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By James C. M. Li

The Petch relation between the flow stress and the gain size is derived from a consideration of gain boundary sources of dislocations without the need of dislocation Pile-ups. Three mechanisms for inierpreting the yield stress: the gain boundary strength, the unpinning of Frank-Read source near a grain boundary, and the generation of dislocations from the grain boundary are compared and the condition of their equivalence is shown. The effect of the average angle of misfit of pain boundaries is found to be sma11 and so is that of the average angle of misfit of subboundaries having impurities. The effect of impurities on the ledge density in the grain boundary is treated thermodynamically and a relatwn is proposed for the variation of Petch slope with impurity activity. The effect of temperature on the Petch slope is interpreted as due to the change of ledge structure in the grain boundary. It is indicated that the effect of annealing temperature may be more important than that of the test temperature and therefore should be studied. The effect of plastic strain on the Petch analysis is deduced from a work-hardening equation in which the generation of dislocations has first-order kinetics and the annihilation of dislocations has second-order kinetics. It is concluded that the Petch slope will decrease with plustic strain if the rate of annihilation of dislocations is sufficiently large. Critical experiments which may shed light on the mechanism for the Petch relation are suggested. THE relation between the yield or flow stress, 0, and the grain size, l, was first proposed by all' and later studied more extensively by Petch and co-workers, who also proposed a similar relation for the fracture stress and deduced from these a grain-size effect of the ductile-brittle transition temperature. The microscopic mechanism used by all' and petch2 involves a pile-up of dislocations of like sign generated from a Frank-Read source. The yielding or flow takes place when the pile-up exerts sufficient stress at the grain boundary so that the plastic deformation can propagate from one grain to another. If the average strength of the grain boundary is ai and the average length of the pileup is lp, the Petch slope, k, is given by" where p is the shear modulus, b the Burgers vector, and v the Poisson ratio. This slope will be independent of the grain size if l/lp is a constant. This is possible, since, if the Frank-Reed source is situated near the grain boundary, lp = 1, and if it is situated in the middle of the grain, Ip = 1/2. cottrell,12 also using the pile-up mechanism, proposed that the stress concentration at the grain boundary will initiate Frank-Read sources near the grain boundary and in this manner a Lüders band can propagate from one grain to another. Assuming that the average distance between the Frank-Read sources and the grain boundary is 1, and the unpinning stress of the Frank-Read sources is op, Cottrell obtained the following Petch slope: This slope will be independent of the grain size if ls is independent of the same, which is not as obvious as the condition, Ip = I for Eq. [2]. In addition to this assumption, the direct relation between the Petch slope k and the unpinning stress, up, was recently questioned by Johnsonon grounds that it is inconsistent with the following observations: the independence of k with temperature and strain rate, and the small k in columbium, which, like iron, has a sharp yield point. As pointed out by ohnson," the most important objection both to the Hall-Petch mechanism, in which the strength of the grain boundary plays the role in yielding, and to the Cottrell mechanism, in which the unpinning of Frank-Read sources plays the role in yielding, is the lack of direct observation of the pile-ups. The dislocation structure in deformed iron has been examined recently in the electron microsope.'-' Dislocations appear to be generated from grain boundaries or other interfaces; they form clusters and tangles within the grain at very early stages of deformation, even in the Lüders band, if the deformation is slow or at normal and elevated temperatures. Although it is still too early to interpret bulk properties from thin-film observations, it does seem worthwhile to look for a mechanism for the Petch relation which does not require dislocation pileup. SUBBOUNDARY SOURCES In order to show that a consideration of grain boundary sources can lead to the same Petch relation as does the consideration of the strength of the grain boundary, we shall first discuss the case of a simple tilt boundary whose elastic properties have been studied in detail.17 The strength of a partially

Jan 1, 1963

By J. Jay Jacobsen

A dynamic regional coal development model is constructed for the Eastern Powder River Basin of Wyoming. Using this model, alternative development schedules from a recent environmental impact statement submitted to the Department of the Interior are simulated (Ref. 1). These alternatives include different mixes of export capacity, different coal conversion techniques within the region, as well as various levels of coal production. Exportation of 70 to 80 percent of an ultimate coal production of 180 million tons (163.3 x l09 kg) per year and the careful phasing of additional public services with population growth effectively reduce the social and environmental impacts of coal development. The alternative involving the addition of 43,000 megawatts of electrical generation capacity has very significant adverse social and environmental impacts on the region.

