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By R. V. Colligan

[CONTENTS PACE Educating and Training Economic Geologists of the Future. By C. H. BEHRE, JR. (TP 2278, Min. Tech., Nov. 1948. Discussions by R. V. COLLIGAN and EVAN JUST) ....... I Mercury Industry in Italy. By EDWIN B. ECKEL. (TP 2292, Min. Tech., Jan. 1948. Discussion .............................. by C. N. SCHUETTE) 3 Chert in the Kingsport Formation at Mascot, Tennessee. By ARTHUR T. ALLEN. (TP 2299, ............... Min. Tech., Jan. 1948. Discussion by M. M. BUTLER) 5 Wall Rock Alteration at Butte, Montana. By RENO H. SALES and CHARLES MEYER. (TP 2400, Min. Tech., May 1948. Djscussions by C. D. HULIN, W. D. JOHNSTON, JR., and L. C. ................................... GRATON) 5] Educating and Training Economic Geologists of the Future R. V. COLLIGAN*-I can best illustrate my opinions by drafting another five year plan (Table 2). This plan is set up following the same stipulations outlined by Dr. Behre, namely: (I) the student is preparing himself for commercial work as a mining geologist; (2) he is attending an institution with a sufficiently broad curriculum (that is, engineering school and mining school as well as liberal arts college) to furnish the courses listed; and (3) he is not planning to continue his studies through to a doctor's degree before going into commercial work. A comparison of my study plan (Table 2) and that submitted by Dr. Behre (Table I) will at once point up the basic similarity, due to the obvious fact that there are so many essential courses which must be included in any outline of study. However, a more detailed analysis will show up certain differences, which, in fact, are only certain refinements on Dr. Behre's program. These I plan to discuss in order of their importance. The first and most important change is the addition of 12 hr of optional subjects, making a total of 24 hr of optional subjects as against a total of 12 hr under Dr. Behre's schedule. This of course entails the elimination of certain courses, which I shall discuss later. However, I wish to make it clear that I suggest eliminating these courses not because I feel that they are unnecessary, but rather because I feel the optional courses are more necessary to the complete education of the individual. I appreciate that Dr. Behre recognizes the importance of the cultural side of education, but I take issue with his thesis that the student will get it without credit and in his spare time. I do not think that the average college student, and certainly not the college freshman, is mature enough to know what he needs and where to get it in his spare time. I think it must be "spoon-fed"; he must be oriented through specific courses. University life (or should I say "college life") is too full of athletics, fraternity activities, dances, "bull sessions," and countless other enjoyable distractions, all of which contribute to the "full man." I fail to see how the average young American male can possibly sandwich in a necessary complement of "cultural activities" in his spare time. Since these latter activities do not fall within the pattern set by the "group," and show less promise of immediate return in enjoyment, or increased social status on the campus, they are bound to suffer in competition with the more popular, "group" activities. No doubt much of the criticism levelled against arts colleges, namely, that the cultural courses are useless, is well taken, for the culture

Jan 1, 1947

By Dean Goodermote, Carla S. Stone

I Introduction Coal fuels China. Roughly 70 percent of all commercial energy demand is supplied by domestic coal production and with the recent Chinese opening to the West, the Chinese Coal Industry may figure prominently in the export market as well. Because of the importance of China's coal industry to the future of China and the Pacific Rim energy balance, this paper reviews the industry and offers some cautious projections for its outlook. II Energy's Position in the Current Political and Economic Climate Traditionally, Chinese society has been dominated by the policies of its most important government leaders. Deng Xiaoping, Vice Chairman of the Communist Party is the current leader of China. Deng and his proteges are pragmatists. Although China's government structure is based on Marxist/Leninist tradition, Deng and his followers are promoting experiments with market economics and expanded relationships with Western Countries, which have encouraged foreign investment in China. Energy companies represent just one type of industry that is interested in helping the Chinese to develop their abundant natural resources. Although China's leadership is committed to a program of economic modernization, that program currently is experiencing what the Chinese government terms "readjustment". Readjustment cuts back in imports due to deficient foreign exchange and deemphasizes heavy industry, while it encourages agricultural and consumer goods output and, most imporant, energy production. Increased Chinese coal and oil production is essential both to fuel industry and, equally important, to provide foreign exchange. If sufficient energy production is not forthcoming, then economic growth will be severely retarded. China's 1979 per capita GNP of $260 is only slightly better than the weighted average achieved by low income countries of $230. (1) Delays in growth could lead to social unrest, threatening the position of the current leadership. Since there is no institutionalized mechanism for leadership succession and policy continuation, it is reasonable to assume that leadership changes could result in energy policy changes. III Energy Consumption Energy production is important to China's future economic health as highlighted by the World Bank. If China's economy grows rapidly, 5 percent to 6 percent during this decade, the Bank noted, a significant energy shortfall could occur as early as 1985. This state of affairs contrasts sharply with China's current position as a net hydrocarbon exporter. (2) To assure a healthy economic future, China's leadership is attempting to reduce its rate of increase in energy demand through conservation as well as to boost energy output. A massive conservation promotion program has been underway since 1979 and there is much room for improvement. China's industrial sector is only about half as energy efficient as is U.S. industry. (3) During the last two decades, each percent of increase in GNP has been accompanied by a 1.8 percent of increase in energy consumption. (4) This compares rather poorly with the United States where a less than one-to-one relationship exists. IV Energy Supply The short term prospects for oil production are uncertain. Production increases were rapid in the 1960's and early 1970's, averaging 20 percent annually, but most of this increase came from one field, Daquing. Now that Daquing's production has peaked and the offshore potential has yet to be developed, petroleum production has maintained a plateau of 2.1 million b/d, at least temporarily, of which approximately 15 percent is exported. (5) Output

