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By J. W. Evans

ONE of the most important and frequent calculations that the extractive metallurgist is called upon to make is that of the standard free energy change of a reaction (?F°). For many reactions of metallurgical interest, the lengthy arithmetical calculations have been eliminated by the use of free energy-temperature diagrams which have been constructed by Ellingham,1 Richardson and Jeffes,2 Kellogg,3 and Osborn4 (e.g., for oxides, sulphides, halides) from critical surveys of existing data. The speed and simplicity of making calculations with these graphs make them of great practical value and, this should be stressed, in the majority of cases no greater accuracy is obtained by the individual calculations from specific heat data, entropies, and heats of reaction. With the increasing industrial application of vacuum methods to the winning of metals, notably at present magnesium and the alkaline earth metals, it is necessary to calculate low metal vapor pressures above reaction mixtures. The existing free energy diagrams usually give values where the solid and liquid metals are at unit activity. To obtain the free energy change associated with the reaction Metal (solid or liquid) = Metal (gas) it is customary to calculate this from either vapor pressure equations or from the appropriate free energy functions. This paper presents graphically the free energies of vaporization of a number of metals of economic importance which can be used in conjunction with other free energy diagrams. Certain metals have been excluded on the following grounds: titanium, tungsten, molybdenum, and platinum have very high heats of vaporization and boiling points and the uncertainty of these values arising from difficulties of high temperature measurements makes free energy values of doubtful accuracy; the data for cobalt, vanadium, and zirconium are uncertain; finally, arsenic, antimony, and bismuth could not be conveniently included. because of the presence of mixtures of polyatomic and mona-tomic vapors in the temperature range considered. Free Energy Diagram In Fig. 1, the standard free energies of vaporization per mol (?F°T) have been plotted for the temperature range 0" to 2000°C for the reaction M (solid or liquid) = M (gas) The data have been obtained from the free energy functions — (F-H298)/T for the solid, liquid, and gaseous elements and the heats of vaporization at 298°K, i.e., ?H298 (vapor). The values of these functions have been taken without change from the recent critical survey by Brewer;' the bulk of this data is from Kelley7 with adjustments in the light of more recent work. Values of the function — (F-H298) /T at T = 298°, 500°, 1000°, 1500°, and 2000°K were employed. Where possible, a further independent value was obtained by using the boiling point, i.e., where ?F°T = 0. All calculations are based on the assumption that the metal vapors are monatomic and that the boiling points refer to those temperatures at which the partial pressure of the monatomic vapor above the metal is 760 mm. For the alkali metals, e.g., sodium, potassium, and lithium, diatomic gas molecules are present as minor species; details of these are discussed by Brewer." On the basis of the above values and allowing for the change in slope at the melting point, straight line graphs were constructed and extrapolated to 2000°C. The deviation from a straight line did not exceed ±500 cal, which in all cases appears less than the probable error in the ?F°T values.

Jan 1, 1954

(Under this heading will he published notes sent to the Secretary of the Institute by members or other persons introduced by members.) No. 488.-Mining engineer, member, technical graduate, married, age 38, desires position of superintendent or assistant superintendent. Has had 15 years' practical experience as miner, millman, machinist, surveyor, engineer, foreman, and superintendent in the West, Southwest, and Mexico. Speaks Spanish. Now employed as superintendent of copper property in Southwest. Can give the best of references. Minimum salary $250. Available now. No. 491.-Mining engineer, member, married, age 43, desires to connect with some-good coal company as superintendent or manager. Is thoroughly conversant with flat and pitching systems of coal mining. Has had 23 years experience from the bottom up; 7 years experience as superintendent and manager. Good organizer. Has handled all classes of labor acid has always made good. Available now. No. 492.-Metallurgist and chemical engineer, member, with 8 years executive experience in research and technical direction of all departments of nom-ferrous metallurgical manufacturing, is open for change in position. Specialist in raw materials-and supplies, reclamation of wastes, and standardized control of processes. No. 493.-Member, age 37, technical education, married. Seventeen years' experience as superintendent, engineer, chemist, and assayer, exploration engineer in United States, Central and South America, Siberia and India. Especially in iron, manganese, copper, and rare metals. Desires to make a change. No. 494. Electrometallurgical engineer, member, age 30, A. M. and Ch. E. degrees, thoroughly trained in electrochemistry, metallurgy and electrometallurgy. Three years in charge of experimental work on and operations of electric furnaces. Desires responsible position in investigative or executive work with commensurate salary.

