Search Documents

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 George W. Friesen

This paper presents the historical trend and de- fines the causes of drilling cost escalation in the Gulf of Mexico during the 1970's. The three major components of escalation are: 1) inflation, 2) supply-demand imbalance (demand pull) and 3) decreases in drilling efficiency. The decade was divided into three periods. During each period one component of escalation was responsible for most of the rise in costs. From 1970 through 1973 only inflation pushed costs upward. During 1974 and 1975 a supply- demand imbalance caused most of the escalation. Since 1975, decreases in drilling efficiency have produced the major component of escalation. During any one year or period of years, the sum of the three components will give the total escalation rate. The reasons why different components contribute more toward escalation during certain years than others are shown by following the timing of oil and gas price increases, the overall quality of the acreage offered each year in offshore lease sales and the resulting drilling activity.

Jan 1, 1982

ALLERTON S. CUSHMAN, Middletown, Ohio (written discussion*).¬ This subject is one to which I have given much thought and study and which I have frequently discussed informally with Mr. Cain and others. I have long been convinced that the gaseous elements, either combined or entrained (occluded), in steel play a much more important role than is ordinarily admitted. This is probably due to the difficulties encountered in the accurate quantitative estimation of gases, some of which Mr. Cain has referred to, as well as to the fact that, considered from the weight-percentage basis, gas content is measurable only in hundredths or even thousandths of 1 per cent. Volumetrically, however, the results ob-tained by modern research are startling, to say the least. Baraduc-Muller,1 as cited by Mr. Cain, pumped out of 1000-lb. ingots of basic Bessemer steel 2100 l. of gas. or about 75 cu. ft., at normal temperature and pressure, per ton of steel. In other words, we are to understand that Bessemer steel normally carries about fifteen times its own volume of gas. According to Baraduc-Müller's table of results, which is given here-with, carbon monoxide, nitrogen, and hydrogen are important consti-tuents of Bessemer steel, the latter gas being undoubtedly formed by the

Jan 11, 1919

By R. A. Bergman, C. J. B. Fincham

THERMODYNAMIC properties of many high-temperature systems containing sulfur, such as slags, metal sulfides, and solutions of sulfur in liquid metals, have been studied by means of equilibration with known gas mixtures.'" This method presupposes a complete and accurate knowledge of the thermodynamic data for all possible components of the gas phase at high temperatures. However, a survey of the data available up to 1952 on the thermodynamics of gaseous sulfur species and compounds, by Richardson and Jeffes,' showed that there was considerable uncertainty in the values of the free energies of formation of S, SO, HS, and CS. In many cases, this uncertainty made it impossible to decide whether or not these species would form a significant proportion of the sulfur present in the gas phase in any given system. After the review by Richardson and Jeffes had been published, St. Pierre and Chipman6 measured, by an indirect method, the free energy of formation of SO. This also enabled a clear choice to be made among the three possible spectroscopic values for the dissociation energy of S2 into atoms10 thereby determining the free energy of formation of S from S2, and fixing the free energy of formation of HS more accurately" The main purpose of the present investigation was to measure the free energy of formation of CS, which was still in considerable doubt. For example, at 1600°C, it could be estimated to be +6 +25 kcal per mole,* most of the uncertainty being in the * Based on the dissociation energles of CS6 and S2,5 the heat of sublimation of graphite, and, the assumption that the entropy of formation of CS is the same as that of CO. value of the dissociation energy." A secondary purpose of the investigation was to determine more accurately the equilibrium sulfur pressures over dilute solutions of sulfur in carbon-saturated liquid iron. General Method Dilute solutions of sulfur in liquid iron, saturated with carbon, were brought to equilibrium at 1600" and 1800°C, with known gas mixtures consisting, initially, of A and CS2. After equilibrium had been reached, the melts were quenched and analyzed for sulfur. In the high temperature region of the furnace, an equilibrium was set up between the various possible sulfur species and compounds in the gas phase; namely, CS2, CS, S2, and S. (It can be calculated that the amounts of S6 and S, are negligible at these temperatures:) Morris and Bueh17 and Kitchener, Bockris, and Libermana had previously studied the corresponding