Jan 1, 1982

By H. D. Attra

The effects of phase behavior on reservoir economics is a function of both fluid composition and flow properties of the reservoir rock. In some operations such as gas injection into volatile crude-oil resertoirs, the stock-tank recovery derived from vaporization of the reservoir oil by the displacing gas can approach the recovery derived from the displacement mechanism. In other cases of gas-cycling reservoirs, the dry injected gas can effectively vaporize a retrograde liquid phase, allowing a substantial reduction in cycling pressure with no appreciable loss in recoverable liquids. Because of these effects, it is essential that phase behavior be considered in developing the economics of any secondary recovery program in which gas is the injected fluid. The inclusion of phase behavior in conventional calculation procedures has been retarded because of the complexity of the calculation and the large volume of laboratory data required. However, by applying high-speed computers and new laboratory techniques, the phase-behavior displacement calculation has been developed to economically include this basic fundamental of gas displacement. The calculation is performed by reducing the reservoir to a series of one-dimensional segments. Phase changes, saturation distributions and changing fluid properties are evaluated for each segment as a function of time. The relative volumes of equilibrium liquid and gas displaced from each segment are determined by a trial-and-error procedure to meet the requirements of phase equilibrium and two-phase flow. The produced fluids are flashed through conditions of surface separation approximating those in the field to obtain actual values for stock-tank liquid recovery and producing gas-oil ratios. Based on the results of successful field studies, the technique appears to have application to reservoirs producing under a nonmiscible gas-displacement mechanism and should substantially increase the reliability of this type of analysis when phase behavior is an important factor. Predicting reservoir performance under gas-injection operations involves three basic principles of reservoir engineering. First, a material balance exists between the displacing gas and the displaced reservoir fluid. Second, the oil and gas flow in relationship with the two-phase flow property of the reservoir rock; and third, phase equilibrium exists between the displacing gas and the native reservoir fluid. To illustrate these three principles, consider the one-dimensional reservoir shown in Fig. 1. The reservoir is divided into a series of segments representing a one-dimensional cross section between an injection area and a producing area. So represents the oil saturation, Cw represents the connate-water saturation and Sg represents the displacing gas saturation. The gas is moving into Segment 1 and the reservoir oil is being produced out of Segment N. Consider the case when gas has just moved into Segment 1 and the displacing gas-oil contact is at position a-a The volume of oil pushed out of Segment 1 is a function only of mobility and the two-phase flow properties of the reservoir rock, that is, Kg/Ko and µo/µg. Behind the front if the injected gas is foreign to the reservoir oil (a nonequilibrium gas), there will either be vaporization of the oil into the gas or condensation of the gas into the oil. In either case the net result is a mass transfer and a re-distribution of composition and liquid and gas saturation. If the displacement is at constant pressure and is continued, the gas moves into new segments, proceeding succesively into Segment 2, 3, etc. The total volume of oil produced from the reservoir

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By L. C. Kern

This paper presents information on the use of a new propping agent (malleable aluminum particles) which has been used successfully for producing high-conductivity fractures. The conductivity of a packed fracture depends on the width of the fracture as well as the permeability of the propping material. It is significant that the flow capacity of a propped crack is often increased many fold by propping the crack with a sparse distribution of particles. However, the flow capacity of a sparsely propped crack can be limited by two phenomena: (I) crushing of the propping particles, and (2) embedment of the propping particles in the formation walls. Malleable aluminum particles exhibit interesting properties which tend to overcome these limitations. As high loads are applied to the particles they will deform slightly, rather than shattering. The deformation results in a greater bearing area against the formation wall. This reduces the stress on the particle and reduces particle penetration into the formation. The behavior of aluminum particles under load and the bearing capacities of serveral formation rocks have been measured in the laboratory. By properly using these data, as explained in this paper, the flow capacities of aluminum-propped cracks can be calculated for a variety of conditions. Aluminum particles have been used successfully in the field to prop fractures. Where high-conductivity fractures were needed, the aluminum-propped fractures have given greater well stimulation than could have been expected for conventional fracturing processes. INTRODUCTION The purpose of a hydraulic fracture treatment is to create a conductive channel from the wellbore out into the oil or gas formation. The word conductive is emphasized because we believe that the fracture conductivity (flow capacity) is one of the most important factors influencing fracturing results. Previous papers have pointed out the additional well stimulation that can sometimes be achieved by increasing fracture conductivity. Several years ago, we investigated in some detail the effect of fracture conductivity on productivity increases to be expeced from vertical fractures. Both electrical analog and theoretical studies of unsteady-state flow behavior were made. A discussion of the electrical analog equipment and some of the results of the study were given in a previous paper' by Dyes, Kemp and Caudle. Further details were given recently by McGuire and Sikora.5 Fig. 1 shows the remarkable influence of relative fracture flow capacity and length on well stimulation. Briefly, the study indicates the following. 1. High-permeability formations require high-conductivity cracks for best results. 2. The longer the crack, the higher the fracture conductivity required for best results. 3. If the conductivity of the crack is very large compared to the formation (i.e., flow is not being limited by crack conductivity), then the longer the fracture, the better will be the results. Judging from recently published articles,1,314 there is current interest in methods for obtaining high fracture conductivities. Hence, we would like to present in this paper a discussion of a new fracture propping process (use of aluminum particle) which we have used successfully to obtain highly conductive fractures. There are several factors which influence the conductivity of a propped crack. Conventional fracturing techniques frequently result in a crack completely packed with fracturing sand. For such conditions, the crack conductivity is the product of the width of the packed fracture and the permeability of the propping material. It is significant that a large increase in conductivity sometimes can be obtained by propping with particles which are distributed sparsely (less than a

