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By D. Perry, G. W. Binkley, G. K. Dumbauld, F. A. Brooks

A new cementing technique has been developed which is particularly applicable to permanent-type well completion operations. The technique makes use of the accelerating effect of calcium chloride on setting time and strength development of cement cake deposited in squeeze cementing. An unique feature is that the accelerator is applied after the unaccelera-ted cement slurry has been squeezed and the excess has been reversed from the well. Laboratory data on the accelerating effect of calcium chloride applied to the fi1ter cakes of three low-water-loss cementing compositions demorzstrate that the procedure results in relatively rapid development of strength and impermeability of the cement cake. Simulated squeeze-ceinenting tests made in the laboratory likewise corroborated the practicality of the procedure. The laboratory tests showed that a newly developed oil-emulsion cemerzting composition is more susceptible to acceleration of set than are modified cements containing high percentages of bentonite. The acceleration procedure has been used successfully in field operations. INTRODUCTION Nature of Problem In squeeze-cementing operations, a substantial amount of time is consumed in waiting on the cement to develop strength after it has been squeezed into the well. Frequently, an interval of 18 to 24 hours or longer is required for the development of strength sufficient to prevent failure of the cement during subsequent operations in the well. Reduction of this waiting-on-cement time offers appreciable savings both in time and in money. A particular type of squeeze-cementing operation to which an increasing amount of attention has been given is encountered in permanent-type well completion operations wherein perforations are to be squeezed off1. In this procedure, it is customary to pump the cement slurry down the tubing and out into the perforated section through a retractable extension pipe. Squeeze pressure is then applied, which forces the cement slurry into the perforations and causes the build up of a compact filter cake of cement within the perforations. The excess slurry remaining in the hole is then removed by reverse circulation. The extension pipe is then retracted, and, if a new interval is to be perforated, a perforating gun is run through the tubing. The newly perforated interval may then be tested by swabbing. In such operations, it has been customary to allow approximately 20 hours or so for hardening of the cement squeezed into the perforations. This time interval is usually measured from the time that the cement is reversed out of the hole to the time that subsequent swabbing is started. If the cement has not developed strength at the commencement of swabbing, the pressure differential caused by swabbing results in failure of the squeeze job. At the time that the work described in this report was initiated, particular consideration was given to the reduction of waiting-on-cement time in squeeze cementing by the permanent-type completion technique. Consequently, much of the experimental work was directed to this specific objective, though the process which was developed for acceleration of strength development has possible application in other than permanent-type completion operations. Method of Attack Although quick-setting cements

Jan 1, 1957

By E. E. Malouf

Rapid depletion of the world's mineral deposits combined with the expanding demand for metals places great pressure on our ability to provide technologically and economically feasible processes to recover greater amounts of metals from progressively lower grade sources. Chemical mining is one area in which expanding research and development can provide new processes or refinements to existing ones. These new techniques could result in increased production of metals from materials now considered uneconomic to process by current technology. To mine by chemicals requires the interaction of such disciplines as hydrometallurgy, microbiology, chemistry (both organic and inorganic), fluid flow, mineralogy, geology, and of course, economics. One of the least understood areas but one which may end up being an essential part of any chemical mining process is microbiology, i.e., the role of microorganisms in altering minerals and metals in solution.