Jan 1, 1977

By A. A. Venghiattis

A rational approach to the selection of the appropriate perforator to use in each specific zone of an oil well is presented. The criteria presently in use for this choice bear little resemblance with actual down-hole condilions. These environmental conditions affect the elastic properties of rocks. One of these elastic properties, acoustic velocity, is suggested as the leading parameter to adopt for the choice of a perforator because, being currently measured in the natural location of the formation, it takes into account all of the effects of compaction, saturation, temperature, etc., which are overlooked in the laboratory. Equations and curves in relation with this suggestion are given to allow the prediction of the depth of perforation of bullets and shaped charges when an acoustic log has been run in the zone to be perforated. INTRODUCTION When an oil company has to decide on the perforator to choose for a completion job, I wonder if it is really understood that, to date, there is no rational way of selecting the right perforator on the basis of what it will do down-hole. This situation stems from the fact that the many varieties of existing perforators, bullets or shaped charges, are promoted on the basis of their performance in the laboratory, but very little is said on how this performance will be affected by subsurface conditions such as the combination of high overburden pressure and high temperature, for example. The purpose of this paper is to show the limitations of the existing ways of evaluating the performance of perforators, to show that performances obtained in laboratories cannot be extended to down-hole conditions because the elastic properties of rocks are affected by these conditions and, finally, to suggest and justify the use of the acoustic velocity of rocks, as the parameter to utilize for the anticipation of the performance of a perforator in true down-hole environment. EVALUATING THE PERFORMANCE OF A PERFORATOR It is natural, of course, to judge the performance of a perforator from the size of the hole it makes in a predetermined target. Considering that the ultimate target for an oilwell perforator is the oil-bearing formation preceded in most cases by a layer of cement and by the wall of a steel casing, the difficulties begin with the choice of an adequate experimental target material. For obvious reasons of convenience, the first choice that came to the mind of perforator designers was mild steel. This is a reasonable choice for the comparison of two perforators in first approximation. Mild steel is commercially available in a rather consistent state and quality, and is comparatively inexpensive. The trouble with mild steel is that it represents a yardstick very much contracted; minute variations in depth of penetration or hole diameter and shape may be significant though difficult to measure. The penetration of projectiles in steel being a function of the Brinell hardness of the steel (Gabeaud, O'Neill, Grun-wood, Poboril, et al), it is often difficult to decide whether to attribute a small difference in penetration to a variation on the target hardness or to an actual variation on the efficiency of the projectile. Another target material which has been widely used for testing the efficiency of bullets or shaped charges in an effort to represent a formation—a mineral target as opposed to an all-steel target—is cement cast in steel containers. This type of target, although offering a larger scale for measuring penetrations, proved so unreliable because of its poor repeatability that it had to be abandoned by most designers. The drawbacks of these target materials, and particularly their complete lack of similarity with an oil-bearing formation, became so evident that a more realistic target arrangement was sought until a tacit agreement was reached between customers and designers of oilwell perforators on a testing target of the type shown on Fig. 1. This became almost a necessity about seven years ago because of the introduction of a new parameter in the evaluation of the efficiency of a perforator, the well flow index (WFI). The WFI is the ratio (under predetermined and constant conditions of ambiance, pressure and temperature) of the permeability to a ceitain grade of kerosene of the target core (usually Berea sandstone) after verforation. to its vermeabilitv before perforation. The value of this index ;or the present state if the perforation technique varies from 0 to 2.5, the good perforators presently available rating somewhere around 2.0 and the poor ones around 0.8, There is no doubt that, to date, the WFI type of test is by far the most significant one for comparing perforators. It is obvious that a demonstration of a perforator

An educated man is distinguished neither by his clothes nor by his knowledge; he is remarkable not for the things he says, but for the way he says them. You cannot even stand with him under an archway in the rain without finding him out. He may talk only of the weather. His words and his phrases alike my be simple. What distinguishes him is the arrangement of his words; however desultory his talk, it will be methodical; he has habituated himself to foreseeing the part to be played by each word he uses and the place to be taken by each sentence he utters. On the other hand, the uneducated man, though shrewd and well-informed, will relate facts and events as they recur to him, generally in disorder; in his effort to recollect and in his attempt to rectify forgetfulness he will pause irregularly, filling the intervals with meaningless phrases, such as "and then", "and so", or "said he to me", "said I to him"; and even the continuous parts of his story will be told confusedly-because he has not learned the proper use of words.* My own experience as an editor of technical manuscripts has taught me that the misuse of 'that' and 'which' is a fruitful cause of obscurity and confusion. The relative pronouns have distinct functions, and no writer can express himself clearly until he has learned to discriminate between these functions. For example : The engineers who refused to submit were discharged. The engineers, who refused to submit, were discharged. The engineers that refused to submit were discharged.