Jan 11, 1918

THE following employment items are made available to AWE a non-profit basis by the Engineering Societies Personnel Service, Inc., operating in cooperation with the Four Founder Societies. Local offices of the Personnel Service are at 8 W. 40th St., New York 18; 100 Farnsworth Ave., Detroit; 57 Post St., San Francisco; 84 E. Randolph St., Chicago 1. Applicants should address. all mail to the proper key numbers in care of the New York Office and include 6c in stamps for forwarding and returning application. The applicant agrees, if placed in a position by means of the Service, to pay the placement fee listed by the Service. AIME members may secure a weekly bulletin of, positions available for $3.50 a quarter, $12 a year. MEN AVAILABLE Executive Engineer, Mining Engineer Graduate, 25 years' management experience from plant operation to vice president in charge of manufacturing for national concern. Management and operational experience in gypsum, asbestos, cement, paper, felt, asphalt products. West Coast or South location preferred. Prefer permanent position but would consider connection on consulting basis. M-663. Geologist and Engineer, E.M. (Geol.), Ph.D., 46, married, excellent health. Nineteen years' broad experience including appraisal, acquisition, large-scale exploration, special problems, planning, organization, and supervision in U.S., Africa, and South America. Sound approach and execution, writes clearly. Currently employed but available short notice. M-660. Mining Plant Designer. Over thirty years' broad mining experience. Graduate mining engineer, registered mechanical engineer, experienced structural engineer. Member AIME, NSPE. Fully experienced all phases design, from initial plant layout to final details. Excellent references. Presently employed but available reasonable notice. M-661-238-Chicago.

Jan 1, 1952

By M. H. Harris

A solution has been obtained to the problem of calculating flow into a cased and perforated well. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. Computer experimentation indicated that the results are within 3 per cent of the exact solution. Computed results are presented as an apparent skin effect, on a series of dimensionless working curves. Productivity ratios can be rapidly calculated from these data for the wide range of wellbore and reservoir properties actually encountered in field practice. Any reasonable vertical unisotropy ratio can be included in the computation. Productivities can be calculated for wells perforated in a regular pattern, a single horizontal plane or a vertical line on one side of the casing. Solutions for asymmetrical perforation patterns can he easily obtained from the working curves. Solutions for flow into sells completed with a horizontal notch are also provided. Results show that productivity can be increased by extending perforation penetration. This is especially true for shallow penetrations. The highest productivity is obtained when perforations are arranged in horizontal planes, as opposed to a vertical line on one side of the casing. Four or five perforations in one plane will approach the maximum productivity. The effect of perforation hole diameter is small, and is rioticeable only in shallow penetrations. INTRODUCTION The perforating method of well completion has been successfully and widely used in most producing areas. In the past, the desired perforation results were achieved by simply shooting numerous large holes in the casing. A perforating scheme for an area, or particular well, was established by evaluating two types of experimental data: the well flow index and the productivity ratio.' 3 The well flow index test is a means of determining the relative flow capacity of perforations in a linear system. This test also gives information on the perforation size, shape and hole damage which can be expected under well-bore conditions. However, relative flow data from this test cannot be accurately tarnsformed into the radial wellbore system. Thus, no true indication of the productive capacity of a perforated well can be obtained from the well flow index test. A well productivity ratio is derived from electrolytic models built to simulate perforated wells. Available productivity ratio data 2,3 are limited in that all important variables are not extensively evaluated. For example, data are limited to well radii of 3 and 6 in., and to maximum perforation penetration of 1 ft. Practically no information is available on the pattern of flow into a perforation. The effect of various perforation patterns on well productivity has not yet been determined and the effect of perforation diameter has not been thoroughly studied. Also, it will be shown that this type of electrolytic model data is probably in error by as much as 10 per cent or more. Modern completion techniques such as limited-entry perforating, single-plane fracturing, steam and hot air injection and chemical consolidation of incompetent formations all rely on injection and/or production from a limited type of completion. These completions may consist of several high-capacity perforations or a horizontal notch which is equivalent to an infinite number of perforations in one plane. Proper design of these new completion techniques requires, in part, accurate estimates of a well's productive capacity. Data on perforated and notched well productivity have been determined in this investigation. Results are presented as a function of the pertinent variables. Equations describing the idealized system were solved by numerical analysis techniques on a high-speed digital computer. DESCRIPTION OF PROBLEM PRACTICAL APPLICATION The computed results can be applied to wells which meet several general specifications. An external drainage radius of the well must be known or assumed, but the well need not be drilled on a regular pattern. The well must be cased and cemented through the entire producing interval. And, the casing must be perforated with one or more horizontal planes of perforations. The perforation pattern itself must conform to three geometrical requirements. 1. The perforations in a plane must divide the plane into equal angular segments (Fig. 1). Four perforations per plane would be 90" apart. 2. Perforations in a plane must be directly above or beneath perforations in adjacent planes. For two shots per plane, perforations would lie in the BB' plane (Fig. 1). 3. Horizontal planes must have equal vertical spacing and be separated from the top and bottom of the formation by one half the spacing interval. Single planes of perforations should be in the middle of the formation. This is shown in Fig. 2 where h is the formation thickness in a single plane conlpletion or the spacnig interval in a multiple plane completion. The spacing interval at the top and bottom of the formation may vary somewhat without causing an appreciable error in the productivity calculation if the formation is reasonably thick and there are many horizontal planes of perforations. A special provision has been made to calculate the productivity ratios of wells with uneven spacing intervals, or for the case where a single plane of perfora-