Jan 1, 1971

By J. D. Livingston

THE hardening of alloys by the precipitation of a second phase has long been an important technological process. One approach towards improving our understanding of this phenomenon has been a correlation of mechanical properties with such parameters as particle size and inter par ticle spacing.' Several reviews of such data have appeared.2-4 A major limitation to this approach has been that for most alloys the particles are submicroscopic in size in the range of optimum hardness. Precipitation-hardening copper-cobalt alloys, therefore, are of interest, because the ferromagnetic properties of the precipitate make it possible to measure particle size, number of particles, and so forth, from magnetic measurements alone.5, 6 Livingston and Becker7 have applied these techniques to a study of precipitation hardening in an alloy of 2 pct Co in copper. It was found from magnetic measurements that nearly all the cobalt to be precipitated was out of solution within a few minutes at 600°C, whereas the peak in tensile yield stress was not attained until a much longer aging time. Thus during the first 1000 min of aging time at 600°C the Yield stress was increasing while a constant volume of precipitate was coarsening, i.e., while particle size and interparticle spacing were increasing. Peak yield stress was reached at an average particle radius of about 70A. The earlier study was confined to one alloy at one aging temperature, so that the volume fraction of precipitate was fixed and, therefore, particle size and interparticle spacing could not be independently varied. The work has now been extended to several alloys of varying percentage cobalt in copper, and to aging at various temperatures. It was hoped that such a study might clarify the relative importance to precipitation hardening of particle size, interparticle spacing, and volume fraction of precipitate. EXPERIMENT The alloys studied contained 0.7, 1.3, 2.0, and 3.2 wt pct Co in copper. They were prepared from electrolytic copper and electrolytic cobalt in a vacuum -induction furnace, worked to 3/8-in.-diam rod, and machined into tensile specimens with a gage section 1 1/2 in. long and 3/16 in. in diam. All specimens were given a solution treatment consisting of a 30-min anneal in nitrogen at 1000° C followed by a quench into iced brine. Subsequent aging was done in nitrogen and followed by a water quench. Average grain diameter was approximately 0.01 in.

Jan 1, 1960

By M. M. Slotnick

It was once aptly said that a sign of approaching senility is ceasing work on a subject and beginning to talk about it. Perhaps that explains why, after many Years in which Part of my duties has been the training of college men in various branches of petroleum exploration geophysics, I have now begun to talk about it. In making an outline of what I believe ought to be discussed under the general heading of the title, I found it almost impossible to subdivide the ideas into an ordered set of discrete subjects. Rather, the pertinent remarks seemed to interlock almost everywhere. The consequence is that it will be necessary to start with the conclusions and then try to justify them by jumping back and forth. However, based on the types of men with whom I have had to deal, the subject naturally divides itself into two parts. In the first part, I should like to deal with the case of those undergraduates whose natural bent is toward the physical sciences and who may decide to enter the geophysical fold as a career. The other part will deal with those many men, geologists and engineers for the most part, who have drifted into exploration geophysics by one means or another, and whom it is necessary to train for geophysical work while they are occupied in their routine jobs. Here it may be in point to remark that most men in exploration geophysics at Present have been developed from precisely the latter group, and that the problem of training here is of great importance even though, in this paper, it will perforce occupy the secondary place. Training oF a Geophysicist The outstanding reason for the perplexing problem on the training of a geophysi-cist is that ideas differ on the answer to the question: "what is a geophysicistp" ln any of the scientific "specialties," like physics, for example, it is relatively simple to pigeonhole a man as being qualified to call himself a physicist. That appellation applied to an individual does not mean that he has mastered only the branches of intellectual endeavor usually associated under the broad name of "physics." we expect him also to have a more than mere acquaintance with mathematics and chemist~ and some understanding of most of the other sciences. But note this important point—we expect our physicist, whom we have chosen as an example, to be intelligently trained so that, if necessary, he can and will know how and where he can get the proper information on a subject in which he is not a specialist; he will know how to absorb that information and turn it to his uses. It seems to me that this is the outstanding characteristic of a man who can truly call himself a scientist: that he is a specialist in one of the broad branches of science in that he has enough training and discipline in the scientific approach so that, when called upon to do so, he can inteugently absorb knowledge from another bordering science (and all sciences not only border upon one another to some extent, but more often, overlap One another), and