Jan 1, 1931

By D. L. Everhart

The search for new deposits raises two important questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? A review of the wide geological variety of recent uranium discoveries tells how these questions are being answered. SOONER or later intelligent exploration for uranium leads to these questions: Where did the metallic ions that formed the orebodies come from? What processes and geologic factors were involved in ore replacement? These matters, of course, make a big difference in how best to look for orebodies. Before these questions are discussed it might be well to point out other factors bearing on the subject. The whole business of uranium exploration is only a little over ten years old, participation by the public is only about six years old, and real interest and activity by more than a few large mining companies has arisen only in the past two or three years. Throughout this short period, uranium exploration has been affected by the unique influences of necessary security measures and by division of the overall job into individual projects by a large number of specialists in diverse fields. This has meant that a normal interchange of information on the nature of uranium deposits has really only just begun. Compared to the vast amount of published studies on iron, copper, lead, zinc, and gold deposits over the past 50 to 75 years, current knowledge of uranium deposits is in its infancy and much of the pertinent information is still scattered about in a number of unpublished sources. The volume of reports on all phases of uranium exploration is now beginning to mount at a remarkable rate, and geologists with widely varying specialized backgrounds in uranium geology are engaging in spirited debates over the origin of uranium and the relative importance of geologic controls of various deposits. One of the most interesting features of known uranium deposits of the world is the wide variation, see Table I, in character and geologic environment. It should be noted that many types became prominent during 1953. The davidite-bearing veins of Radium Hill, South Australia, are almost unique, although the same mineral occurs in a different kind of deposit in Mozambique. Recent studies indicate that brannerite disseminated in the granite near Cracker's Well, South Australia, may soon constitute uranium ore. Basalt has been added to the list of favorable host rocks in the Northern Territory of Australia. Basalt is also the host of the pitchblende veins of the Martin Lake deposit, Beaverlodge district, Saskatchewan. The truly remarkable rich and extensive Steen deposit near Moab, Utah, is of the uraninite-vanadium oxide type. Secondary hydrous uranium arsenates and phosphates constitute the uranium minerals in the disseminated deposits of the Wind River Basin, Wyo., a new district discovered in the summer of 1953. Uranium minerals in shales adjacent to fractures were newly reported in New Mexico and several other parts of the world during the year. The well-known important uraninite dissemination in the Rand conglomerates of South Africa has a counterpart, as discovered in the summer of 1953, in the Mississagi quartzite and conglomerate of the Blind River district, Ontario. Gunnar deposit of the Lake Athabaska district, Saskatchewan, consists of uraninite in both granite and sedimentary gneiss beneath a granite cap, and large new orebody of the Eldorado Co. in the same general area follows a preferred stratigraphic horizon in schists. Uranium is, generally speaking, a very soluble and ubiquitous element. It occurs in at least two valency states and for this reason is not easily tied down in natural solutions. As Gruner' has pointed out, it is probable that uranium starts in the hexava-lent state in nearly all solutions instrumental in its transfer. It is believed that under oxidizing conditions the uranium moves in solution as the uranyl ion, UO. In solutions ranging in pH from 1 to 5, the uranyl ion is most commonly in association with

Jan 1, 1955

By Francis Peabody

THIS paper will not be a technical paper, because, although I have been in. the business of mining and selling coal for 30 odd years, I am neither a mining engineer nor a practical miner. If I digress from time to time from my thesis, I must be forgiven by the expert engineers and highly technical gentlemen for whose proceedings this article is written. Waste of the wonderful store of power that the Creator placed at our disposal appears to have been the theory and the basis of our methods of extracting this power-waste from the time the coal is mined to the time it is consumed. Let us consider the prime causes of this wastage which has been the heritage of the coal mining industry. In the early days-about 150 years after "Stone Cole" was discovered in Illinois by Joliet and Marquette, and Father Hennepin noted a, "sole" mine on his map-the mode of mining prevalent among farmer land-owners, on whose property coal was discovered near the surface or outcropping on the hillsides, was to enter the seam by a shallow shaft or drift into the hillside and remove the coal by wedging it down until a large room was left. The roof without support would fall and our primitive coal operator would then sink another shaft or drive another drift. In these early operations only the large lumps were taken and all small pieces and screenings were left to be covered by the fall of the roof-in fact this condition prevailed in Illinois up to about 1885. Gradually the method of mining changed from the open chamber, to a single entry with rooms turned to the right and left. Later, as the demand for coal increased and the necessity for larger mines became evident, the "room and pillar" system grew to be regular practice.