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 J. F. Gormley

Drill pipe, and the connections used to join the pipe together, have had a long history of development and improvement. With the growing use of high tensile-strength pipe, the rotary shouldered connections used to join the lengths of drill pipe have become more critical. Fatigue-type failures of rotary-shouldered connections, or tool joints, have become a cause of much conern to operators and manufacturers. Most fatigue tests on tool joints have been made on the basis of bending moment applied vs number of cycles, rather than on the basis of stress vs cycles. A desire to learn more about the nature of stress in a tool joint due to bending caused a rather intensive experimental study to determine what actually happens to cause fatigue failure. It was known that a tool joint with insufficient make-up torque was subject to early fatigue failure. Therefore, the establishment of the relationship between make-up torque and allowable bending moment would enable a testing engineer to better correlate the results of various tests. The problem of calculating the stress in a tool joint due to an applied bending moment was complicated by: the effect of unknown stress concentrations; the applicability of the well known formula S = Mc/I; and the question of whether to use the combined cross section of the pin and box in calculating the moment of inertia I. TEST EQUIPMENT The test equipment consisted of the following. 1. A lathe modified to act as a fatigue machine for full-size tool joint or drill-collar specimens. 2. An adapter plate bolted to the headstock of the lathe and into which a short adapter was screwed. 3. Tool-joint pins on sections of drill collars bucked into the adapter. 4. A hydraulic load cylinder which rested on the bed of the lathe and applied bending moments to the joints. 5. Paper-backed strain gauges (FAP-12-12, 1/8-in. gauge length and A-5-1, 1/2-in. gauge length). 6. Eastman 910 contact cement for bonding gauges to joint and Epoxylite 222 waterproofing. 7. A 12-position switchbox, SR-4 bridge balancing unit connected to an SR-4 strain indicator to read the gauge output. 8. A four-channel Sanborn recorder, Model 150, was used as the readout instrument for part of the testing. The fatigue machine was well suited as a loading device. Because of the long lever arm available, the change of moment with distance was small; consequently, the vertical shear stress was small, less than 300 psi. Some difficulty was experienced with the hydraulic load cylinder at high bending moments due to leakage. The strain gauge equipment was simple and quite reliable. A 41/2-in. extra hole (E. H.) joint with "as machined" threads and shoulders and a 2 7/8-in. internal flush (I. F.) joint with copper-plated threads and shoulders were selected for testing because of their common usage in the field. In addition, the 4 1/2-in. E. H. was suitable because it had an inside diameter large enough to permit the insertion and accurate positioning of strain gauges without using special jigs, while the 2 7/8-in. I. F. joint required much lower bending loads to cause separation of the shoulders of the joint when made up to the recommended torque. The joints were made to standard API specifications, except for very small bevels on the box and pin shoulders and cylindrical stress-relief grooves added to the pins. Larger bevels would have

By G. Y. Chin, A. R. Von Neida

The relationship between crystalline texture and magnetic anisotropy in a Co-10 pct Fe alloy has been investigated by means of X-ray pole .figures, hysteresis-loop tracings, and magnetic-torque measurements. The cold-rolled texture of a sample after 95 pct thickness reduction is of the "brass-type", that is, (110)[112/. At 500°C the cold-rolled material recrystallizes fo a (311)[112] orientation, plus a minor (210) [001] component. This texture persists up to 1400°C, at which point it is replaced by a secondary recrystallization texture, (111)[112]. Magnetic-torque measurements show that the easy axis of magnetization lies along the transverse direction in the cold-rolled material and changes to the rolling direction after primary recrystallization. This change is also reflected in the hysteresis characteristic; whereas the B-H loop along the rolling direction is nonsqunre with a low value of residual induction (750 vs 19,000 gauss at saturation) for the cold-rolled material, the annealed sample exhibits a very square loop with a large value of residual induction (16,000 gauss). Theoretical torque curves calculated from the texture data on the basis of magnetocystalline anisotropy energy compare favorably with the observed torque curves. Values of the crystal anisotropy constant, K1, obbained from these comparisons are in good quantitative agreement with single-crystal data. Furthermore, both the torque amplitude of the poly crystalline material and the magnitude of K1 obtained with a single crystal show an identical temperature dependence over the range from —195° 10 +220°C. It is thus conclzided that the magnetocrystalline anisotrpopy erlergy is chiefly I-esponsible. for the nzagnetic allisotropy of textured Co-10 pct Fe alloy. THE results of a study on the relationship between crystalline texture and magnetic anisotropy of an alloy containing 90 pct Co and 10 pct Fe by weight are reported in this paper. The alloy has an fcc structure: a saturation magnetization of about 19,000 gauss,2 and a nearly zero value of magnetoatriction.3 puzey4 has reported a large crystalline anisotropy constant of -7.4 X 105 ergs per cu cm, indicating the (111) directions as the easy axes of magnetization. Hence, texture variations resulting from cold work and annealing are expected to introduce a magnetic anisotropy in the polycrystalline material through the alignment of these (111) easy directions. In the present study, magnetic anisotropy of both rolled and annealed strips was determined by magnetic-torque measurements and hysteresis-loop tracings The results were correlated quantitatively with calculations based on texture data obtained by the X-ray pole-figure technique. It is established that the magnetocrystalline anisotropy energy is indeed chiefly responsible for the magnetic anisotropy of textured Co-10 pct Fe alloy. EXPERIMENTAL Material Preparation. The alloy nominally contained 90 pct Co, 9.5 pct Fe, and 0.5 pct Mn by weight, the chief impurities being nickel, carbon, and silicon (less than 0.5 pct total). The cast ingot was rolled to strips 10 mils thick and slit to 1 in. in width. After strand annealing at 900°C in a hydrogen atmosphere, these strips were further cold-rolled to various thicknesses down to 0.25 mil (97.5 pct reduction), with samples collected for study of the development of texture and magnetic anisotropy as a function of thickness reduction. subsequently, samples cold-rolled from 100 mils to 0.25 mil were obtained, thus extending the thickness reduction range to 99.75 pct. In addition, 0.5-mil samples cold-rolled from 10 mils were selected

Jan 1, 1965

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf's CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By W. R. Wilcox