Jan 1, 1967

By W. S. Ayres

A BRIEF history of the growth of the anthracite-coal preparation will give a better view-point from which to judge the present problem of separating slate from coal. At the beginning of the commercial value of anthracite, 70 years ago, only the pure portions, or " splits," of the veins were mined and shipped to market, and without any preparation or screening other than the selection, while loading, of the glassy lumps, and the rejection of the fine material and the slate that had strayed accidentally into the coal. The next step was the crushing or breaking of the coal (hence the name Lt breaker" as applied to the preparation-building), and the sizing of it by means of bars or revolving screens. This stage of its development marked the advent of the "breaker-boy " as a slate-¬picker, with his ever-increasing capriciousness. As the richer veins or ? splits " became exhausted and the market demanded a still greater output, the less-pure " splits " and the thinner veins were utilized to produce the coal. Carrying as they do a far greater percentage of impurities; particularly when removing the pillars, it became necessary to build new and better equipped preparation-plants. Finally, we are now at the highest stage of complication yet known to the art of coal-preparation. We are dealing with varying specific gravities, frictional difference, hardness, structure, and form in the pieces of coal and slate coming from many different veins, and

Dec 1, 1909

By Max Boehmer

(Pittsburg Meeting, March, 1910.) AFTER 30 years of development and after an output of $350,000,000 in value of gold, silver, lead, zinc, and copper, there has not been published a satisfactory explanation of the origin of the immense deposits of the Leadville district. The original examination find survey of Leadville by members of the U. S. Geological Survey was a most magnificent piece of work, but their attempt to explain the origin of the ores was based upon the then-accepted theory of lateral secretion, originated by Sandberger, which theory was afterwards disproved in many cases by further development in numerous districts. This theory contended that the ore in the veins had been leached by surface-waters from the eruptive rocks in the immediate vicinity, and it had its origin in the fact that the neighboring eruptive rocks all contained, to an appreciable degree, the several metals found in the ore-deposits. But the practical miner, reasoning in a simple manner from the condition of things as he found them underground, soon discovered the fallacy of this proposition. He reasoned that, in the case of the Leadville deposits, this theory could not be true, because, if the ores were leached from the overlying eruptive rocks by surface-waters, they would as a matter of necessity be controlled by the action of gravity, and the main bodies would collect in- natural depressions of the underlying limestone, and at all points where such depressions existed. But this was not in accord with the channels of ore as he found there ; and hence the theory of lateral secretion in this district was never accepted. Another objection to it consisted in the fact that large areas within the ore-bearing district contained no ores whatever, although their formation was the same, and the same limestones were covered by the same thick sheet of