Jan 5, 1917

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's data on the bases of these analyses was an elementary problem in least-squares statistics. ADP demonstrated that the wy'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:'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

By A. H. Geisler

INTRODUCTION THE correlation of property changes during precipitation with structure has progressed, sometimes rapidly but other times more slowly, since the fundamental discovery of Merica, Waltenberg and Scott.1 The predominent factor that hampered the progress has been limitations imposed by the various detection methods. Refinements in X ray diffraction techniques and in metallographic methods, which have been extended by the electron microscope, have contributed new information within the last few years. These permit an extension of the theory as proposed by Mehl and fetter in 1940.2 Now that a suffcient number of alloys has been investigated to establish a general mechanism of the precipitation process, a correlation of the facts into a generally applicable theory of age-hardening is both warranted and desirable. 'I he purpose of the paper is to provide an orderly correlation of the phenomenological facts of precipitation hardening. Speculation on mechanism of hardening will be confined to that consistent with existing theories of hardening. Age-hardening accompanies the formation of a new structure, the precipitate, as provided by an alloy system in which solid solubility decreases with decreasing temperature. Upon this premise alone all such systems would be expected to include age-hardenable alloys. Alas, this is not always the case. Few attempts have been made to explain the variable degree of age-hardening among different alloys or to explain the influence of small alloying additions upon the hardening. Dispersion hardening as originally postulated3 is not adequate.* Coherency hardening-the term that will be used to distinguish the properties of a two-phase mixture in the unique and unstable transition state at which the phases are strained into precise atomic registry (continuity or coherency) in planes

Jan 1, 1948

By Thomas R. Cunningham, A. B. Kinzel

Silicon, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have developed procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, arid the term "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.' In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve and further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treatment, he does not mention the existence of carbon in the alloy; nevertheless, he reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1940

By A. B. Kinzel, Thomas R. Cunningham

Silicon, unfortunately, is not in the same category as some other metals with respect to the absolute value of the highest purity material prepared. Tucker, in England, and Becket, in this country have developed procedures for the purification of silicon, and Becket's process has made industrially available silicon of a purity of 99.8 per cent or better. However, even the term "silicon metal" may be a paradox to some people, although not more so than the term "amorphous" as applied to silicon. These terms come from commerce, and "metal" is used to distinguish industrially high-purity silicon from ferrosilicon, silicon-aluminum, and other high-silicon alloys. Alloys of iron and silicon with 95 per cent Si or less are known as ferrosilicon, with a designation of silicon content where necessary, arid the term "silicon metal" is invariably applied to the grades containing 96 per cent Si and higher. The Becket method of purification was referred to in a monograph on the Alloys of Iron and Silicon, and the Tucker procedure was described in some detail in that publication.' In order to get silicon of still higher purity, a sample, prepared by the Becket method, analyzing 99.84 per cent Si, 0.020 Fe, 0.016 Al, 0.005 Ca, 0.025 C, 0.033 per cent 02, 0.006 H2, 0.006 N2, and 0.001 per cent Mn, was crushed to pass a 100-mesh sieve and further purified by a modification of Tucker's procedure. This modification differs from Tucker's method in that after treatment the 100-mesh alloy was centrifuged to remove the last traces of acid. Our directly determined analysis of this purified sample shows: Si, 99.952 per cent; Fe, 0.009; Al, 0.012; Ca, 0.003; C, 0.006; or 99.982 per cent. Silicon by difference equals 99.97 per cent. The variation between silicon by difference and silicon as directly determined is important. Although Tucker mentions the amount of insoluble matter in commercial silicon both before and after his treatment, he does not mention the existence of carbon in the alloy; nevertheless, he reports silicon by difference. Any final figure as to purity obviously results from agreement between direct determination and

Jan 1, 1940

In 1820, the Board of Public Works was considering some improvements to the canal, in order to reduce the cost of transportation, and in its annual report for that year gives a description of the method of loading the coal from the pit to the boat, and also from the boat to the dealer's yard, which is illuminating in showing how coal of this type should not be handled. It follows:- "It will be seen by the estimates, that the improving the present canal, forming a canal of large dimensions, from the head of the present lower canal to Sabbot Island; erecting locks of large capacity, and making a communication with the river, so as to completely accommodate the coal trade, (except it should hereafter be found necessary to make another communication with the river,) will not cost more than 126,000 dollars. But as there is some doubt whether the streams that may be received into the canal between Sabbot Island and the upper arch, will at all times be competent to supply the locks on that portion, we will extend our calculation to a point nearly half a mile above Pleasants' Island; where, by erecting a dam, any desired quantity may be thrown into the canal. This extension of the canal with one lock, and the dam across the river, is estimated at 34,000 dollars, making in the whole a little over 160,000 dollars. There will then remain a surplus of 40,000 dollars after completing the works to the point last mentioned. "In order to discover what effect the improvement of this first section will have on the tolls, it will be necessary to take a view of the present state of the coal trade, and endeavor to ascertain what change will result from the increased facility of transportation. "That part of the business which is carried on by water, is conducted nearly in this way. When the coal is drawn out of the mines, it is thrown in a heap near the mouth of the mine, or shaft; it is then loaded into carts, and carried to the river bank, where, in some instances, it is discharged from the cart at the brow of the bank, and runs down to the beach near the water's edge; then shovelled into wheel-barrows, and wheeled aboard of the boat, and discharged from the barrows by upsetting. In other instances, the carts are driven on to a kind of scaffold, furnished with a wide spout or director at the edge; by which the coal is conveyed immediately into the boats. These boats are the common James river poplar batteaux, and require three men to each. The up-stream navigation being laborious, the boats are built of light materials, and continue fit for service but a short time, (say) from two to three years; their cost, when new, from fifty to one hundred dollars. "When the river is tolerably flush of water, one of these boats will carry about two hundred bushels; but in low water their load is sometimes diminished to one hundred, and even as low as eighty bushels. They pay for passing the canals and locks to the Basin, one dollar per load; so that when full loads are taken, it will amount to half a