The camphor-anthracene system was chosen as a transparent low-melting analog of the zirconium carbide -graphite system. Camphor and zirconium car -bide both grow nonfaceted, while casting of mixtures yields platelets of both anthracene and graphite. Zone melting of thin layers of organic was observed under the microscope. Irregular lamellar structures were produced at high values of the ratio of the temperature gradient G to the zoning rate V. The anthracene invariably led the camphor, indicating lower kinetic undercooling for the anthracene. The lamellar spacing was an order of magnitude greater than typical spacings for metal eutectic systems. Exact behavior depended on orientation of the anthracene. Oriented dendritic structures were produced at low values of G/V. Transient and oscillatory behavior were also observed—much of it unexpected. A.RC-CAST refractory carbide-graphite mixtures are promising thermal-shock resistant materials. Oriented structures of these materials would be superior to arc-cast materials for many applications. Mollard and Flemings1 and Cline2 have shown that aligned structures can be obtained for a wide range of Pb-Sn alloys. However, these metals both solidify in a nonfaceted manner while graphite yields platelets or flakes. In addition only small diameter samples of Pb-Sn alloys were produced because it was necessary to avoid free convection and to have high temperature gradients. The purpose of the present work was twofold: 1) To observe the solidification of a transparent low-melting analog of carbide-graphite systems and 2) to see if larger diameter samples can be produced. EXPERIMENTAL PROCEDURE When zirconium carbide-graphite mixtures are cast, the resulting structure naturally depends on composition. Carbide-rich mixtures yield metal-like nonfaceted carbide dendrites in a eutectic matrix. Graphite-rich alloys have graphite platelets in a eutectic matrix. Empirically it was found that camphor-anthracene mixtures produce similar structures with camphor being nonfaceted and anthracene forming plates. The organic eutectic melted at 116°C and was composed of 78 wt pet camphor.3 The camphor used was U.S.P. grade from Fisher Scientific Company; the anthracene was 98+ pet fro Aldrich Chemical Co. The impurity content is judged to be on the order of 1 pet. Mixtures ranging from 50 to 88 wt pet camphor were employed for the experiments. All but one of the experiments were performed on the microscope-stage zone melting apparatus described in detail elsewhere.4 The organic mixtures were contained in horizontal cells made of microscope slides or cover glasses. In most of the cells the organic was present as a very thin layer, thus giving almost two-dimensional growth behavior. The cells were moved slowly under a heated wire, which caused a molten zone to move through the solid at rates ranging from 0.01 to 5.4 cm per hr. The temperature gradient was estimated before moving the zone by measuring the distance between the line where all solid was melted (freezing point) and that where solid first began to melt (eutectic temperature). The temperature gradient was found to be 465°C per cm in the thinnest cells used, which were made by pressing together two microscope cover slips in the organic melt and then rapidly withdrawing them. RESULTS The experimental results are described in four parts: simultaneous growth, dendritic growth, irregular growth, and transients and erratic phenomena. Steady state data are summarized in Fig. 1. Except where noted all comments are for the cells containing a thin layer of organic. A) Simultaneous Growth. Simultaneous and roughly parallel growth of anthracene and camphor was obtained over the full range of compositions investi-

Jan 1, 1970

By Leonard R. Weisberg

HE procedure of directional freezing by the Bridgman technique1 is frequently used in crystal preparation. On those occasions where the crystal is regrown, it can be advantageous to Crop part of the ingot before regrowth to achieve purification. This note describes some simple, yet interesting, observations concerning the effects of cropping an ingot between successive freezes. First, it is not effective to Crop the front end of an ingot, whether or not the distribution coefficient, k , of the impurities is greater or less than unity. This can be shown as follows. The concentration C, of an impurity in a directionally frozen ingot of length d with a uniform cross section is given by where x is the distance along the ingot, and C0 is the initial concentration per unit length. It is assumed in deriving this equation that diffusion is negligible in the solid, is complete in the melt, and that k is constant. Consider that a section of the ingot Ad is removed from the front end. Then the average impurity concentration in the remaining (d- Ad) section of the ingot can be shown by integration to be given by When the ingot is remelted and refrozen, the new impurity distribution is given by where xl is the distance along the refrozen ingot. Substituting the value of c into Eq. [3], one finds This is identical to Eq. [11 when x = (x, Ad), which represents the original impurity distribution in the (d - Ad) section of the ingot after the first directional freeze. Therefore, the cropping and re-freezing accomplished nothing. This can also be seen physically by realizing that the average impurity content in the melt after the first Ad section is frozen, is identical to that after the resulting ingot has been cropped and remelted. Hence, it is assumed in the following sections that only the tail end of the ingot is cropped. However, it must be realized that for impurities with k greater than one, the pieces cropped from the tail end are purer, and are therefore saved. After cropping an amount Ad from the tail end of an ingot, the average impurity concentration of impurities in the remaining portion of the ingot is given by wheref= d/d. For the case of k < 1, the purification is defined as c,/c. It is obvious from Eq. [5] that the purification increases asf increases, but the increase in purification is not large. For example, iff is doubled from 0.1 to 0.2, the purification increases by only 10 pct for k = 0.5, by only 24 pct for k = 0.1, and by 32 pct for k =0.01. Much smaller values off than 0.1 are not desirable since insufficient purification is achieved. These figures indicate that much larger values off do not lead to substantial improvement, especially considering that much of the original ingot is lost. Therefore, it is generally useful to Crop about 1/10 of the ingot to achieve purification. As compared to doubling the value off, it is much more helpful to remelt, refreeze, and crop the ingot twice. Using Eq. [51 reiteratively, and assuming f= 0.1, it is found that the purification after this process is found to be increased over the purification after a single freeze and cropping by 33 pct for k= 0.5, 450 pct for k = 0.1, and 4100 pct for k = 0.01. This indicates that considerable purification can be obtained by this procedure. However, if purification is the main goal, one should resort to zone refining,3