Jan 1, 1958

By N. M. Langdon

INTRODUCTION. IN considering the magnificent success of Mr. Gayley's Bold experiment of applying dry blast to the blast-furnace, whereby , saving of 20 per cent. of fuel per ton of iron is effected, the question arises whether, still further economy in fuel is possible, and, if so, how it is to be attained? The manner in which the heat generated in the furnace is utilized in the production of pig-iron may be determined, by the method of Bell and Gruner, for any furnace for which the necessary data are obtainable ; and the study of the operation,. tinder various conditions, of a number of furnaces, for which such information has been worked out., should enable us to form some conclusion on the subject. The tables and calculations given below cover the operations of several furnaces reported in our Transactions; also the two furnaces using natural and dry blast in ,Mr. Gayley's experiment, for which the heat-equation has been worked out by Prof. Joseph W. Richards in his admirable discussion' of Mr. Gayley's paper, The Application of Dry Air Blast to the Manufacture of Iron, and, finally, various hypothetical furnaces.. The full list is as follows : A. Isabella furnace, with natural blast. B. Isabella furnace, with dry blast. The data stated. for A and B in Table III. are those given by Professor Richards; except that the heat-units are given for one unit of iron instead of 100 units, and some items of heat supplied, as stated by Richards, have been subdivided, the total being the same as given by Richards. (Columns A and B are introduced in Table III. for comparison with C and D.)

Oct 1, 1909

By E. B. Thornhill

In this paper on the recovery of mercury as sulphide, from the residues from the amalgamation and cyanide treatment of high-grade ores and concentrates, I will not discuss the many reactions, chemical and other- wise, that take place in the general process, but confine myself more particularly to the methods of recovering the mercury. I submit charts of two amalgamation-barrel charges, Figs. 1 and 2, which are self-explanatory. The flow sheet of the high-grade and the mercury extraction plants is showh in Fig. 3.

Jan 1, 1916

By AIME AIME

AWRDED jointly by the four AW Founder Engineering Societies the John Fritz Medal is generally regarded as the most signal honor that American engineers can confer on a fellow engineer. The roll of 34 recipients contains the names of Lord Kelvin, George Westinghouse, Alexander Graham Bell, Thomas. A. Edison, George W. Goethals, Guglielmo Marconi, and Michael I. Pupin; and among members of the A.I.M.E. now living, Sir Robert A. Hadfield, Herbert Hoover, and Daniel C. Jackling. On the evening of March 1 7 the name of Paul Dyer Merica was formally added to this list of illustrious engineers when the medal was presented to him at a dinner at the Metropolitan Club in New York. The citation read. For important contributions to the development of alloys for industrial uses. Arrangements for the dinner were made by the following committee representing the four Founder Societies: R. C. Allen, George S. Davison, A. A. Potter, and J. B. Whitehead.

Jan 1, 1938

By E. B. Thornhill

(San Francisco Meeting, September, 1915) IN this paper on the recovery of mercury as sulphide, from the residues from the amalgamation and cyanide treatment of high-grade ores and concentrates, I will not discuss the many reactions, chemical and other- Fig. 1. wise, that take place in the general process, but confine myself more particularly to the methods of recovering the mercury. I submit charts of two amalgamation-barrel charges, Figs. 1 and 2, which are self-explanatory. The flow sheet of the high-grade and the mercury extraction plants is shown in Fig. 3.

Jan 8, 1915

By Douglas Bunting

(Wilkes-Barre Meeting, June, 1911.) WITH the gradual exhaustion of the upper veins in the anthracite coal-fields, the problem of mining at greater depths acquires increasing importance and demands the consideration of a number of important factors, one of which is the greater earth-pressure and the consequent necessity of stronger support o for the roof. Under the pillar-and-chamber system, almost exclusively followed in the Northern anthracite-field, the highest economy in mining is generally secured by leaving, on first mining, pillars only sufficient to support safely the overlying strata. As to the necessary size of such pillars, the opinions of mining experts are widely divergent. In establishing the width of chambers and pillars, the thickness of vein and its depth below the surface have received little consideration. For. instance, it has been quite usual to work both overlying and underlying veins with the same width of chambers and pillars, when the lower vein was two and one-half times as thick, and twice as fits below the surface, as the upper. In view of the generally-accepted theory that the crushing-strength of coal-pillars of the same base-area becomes less with increased height, it is probable, in this instance at least, that the most economical mining has not been secured. This question of adequate pillar-support is economically less important down to about 800 ft. than at greater depths; and it is with reference to mining at these greater depths that the study of the subject here presented has been prompted. The necessity of leaving larger pillars, involving greater mining-costs per ton and also smaller yields per acre, is one of the troubles of deep working. To mine without leaving adequate pillar-supports will result, sooner or later, in a squeeze. Limited areas, it is true, have been mined at certain widths of