Jan 1, 1942

By L. V. Gregor, C. F. Aliotta, P. Balk

The structure of silicon surfaces, thermally oxi&zed in dry oxygen and in steam, was studied using the electron microscope. It was found that the structure on the original (etched) surface is retained at the outer surface of the oxide, whereas the oxide-silicon interface is smoothed out considerably. This supports the idea that, both in oxygen and in steam, the oxidation reaction occurs at the oxide-silicon interface. Mechanical damage of the original silicon surface affects the rate of oxidation. It also changes the chemical properties of the oxide, as shown by the enhanced rate of etching in buffered HF at the locations of damage. However, the oxide at the originally damaged surfaces still exhibits a high electrical breakdown strength. Exposure of thermal oxides to P205 or BzOs vapor, which will yieldphospho- or borosilicate layers, results in complete annihilation of all fine structure on the surface. Reaction of silicon with C02 gives a surface film which probably does not consist of pure SiO,. THERMAL oxidation of silicon yields uniform and strongly adhering oxide films which are normally amorphous and continuous. Contamination and surface imperfections have been reported to cause local crystallization and the formation of pinholes."' The parabolic-rate law of film growth observed by several workers for the oxidation both in steam and in dry oxygen at higher temperatures suggests that diffusion of one or more reactants through the oxide is the rate-deter mining step. One of the dif-fusants is an oxygen species and oxide is continuously formed at the oxide-silicon interface. This was concluded for high-pressure steam oxidation by Ligenza and spitzer5 from an infrared-absorption study of the isotopic exchange of oxygen. Jorgensen arrived at the same conclusion for the oxidation in dry oxygen by measuring during oxidation the resistance change between silicon and a porous platinum marker electrode in the oxide. Recently, Pliskin and Gnall' reported similar conclusions concerning the growth mechanism from controlled etch studies using a phosphosilicate marker. The work communicated in the present paper was aimed at studying oxide growth on locally damaged silicon substrates and relating it to the chemical behavior and electrical breakdown properties of the films. Since etched and oxidized silicon surfaces normally appear to be very smooth when examined by optical microscopy except for some occasional pits, it was decided to use the electron microscope as a tool. In this way, the detection of surface roughness and damage on a scale comparable to or smaller than the thickness of the film is possible. Also, the microstructure of the original substrate surface constitutes a built-in marker which represents a minimum of perturbation to the growing oxide layer, and no foreign material is introduced. Thus information on surface reactions and additional evidence on the location of oxide formation in steam and in oxygen could be obtained. EXPERIMENTAL Electron micrographs7 were obtained using a Philips EM100 electron microscope. Collodion surface replication was used since this is a nondestructive technique and thus permits replicating the same surface at different stages of processing. In order to establish the effect of different treatments it was found essential to make successive observations of the same area by using a reference point. Reference points were conveniently provided by scribing a small v mark on the original surface with a silicon carbide tip. This procedure yields damaged and damage-free areas near the reference point. Upon replication, the samples were thoroughly cleaned before subjecting them to the next process step. Mechanically lapped silicon wafers (Dow-Corning, 100 ohm-cm p-type, cut perpendicular to the (111) direction) were chemically polished in a rotating beaker with a mixture of 1 part HF (48 pct), 2 parts glacial acetic acid, and 3 parts HNO3 (70 pct) by volume. This procedure yields a smooth surface with a faint "orange peel'' structure due to a "ripple" less than 20002i deep. Oxidation in steam or oxygen was carried out in an Electroglas tube furnace. Steam oxidations were always preceded and followed by a brief exposure to oxygen at the same temperattre. The thicknesses of the oxide films under 3000A were determined with a Rudolph Model 436-2003 ellipsometer,' whereas those over 3000A were measured using the VAMFO technique. In the present study, a solution of 300 g of N&F in 25 ml HF (48 pct) and 450 ml water was used to detect areas of increased chemical reactivity in the

