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By G. S. Cole, G. F. Bolling

A series of Al-Cu alloys has been cast from constant superheat to solidify either with a hot top or with a free liquid/air interface. All the other variables which affect relative fluid motions were kept constant except the imposition of slow rotations m oscillations of the mold. Depending upon the exact circumstances, evi-dence could be found for the nucleation of equiaxed grains from dendrite bits detached from the columnar zone, or from the free surface, or from solid bits induced at pouring; a special experiment showed the solute buildup during ingot solidification and by inference the reality of constitutional supercooling. All methods of grain nucleation are thus supported. When solidification is arranged in a static mold the columnar- to-equiaxed transition occurs by one of these nucleation paths, subject to the natural decay of temperature gradients which promotes nucleation or the survival of nuclei. But when solidification is forced under special fluid flows it may display odd transitions. In one of these the equiaxed zone is synihesized from. dendrite bits detached from the solid/liquid interface. These survive under the concurrent lowering of temperature gradients and eventually cause transition by impeding columnar growth. GRAIN structure control is desired because real experience shows that specific properties are associated with specific cast grain structures. But since control is thus a matter of need and does not require understanding, much of casting remains art. For example, the manipulation of relative fluid motions in simple ingots provides a control of grain structure development,1-4 but theoretical insight is not required in order to broaden its potential applicability. Fortunately, however, once a variable like fluid flow is recognized it can also provide paths toward new insight. New observations using this variable have provided an insight which is curious. All the theories or descriptions of the columnar-to-equiaxed transition (CET) seem to be supported as long as the appropriate experiment is carried out. In order to develop this idea, let us ignore segregation, the chill zone (until a later section of this paper), and the origin and development of the columnar zone.= The details of questioning how equiaxed material forms in a casting may be divided in two. The first part is simply a questioning of the origin for equi-axed grains: are there fresh nuclei from heterogeneous nucleation, or dendrite bits broken off or melted from the columnar zone or elsewhere,6 or other solid bits surviving from the outset of freezing? The second is more complex, a questioning of the CET: does columnar growth slow down and allow the dominance of equiaxed grains, however they are formed, or do equi-axed grains take over and force columnar growth to stop? This "chicken-or-the-egg" second question can be quite useful, especially because it allows us to delineate the ordinary or NATURAL EQUIAXED ZONE and the induced or SYNTHETIC EQUIAXED ZONE. A natural equiaxed zone occurs if solidification proceeds in the absence of disturbances or extraneous forces such as ultrasonics, stirrings, and so forth. Both the CET theory proposed by Winegard and Chal-mers, 7requiring constitutional supercooling, and the CET theory suggested by Chalmers,8 requiring nuclea-tion only on pouring, pertain to the natural equiaxed zone. The best collating evidence to date for both these theories is contained in the work by Biloni and Chal-mers;9,10 the former theory7 is supported by special versions of the unidirectional growth experiment performed by Plaskett and winegardl1 and the latter theory' is supported in detail for the solidification of small ingots. An equiaxed zone can be synthesized when disturbances caused by forced fluid flows2-4 or other artificial means9,10 break off or melt off dendrite tips from an advancing solid/liquid interface,* if (and only if) temperature gradients in the melt are (forcibly) reduced enough to ensure the survival of these bits of dendrites, 2'3 Willful disturbances even so trivial as those produced by rapping a mold might be included here; as will be shown for example, this follows Southin's suggestion that the free liquid/air interface

Jan 1, 1970

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By Richard Hamburger

(1) Introduction: The purpose of this paper is to call attention to certain methods which will shorten and simplify the calculation of plane tri-angulation. These methods, though not new,',2 do not appear to have been properly publicized in the United States. The cotangent (or tangent) solution of a triangle permits calculation of coordinates in a smooth series of operations of the calculating machine with a minimum of notation. The semigraphical solution permits the simultaneous solution of a number of intersections, at one station, without the added burden of solving additional triangles. This in turn encourages more numerous field checks and more complete office computation than would normally be undertaken. RICHARD HAMBURGER, Junior Member AIME, is Junior Engineer, Inspiration Consolidated Copper Co., Inspiration, Arizona. TP 2798 A. Discussion (2 copies) may be sent to Transactions AIME before March 31, 1950. Tables I and I1 show the distinct advantage which the combined use of the cotangent and the semi-graphical solutions hold over, what might well be called, the standard solution. It will be shown that the positions for the entire net in fig. 1 may be calculated without computing any distances, thus saving much computation. (2) Comparison of Cotangent and Standard Solutions: To compare the cotangent method with the standard method, the notation involved in the solution of triangle 1-X-4, fig. 1, by both methods is shown. Fig. 2 shows the given information, that is, the coordinates and azimuths of Stations 1 and 4, and angles of the triangle or the azimuths from Stations 1 and 4 to Station X. (Azimuths are used here because the author feels that they are easier to handle, but bearings may be used by those who prefer them). It will be seen from the above comparison that the advantages of the cotangent solution of a triangle are: (a) rapidity, (b) full use of the calculating machine, (c) the small number of

