are valid. The coefficients Lik, depending upon the choice of the conjugate fluxes and forces, may be more or less dependent upon the parameters defining the state of the system. In general, the proper choice of fluxes and forces utilizing Eq. I-1, makes the coefficients Lik independent of time. Also, because many of the three classes of irreversible phenomena have already been treated,1,2 a proper choice can be made by analogy. In any case, the validity of Eq. 1-2, from whatever choice made using Eq. I-1, must be tested by experimentation. The theory, thus, comprises the following steps: 1—The irreversible entropy production is calculated to yield Eq. I-1. 2—The terms in Eq. I-1 are grouped

Jan 1, 1954

By J. W. Pugh, J. D. Nisbet

F. B. Foley—The use of data published by Wever and Jellinghaus in 1931 to fix boundaries of the sigma phase in the Fe-Cr system, in the face of the author's own references to the suggestions of Bradley and Goldschmidt, Aborn and Bain, and Hougardy that the phase is much more extensive, and the very much more accurate work, which weighs heavily in favor of these suggestions, of Cook and Jones, published in 1943 and evidently disregarded by the authors, makes their derived ternary diagram, especially fig. 15 for 400°C, quite inaccurate on the Fe-Cr side and affects the extent of phase boundaries in the most controversial and important part of this ternary system. In commercial Fe-Ni-Cr alloys the occurrence of sigma has been observed time and time again at lower chromium contents than that of the 24 pct Cr, 16 pct Ni, 60 pct Fe alloy which is the lowest permitted by fig. 15 of practically carbonless metal. Newel1 reports sigma in 27 pct Cr-Fe even with some carbon present to be one of the greatest detriments to its extensive application, whereas Pugh and Nisbet set a low limit of 36 pct Cr for sigma in the binary Fe-Cr system. J. J. Heger—The diagrams presented by the authors do not agree with observations made on commercial Fe-Cr and Fe-Cr-Ni alloys, nor do they agree with two recent investigations made on the Fe-Cr and the Fe-Cr-Fe systems. I refer first to the investigation made by Cook and Jones1' on the sigma region of the Fe-Cr system. On the basis of their results which were published in 1943, Cook and Jones established new boundary limits for the sigma and the alpha plus sigma regions. These new limits have been accepted and are incorporated in the Fe-Cr diagram that appears in the 1948 edition of the Metals Handbook. This diagram is shown here as fig. 34. As will be noted, the boundary limits of the alpha plus sigma region in this diagram extend to much lower chromium contents than do those in the diagram presented by the authors in fig. 2. These new limits indicate that sigma phase should form in an Fe-Cr alloy containing 26 pct Cr, and experience with commercial alloys confirms this finding. Indeed, recent studies on a commercial Fe-Cr alloy containing 17 pct Cr have shown sigma phase to be stable in this alloy at 550°C. I recognize that the authors' work did not include studies on the sigma region; however, I believe this is a serious omission because sigma phase may profoundly affect the physical properties of these alloys and should be evaluated in any investigation which attempts to relate physical properties to the equilibrium diagram. The second investigation to which I refer is that made on the Fe-Cr-Ni system by Rees, Burns, and Cook,'' who used pure alloys and employed heating 17 W. P. Rees, B. D. Burns, and A. 3. Cook: Journal Iron and Steel Institute. (July 1949) 162, Part 3. p. 325. times that extend to 200 days. These investigators published their results in July 1949 and from these results constructed isothermal sections at 800" and 650°C. The isothermal section at 650°C is shown here as fig. 35. This diagram indicates sigma phase should form in a pure 18 pct Cr-8 pct Ni alloy. Although sigma phase has not been observed after 10,000 hr at 1200°F in commercial 18-8 alloys containing carbon and nitrogen, it has been observed under the same conditions in 18-8 alloys modified with titanium and columbium, both of which serve to reduce the effect of carbon and nitrogen. This section and the one at 800°C suggest that the constant iron sections which are presented by the authors, should be considerably altered, if they are to represent an accurate picture of the system. A few of the suggested alterations are as follows: In fig. 9, the section at 50 pct Fe, the gamma plus sigma region should be widened, not narrowed at 800" and 650°C. In fig. 10, the section at 60 pct Fe, the gamma plus sigma region should be widened at 800° and 650°C. In fig. 11, the section at 70 pct Fe, an alpha plus sigma, an alpha plus gamma plus sigma, and a gamma plus sigma region should be added. In fig. 12, the section at 80 pct Fe, the alpha plus gamma region should be widened at 800°C. In fig. 13, the section at 90 pct Fe, the alpha plus gamma region should be widened at 650° and 800°C. Undoubtedly, the chief reason for the discrepancies between the authors' data and those of Rees, Burns, and Cook is that the authors did not employ long enough heating times to allow for transformation. In this connection, I wish to warn that transformations in these alloys, particularly transformations at temperatures below 800°C, are extremely sluggish and may require a year or more to approach completion. Therefore, unless extremely long heating times are employed or steps are taken to accelerate these transformations by such means as mechanical working, the results will not yield an accurate picture of the alloy system. Certainly, an accurate picture is needed for the development of better high-temperature materials. E. J. Dulis-The purpose of this work is not clear. If an improvement of the ternary equilibrium diagram of the Fe-Cr-Ni system was wanted, it seems logical that testing techniques superior to those previously used would be a prime requirement. To approach equilibrium in this system, long holding times are needed; a fact established long ago but apparently ignored by the present authors, who used the continuous heating and cooling tests in equilibrium studies. A publication on the same system by Bradley and Goldschmidt6 was criticized by Monypenny in a