Jan 1, 1965

By Alfred R. Powell

FOR the purposes of this discussion, the direct gasification of coal means the of hydrogen and carbon monoxide by the well-known water-gas reaction. Chemicals or other synthetic products may be made from these constituents of the gas and under such circumstances the gas is called synthesis gas. Or, if the same gas is used as a fuel, it is called blue gas or water gas. This type of gas has usually been made from coke, especially in this country, and has been used both for fuel purposes and for manufacture of chemicals. Recently, natural gas has gained the ascendancy as a source of synthesis gas for manufacture of chemicals because of its relative cheapness. As natural gas becomes less readily available and more expensive, coal will take its place as a raw material for the preparation of synthesis gas. This substitution will probably take the form of direct gasification of the coal rather than the present two-step procedure of carbonization of the coal followed by gasification of the coke. The chief reason for this probability is the intensive research now being carried on by several organizations to develop successful and economical processes for the direct gasification of coal, which is a considerably cheaper fuel than coke. In the following pages an attempt has been made to predict the chemicals that will result from this future production of synthesis gas by the direct gasification of coal. CHEMICAL REACTIONS OF SYNTHESIS GAS Given the proper conditions, there are many chemical reactions leading to production of useful products that can be carried out with this mixture of hydrogen and carbon monoxide. These many reactions may be grouped into three classes: (1) interaction of hydrogen and carbon monoxide, possibly with addition of other reactants; (2) reaction of hydrogen with various substances; (3) reaction of carbon monoxide with various substances. Thus sometimes hydrogen and carbon monoxide are utilized together in the same chemical reaction while in other instances only the hydrogen or only the carbon monoxide is required as a reactant. Fortunately, practical methods are available for securing either hydrogen or carbon monoxide from synthesis gas, some of which are also applicable for changing the ratio of these two constituents in the gas when that is desirable.

Jan 1, 1953

By David P. Hale

THE Cartersville barite district is near Cartersville, Ga., in the southeastern part of Bartow County, about 43 miles northeast of Atlanta. The area over which active mining is being done extends about six miles in a northeasterly direction and is about three miles wide. Barite production in Georgia began about 1907,1but the existence of the mineral was known much earlier. At present four companies are operating washing plants and three other plants are operating on leases from those companies. The chief impurities in the ores are silica and iron oxide. The silica is easily washed and jigged out and gives little trouble. Any gravity separation between the iron and the barite is generally poor, owing to the slight difference in specific gravity. Two operators have turned to magnetic separation as the solution to the problem and have made remarkable improvements in the finished product. By very close sizing prior to jigging, the separation between iron and barite has been greatly improved. In some localities manganese occasionally appears as an impurity, but is fairly easy to eliminate by gravity methods. A considerable percentage of iron and silica is eliminated by being broken free in crushing. Until methods for the recovery of fine ore were introduced a minimum of crushing was done, but modern methods allow more than formerly. The depression years brought about the need for increased recovery of ore handled on the part of the producers and a demand for a higher grade of product on the part of the buyers. Improvements in milling and mining practice have had a far greater effect, however, than merely the production of a better grade of ore with greater recovery. They have opened for mining large areas that a few years ago were considered noncommercial deposits because of their inaccessibility and their high iron content. It is no exaggeration to say that the new methods have more than doubled present known reserves of barite ore of economic value.

Jan 1, 1938

By A. D. Bryant

APPROXIMATELY 2 1/2 million tons of silica sand and ground silica with a value of $7.25 million is produced annually from the Ottawa, Illinois, district. These silica products come from the well known St. Peter sandstone formation which covers part of the Mississippi Basin extending from St. Paul on the north to the central part of Arkansas on the south and from Muncie, Ind., on the east to Kansas City on the west. Practically the whole state of Illinois is underlain by this formation except where removed by erosion. Sand produced from the St. Peter sandstone in the Ottawa district is noted for its purity, uniformity, and quality. In addition to various screened grades for industry about 10 pct of the total production of the Ottawa district is ground into silica flour for use in glass, abrasives, enamel, porcelain, tile, for foundry and filter sand, and other uses.