Feb 1, 1910

By Wallace Ralston

The East Texas area includes the northeast 38 counties of the state of Texas. It covers all, and extends beyond, the borders of what is commonly described as the East Texas Basin. It is one of the most important oil and gas-producing areas of the Mid-Continent Province. It includes four important oil fields—Van, East Texas, Cayuga and Long Lake— and the recent extension of Rodessa field into Cass County, Texas, may prove to be of major size. Four commercial gas fields are in this area— Bethany, Waskom, Cayuga and Long Lake. Up to January, 1936, all of the oil has been produced from the Upper Cretaceous formations, and most of that from the basal member, the Woodbine sand. Gas is produced from both the Upper and Lower Cretaceous formations. Development in Fields East Texas Field.—This field continued to dominate the drilling and production situation throughout the United States. There were 4036 wells completed in this field during 1935; that is, 365 more wells than were completed during 1934. Drilling activity was due to close spacing of wells and the addition of 10,000 acres to the field. The field is now drilled to a density of one well to 6½ acres, which is certainly more wells than necessary for economic production of the field. The close spacing of wells is due mostly to the type of proration, which is per well allowable based on a potential test, and does not take acreage into consideration, and also to the numerous small acreage tracts such as town lots and excess strips. The field now has 19,519 producing wells. The allowable production for the field during 1935 was 161,118,659 bbl.; estimated production, including illegal or "hot oil," was 174,200,150. The illegal production of oil gradually decreased throughout the year, until an estimated low was reached of 20,500 bbl. daily during the months of November and December. The price of oil remained at $1.00 per barrel throughout the year. As stated, about 10,000 acres were added to the field during the year, making a total of 128,000 productive acres. There is a possibility that