Jan 1, 1946

By M. M. Slotnick

It was once aptly said that a sign of approaching senility is ceasing work on a subject and beginning to talk about it. Perhaps that explains why, after many Years in which Part of my duties has been the training of college men in various branches of petroleum exploration geophysics, I have now begun to talk about it. In making an outline of what I believe ought to be discussed under the general heading of the title, I found it almost impossible to subdivide the ideas into an ordered set of discrete subjects. Rather, the pertinent remarks seemed to interlock almost everywhere. The consequence is that it will be necessary to start with the conclusions and then try to justify them by jumping back and forth. However, based on the types of men with whom I have had to deal, the subject naturally divides itself into two parts. In the first part, I should like to deal with the case of those undergraduates whose natural bent is toward the physical sciences and who may decide to enter the geophysical fold as a career. The other part will deal with those many men, geologists and engineers for the most part, who have drifted into exploration geophysics by one means or another, and whom it is necessary to train for geophysical work while they are occupied in their routine jobs. Here it may be in point to remark that most men in exploration geophysics at Present have been developed from precisely the latter group, and that the problem of training here is of great importance even though, in this paper, it will perforce occupy the secondary place. Training oF a Geophysicist The outstanding reason for the perplexing problem on the training of a geophysi-cist is that ideas differ on the answer to the question: "what is a geophysicistp" ln any of the scientific "specialties," like physics, for example, it is relatively simple to pigeonhole a man as being qualified to call himself a physicist. That appellation applied to an individual does not mean that he has mastered only the branches of intellectual endeavor usually associated under the broad name of "physics." we expect him also to have a more than mere acquaintance with mathematics and chemist~ and some understanding of most of the other sciences. But note this important point—we expect our physicist, whom we have chosen as an example, to be intelligently trained so that, if necessary, he can and will know how and where he can get the proper information on a subject in which he is not a specialist; he will know how to absorb that information and turn it to his uses. It seems to me that this is the outstanding characteristic of a man who can truly call himself a scientist: that he is a specialist in one of the broad branches of science in that he has enough training and discipline in the scientific approach so that, when called upon to do so, he can inteugently absorb knowledge from another bordering science (and all sciences not only border upon one another to some extent, but more often, overlap One another), and

Jan 1, 1946

By W. G. Matteson

IN 1915, the State of California passed a law of great scope and importance. This law has been in successful operation for., year and may be briefly described as an act "establishing and creating a department of. the State Mining Bureau for the protection of the natural resources of petroleum and gas from waste and destruction through improper operations in production; providing for the inspection of petroleum and gas wells; requiring all persons operating petroleum and gas wells to make certain reports" and providing the necessary officers and assessments-to carry out the provisions of the act. The statute provides for a separate department of the State Mining Bureau, under the general supervision of the State mineralogist, with a staff composed of a "state oil and gas supervisor" and four deputies. It rules that all petroleum and natural gas wells shall be drilled, operated or abandoned under the supervision of the State supervisor, who shall order such tests or remedial work as seems to him necessary to protect the interests of property owners and the general public. It also provides for a board of arbitration to consider orders given by the supervisor which are not acceptable to the well owner. Section 18 of the, act, which is the provision that is directly related to, this paper, requires "the owner of any well referred to in this act to keep a careful and accurate log of the drilling of such well;" and further requires that this log shall show the character and depth of the formations passed through or encountered in the drilling, particularly the location and depth of the water-bearing strata; the character of the water encountered (so far as ascertained); whether the water was shut off, and, if so, at what point; that it shall show completely the amounts, kinds and size of casing used; the depth at which oil-bearing strata are encountered; the depth and character of the strata, and whether all water was successfully and permanently shut off so as to prevent percolation or penetration into the oil-bearing strata. -