Jan 3, 1953

By R. E. Cook

This work presents the development and application of equations of the form developed by Martin1 to describe gravity segregation performance during natural depletion. One-dimensional depletion analyses are applied to several hypothetical reservoirs. Considerable attention is given to the changes in saturation distribution in the dip direction resulting from depletion at various rates. Vertical gas saturation distribution within a sand having vertical permeability is studied to illustrate conditions which provide For low gus-oil ratio production from wells selectively completed away from sand tops, as observed from well performance. Results of performance calculations are shown graphically and illustrate the rate sensitivity of the gravity segregation mechanism and the influence of reservoir geometry and withdrawal distribution. It is shown that for sufficiently high depletion rates gas saturation distribution in the dip direction is characterized by the formation of two discontinuities, or saturation "fronts"; the updip front being the gas-oil contact of the secondary gas cap and the downdip front occurring at a position dependent upon the reservoir depletion rate, withdrawal distribution and reservoir geometry. The gas saturation in the region between fronts is shown to continually increase with time, while that downdip from the lower front remains very low and relatively stable. The effect of increased depletion rate is to reduce the region of stable gas saturation and thus enlarge the portion of the reservoir producing with continually increasing gas saturation. Special attention is given to the performance of reservoirs having sufficient vertical permeability to permit liberated gas to segregate vertically within the sand section before proceeding in the updip direction. It is shown that reservoirs of this type are far less sensitive to depletion rate due to the mechanical control of producing gas-oil ratios afforded by selective well completions away from sand tops. It is shown that gravity segregation performance is adversely af- fected by decreasing reservoir cross-section area in the updip direction. It is also shown that down-dip withdrawal concentrations can restrict gas segregation rates in the dip direction. INTRODUCTION The natural depletion performance of several large producing reservoirs in Western Venezuela has unmistakably shown the significant role that gravity forces play in governing the gas-oil ratio behavior of individual wells and the over - all pressure-production performance of the reservoirs. Analysis and prediction of the natural depletion performance of these reservoirs is of great importance in determining the economics of pressure maintenance operations. In 1957, a method for the analysis of pressure maintenance performance was presented by Martin1 which, in the original and more general form of the equations involved, provides a physically sound basis for the analysis of one-dimensional gravity segregation performance during natural depletion. The work reported herein is an application and extension of Martin's outstanding developments to a series of hypothetical reservoirs in an attempt to explain the general behavior of the gravity segregation mechanism and the influence of such parameters as depletion rate, reservoir geometry and withdrawal distribution. The study considers two types of flow: "distributed flow", where vertical permeability in the reservoir is zero and fluids flow only in the dip direction while uniformly distributed over the sand thickness; and "segregated flow", where vertical permeability is sufficient to permit gas to segregate against the sand top before proceeding updip. This latter type of flow has been recognized as an important mechanism active in the massive sand reservoirs of Western Venezuela. ANALYSIS OF ONE-DIMENSIONAL DISTRIBUTED FLOW SYSTEMS For an inclined reservoir having zero vertical permeability, the velocities of oil and gas flow at any point in the reservoir can be derived from Darcy's equations as

By Joe L. Ratigan

INTRODUCTION Rock mechanics engineers are seldom concerned with obtaining the tensile or fracture strength of brittle rock at low mean stresses. The reason for this is two fold. Firstly, the behavior of many excavations in brittle rock is controlled by the inherent discontinuities in the rock mass. Because of the jointing and faulting, tensile strength is usually taken to be negligible. The second reason that tensile strength is seldom obtained in the laboratory is that the technology of utilizing this strength measure in design is undeveloped. Despite the fact that tensile strength of brittle rock is often ignored, there are a number of applications in rock mechanics wherein the knowledge of tensile strength is of fundamental importance. The apparent tensile strength must be known in a hydraulic fracture experiment if the state of in situ stress is to be determined from the initiation of the hydraulically induced fracture. In certain underground situations, the apparent tensile strength of intact rock beams defined by jointing or bedding planes is important in determining required rock bolting. Numerous other situations require a knowledge of apparent tensile strength including such high technology uses of underground space as geothermal energy extraction and LPG storage. Three observations are invariably made when intact rock samples are taken into the laboratory and tested to determine tensile strength. (1) The apparent tensile strength depends on the sample size (the 1 arger the specimen, the lower the tensile strength)

Jan 1, 1982

By Luckie. Peter T., Deurbouck. A. W., Harold L. Lovell, E. R. Palowitch, James K. Kindig

PART 1: DENSE MEDIUM SEPARATION by E. R. PALOWITCH and A. W. DEURBROUK INTRODUCTION During 1974, 43.9% of the 603,406,000 tons (549,099,000 mt) of bituminous coal and lignite produced was cleaned mechanically, of which 82,280,000 tons (74,875,000 mt) was cleaned by dense medium processes.l The percentage of bituminous coal and lignite cleaned mechanically by dense medium processes increased from 7 to 31 % between 1938 and 1974. Dense medium separations include those coal preparation processes which clean raw coal by immersing it in a fluid having a density inter- mediate between clean coal and reject. As there is a general correlation between ash content and specific gravity, it is possible to achieve the required degree of removal of ash-forming impurities from a raw coal by regulating the specific gravity of the separating fluid. Dense medium processes offer the following advantages over other coal cleaning processes: 1) Ability to make sharp separations at any specific gravity within the range normally required even in the presence of high percentages of the feed in the range of 2 0.1 sp gr units. 2) Ability to maintain a separating gravity that can be controlled with ± 0.005 sp gr units.