Jan 1, 1962

By J. D. Forrester, Erich Sarapuu, T. C. Cheasley

Electrocarbonization of coal will produce cheap fuel for electric power plants. The complete electrification of industry and domestic power consumption of gas generated as fuel in situ is a worthwhile goal for the coal industry. Production of synthetic oils, gasoline, and coal chemicals from coal gas will create additional new markets for the coal industry. RANKING high in the nation&apos;s wealth of natural resources, readily available liquid and gaseous hydrocarbons are nevertheless falling steadily in supply, while industrial requirements for hydrocarbon compounds are greater today than during the peak period of World War 11. Theoretically, several processes will increase the future supply of liquid and gaseous fuels, but the practical application of these methods depends on two controlling factors: 1—that enough carbon-bearing material be available to warrant industrial exploitation, and 2—that the given process be physically, chemically, and economically applicable. With regard to the first factor, the Western Hemisphere is fortunately well supplied, see Table I. Table I not only shows the extensive occurrence of many fuel sources, but also the wide discrepancy among quantities of fuel substances in various materials. Great quantities of potentially available fuel have not been recovered. Many coal seams and other hydrocarbon-bearing deposits are so situated that production is uneconomical by present-day mining or oilwell pumping methods, and even in many exploitable deposits where the most efficient production methods are used a large proportion of material is never recovered. Industrial production of hydrocarbon liquids and gases must be better balanced, and processes must be developed which will convert coals, oil sand, and oil shales into fabricated commodities. Among the techniques employed by scientists and engineers to secure fuel masses not economically available at present are several processes of underground gasification. These are all concerned with converting raw materials into gaseous products by thermal treatment of source substances while they are still in the ground and therefore require that a subsurface heat (fire) zone be induced to affect pervasively the buried raw fuel deposit. This is possible only where sufficiently high temperature exists and where the fuel material is satisfactorily opened or channelized. Also, to compete successfully with common mining or oilfield practices, a given method must be controllable and must not involve greater operational expense than regular methods. Preferably, it should be less expensive. Since the close of World War 11, England has continued field studies of underground gasification methods. Experiments have also been conducted in Sweden, Estonia, France, Belgium, Italy, and Germany. The U. S. Government has sponsored field studies at Gorgas, Ala., and because gasification in situ is vitally important to establishment of the nation&apos;s fuel resources, the mining engineering department at the Missouri School of Mines has been actively interested in developing the process of underground electrocarbonization. Research was conceived by Erich Sarapuu, and preliminary experiments in treating bituminous coal were begun at the school in September 1947. The work consisted of laboratory experimentation until June 1948, at which time, through a cooperative agreement with the Sinclair Coal Co. of Missouri, pilot plant studies were instituted at the Tiger mine of the Hume-Sinclair Coal Co. near Hume, Mo., to test the encouraging laboratory findings. This comprehensive field program was pursued continuously until the beginning of 1952."&apos;" The broad term underground electrocarbonization describes a unique gasification process that releases by electricity the desired economic constituents from a raw carbon-bearing material, converting the substance of such deposits into deliverable form and greatly reducing the cost-of-mining factor. Underground electrocarbonization is not subject to the major limitations of many other underground gasifi-

Jan 1, 1955

By R. J. Blackwell, A. L. Pozzi

Scaled laboratory-model studies provide a powerful method for evaluation of a proposed oil-recovery process. In recent years, models have been used extensively to evaluate processes in which solvents displace oil, both for general cases and for specific reservoir conditions. Since the performance of a miscible flood in a horizontal reservoir can be significantly affected by transverse mixing between solvent and oil, this displacement mechanism must be accurately simulated in the scaled model studies. Unfortunately, precise scaling of transverse dispersion coupled with the requirement of geometric similarity requires impractically large laboratory models and long times for experiments. If scaling requirements for miscible displacements could be relaxed while accurate simulation of essential displacement mechanisms is maintained, the utility of model studies would be greatly enhanced. The purpose of the work reported herein was to evaluate the relative importance of various mechanisms affecting miscible displacement and to ascer tain whether the essential features of the displacement process can be simulated even though some scaling groups are not satisfied. These studies were performed with completely miscible systems in linear, horizontal models packed with unconsolidated media. From the experimental results, a set of relaxed scaling criteria was formulated which allows the requirements of geometric similarity and equality of the ratio of viscous to gravity forces to be omitted for specified conditions. The relaxed criteria are valid whether transverse mixing is by molecular diffusion or by convective dispersion. Correlations which permit prediction of vertical sweep efficiencies in linear, horizontal reservoirs were developed from the experimental data when transverse mixing is by molecular diffusion. These same correlations may be used when transverse mixing is by convective dispersion if an empirically defined, effective, transverse dispersion coefficient is used in the description of the mixing process. The effective transverse dispersion coefficient correlation essentially duplicates the dispersion coefficient correlation for equal-viscosity, equal-density fluid systems. Experimental values for the effective transverse dispersion coefficient can be measured readily. INTRODUCTION One of the most effective methods for evaluation of miscible-displacement oil-recovery processes is that of displacements in laboratory models scaled to simulate reservoir conditions. For these laboratory studies to be meaningful, however, the essential displacement mechanisms affecting reservoir performance must be accurately simulated. Since the performance of a miscible flood in horizontal reservoirs, or in dipping reservoirs at high rates, can be significantly affected by transverse mixing of solvent and oil, this mechanism must be considered in the design of laboratory experiments. Unfortunately, precise scaling of transverse dispersion coupled with the requirement of geometric similarity requires impractically large laboratory models and long experiment times. This difficulty seriously limits the utility of laboratory model studies. Craig,et al,1 demonstrated that geometric similarity is not required when mixing is unimportant. Their experimental data indicate, for the cases studied, that the displacement is sufficiently characterized by scaling the ratio of viscous-to-gravitational forces. This work suggests that relaxation of the requirement of geometric similarity and, possibly, other criteria might also be permissible when mixing is important, provided suitable groups describing the mixing process are scaled. The purpose of the work reported here was to evaluate the relative importance of various mechanisms affecting miscible displacement and to ascertain whether the essential features of the displacement process can be simulated even though some scaling groups are not satisfied. Consequently, laboratory investigations were made of the dependence of recovery on dispersion and other variables,