Jan 2, 1917

By Carl J. McHargue

Rods of 99.99 + pct Al which had initial orientatzons of <001>, <118>, <115>, <111>, and random were swaged at room temperature. Changes in orientation as a function of deformation were studied on axis distribution charts. The <001> orientation appeared to be relatively stable due to the inhomogeneity of the deformation process. near the <100> zone were quickly reoriented towards <001>. Orientations on the <110> zone between <118> and <115> appeared to be stable to reductions of about 50 pct, then were reoriented toward <001>. At very high reductzotzs. movement away from the <111> orientation was observed. the requirement that a circular cross section be maintained. In addition to these mechanical factors, there are grain-boundary effects in poly crystalline materials which are not yet understood. Hartmann and Macherauch conclude, for example, that multiple slip occurs for all orientations in fine-grained aluminum and copper and that the choice of operative slip systems has no simple relationship to orientation.? Many investigators have attempted to avoid problems of interpretation caused by an initial texture by treating the starting material to obtain as ran- IT has been generally accepted that the deformation texture obtained at high reductions, e.g. 90 pct, will not be noticeably affected by a prior texture; whereas, that obtained at reductions of 40 to 50 pct may be significantly influenced by the specimen history.&apos; Some recent studies, however, have been interpreted as showing that an initial texture strongly influenced the deformation textures in rods at reductions greater than 90 pct. Freda and Cullity suggested that the <001> texture in a heavily cold-worked copper rod was due to a <001> texture in the original casting. McHargue, Jetter? and Ogle concluded that the <001> component in an aluminum rod extruded at liquid nitrogen temperature was remanent from a <001> texture in the cast extrusion billet.3 Most of the published work on the effect of initial orientation on deformation textures has been for cold-rolled or compressed single crystals,4-6 The primary interest in these studies was to examine various orientations with regard to their stability under flow? thus determining the possibility of such orientations being stable end orientations. There appears to be no published studies on the effect of initial orientation on fiber textures in polycrystalline specimens. A recent study, however, is concerned with the reorientation of individual grains in polycrystalline specimens pulled in tension.? Although the reorientation of single crystals loaded in simple tension is well known, the movements in the forming of wires and rods would be expected to be different due to the circular array of radial-compressive stresses exerted by the die walls or the rolls, and to

Jan 1, 1962

By C. M. Means

CONSIDERING the hazard involved in mining operations, statistics show, that a very small percentage of accidents is chargeable to electricity. These accidents do represent quite a large percentage of those that are preventable and they are the direct result of the introduction, for purely economical reasons, of a dangerous element. The introduction of electricity in mines should decrease the hazard, and in no case should electricity be applied to the mechanical operation of equipment if by so doing the dangers incidental to mining are increased. The greater number of accidents are the result of persons coming in contact with exposed conductors at potentials varying from 250 to 500 volts direct current. The use of alternating current at higher potentials than these is quite common in large mines, but it is very rare that an accident happens from this source. This is explained by the fact that where these high voltages are warranted, proper precautions are taken, and the installations are directed by those who fully appreciate the dangers incidental to the work. Direct current is in much more general use than alternating current because of its adaptability to haulage locomotives and the low cost of installation in small operations. We are, however, coming to a more extended application of alternating current for the operation of mechanical devices used in connection with mining. Our underground direct-current wiring system is an evolution from the surface trolley and feeder systems. This is probably due to the fact that our earlier successful applications were electric locomotives, which required the use of a trolley wire. The trolley current has been almost banished from industrial establishments on the surface because of the hazard involved, yet we use it indiscriminately underground, where the dangers from accidental contact or fire are infinitely greater. This does not mean that the underground trolley systems should be eliminated, but it does imply the proper safeguarding of such equipment as is necessarily a part of the trolley systems.

Jan 4, 1914

By M. Gensamer

IN applied mechanics and in metallurgy the transition from elastic to inelastic action is a matter of considerable interest and importance. Often the first inelastic deformation is apparently quite homogeneous; that is, uniformly distributed throughout the specimen. Sometimes this deformation is heterogeneous; that is, localized; inelastic deformation proceeds to some definite amount in restricted regions before adjacent regions of the specimen are inclastically deformed. In such cases the deformation does not become homogeneous until the whole specimen has been deformed the amount corresponding to that for each localized deformation. If the test is stopped before uniform extension sets in, the heterogeneous character of the deformation is apparent on the surface of the specimen through characteristic markings, which have been called "Lüders"&apos; lines, "Hartmann&apos;s" lines, the "Piobert effect," or simply "flow figures." These markings are the source of considerable trouble in fabricating operations, particularly in the deep drawing of steel sheet. In many cases where the transition is of this nature, the stress developed at the upper limit of the elastic range is greater than the stress during the period of heterogeneous deformation, giving rise to the familiar "drop of the beam" effect in testing. The amount of the yield-point elongation, as well as the value of the stress at the lower yield point (the value to which the stress drops when yielding begins), are functions of the tempera-ture and the testing speed. Lower temperatures and faster rates of testing increase both the yield-point elongation and the yield-point stress. These matters have been ably discussed in a recent paper by Winlock and Leiter1 though, as brought out by the discussion of that paper, the phenomena are but little understood. The purpose of the present paper is to clarify the problem through the application of a simple principle, and to show that, through the application of this principle, a number of phenomena in the plastic deformation of metals become more read-ily understood.