Jan 1, 1951

By K. C. Ten Brink, Allen D. Garrison

A rrevious paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their composition, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions. Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. Experimental Procedure The difficulties involved in the measurements of the flow characteristics of plastic fluids are too familiar to recite. The possible applications of some of the well-known instruments to this problem have been adequately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measurement of clay or shale suspensions. Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first requirement is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1940

By Prof. B. Hopkinson

Introduction.-A short time ago Professor Stoughton asked the writer if he would present a paper for the February meeting of our Institute. In reply to this suggestion, some notes have been prepared relating to the subject mentioned in the title. It is to be hoped they may be of interest to our members. The research now described is the joint work of Prof. B. Hopkinson, F. R. S., and the writer. Those interested in the subject will find further data in a paper entitled The Magnetic and Mechanical Properties of Manganese Steel, which will probably be read at this year's May Meeting of the Iron and Steel Institute in London. This paper was submitted to the Institute in October last, and advance copies will shortly be available. The present paper has been drawn up by the writer on this side the water, and he has not had time to communicate with Professor Hopkinson with regard to the statements or opinions expressed herein. While the writer believes that Professor Hopkinson would in the main agree with the statements herein set forth, it should be understood that apart from the actual work described he is not otherwise responsible. The experiments described have been carried out on the material known as manganese steel, which one of the writers of these notes discovered in 1883. A paper by him describing this material was read before this Institute in 1893, entitled Iron Alloys, with Special Reference to Manganese Steel. It is not necessary to describe manganese steel nowa-days; its qualities are so well known, and its use throughout the world is on a very extensive scale.

Jan 3, 1914

By Lee Morris, Charles E. Lawall

This paper represents the results of a study to determine the source, mode of occurrence and conditions influencing the flow and liberation of large volumes of inflammable gas in the Pocahontas No. 4 coal bed in southern West Virginia. A study of this kind is of interest in connection with mine ventilation, because in the removal of gases from coal mines it is very important to know the origin, the occurrence and laws of gas flow. The study was started in April, 1931, and the data and observations were obtained throughout a period of 15 months of field work. Geology The country where this study was made is mountainous and rugged; great cliffs, precipitous slopes and deep narrow gorges are found throughout the area. The outcropping rocks consist of stratified layers of sandstone, shale, limestone and deposits of coal of Carboniferous age. The Pottsville series of the Pennsylvanian, lying at the base of this period, cover the greater portion of the area. A stratigraphic section of the Pocahontas group of the Pottsville series is shown in Fig. 3. The older rocks outcrop in the extreme southeastern part of the area, but are under drainage in the central and northern parts due to the gradual northwest dip of the strata. The structure has a general northeast-southwest trend (Fig. 1). North of Dry Fork anticline the strata have been only slightly disturbed by movements of the earth's crust; it is now a long monocline. Southeast1 of Dry Fork anticline the strata are warped into great arches and deep troughs and are broken by overthrust faults. All of this folding is probably the result of the intense folding associated with the formation of the Appalachian Mountains. Pocahontas No. 4 Coal Bed The Pocahontas No. 4 bed, lying approximately 550 ft. above the base of the Pottsville series, is one of the thickest and most gassy coal beds in