By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith&apos; concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin&apos;s value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By D. H. Forbes, I. B. Cadoff, H. M. Manasevit

Single-crystal silicon films have been obtained on several natural crystal faces of BeO using the thermal decomposition of silane and the hydrogen reduction of silicon tetrachloride. From an analysis of X-ray diffraction data it was determined that the following film-substrate orientation relationships exist: (111) Si 11(0001) BeO, (111) Si 11(1011) BeO, (100) Si 11f1010) BeO. and (110) Si 11(1010) BeO. An analysis of the crystallographic relationships between the film and substrate indicates that a match occurs between the silicon atoms in the film and the berylliuni ion sites in the substrate. This correspondence is in agreement with previous work on the deposition of silicon on sapphire.1-3 silicon on spinel: and tungsten on sapphire. The high resistivity, thermal conductivity, and radiation resistance of beryllium oxide make it an important substrate material for the deposition of thin films of silicon or other semiconductors. The importance of semiconductor-insulator composites to the field of integrated microelectronics has been well-documented in the case of silicon on sapphire.&apos;-&apos; The successful growth of large-area single-crystal silicon on an insulator, sapphire, was first reported in 1963.1,2 Since that time studies have been made of the crystallographic relationships between the deposited film and the sapphire substrate. On the basis of the observed relationships, a model has been proposed relative to the crystallographic requirements for epitaxy between the semiconductor film and the metal oxide substrate.3 It is proposed in this model that epitaxy is the result of a match between atoms of the deposited film and the metal ion sites of the substrate plane. This match is not limited to a 1 to 1 correspondence between sites in the two lattices. Sub- sequent studies of the deposition of silicon on spinel4 and tungsten on sapphire5 have yielded data which support this model. On the basis of this previous work it was felt that silicon on BeO should also fit this model. In the present study, the choice of substrate orientation was limited to the natural faces of synthetic BeO crystals. Of the faces available, the (0001) plane seemed the most favorable for epitaxial growth. EXPERIMENTAL PROCEDURE Silicon films were deposited from silane and silicon tetrachloride in the apparatus shown in Fig. 1. The hydrogen ambient gas was purified by passage either through a DEOXO unit, molecular sieves, and a liquid nitrogen cold trap, or through a heated Pd-Ag thimble. The gas was then mixed with the silicon source materiai and passed over the substrate which lies on a spacer above an inductively heated silicon pedestal. The following deposition conditions were used: a hydrogen flow rate of 3 liters per min with silane and silicon tetrachloride concentrations of 0.2 mole pct and a pedestal temperature of 1175" * 5°C as observed with an optical pyrometer assuming an emissivity of 1.0. Deposition was preceded by a 15- to 30-min hydrogen-etch period conducted at a temperature of 1275°C (obs). Adherent silicon films from 2 to 10 u were grown on the various BeO faces. The substrates were synthetically grown beryllium oxide single crystals ranging from 5 to 10 mm in

Jan 1, 1967

By G. R. Speich, Morris Cohen

The growth rate of bainite has been determined by hot-stage metallography in five hypereutectoid high-purity iron-carbon, iron-carbon-chromium, and iron-carbon-nickel alloys. The studies have been confined essentially to lower bainite. The growth rate is independent of time at constant temperature, but both the edgewise and sidewise growth rates increase with increasing temperature. Increasing the carbon content, or adding chromium or nickel, decreases the growth rate without greatly affecting the temperature dependence. The results lead to separate diffusion-controlled models for the edgewise and sidewise growth rates. ALTHOUGH bainite has been subject of many detailed investigations,1,2 the growth mechanism of this intermediate transformation product of steel remains unclear. One difficulty has been that practically all the kinetic measurements have been restricted to studies of the overall reaction rate. Only a limited amount of information3, 4-6 is available on the growth process itself. The purpose of the present work was to investigate the effect of time, temperature and composition on the growth rate of bainite using hot-stage metallography. This method makes it possible to observe continuously the isothermal growth of individual bainitic units because of the surface upheavals accompanying their formation.3 This information is needed to test the existing growth models and to obtain a better understanding of the factors controlling the bainitic transformation. EXPERIMENTAL PROCEDURE Alloys—The compositions of the alloys used in the present work are shown in Table I. The five alloys were vacuum-melted and cast, and were prepared from high-purity materials. The three iron-carbon alloys were available from the work of Roberts et al.7 in the form of 3/8-in. diam rods.* To facilitate machining, the rods were ing. The rods were then tempered for 3 hr at 650°C to allow machining. The iron-carbon alloys in Table I were selected for investigating the effect of carbon on the bainitic growth rate. Due to the rapidity of the transformations involved, it was not feasible to measure the growth rates in iron-carbon alloys having carbon contents much less than 0.9 pct C. The iron-carbon-chromium and iron-carbon-nickel alloys were selected to study the influence of chromium and nickel on the growth rate at a carbon level of about 1.1 pct C, since this carbon content was intermediate among the iron-carbon alloys. The concentrations of chromium and nickel were chosen to match isothermal trans formation diagrams in the literature.8&apos;9 Hot-Stage—Since the iron-carbon alloys had such low hardenabilities, it was necessary to quench the hot-stage specimens drastically from the austentiz-ing temperature to the isothermal transformation temperature to prevent the formation of pearlite or proeutectoid constituents. A rapid-quenching metal-lographic hot-stage was built for this purpose. A maximum temperature of about 1100°C and quenching rates up to 500°C per sec could be attained with this equipment. The details of the apparatus are described in a recent publication. After being polished and mounted on the hot-stage, the specimen (0.020 in. thick) was protected from oxidation and decarburization during austenitizing by a vacuum of 10-4 to 10-5 mm. The quench to the reaction temperature was accomplished with a helium blast, and the isothermal run at this temperature was conducted in a helium atmosphere. A fine-wire thermocouple spot-welded to the sample and a high-speed