Jan 1, 1938

By James Kemp

PostScript to a paper presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 129 to 154. The writer looked over the quarry with care in the search for fossils, having in mind shells or corals of fairly large size. In the brilliant summer sunshine, none were observed on the glaring white ledges. The impression was gained that none were present and the statement to this effect was made in the edition of this paper published in the Bulletin&apos; of the Institute for February, 1915, p. 136. On closer examination in the laboratory it has been discovered that the limestone itself is made up of minute organisms, which are clearly revealed by microscopic examination of thin sections. The principal component of the rock is a small foraminifer, 0.1 to 0.3 in. (2.5 to 7 mm.), of the genus Orbitoides, presumably an Oligocenic form. Figs. 1 and 2. illustrate it. The accompanying description has been kindly summarized by Marjorie O&apos;Connell, M. A., Curator in Paleontology in Columbia University, who first detected the evidences of organisms in the rock. Orbitoides kempi O&apos;CONNELL N. SP.1 The foraminiferan which makes up the Seboruco limestone is an Orbitoides of a Species new to North America. The only Orbitoides heretofore described from this country is 0. mantelli from the lower Oligocenic of the Gulf States. This form from Cuba, then, so different in all of its characteristics from the 0. mantelli, is of great interest as perhaps forming a basis of correlation over wide areas. The most closely related Species is 0. dispansa Sowerby, which occurs in the Nummulite limestone of the Eocenic of the Bavarian . Alps, in the Priabona beds of the lower Oligocenic of Massano, and elsewhere in Italy, as described by Gümbel.2 The age of the limestone in Cuba would thus Seem to be of upper Eocenic or lower Oligocenic age, probably the latter. The fossil has the form of a sphere Surrounded by a wavy rim of horizontal extent, the whole resembling two flat-brimmed, round-crowned hats placed base to base. The total extent of the Shell ranges up to 7+ mm., while the thickness of the central sphere is 2.5 mm. in one of the largest individuals. Like all of the other Species of Orbitoides, this form begins with a Single layer of chambers which multiply in one plane and assume a circular outline; but it is in the subsequent growth that the distinguishing specific characters appear, for the chambers at the central portion of the shell increase more rapidly than do those near the periphery and in consequence a Swelling is produced which finally gives the Spherical form which is so characteristic. The rim, on the other hand, shows little chamber-increase and remains thin. This is clearly Shown in the sections figured, where the central row of larger chambers forms the equatorial zone. Radiating from this row, in section, there appear, a number of solid cones alternating with broad reticulated ones. The solid cones mark the more dense structure forming the walls surrounding the reticulated or chambered cones. These appear upon the Surface as distinct pits, whereas the solid part appears as raised walls.