Jan 1, 1979

By O. R. Wagner, R. O. Leach

Immiscible displacement tests were performed in a consolidated sandstone core over the interfacial tension range from less thdn 0.01 to 5 dynes/cm to better define how interfacial tension (IFTJ reduction can lead to increased oil recovery. Data obtained were displacement efficiency at breakthbrough vs IFT for both drainage and imbibition conditions. These tests simulate water flooding under oil-wet and water-wet conditions, respectively. Results of the study have shown that displacement efficiency under both oil-wet and water-wet conditions can be markedly improved by a sufficient reduction in IFT. In the particular porous media used and for the low pressure gradients employed, the IFT must be reduced to a value less than about 0.07 dynes/cm to achieve increased recovery at the time of breakthrough of the injected phase. Below 0.07 dynes /cm, further small reductions in IFT result in large increases in displacement efficiency. Observed increases in recovery were obtained at pressure gradients which are well below those which can exist in the interwell area of a reservoir under water flood. The effect of pressure gradient on recovery is discussed. INTRODUCTION A residual oil saturation remains in rock which has been water flooded because, under usual reservoir conditions, the driving force which can be generated is inadequate to expel oil trapped by capillary forces. Since these capillary forces can be reduced by reducing the IFT a frequently studied method of increasing oil recovery has been the use of surfactants to reduce the water-oil interfacial tension. Mungan l observed improved recovery in both water-wet and oil-wet systems at 1.1 dyne /cm IFT, finding that the amount of improvement was greater in oil-wet systems. Moore and Blum,2 working with visual flow cell micro-models, con- cluded that recovery cannot be improved in water-wet systems by injecting surfactant solutions. They calculated that, for a pressure gadient of 1 psi/ft in their model, the IFT must be reduced to 0.03 dynes/cm to release oil trapped under water-wet conditions. Berkeley et al.3 indicated that, at representative field flooding rates, the IFT must be reduced to 0.001 dyne/cm to improve recovery, Thus, there is a wide variation of opinion about the IFT levels needed to improve recovery under field conditions. These previous investigators all have used as their experimental method the addition of surfactants to the injected water. The use of surfactant solutions to reduce IFT creates two experimental problems: (1) the loss of surfactant through adsorption on reservoir rock can obscure the true IFT value which exists at the displacement front, and (2) at very low values of IFT emulsifica-tion of oil and water commonly occurs. It is difficult, therefore, to determine whether the increased recovery is caused by IFT reduction as such, or is instead caused by emulsification. Also the properties of the available surfactants limit the IFT range which can be studied. In the present study the purpose is to better define how interfacial tension reduction can lead to increased oil recovery. A matter of great interest is the amount of recovery improvement potentially achievable in this way. The study was made using very low pressure gradients which was well within the range achievable by water flooding in the interwell region of petroleum reservoirs. A unique experimental approach was chosen to avoid adsorption and emulsification problems, and to allow convenient control of IFT. The fluid phases used were the equilibrium vapor and liquid phases of the methane-n-pentane system. The interfacial tension level was varied by changing the equilibrium pressure of the methane-pentane system over the range from 1,200 psia to near the critical pressure (2,420 psia). All tests were performed at a controlled temperature of 100F. The IFT-vs-pressure relationship for the methane-pentane system was based on the data of Stegemeier and Hough,6 and on new data obtained in this study. With this experimental approach it has been possible to study displacement at lower values of IFT than have been previously investigated.

Jan 1, 1967

Although the Suggestions to Institute Authors, as revised and amplified over the years to meet changing conditions and experience, have had as their primary objective the guidance of the author who is preparing a paper for record in the TRANSACTIONS, there are in this current version many excellent suggestions for the preparation of any material for publication by the Institute In this connection it should be emphasized that in a sense, and to a degree determined by the editors, the Institute has in its journals "a place for everything," especially a place for the article of practical nature that is of immediate but not necessarily permanent interest Such articles may be referred by the Institute Technical Publications Committee to the editors or submitted directly to them , [Papers (TECHNICAL PUBLICATIONS and TECHNICAL NOTES) authorized for the TRANSACTIONS are, with the discussion, gathered together at the end of the calendar year and with a table of contents and index, bound, according to Branch classification, as volumes of the TRANSACTIONS

Jan 1, 1952