Jan 1, 1961

By Danforth R. Hale, R. E. Blair

Minerals for electronic and optical uses divide easily into two sections: (1) quartz and (2) minerals other than quartz. Quartz Quartz, having a great usefulness discovered by the radio communication enthusiasts about 1918, has become a subject of amazingly expanded interest in the US over the past decade as a man-made mineral and a multimillion dollar crystal-growing business. An economic summary of the commercial growing of quartz crystals has a place in a handbook directed to the mineral engineering industry when it is remembered that quartz crystals have long been an important commercial mineral, and that the raw material for "cultured quartz"-that is to say, quartz crystals grown through the ingenuity of man-is still natural quartz. Nearly all the natural crystals come from Brazil. The larger pieces which meet rigorous standards of quality are used for electronic and, to a lesser extent, optical components. Smaller pieces and fragments are used for vitreous silica. The need for high quality material in quantity led to US government-sponsored research programs in the 1940s that have resulted in the factory growing of beautiful crystals of prescribed shape, size, and quality. The development of the cultured quartz crystal is typical of man&apos;s success in adapting the product of the mine to increasingly sophisticated uses. A remarkable achievement perhaps, but foreshadowed by experiments in 1908 by Giorgio Spezia (1908), an Italian geologist studying the relative effects of temperature and alkaline environment on the solubility of quartz. Modern radio equipment is most often controlled as to frequency by the presence in the circuit of a separately added "crystal"-the 1918 discovery responsible for the existence and growth of the quartz industry. The "crystal" is quartz, but this component is a carefully oriented and prepared slice from a crystal, but not a crystal as recognized by a rock hound or seen in a museum. How quartz operates to control frequencies is not a proper subject for a handbook on industrial minerals, and references should be consulted (Cady, 1964; Mason, 1964). Quartz belongs to that class of materials called dielectrics: those that do not conduct an electric current but permit electric fields to exist and act across them. Quartz shows the "piezoelectric effect," which means that when a quartz plate is mechanically deformed against its natural stiffness, one of its surfaces becomes negatively charged, the other, positively charged. When the plate is released from the stress quickly, the charges disappear as the plate regains its original shape, but because of mechanical momentum the plate deforms in the opposite direction (to a lesser amount) and the surfaces correspondingly become charged in the opposite direction. By coating the two surfaces thinly with metal and attaching flexible wires, these charges may be brought into an electronic circuit. If the surfaces are suddenly electrically charged by movement of current through the wires, the "converse piezoelectric effect" occurs -the plate deforms. Carry the thought further and it is realized that an alternating current flowing through the wires responds to the mechanical oscillation of the plate and is keyed to this oscillation. By controlling the thickness of the plate its mechanical vibration frequency can be varied through a wide range. One type of quartz plate, called the AT-cut, having a precisely defined orientation with respect to the crystallographic axes of the crystal, vibrates on a microscopic scale much as a book would deform when placed flat on a table and the top cover moved parallel back and forth with the hand. There are at least 17 other orientations which have been studied, some of

Jan 1, 1983

By Frank C. Aplleyard

The two calcium sulfate minerals-gypsum and anhydrite-occur in many parts of the world, and gypsum has long been of economic importance in the family of industrial minerals. Gypsum, the dihydrate form of calcium sulfate (CaSO4•2H2O) and anhydrite, the anhydrous form (CaSO4) are frequently found in close association, and it is seldom that a calcium sulfate deposit will consist exclusively of one mineral or the other. Although known gypsum deposits are extensive, anhydrite makes up the largest part of total calcium sulfate reserves. However, it has very minor economic use, and most of the following discussion will be devoted to gypsum. Calcium sulfate is one of the principal constituents of evaporite deposits, and when pure, has the following composition: [Sulfur Combined Lime Trioxide Water (CaO) (SO,) (H2O) Gypsum 32.6% 46.5% 20.9% Anhydrite 41.2% 58.8% -] Deposits of pure gypsum or of pure anhydrite which are large enough to be considered commercial have never been found because of both the metastable relationship between the two minerals, and the presence of impurities such as calcium or magnesium carbonates, chlorides, other sulfate minerals, clay minerals, or silica. As a result most mine production of gypsum will range between 85 and 95% pure. Often it is used as mined, although in certain cases, one or more forms of mineral beneficiation are employed to upgrade the product. End Uses The largest use for gypsum is based upon the unique property which calcium sulfate has of readily giving up, or taking on, water of crystallization. With the application of a moderate amount of heat in a process known as calcining, gypsum is converted to plaster of paris (the hemihydrate of calcium sulfate, CaSO4 ½ H2O) which when mixed with water will set or harden as the calcium sulfate returns to the dihydrate form. This semifinished product, usually called stucco, is then manufactured into a large variety of plasters, wallboard, and block for construction use, or into plasters for industrial applications. About 75% of the gypsum used in the United States is calcined for these purposes. Uncalcined uses of gypsum are principally as a retarder for portland cement, as a soil conditioner, as a mineral filler, and other minor industrial applications. About 25% of the gypsum mined in the United States goes into these markets; however, in less developed countries where construction and other industrial uses may be quite limited, the use of uncalcined gypsum for portland cement retarder may well be the dominant-if not the only-market for the mineral. It has often been noted that calcium sulfate constitutes the world&apos;s largest reserve of sulfur, and minor use of both anhydrite and gypsum has been made to produce sulfuric acid or other sulfur compounds such as ammonium sulfate. However, because sulfur is readily available at lower cost from other sources, use of calcium sulfate has been limited to only a few locations where it could compete economically. No such use is reported in the United States at this time. Mineralogy Anhydrite, CaSO4 because of its geologically rapid conversion to gypsum, and relatively high solubility (about 0.2 g per 100 g H2O) is not often found outcropping in climates wet enough to support abundant vegetation except on steeply dipping slopes or other places where hydrated material is continuously removed. Anhydrite rock is most often light to bluish gray in color, and under the microscope, varies