Jan 7, 1915

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors&apos; reply)— -Williams&apos; arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams&apos; model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams&apos; model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams&apos; strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams&apos; model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By Theodore B. Comstock

Prior to 1885, the College of Engineering in the State University was under the care of such professors and instructors as were required for efficient work in the Schools of Mechanical Engineering, Civil Engineering and Architecture. The development of the coal and other important mineral resources of the commonwealth led gradually to a considerable demand for instruction in the branches more closely related to mining engineering, and a very creditable effort was made to meet this want by arranging special work in the field and in the laboratory for students of mining and metallurgy. This plan, while it gave much added labor to several already heavily taxed professors, caused such students to become something like undesirable excrescences upon the regular courses. But its partial success gave abundant proof of the real necessity for a complete course in Mining Engineering. The famous Braidwood disaster emphasized anew the importance of thorough training on the part of those to whom the responsible duties of mining must be confided. As is well known, a very excellent beginning was made some years ago by the Legislature in the matters of inspection and regulation by the enactment of a reasonably effective law, which was afterward much improved.* About the date of the last Acts, it was deemed wise to enlarge the facilities at the University arid to furnish adequate training for the increasing number of applicants. Accordingly, in August, 1885, the writer was requested to assume the duties of the professorship, it being the expressed desire of the Board of Trustees and the Regent of the University that a School of Mining Engineering should be founded which might eventually come to rank with the other engineering schools already flourishing here. It is the main object of this paper to state plainly the steps thus

Jan 1, 1887

By B. N. Whittaker, C. J. Bonsall

The paper gives an account of the factors influencing the stability of coal mining tunnels and goes on to examine various bases of support and lining design of such tunnels in relation to geological and mining conditions. The different types of coal mining tunnels are compared and comments made regarding the factors influencing their choice and basic design features. Foremost amongst design considerations is the design method and special thought has been given to the validity of different formulae as related particularly to UK Carboniferous geological conditions. Emphasis is placed on the role of the stress field in relation to tunnel stability. Shape of mining tunnel has been investigated and conclusions drawn regarding the merits of different commonly excavated geometries from a stability point of view. Detailed design aspects pertaining to determination of tunnel lining strength and resulting stability are critically examined and current design methods are compared. Data from UK mining tunnels are included as the basis for comparison of these design methods.

Jan 1, 1983

By C. L. Dake

Iron is much more soluble in the ferrous than in the ferric form. Where, as in the case of the ferrous silicates and. the sulphides, the iron is already in the ferrous form, it may go at once into solution and be removed, upon the breaking down of the parent rock. If in the ferric form, it must first be reduced; usually by the decay of organic matter, the demand of the decaying carbonaceous matter for oxygen being so great that the latter is abstracted from the ferric compounds and the iron is thereby reduced and rendered soluble. The iron may go into solution as the sulphate, or in the presence of excess CO2 as ferrous carbonate. It is probably soluble as salts of the organic acids.&apos; Recent work indicates that these are important in the formation of bog ores.2 There is considerable variety of opinion concerning the behavior of these organic compounds.3 The secretions about the roots of plants and trees also cause the solution and removal of iron and a consequent bleaching of the soil,4 While the matter is not yet well understood, we can probably say definitely that the so-called organic acids are a group of colloids which possess slightly acid properties, and the salts of which are partly soluble and partly insoluble.5 Their iron salts readily change from the ferrous to the ferric form, and their solubility is greatly modified by the presence of ammonia.

Jan 1, 1916

CYRIL STANLEY SMITH, Chairman CARL E. SWARTZ, Past-Chairman ARTHUR PHILLIPS, Vice-Chairman E. E. SCHUMACHER, Vice-Chairman H. A. MALONEY, Treasurer FRANK. T. SISCO, Secretary 9 West 39th Street, New York, N. 1. Executive Committee 1944 1945 WILLIAM C. ELLIS C. S. BARRETT ALAN MORRIS T. A. WRIGHT KENT R. VAN HORN L. L. WYMAN

Jan 1, 1943

By John D. Gill

The purpose of this paper is to invite attention away from the obvious. direct monetary costs of oil-field overdevelopment (as distinguished from "social costs") to a consideration of the role played by the exercise of freedom to create even allegedly excessive1 plant facilities in contributing to the maintenance of equilibrium in the wholc economy and in promoting material progress. The obvious and most commonly discussed effect of overdevelopment of oil fields is illustrated by the allegation that already the excessive development of the East Texas field has cost upward of $162,000,000;2 in other words, the drilling of 12,500 wells more than the number estimated as the requirement for economical recovery of the reserve has unnecessarily raised the total cost of development that amount. Many other illustrations of so-called excessive development of oil pools could be presented. Some of them, like Cushing, Powell and Long Beach, might be drawn from the era antedating widespread discussion in the trade of such matters as optimum well spacing, reservoir energy, the conservation rate of depletion of reserves, etc. Numerous other cases can he found in the records of the current era, which began with the introduction of rationalized restriction of production. Besides East Texas, there may be mentioned Oklahoma City, Centralia and. more recently, the town-lot development of Bloomingdale, Michigan.