Sep 1, 1911

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By AIME AIME

Acid Open-Hearth Manipulation.. By ANDREW MCWILLIAM and WILLIAM H. HATFIELD, ii, 279. Discussion by J. J. MORGAN, iii, 647; E. H. SANITER, iii, 648; MCWILLIAM and HATFIELD, 111, 648. ADDICKS, LAWRENCE. The Effect of Impurities on the Electrical Conductivity of Copper, iii, 559. Address of Welcome to the U. S. National Museum, Washington, D. C. By RICHARD RATHBUN, .iv, 923. ALLDERDICE, TAYLOR. Discussion of MR. ROE'S paper, The Mann¬ facture and Characteristics of Wrought Iron, v, 1091. American Mining Engineer. Discussion by ARTHUR JARMAN, iii, 641. An Automatic Stock-Line Recorder for Iron Blast-Furnaces. By J. E. JOHNSON, JR., iii, 509. Anthracite-Washeries. By GEORGE W. HARRIS, vi, 1263.

Jan 1, 1907

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.' According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.' In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By N. S. Wagner, R. S. Mason

The production of lightweight aggregates in Oregon is a new industry, and, like all new enterprises, it is suffering from growing pains characterized by numerous, small operations some of which flourish for a short time and then cease altogether. Norinally all industrial mineral products are produced in a highly competitive atmosphere. At the present time this condition does not exist to a very marked degree in the state because as yet producers have not saturated the constantly expanding market. This paper has been prepared with the intention of outlining very briefly the current status of the various products now heing used as lightweight aggregates in Oregon. The present piche will surely change, perhaps quite radically within even a short space of time. Lightweight Aggregates Used in the Northwest PUMICE Interest in Oregon pumice is not new. Deposits are abundant. Successful development, however, dates only from 1946. During 1948 a total of nine operations was engaged in full or part-time production of aggregate. The postwar building boom and increased public consciousness regarding the value of insulation are the immediate reasons behind the current development. Just how firmly this production of pumice aggregate may be established is something which cannot be foretold at the present time. Much will depend upon how successfully the pumice aggregate construction already installed stands the test of time. Some fine pumice aggregate products have been made and it seems probable that because of its unique properties a certain demand for pumice aggregate will continue in the future. Fire-proof, rodent-proof, decay-resistant properties supplement the lightness in weight and insulation properties of pumice aggregate products in rendering them particularly ideal for many types of construction. In addition there has been fabrication in the form of reinforced fence posts, street markers, and similar products of a specialized-product nature and these are not to be overlooked in terms of future production. Also pertinent to how soundlj pumice aggregate production is established will be possible future competition with other lightweight aggregates. However, this situation will be governed largely by competitive costs of production and marketing. For its present use, which is almost exclusively limited to the manufacturing of building blocks, the market for Oregon pumice aggregate has been extended from the mining area around Rend and Chemult to points as far distant as San Francisco and Seattle. Naturally enough the bulk of the production goes to the Portland and eastern Oregon consumers. Shipments are made by both rail and truck. Early in 1947 the State Department of Geology and Mineral Industries made a canvass of all pumice producers in the state. The production for 1956 amounted to 26,614 cu yd and was valued at $13,649 at the plants. The United States Bureau of Mines estimates the production for 1947 as 33,240 short tons valued at $111,380. This is roughly 65,000 cu yd. No data are available for the 1948 production but it is understood to exceed that for 1947. The Oregon pumice occurrences originated largely from the eruption of Mount Mazama, the name of the formerly active volcano and the location of Crater Lake. Other lesser volcanoes throughout the area contributed to the present occurrences, however, and it has been estimated by Moore' that the pumice deposits cover an area of some 3500 square miles. This area lies east of Crater Lake between Bend and Klamath Falls and embraces the southern portion of Deschutes County, the northern part of Klamath County, and the northwest corner of Lake County. Thickness of the pumice ranges from thin skims to local thicknesses of as much as 30 to 40 ft. Fragment size also varies greatly. Any attempt to describe the situation by giving screen analyses would be confusing because of the wide variations to be found in all area of this size. The picture can best be summed up by stating that places showing great variations in fragment size can be found if a search for extremes is made. For mining purposes in connection with aggregate production, it call be stated that miles and miles of pumice exist in which the fragrnent sizes range from an inch or so downward. The usual color of the pumice is a light gray to off-white. A typical pumice analysis shows a silica content of about 69 pct, alumina 15 pct, and sodium oxide about 5 pct. Potash, lime, and water are the next three most abundant constituents, running just a little over 2 pct each. Iron oxides are fairly constant at 2.75 pct. Titanium, manganese, magnesium, and phosphorus occur in amounts of less than 1 pct. All of the foregoing substances are combined as a glass exhibiting cellular structure. The weight of crushed but otherwise pit-run (undried) pumice runs around 1100 Ib per cu yd according to figures furnished by various producers. The minimum and maximum weights per cubic yard reported are 1050 and 1400 lb, respectively. The 1400 lb per cu yd pumice contrasts with the pumice from most of the other