Jan 1, 1934

By R. J. Schilthuis

In 1929, Coleman, Wilde, and Moore1 undertook an investigation of the theoretical decline in reservoir pressure as related to the production of oil and gas. The most important part of this work was presented in an equation defining the relationship between the reservoir pressure, the quantities of oil and gas produced, the oil and gas content of the reservoir, and the properties of the reservoir fluids. With this equation, it appeared that, with sufficient data, it would be possible to calculate the oil content of the reservoir and predict quantitatively the effect of gas-oil ratio on the decline of reservoir pressure. Needless to say, such an expression would be highly important in evaluating fields and in arriving at a choice of production methods to be used. Unfortunately, at the time these investigators published their work, there were not sufficient data available to permit application of the equation. The technique of measuring reservoir pressures had not been developed, gas measurements were uncommon, oil and water production records were in most cases inadequate, and little was known of the properties of the complex hydrocarbon mixtures making up the oil and gas in the reservoirs. For these reasons, little additional work of a similar nature could be done. However, during the past four years many data have been systematically accumulated on reservoir pressures and the properties of oil and gas, and it is now possible to use these data in furthering the studies on the behavior of oil and gas reservoirs. It is the purpose here: first, to present the derivation of a modified form of the equation given by Coleman, Wilde and Moore, which will permit the calculation of what later will be defined as the "active oil" content of a reservoir; second, to derive formulas for calculating the reservoir-energy changes that occur during the course of production, and finally, to discuss the limitations and application of the equations developed.

Jan 1, 1936

By R. J. Charles

Previous study of simple impact systems indicated that energy required for fracture and size reduction of brittle materials is greatly dependent on the type of loading that is employed. In this regard it was postulated that fracture and size reduction of a brittle specimen might be accomplished by a high velocity impact at an energy level at which a low velocity impact would leave the specimen relatively undamaged. The finite time required to propagate energy away from the point of loading of an impacted object to other parts of the object and to its supports may permit a concentration of energy at the point of impact if the rate of loading is high. Localizing of energy at the point of impact could quickly initiate fractures that would propagate through the impacted material along with the traveling stress waves. As the cracks form, the initially absorbed strain energy would be released and portions of it travel ahead of the crack tips as stress waves. These secondary stress waves, combined with the initial stress waves derived from the impact, would produce high localized strain conditions in front of the fracture zone. The fracture zone would propagate and the specimen shatter. High rates of loading are brought about by short impact times, in turn obtained by employing high velocity projectiles that are of small mass compared to the impacted object.

Oct 1, 1956

By Henry F. Adams, Guy H. Ruggles

IN this paper the authors aim to chronicle the experience and salient points brought out in changing flotation reagents at a concentrator which had probably been using a mininium amount of oil at a minimum cost per ton, to a more complicated system requiring a partial chemical control. The original oils were coal tar and pine oil. The new reagents are lime, xanthate and pine oil. It was found that there were no insurmountable difficulties and eventually the cost of the new reagents per ton of ore proved to be very little more than that of the old. LIME PLANT When the question of handling lime came up there were two propositions open: (1) to handle the lime dry; (2) to handle it wet in the form of an emulsion. Granting that a dry lime feeder would function properly, delivering lime uniformly, the chief objection was the dust that would be raised when these feeders were being charged or operated, as the only possible location was on a gallery beneath which men were working. With this objection the handling of lime as an emulsion seemed to be the better scheme. The lime plant which was first installed was for experimental work on one section. This was gradually changed and developed until it was of sufficient size to accommodate 20 sections. The various changes will not be discussed and the following description deals only with the fully developed plant. Crude as it is, and perhaps somewhat expensive to operate, the lime-handling plant has been quite successful. Much has been learned which will pave the way for a better installation in the future. Burnt lime is received loose in standard gage box cars. This is the product of the kilns and has had no screening or sorting. A grab sample is taken from each car as it is unloaded. An average of the analyses of samples from 44 cars gave the following: [ ]

Jan 1, 1928

By K. C. Ten Brink, Allen D. Garrison

A rrevious paper1 reviewed some of the properties of clays and shales and presented some data on the nature of the gelling phenomenon. It included a brief discussion of origin of clays and shales, their composition, structure, retention of water, ionization, base exchange, and the nature of the gelling of water suspensions. Other publications of the Institute2-8 have discussed the properties of clays and their relations to drilling-fluid behavior and control. It is the purpose of this article to present some new data obtained and arranged in a different manner and making possible a better understanding of the chemical reactions involved in the control of drilling-fluid characteristics during the normal drilling operations. Experimental Procedure The difficulties involved in the measurements of the flow characteristics of plastic fluids are too familiar to recite. The possible applications of some of the well-known instruments to this problem have been adequately discussed by Hobson9 and he has given an excellent bibliography. Although there are many viscosimeters of varied design, none of them appear to fulfill the most obvious demands of accuracy in the measurement of clay or shale suspensions. Since the fluid characteristics are dependent on the rate of flow of the fluid, and the viscosity usually falls off very rapidly as the rate is increased, it is clear that the first requirement is that the instrument shall be capable of a wide variety of speeds. The viscosity of the fluid at any fixed and constant rate of flow is also a function of time, so that the second demand is that the instrument shall be capable of a constant and continuous motion for a prolonged period of time.