Jan 1, 1940

By John D. Gill

The purpose of this paper is to invite attention away from the obvious. direct monetary costs of oil-field overdevelopment (as distinguished from "social costs") to a consideration of the role played by the exercise of freedom to create even allegedly excessive1 plant facilities in contributing to the maintenance of equilibrium in the wholc economy and in promoting material progress. The obvious and most commonly discussed effect of overdevelopment of oil fields is illustrated by the allegation that already the excessive development of the East Texas field has cost upward of $162,000,000;2 in other words, the drilling of 12,500 wells more than the number estimated as the requirement for economical recovery of the reserve has unnecessarily raised the total cost of development that amount. Many other illustrations of so-called excessive development of oil pools could be presented. Some of them, like Cushing, Powell and Long Beach, might be drawn from the era antedating widespread discussion in the trade of such matters as optimum well spacing, reservoir energy, the conservation rate of depletion of reserves, etc. Numerous other cases can he found in the records of the current era, which began with the introduction of rationalized restriction of production. Besides East Texas, there may be mentioned Oklahoma City, Centralia and. more recently, the town-lot development of Bloomingdale, Michigan.

Jan 1, 1940

By R. H. Jacoby, M. J. Rzasa

Experimental equilibrium vaporization ratios were obtained for nitrogen, methane, carbon dioxide, ethane, and hydrogen sulfide in natural gas-condensate systems. Two different overall mixture compositions were investigated over the pressure range 500 to 4,000 psia at 100°, 150°, and 200 °F. Partial phase diagrams of the mixtures were obtained; one of these showed a critical point at 204°F and 3,875 psia. These and earlier data&apos; were compared with the Kellogg correlation&apos; at! 100°F and 1,000 psia. INTRODUCTION The authors&apos; have presented equilibrium vaporization ratios for nitrogen, methane, carbon dioxide, ethane, and hydrogen sulfide in complex mixtures, such as natural gas-crude oil and natural gas-absorber oil. Since mixtures of the natural gas-condensate type also occur widely in petroleum reservoirs and often contain the non-hydrocarbons mentioned, it would be useful to have appropriate K data for calculating equilibrium vaporization conditions. Roland, Smith, and Kave-ler&apos; obtained K&apos;s for methane and the light hydrocarbons in gas-condensate mixtures; and Poettmann and Katz3 obtained K&apos;s for carbon dioxide in a gas-condensate system. The data presented in this paper extend this coverage to include K&apos;s for nitrogen and hydrogen sulfide and phase diagrams for the experimental mixtures. EXPERIMENTAL WORK The equipment and experimental procedure was essentially as described previously, except for analysis of the vapor samples. The vapor sample bombs were filled at the pressure and temperature of the run. Immediately after sampling, a portion of this sample was flushed from the bomb into a 650 cc glass bulb, filling it to near atmospheric pressure. The sample in the glass bulb was then analyzed by the mass spectrometer. Some checks were made on this analytical procedure to find the accuracy of measurement of the C + content of the vapor samples. The modifications tried were complete fractionation of the vapor sample and the use of several liquids (depropanized condensate and retrograde liquid from several vapor samples) as calibrating materials for the mass spectrometer. The results obtained from these various checks differed by about 10 per cent relative and this is believed to be the order of accuracy of the vapor C+ concentrations.