Jan 1, 1950

By Joklik, G. F.

Most publicity about the copper industry nowadays is focused on the adequacy of ore reserves and on excessive mining capacity. These concerns, stemming from public awareness of actual and potential shortages and oversupplies, relate to production rather than consumption. Perhaps the reason for this one-sided view is that copper is thought of as a commodity which is conspicuously traded in world markets, rather than as one of many industrial materials that serve today's rapidly changing technology. Copper differs from other widely traded commodities in that its real cost of production has progressively increased since World War 11. The reasons for the increase are identifiable by analyzing operations in one of the world's large producing centres, the copper province of Arizona. Another respect in which copper differs from some other commodities is that increases in demand occur less automatically in the case of copper than they tend to in commodities whose consumption is more directly related to population growth. The copper industry's current inability to generate and attract needed investment capital is attributable to these differences between copper and other commodities; it suggests that the concept of copper purely as a commodity is outdated. The key to the problem is better integration between the activities of copper producers and users. Depending on circumstances, integration takes various forms- for example, investment tied to long-term sales con- tracts between producers in developing countries and consumers overseas; common ownership of producing and manufacturing facilities in industrialized nations like the U.S.; and consumer-oriented research and marketing by the copper producers.

Jan 1, 1978

By ALFRED T. BARR

In certain areas of the New Cornelia pit, considerable secondary blasting is necessary to reduce oversized boulders, formed from primary blasting, to pieces which will pass the 41/2-cu yd dippers on the shovels. Some of the boulders are 'dobied, but when time permits they are blockholed and blasted. In most instances one hole drilled to a depth of 2 to 3 ft and blasted with 1/3 to 1/2 of a stick of powder will break a boulder satisfactorily. Blockholing is normally done by using a jackhammer of the 55-lb class, 1-in. round drill steel, and detachable steel bits, 2-in. gauge when new. A bit change is usually made after the completion of each hole. The use of light drilling equipment in blockholing is desirable, both from the standpoint of safety and ease of doing the work, and when it was seen there was a possibility of using a lighter jackhammer through the use of tungsten-carbide bits and at the same time get at least the same drilling efficiency as with the standard equipment, it was decided to test tungsten-carbide bits. The claims for long life of the bits and footage drilled before resharpening gave hopes of eliminating much of the delay time in changing bits which is unavoidable with the use of steel bits. and thus gain in actual drilling time.