Jan 1, 1940

Discussion of the paper of, RICHARD H. RICE, presented at the Pittsburgh meeting, October, 1914, and printed in Bulletin No. 89, May, 1914, pp. 721 to 743. S. G. VALENTINE, Oxford, N. J.-In a paper read at the New York meeting of the Institute last February I presented some notes taken from our experience with the turbo blower operating on a blast furnace. In connection with Mr. Rice's very interesting paper there are a few items that might be of further practical interest. The question of the reliability of this type of blower will naturally be presented. In this connection we would say that our turbo blower has been in practically continuous use during the present blast, which was begun June 7, 1912, with only three interruptions for repairs of any consequence. Soon after blowing in there was developed a tendency of the blower to surge or pulsate. This occurred on operating at a point considerably below the normal capacity of the machine, and was checked with comparatively little trouble by throttling the intake slightly and taking up a small lost motion on the governor connections, a legacy of the previous blast that had not been attended to. All this required only a few hours' time. In. March, 1914, the furnace being banked on account of a blizzard that cut off our freight deliveries for five days, the opportunity was used to replace the carbon packing on the steam-turbine shaft and to repack the steam inlet valves. In June, 1914, the blower was off 8 hr. to replace an oil ring and scrape a bearing. With these exceptions we have made continuous use of the machine and find we can depend upon it with entire safety as a piece of machinery.

Jan 4, 1915

By Charles Bell

THE Telluride mining district of southwestern Colorado is defined by the 37° 45' and 38° parallels of latitude and 107° 45' and 108° meridians of longitude. Telluride was never a boom camp, but has had a steady growth. In recent years, notwithstanding the business depression of 1920, the business has been the same as in normal years. The first prospector is said to have appeared in 1875, in which year locations on the Smuggler vein were made. Shipments were made in 1877 and 1878, and in 1879 milling the ores was attempted. While the district produced high-grade ores, it did not become important until 1890, when the Rio Grande Southern R. R. was completed from Ridgway to Telluride. The railroad has since been extended to Durango. In the fall of 1896, 400 stamps were in operation, and the annual production was $3,000,000.00, two-thirds of which was gold. The total production from 1875 to 1923 was: Gold $58,274,527; silver 41,830,920 oz., valued at $31,016,893; copper 15,258,866 lb., valued at $2,533,291; lead 166,056,484 lb., valued at $8,324,910; zinc 18,141,182 lb. valued at $1,323,787; or a total production of $101,473,408. All: claims are held in fee. Most of them are 1500 by 300 ft. but claims located within the last few years are 1500 by 600 ft. General supplies are obtained at Telluride, Denver, and Salt Lake. The largest mines are within 6 miles of the town of Telluride. Denver is 422 miles and Salt Lake is 439 miles, by rail, from Telluride. One-half of the distance to Denver and one-sixth of the distance from Telluride to Salt Lake is by narrow-gage railroad. The labor is efficient. The best miners are Italians and Austrians, then Slavs, Greeks, and Mexicans follow in the order mentioned. There are no labor unions. There are no serious mine pumping problems, the drainage being through adits. The Tomboy and Smuggler companies pump water from their reservoirs, the former for, milling and domestic purposes and the latter for milling, power, and domestic purposes.