Jan 1, 1953

By H. I. Aaronson, W. L. Winterbottom, G. M. Pound

On the basis of a statistical thermodynamic treatment of the data of smithz2 on the activity of carbon in austenite, a Darken and smith23 deduced that the interaction energy, wy, between carbon atoms occupying nearest-neighboring interstitial sites is repulsive. Aaronson, Domian, and pound 24 (ADP) have applied two different statistical thermodynamic analyses to the same data. One analysis, a composite of the treatments of Darken and Smith,23 Speiser and Spret-nak," and Kaufman, Radcliffe, and Cohen,26 primarily takes account of the positional entropic effects of wy in dilute solutions. The other, due to Lacher 27 and Fowler and Guggenheim," is also applicable to more concentrated solid solutions. The equations which both analyses produce for a,, can be rearranged so that, when In a,, is plotted against the appropriate function of the carbon content of the austenite, the plot will have a slope of unity when the correct value of wy is employed. Since no other constant need be simultaneously evaluated in order to make this determination, ascertaining the most probable value of wy from Smith&apos;s data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy&apos;s obtained from both analyses vary with temperature in a statistically significant manner. McLellan, Gerrard, Horowitz, and sprague 29 (MGHS), on the other hand, have recently made a new statistical thermodynamic study of a,, and have concluded from this study that wy is independent of temperature. The equation which they derived for a,, is: where 0 = ratio of the mole fraction of carbon atoms to that of iron atoms, z = number of sites from which occupancy is excluded by the presence of a carbon atom and the repulsive character of its interaction with nearest-neighboring carbon atoms (z = zb in Ref. 24), and x = a geometric parameter taking account of overlapping of the exclusion shells of nearby carbon atoms. z is 1 when wy = 0 and 13 when wy = Q. For a given value of z there is a definite value of X . In the absence of an equation connecting z and X, MGHS computed geometrically the value of x at several integral values of z; x increases from 0.47 to 8.67 as z is increased from 2 to 5. MGHS fitted Eq. [I] to the a,, data of Ellis, Davidson, and Bodsworth30 at 925° and 1050°C and to the data of smithz2 at 1000°C. Confining z to integral values in the range 4 to 6, and also somewhat restricting AG, the values of z, X, and AG were sought which would minimize the average root mean square percent deviation, D, of the calculated a,, values from those obtained experimentally. Finding that D was almost always smallest when z = 5, they concluded that z is independent of temperature. Since:23, 26 where R = gas constant and T = absolute temperature, and w,, was considered to be similarly invariant, this statement cannot be strictly true. The temperature range employed, however, was small and the interval between the values of z tested was sufficiently large so that the results could still be consistent with a constant The statistical treatment of the a,, data applied by MGHS is clearly quite approximate. Since more than three values of a,, are available at each temperature, z, and X, and AG have actually been over deter mined, rather than underdetermined as their treatment implies. In order to make more complete and exact use of the a,, data, we shall employ the Legendre Method of Least Squares, as described by Whittaker and Robinson. This technique permits conversion of the overdetermined system of equations produced by the substitution into Eq. [I] of the available pairs of a,, and 0 data at a given temperature into an even determined system. Solution of the latter system yields the most probable value of each of the three constants. This procedure will allow a statistically rigorous test to be made of the conclusion drawn by MGHS in respect of the temperature dependence of In order to obtain linear iiequations of conditions" from Eq. [I], the exact values of the three unknown constants are replaced by G/RT = =/RT + y, where z, i, and aG are estimated values of the constants. This allows the conditional equations to be written in the form:&apos;l where fi -f6, i, =/RT) = the right-hand side of Eq. [I] for a given pair of ayi and values. When applied to Eq. [I], these relationships become: The i equations of condition are reduced to three "normal equations" in the manner discussed by Whittaker and Robinson. The normal equations are then solved for a, ß, and y. Both of these operations are most conveniently performed by means of the computer technique of Winterbottom and Gjostein.32 This technique was used iteratively until the value of 0 (the most sensitive of the three correction factors) became 10.01. (Until they became small, a, 8, and y

Jan 1, 1969

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Jan 3, 1950