Jan 1, 1949

By Richard J. Lund

Stock piling-and by that I mean well-organized stock piling on a substantial scale-is almost as old as the hills themselves. It was back in early Biblical times, as recounted in the Book of Genesis, that Joseph was charged by Pharaoh with the responsibility of stock piling food during the seven years of plenty to guard against the seven subsequent years of famine that were revealed by the Pharaoh's dream. And this same policy of storing up food or materials to provide for future anticipated emergencies can be traced repeatedly down through the ages. So our own efforts are anything but new. Our modern concept of stock piling-the purchase and storage of strategic materials to assure supplies needed in time of some future war- stems from our experience in World War I. In 1920, the War Department was charged by Congress with the responsibility of procuring all War Department supplies and mobilizing industry in the event of another war. During the two decades that followed there were many authoritative studies made of our deficient mineral problem, all of which pointed out the urgent necessity of stock piling certain strategic materials as a reserve against future war. One such study, made in 1925 through the combined efforts of the Mining and Metallurgical Society and the AIME, was done at the ex- press request of the War Department. Eight years later another more de-

Jan 1, 1949

By E. B. Brauer, W. Hurst, J. D. Clark

Because of drilling, completion, and workover practices, the permeability around a wellbore generally is different from the permeability of the formation. The zone with the altered permeability is called "skin" and its effect on the pressure or flow behavior of the well is called "skin effect". Hawkinsl has shown that the radius and the permeability of this zone are related to the skin by: If the permeability in the skin zone is less than that of the formation, the skin is positive; if it is more than that of the formation, the skin is negative. If the two permeabilities are equal, s is zero; that is, there is no skin. Van Everdingen2 and Hurst3 have given mathematical solutions to the case of a zone of reduced permeability around the wellbore. This skin effect is illustrated in Fig. 1. They treat the positive skin as a zone of reduced permeability of infinitesimal thickness around the wellbore. When applied to a well with negative skin, however, their solutions lead to the calculated flowing well pressure which is smaller than the formation pressure, i.e., an injection situation. This is a physical contradiction. In this paper, it is shown that this mathematical difficulty can be overcome by assuming an effective wellbore radius larger than the actual wellbore. Existing solutions2"4 are modified to include the effect of an enlarged wellbore radius, and thus enable the engineer to deal with negative as well as positive skins. Theoretical Development Van Everdingen and Hurst,4 through the use of Laplace transformation, obtained the following expression for transient fluid influx into a wellbore: The values for QtD, reported extensively by van Everdingen and Hurst,4 are obtained from the following integral:

Jan 1, 1970

By A. S. Malicsi, I. Iwasaki

The removal of hydrophobic coatings of flotation collectors from iron ores becomes of interest when a duplex flotation process is considered for upgrading, when a pelletizing process is considered for a concentrate floated with a fatty acid or a soap collector, or when a disposal of froth products from cationic silica flotation is of environmental concern. Ozone can oxidize organic compounds rapidly, thereby removing the hydrophobic coatings of flotation collectors. Ozone is widely used for treating and purifying drinking water, waste water treatment, and for chemicals processing (Murphy and Orr, 1975; Rice et al., 1980). Its uses in metallurgical operations, however, are very sparse (Allegrini et al., 1970; Chernobrov and Rozinoyer, 1975; Ishii et al., 1970; Iwasaki and Malicsi, 1985; Matsubara et al., 1978). Yet, its high reactivity and the absence of potentially hazardous byproducts become of interest in destroying flotation reagents adsorbed on mineral surfaces or remaining in mill water for recycle or for discharge. Duplex Flotation A duplex flotation process, as applied to oxidized iron ores, would involve a fatty acid flotation of iron minerals followed by an amine flotation of the siliceous gangue from the rougher iron concentrate. Such a process has been used in the Florida phosphate fields. Fatty acid coatings cannot be removed as readily with a simple acid or alkali treatment from iron oxide surfaces as from Florida phosphates. A combination of reagents, such as lime and quebracho, lime and alkali phosphate, or sulfuric acid and oxalic acid, has therefore been proposed. In a previous article (Iwasaki et al., 1967) , the use of activated carbon was found to be effective in removing fatty acid coatings both in the duplex flotation and the pelletizing processes. The use of ozone offers another approach to the removal of fatty acid coatings from iron oxide surfaces. To investigate the possible application of the duplex flotation process, a specularite ore from Michigan analyzing 36.5% iron was used. A 600-g (1.3-1b) sample was ground in a laboratory rod mill together with 250 g/t (0.5 lb per st) of sodium silicate to -150 µm (-100 mesh). This was transferred to a Fagergren laboratory flotation cell, and deslimed four times at 20 µm (quartz equivalent). The deslimed pulp was transferred to a laboratory conditioner, diluted to 40% solids, and conditioned with 250 g/t (0.5 lb per st) of soda ash and 250 g/t (0.5 lb per st) of oleic acid. The conditioned pulp was then transferred back to the Fagergren cell, floated until barren of froth, and the rougher froth product was returned to the cell and cleaned. The results are presented in Table 1. The cleaner concentrate at this point analyzed 45.3% Fe. The cleaner concentrate coated with fatty acid was transferred to a 2-L (0.53-gal) beaker. While the pulp was agitated with a glass T-stirrer, ozone was bubbled into the agitated pulp for 15 minutes at a rate of 10 mg/min (0.00035 oz per min) ozone (250 g/t or 0.5 lb per st 03 feed). It was observed that the pulp ceased to froth after about 10 minutes. The amine flotation of siliceous gangue from the ozonated pulp was carried out first by conditioning with a dextrin, a commonly used starch depressant for iron oxides. This was followed by flotation with a stage addition of an ether amine at increments of 100 g/t (0.2 lb per st). Three stages were required to float the siliceous gangue to near completion. The three froth products were combined and cleaned twice. When the cationic flotation Rougher, Cleaner 1 and Cleaner 2 cell products were combined, an iron concentrate analyzing 64.5% iron was obtained at an overall iron recovery of 72.8%. Pelletizing Fatty acid flotation concentrates have been pelletized successfully in northern Michigan mills. But at other locations, fatty acid coatings on iron flotation concentrates proved so undesirable in agglomeration that other methods of concentration had to be sought. For example, a sinter mix containing iron ore concentrates upgraded by fatty acid flotation resulted in decreased productivity. This occurred because the micropellets of particles with the hydrophobic coating are less tolerant of moisture. Thus, the bed permeability is lost (Beebe, 1965). The agglomeration of concentrates obtained by the fatty acid flotation alone, and the hydrophobic coatings destroyed by ozonation or by the duplex flotation process, is not expected to cause any difficulty since the surfaces of the concentrates would be hydrophilic. Removal of the fatty acid coating with activated carbon, indicated by the loss of floatability, was shown to restore the decrepitation temperature of wet balls during drying cycle (Iwasaki et al., 1967). Disposal of Cationic Silica Flotation Froths Recent demands of iron blast furnaces place the silica content of the magnetic taconite pellets at about 5%. Conventional process for magnetic taconite involving fine grinding and magnetic separation often produces magnetic concentrates analyzing in excess of 5% silica. This is due to the presence of the middling grains of siliceous gangue and magnetite. Cationic silica flotation of magnetic taconite concentrates (DeVaney, 1949) may be used to reduce the silica content. But the amine coating on siliceous gangue becomes of environmental concern when the flotation tailings are discarded in tailing ponds.

Jan 1, 1986

By Henry M. Howe, Joseph Winlock, Francis B. Foley

This investigation was undertaken for the purpose of determining, in a systematic way, the effect of the rate of cooling of steels, heated to above the transformation range, on their various mechanical properties. This paper gives the results obtained in the investigation of the heat treatment of carbon steels carried out under the auspices of the Committee on The Heat Treatment of Carbon Steels of the Engineering Division, National Research Council. The objects of this committee, of which Dr. Henry M. Howe was chairman, were to increase knowledge of the influence of heat treatment on the mechanical properties of carbon steel. The mcthod pursued was to subject specimens of steel of the carbon contents most used for engineering work, 0.34 per cent., 0.52 per cent., and 0.75 per cent., to various heat treatments, and to test the mechanical properties thus induced. The steels were the same as were used by the committee on fatigue phenomena. This project was financed jointly by the U. S. Bureaus of Mines and Standards; industries and university laboratories have cooperated. A large part of the work was done at Doctor Howe's private laboratory. The committee consisted of F. B. Foley, H. AT. Boylston, H. C. Boynton, G. K. Burgess, H. J. French, J. H. Hall, Zay Jeffries, R. S. Johnston, F. C. Langenberg, H. F. Moore, E. H. Yeirce, H. S. Rawdon, W. E. Ruder and 11. J. Stagg. The work was undertaken at the suggestion of Doctor Howe, who thought, at the outset, that steel in the sorbitic state might have properties which, for most engineering purposes, would be better than those of the usual or pearlitic state. By a systematic variation in the heating

Jan 1, 1923