Jan 2, 1924

By William Colby

INCREASING governmental control of human activities seems inevitable. Within the present generation railroad rates and the public sale of water, gas and electricity have been subjected to rigid regulation. The field of control is slowly but surely being enlarged, and it is the object of this paper to outline in brief space this tendency toward increased governmental regulation, as far as mineral resources are concerned. Our, dual form of government complicates the problem. We must deal not only with the powers of the Federal Government, but also with those of the individual States. In order to approach this question intelligently we must have some conception of the powers and jurisdiction of the States and the United States, respectively, over mineral lands and mineral production. Starting with the Federal Government we find it never owned any public domain within the States that formed a part of the thirteen original colonies and, for historical reasons, the same is true of Tennessee and Texas. The Mid-Western States were erected out of the public domain which was acquired by the United States through cession from the original States or by purchase from foreign nations. Congress early in the last century adopted a policy of leasing public lands containing lead deposits in a portion of this Mid-Western territory, but later abandoned that policy and disposed of such public, lands, mineral and non-mineral, outright so that they long since have practically all passed into private ownership and become subject to the general jurisdiction of the respective State governments. In the great public domain lying west of the Mississippi River, and in portions of some of the Southern States, the Federal Government adopted a new mineral land policy following the discovery of gold in California. (Acts of Congress of 1866, 1870, and 1872.) The mineral lands within these States, instead of being disposed of on the game basis as agricultural lands, as occurred in the Mid-Western States, were segregated from agricultural lands and sold under special laws intended to encourage mining, giving the miner the free right to locate and work these mineral lands without paying any royalty to the Federal Government. A miner could also obtain at slight expense a complete

Jan 1, 1930

By K. E. Gray

The status of rock mechanics as applied to petroleum production might be termed, "Rock Mechanics-A New Name for Old Problems." The petroleum industry's efforts, from its earliest days, have been concerned with rocks, hopefully containing hydrocarbon accumulations in economic quantities. Geophysical and geological studies, wildcat and development drilling procedures, well bore mechanics and reservoir engineering operations, and certain aspects of production operations involve rock mechanics in various ways. Stress states and temperatures of interest range from low values in surface or near-surface activities, to very high values encountered at depths now exceeding 25,000 ft; deeper and deeper drilling will continue to increase this range. Time scales vary from a few microseconds in wave propagation measurements and some aspects of rock behavior during drilling, to seconds, minutes or hours for other drilling and well bore mechanics problems, to several years during which the efficient and economical depletion of reservoir systems is achieved. Subsurface sedimentary formations contain various fluids, of course, and reservoir fluid movement commonly involves three-dimensional, three-phase (oil, gas, and water) fluid flow. Many extremely difficult problems in rock mechanics arise for the Petroleum Engineer because of fluid movement (or lack of desired movement) in a well bore or reservoir. The discussion to follow illustrates just a few of the many topics in rock mechanics of significance to the petroleum industry. Time precludes anything other than a superficial treatment of the topics mentioned. A great deal of work has been carried out by various research groups in the petroleum field and significant efforts are continuing, as a review of the technical literature will reveal.

Jan 1, 1968

By C. H. Gerould

I would like to take a moment to consider our polystyrene-silica replica technique, which was developed at the Dow Chemical Co. and which was mentioned in the paper just given by Mr. Thielsch. He stated that he feared that our replica technique would cause difficulty due to deformation of the metal as a result of the application of pressure during the molding process. We at the Dow have never had any reason to suspect that any deformation of the metal was occurring during the molding process. Our procedure has been to heat the polystyrene to a temperature of 160°C. before applying any pressure, at which temperature the polystyrene is a viscous liquid. By so doing the pressure of the polystyrene against the metal is essentially hydraulic and is therefore applied equally in all directions, which we feel should not cause deformation. Our work using this replica technique has brought forth several indications that deformation of the specimen is negligible. These indications are: I. Direct comparisons have been made between the light and electron microscopes when studying a specific spot on a metal surface. These "same spot" studies were obtained by first taking micrographs at high magnification, with a light microscope, of a specific structure that could be readily recog-

Jan 1, 1947

For the seventh consecutive year, the value of nonfuel mineral raw ma¬terials produced in the US set a new record, reaching almost $20 billion-up 12.7% from the previous year, according to the US Bureau of Mines. The Bureau reported that this mineral production was the basis for about $200 billion worth of processed materials of mineral origin.