Jan 1, 1951

By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942

By William H. Spice

The area on which oil and gas development is reported covers 30 counties, which are included in the Texas Railroad Commission's District No. I. This area not only includes the old established Balcones fault-line group of producing fields but also includes the southwest extension of this trend and some of the deeper Wilcox (Eocene) exploratory development. (Fig. J.) In the old Balcones fault-line zone, three new fields were discovered during 1941. These fields are comparatively small, producing from Dale limestone or Austin chalk. No new fields were discovered during the year in the Edwards (Lower Cretaceous) limestone horizon. One new shallow field was discovered in the Reklaw (Eocene) sand horizon and, in the southwestern part of the district, one oil field and one gas field were discovered in the Navarro (Upper Cretaceous) sand horizon. An extremely important extension was made to the one producing Wilcox (Eocene) field of the district in the Washburn Ranch field of La Salle County. The district produced 6,650,357 bbl. during 1941, which was a 12 per cent decrease under production for 1940. Approximately 4,954,000 bbl. of this total production was produced by the three Edwards limestone fields, Luling, Salt Flat and Darst Creek, the remaining production coming from the other 43 active fields in the district. In all, 3694 wells were producing at the end of 1941, compared with 3559 wells at the end of the previous year. During the year, 139 new producing wells were completed and 29 wells were abandoned in the producing fields. The increase in producing wells represents an increase in new wells over abandonments in these fields, together with a decrease in wells temporarily shut down as of the end of 1941. The majority of production drilling was carried on in the following fields; Bee Creek, Chicon Lake, Elm Creek, Gas Ridge, Pearsall and Tenney Creek. Approximately 250 wells were drilled during 1941, of which 110 were exploratory wells completed as failures throughout the district. Considerable exploratory work was continued during 1941 along the Wilcox trend. Geophysical work employing various types of geophysical methods and leasing activity was continued along this trend, particularly by the major companies. The significance of this activity is apparent from the successful extension and development in the Washburn field of La Salle County, where several well-developed gas-and-oil producing horizons have been developed in the lower Wilcox section between 5100 and 5600 ft. as noted in the following paragraphs. Continued exploratory activity along this general trend as far as present conditions will permit is predicted for 1942. New Fields Elgin Field, Bastrop County.—No. I-A Hiram Walker, Marts and Beaven, Inc., discovery well of the Elgin field, was com pleted on Apr. 22, 1941, in broken Austin chalk from 2820 to 2840 ft., pumping 105 bbl. per day, 36.8°A.P.I. gravity. The well apparently is producing from a crevice in

Jan 1, 1942