Jan 1, 1936

By W. A. Hutchins

Water laws important to the mining industry are those which govern or affect the right to use water, to dispose of water after using it in mining or milling, and to discharge waste material into watercourses. They include statutes and court decisions having general applicability, as well as others that pertain specifically to mining. THE INDUSTRY'S CONTRIBUTION TO WESTERN WATER LAW Despite sharp differences of opinion, the water law the Spaniards brought to the Southwest appears to have included some form of appropriation of water. The Mormons, who settled in Utah in the mid-nineteenth century, also developed a system of appro-priative water titles. But by far the most profound impact on western water law was made by the gold-seekers who flocked to the Sierra Nevada foothills of California after the discovery of gold in 1848. Much of the gold was extracted from the ground by hydraulic or placer mining, and so the miners' rights to the use of water became fundamentally important. Since there was no organized government in the foothills and no laws other than those made by the miners, they helped themselves to the land, the gold, and the water needed to work their claims.1 They established and enforced regulations governing the acquirement and holding of mining claims and their rights to the water they needed.' In 1879 Justice Field, former Chief Justice of the California Supreme Court, spoke for the U. S. Supreme Court in saying that the miners were "emphatically the law-makers, as respects mining, upon the public lands in the State."" Rules of the California mining camps were based on two essential principles: 1) priority in discovering claims and appropriating water by diverting it from streams and putting it to use, and 2) diligence in working claims and applying water in mining. The customs so developed, which were copied in mining areas of other states and territories, were enacted into law in one western jurisdiction after another. They form the basis of what is called the arid-region doctrine of prior appropriation of water, which received the attention of Congress in legislation recognizing and protecting appropriations of water for mining, agriculture, and other purposes on the public domain.' In several western states a great number of water cases decided in the early years involved relative rights to the use of water for mining purposes or for milling connected with mining." The miner's inch, the customary unit for measuring water in the mining camps, is still used in various western communities, although its relation to the cubic foot per second varies from one area to another. Undoubtedly, the miners of a century ago made the major contribution to the appropriation doctrine as it is now recognized and applied throughout the West. What inspired the California gold-seekers to develop these principles? Thoughtful writers have pointed out that their regulations and customs were strikingly characteristic of much earlier mining enterprises in the Old World.D It is said that the right of free mining and free use of flowing water therefor —so similar to the California conditions and practices—-was a part of the customs of Germanic miners in the Middle Ages, that it spread from middle Europe to other countries and colonies, and that the doctrine of prior appropriation was widespread in the important mining regions of the world. Certainly the Forty-niners came to California from many countries. It does not tax the imagination to consider that they may have brought with them some knowledge of the old Germanic customs and applied this knowledge in their new environment. RIGHTS TO USE OF WATER IN GENERAL In the West, rights to the use of water of watercourses fall into two categories—appropriative and riparian. The doctrine of prior appropriation is recognized in each of the 17 western states. The riparian doctrine is recognized concurrently with the appropriation doctrine in some of these states but has been abrogated in the others. The riparian doctrine prevails generally throughout the East, although there is now considerable interest in developing something else. Generally speaking, the appropriation doctrine has been highly developed in the West, whereas the principles of riparian doctrine have been comprehensively established in only a few states throughout the country. The subject of water rights is a big one. Space permits no more than a brief discussion of aspects that bear upon the title of this article. RIGHTS OF PRIOR APPROPRIATION Fundamental to the doctrine of prior appropriation is the principle first in time, first in right. Although in some states there are statutory exceptions. the original and still generally prevailing rule is that the first one who initiates a right to divert and use water of a stream, and who completes his undertaking with reasonable diligence, acquires thereby the first right of appropriation of the specific quantity of water involved. Each succeeding right in point of time is junior to all earlier rights but senior to all later ones. The practical effect of this priority system is that when the water supply is not enough for all, the earliest rights must be fully satisfied before any water may be taken by those later in time. Acquirement of Appropriative Rights: Each of the 17 western states has a statute under which water may be appropriated pursuant to a prescribed procedure. Generally, the first step to be taken by the intending appropriator is to file application in the office of the State Engineer for a permit to make the appropriation. In most but not a11 states, valid ap-