Jan 1, 1983

By R. F. Rolsten

The preparation of pure metals by the thermal decomposition of volatile halides was developed byde boer&apos; and van Arkel.2 This has proved to be a useful technique for the refining of columbium,the mechanical and physical properties of which are seriously altered by such interstitial contaminants as oxygen, nitrogen, hydrogen, and carbon. The conventional deposition surface of a resis-tively heated metal filament was replaced, Fig. I, with an indirectly heated clear quartz surface. The impure columbium (feed) was contained in the annular space between the Vycor deposition bulb and the perforated molybdenum retaining cylinder. The head assembly was attached to the deposition bulb by fusing the Vycor at "A". This unit was then connected to a vacuum system composed of a three-turn glass coil to eliminate fracture due to vibration or expansion, a McLeod gage, a cold trap, a two-stage mercury diffusion pump, and a mechanical pump. The entire system was cold outgassed, and the 10 to 20 g of iodine in the auxiliary bulb (reservoir) was held in dry ice to prevent excessive loss of iodine. The columbium was hot outgassed at 800" to 825oC with the pressure maintained at l0-5 to 10-6 mm Hg for 48 hr and cooled under vacuum to 200° to 240oC. Iodine was sublimed from the reservoir and collected in the deposition bulb. The feed material temperature was adjusted to give the desired iodide vapor pressure and the finger temperature of 1000" C was independently attained and measured with a platinum-platinum 10 pct Rh thermocouple located in the center of the nichrome wire helical heating element, "F." The system was attended until temperature equilibrium was established, whence it operated without attention. This is a definite ad- vantage over the conventional "hot-wire" technique which required either constant attention or automatic control. In operation, the iodine vapor originally introduced into the vessel reacted with the crude metal to form a columbium iodide. This iodide vapor diffused to the hot deposition surface where it thermally decomposed, depositing columbium and releasing iodine. This liberated iodine then diffused back to the crude columbium where iodide was formed again. Thus, by repetition of this process, the iodine carried pure columbium from the crude material to the filament, where it deposited. The success of the "iodide" process in producing ductile metals depends on preventing the transfer of oxygen, nitrogen, hydrogen, and carbon from the feed material to the deposit. In many cases relatively minor quantities of these interstitial contaminants impair the ductility of metals. The material produced by the iodide process has such exceptional ductility that it is frequently and mistakenly assumed that iodide metal is always of very high purity. This assumption is not necessarily true since a number of metallic impurities can also be transferred. In the present investigation, the temperature of the feed material was adjusted to iodinate selectively and the deposition temperature adjusted to decompose the iodides selectively. By this technique, some metals present in the feed material were prevented from codepositing with the columbium. It is quite important to have the feed material symmetrically located around the deposition surface in order to obtain a uniform deposit at the maximum rate. For example, Runnalls and pidgeon3 observed that, when the base of a titanium filament was about 1 cm from the feed material, deposition was rapid on that section close to the feed, but that the rate decreased with distance from the feed so that a

Jan 1, 1960

By T. C. Poulter, B. M. Caldwell, D. E. Brink

The flash X-ray has been used more than a decade to study the configuration of the jet from a shaped charge. The high-speed, rotating-mirror smear camera has provided time-distance graphs of detonations and shock fronts in transparent materials, and the high-speed framing camera has given pictorial representations of the progress of explosive phenomena. Adequate means for measuring the paths and velocities of all parts of the shaped-charge cavity Iiner during the collapse phase have not existed heretofore. A technique enabling the single-lens framing camera to make stereoscopic photographs of the cavity liner while it is collapsing has been developed. Analysis of this photographic record gives the directions and velocities of various parts of the Iiner surface, permitting direct quantitative measurement where this has previously been impossible. Significant improvements in shnped-clrarge design are expected to result. INTRODUCTION The familiar oilwell jet perforating charge, generally referred to as a "shaped charge", is related to the Mun-roe charge first described by C. E. Munroe in 1888 and later by Neumann in 1910. It differs in construction from the Munroe charge in that its cavity is lined with some inert material (usually metal)&apos;, and it differs in performance by projecting a fast jet of dense liner material against the target instead of a stream of expanding detonation products. Fig. 1 represents a typical shaped charge in axial cross section. The charge is circularly symmetrical about its longitudinal axis. The cavity at the right is lined with metal, usually copper; and, with the exception of air, the liner is otherwise completely empty. High-explosive material is intimately in contact with the convex surface of the liner and extends in the other direction to the booster. This is a pellet of high explosive having somewhat different characteristics and serves to couple the detonator to the main charge. When the detonator is fired, a small hemispherical reaction zone of very high temperature and pressure occurs at its output end. The booster responds, adding its own latent energy to the reaction, thereby initiating the main charge. The reaction progresses throughout the main charge at a velocity of 7 to 8 mm/microsecond until all the explosive material has reacted. With a reaction pressure of about 160,000 atm, the surrounding material is moved rapidly away from the high-pressure zone. As the detonation proceeds along the cavity liner, moving from apex to edge, the liner is collapsed toward the axis of the cavity, where liner material from all parts of the concave surface converges. A zone of extraordinarily high pressure results. with only one escape path—outward along the axis. The particles from the liner, thus, become a jet of very high velocity, with a density characteristic of the material from which the liner was made. The kinetic energy of the jet, concentrated in a small area of the target, has great penetrating power. It overcomes the strength of any target, and the target material crumbles or deforms plastically to escape from the path of the jet. An unlined cavity charge, on the other hand, projects a turbulent body of hot gaseous material against a target and erodes the exposed surface. With equal quantities of explosive, the penetration effectiveness of an unlined charge is a small fraction of that of a lined charge. Given an explosive charge with a detonator at one end and an axially symmetrical metal-lined cavity at the other, one has a perforator of considerable potency. To maximize the penetrating and other desirable effects,