Jan 5, 1979

By C. R. Van Hise

Introduction.............29 The Three Zones of the Lithosphere ..30 Zone of fracture............31 Zone of flowage............ 31 Factors influencing depth at which flowage occurs.. 32 Zone of combined fracture and flowage.. 33 The Water-Content and Openings in Rocks....36 Condition of rater in the zone of fracture.. 36 The openings in rocks...........38 Size and number of openings..... 40 Ore-deposits derived from zone of fracture..45 The source of underground water......... . 47 The cause of the flowage of underground water..47 Belts of underground circulation.. 51 Upper belt of underground circulation.. 51 Lower belt of underground circulation.. .... .52 Capacity of water for work in the lower belt of underground circulation........... 53 Movementsof water in the lower belt of underground circulation. 54 The preferential use by water of large channels.. 60 Physico-Chemical Principles Controlling the Work of Under ground Waters..........62 Chemical action............63 Underground aqueous solutions..64 The relations of solution and temperature..... 65 The relations of solution and pressure..66 Precipitation........... 67 Precipitation by change in temperature..68 Precipitation by change in pressure..69 Precipitation by reactions between aqueous solutions.. . 69 Precipitation by reactions between liquid solutions and solids. 70 Precipitation by reactions between gases and solutions. and solids............71 The General Geological work of Underground Waters.. . 71 Division of the zone of fracture into a belt of weathering and a belt of cementation............72

Jan 1, 1901

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By M. A. Childers

Recent work with controlled laboratory tests.' field experience and a new analytical approach indicate that casing centralization, pipe movement and relative rheological properties between the mud and cement (yield point and density) are the three controlling factors in successfu1 primary cementing of dual casing. Turbulent flow has been demonstrated to be unnecessary under the severe displace ment conditions of parallel dual strings of casing. Simultaneous reciprocation of dual casing in directionally drilled boreholes is highly dependent on centralization and on the rapid initiation of pipe movement once the casing has been run to total depth. Successful cementing of 30 out of 32 dual, 3%-in casing wells substantiated these conclusions. A review of 15 dual, 3 1/2-in. casing wells completed prior to the adoption of these principles disclosed only one success. Mathematical and graphical techniques permit the engineer to analyze and anticipate the success or failure of a cementing operation. Standoff, mud displacement and reciprocation can be analyzed mathematically and planned in deep, directional or straight boreholes by review of annular geometry, relative rheological properties between the mud and cement, and forces caused by caring weight, functional drag and differential sticking. Introduction The objective in primary cementing is to displace the drilling fluid with cement that will bond to the formation and casing to prevent communication through the annulus. The predominant cause of failure appears to be channels of gelled mud that remain in the annulus after cementing.1 '* Past investigations have noted many procedures that could improve the displacement process.2-' These procedures include centralization, chemical preflushes, mechanical mud cake removers, controlled flow rates in certain regimes, pipe movement an1 control of mud and cement properties. Not until recently have the effects of many of these procedures been isolated so that their individual importance could be determined. In a recent paper,' a comprehensive and analytical laboratory study of various factors controlling the displacement process concluded that there are three major factors in obtaining complete mud displacement by the cement slurry. 1. Good relative rheological properties between the mud and cement. The cement should be heavier and have a yield point and plastic viscosity higher than the mud being displaced. Buoyancy forces often can dominate the displacement process. 2. High degree of standoff or centralization. The more centered the casing, the greater the likelihood of complete mud displacement and removal. 3. Pipe movement obtained by rotation or reciprocation. Often unfavorable rheological properties between the mud and cement, and poor standoff can be compensated by pipe movement. This work demonstrates the compatibility of the latter concepts with field results extended to the more severe dual casing displacement process. Early Experience With Dual 3'/t-In. Primary Cementing Early slim casing completions in the West Delta Block 73 field, offshore Louisiana, included 17 dual 3%-in., 3 single 3% -in. and 1 dual 2% -in. casing installations. Table I provides data on these earlier wells. Usually, common Class A cement was placed across the pay zone and 12 percent gel cement was placed to a height of 500 ft above the highest productive sand. Centralizers (6%-in. OD maximum expansion) were placed two or three per joint on both casing strings from total depth through the completion intervals and at least one per joint for the remainder of the cement sheath. A number of techniques and procedures were attempted to improve cementing success. Casing was run simultaneously or separately with a number of mud conditioning and circulating techniques. Mechanical aids such as cement bonders, slmiding sleeves, turbulizers and various sizes and strengths of centralizers were used. Common and gel cements were mixed with fresh or sea water with a number of different additives to control retardation and dispersion. Cements were thinned and mixed at high rates to try to induce turbulent flow in the annulus. On one well the "slow flow" method was used." Perforating was accomplished with a jet orienting gun. Unsuccessful cement jobs were indicated by production of extraneous fluids or by pressure communication between zones. On test, five wells flowed water, four flowed sand and six had pressure communication with the other string or the 10%-in. casing. A total of 25 remedial squeeze ce-

Jan 1, 1969

Jan 1, 1932