Jan 1, 1961

By William Hurst

Muskat's depletion performance equation is here derived considering the expansion behavior of the reservoir hydrocarbon system and a simple fractional-flow equation. This nietkod of derivation leads logically to the two extensions that follow. The first of these is concerned with gravity segregation in a depletion-drive reservoir. The second is concerned with including an empirically determined tern? for water influx in the performance equation. The more general equation for gravity segregation when there is a primary gas cap and empirically-determined water influx is stated for completeness. These equations have been found useful in reservoir performance calculations in Eastern Venezuela. A discussion on the methods of solving these equations follows, and considers firstly the effect of taking finite intervals in the numerical integration, and sec-ondly, methods of incorporating the time functions involved in segregation in with the expansion behavior. The paper concludes with a brief general discussion on further extensions to the depletion performance equation. INTRODUCTION The two fundamental sources of energy by which oil is produced from a reservoir result from pressure depletion inside the boundaries of the reservoir and fluid encroachment across the boundaries of the reservoir. The wells in either case form low pressure outlets through which oil and gas may be produced by the expansive force of the reservoir fluids and associated encroaching fluids. When the reservoir pressure is higher than the bubble-point pressure of the oil, so that there is no free gas in the reservoir, these expansive forces are the only ones available for the production of oil. However, when the reservoir pressure is less than the bubble-point pressure of the oil, free gas is vaporized as the pressure falls. With both oil and free-gas phases present, the additional forces of gravity and capillarity may operate on the gas-oil system, as they have previously operated on the oil-interstitial water system. Gravity tends to segregate the free gas from the oil due to their density difference. Capillarity opposes and eventually balances gravity as the more extreme free gas and oil saturations are reached, preventing the independent move- ment of free gas until it is above a certain saturation, and the independent movement of oil when it is below a certain saturation. The type of depletion performance equation chosen for predicting the future performance of a reservoir depends on the amount of past history available. When the reservoir is somewhere past the halfway mark in depletion, some form of decline curve is often used. With less past history, material balance equations which incorporate empirical factors based on the past performance are often used. When, however, the amount of past history is small, the Muskat depletion performance equation will usually be used. The distinguishing feature of this type of equation is that empirical factors based on the over-all or macroscopic reservoir behavior are almost or entirely absent. Each parameter affecting the reservoir performance is ascribed an independent set of values based on measurements made on laboratory samples; that is, incorporating microscopic empirical factors. In establishing Muskat-type depletion performance equations, it is necessary to consider the reservoir as consisting of a number of associated blocks, in each of which the saturations and pressures may be considered uniform, and in each of which all substances have uniform pressure-volume characteristics. Thus, a primary gas cap can usually be considered as one block and an aquifer as another. Gravity segregation may be negligible for practical purposes when the rock and oil properties are adverse and/or the dip or thickness of the reservoir is too small. In this case the whole oil leg may be considered as one block, except in very large reservoirs. In very large reservoirs the fluid and rock properties may vary enough, particularly in the dip direction, for it to be necessary to divide the oil leg into a number of blocks, in each of which the relevant quantities may be considered uniform. When gravity segregation of the oil and free gas is not negligible, it is necessary to consider the space occupied by the initial oil leg as divided into two blocks, a secondary gas cap and an effective oil leg, in each of which saturations may be considered to be uniform. The total volume of these two blocks is thus constant, but the secondary gas cap grows continuously at the expense of the oil leg. Muskat1 derived depletion performance equations for the basic case of an oil reservoir with closed boundaries and without segregation, and for the case of an oil

By J. E. Hove

The high temperature physical properties of graphite are reviewed and interpreted in the light of present day knowledge of the mechanisms affecting these properties. The thermal and mechanical behaviors only are discussed and, whenever possible, comparisons are made with other refractory materials. Possible further studies are indicated, including some carbide work. AS long as the term high temperature implied only temperatures up to about 1000°C, the materials problems which arose could usually be handled by fairly conventional metal alloy types, such as the Co-Cr-Ni superalloys, for which there exists a great deal of technology. Perhaps this temperature can still be considered an upper limit for normal applications, but it is certainly true that the number of abnormal applications is increasing rapidly. The advent, in recent years, of ram-jet and rocket missiles and of high power nuclear reactor heat sources has raised a host of questions concerning the basic problem of what material to use in the temperature range up to 2000°C and higher. While there are, of course, many metals, in the second and third transition series, which melt at considerably higher temperatures than this, these metals are, at present, pretty well excluded from practical use by other considerations, such as re-crystallization, chemical activity, or excessive plastic deformation. The behavior of metals, from the standpoint of dislocation theory, is just beginning to be understood and thus there is some hope for the future development of very high temperature metals, but the immediate problems would most logically appear to have solutions involving the nonmetals, such as the refractory ceramics and graphite. For this reason, there is presently a great deal of engineering and experimental research being performed on the latter materials, much of this research being exploratory in the sense of gathering new property data. The situation, so far as graphite is concerned, is somewhat more fortunate than with the other refractory solids in the sense that a great deal is already known about its basic properties. This stems both from the fact that the carbon-carbon bond has been of interest to chemists for a long time (and graphite can be considered as a very large aromatic molecule, if desired) and the fact that its properties, both as a function of temperature and of radiation damage, are of critical importance to nuclear reactor designers. It is still true, of course, that such fundamental questions as why graphite remains solid to such a high temperature and why it has such a high thermal conductivity cannot entirely be answered at the present time. It is, nonetheless, meaningful and instructive to consider such problems in the light of existing knowledge. This is what the present paper will attempt to do. Before going on, it may be appropriate to classify graphite and justify its discussion before readers primarily interested in metals. Graphite is comparatively unique among materials in that there is always a property or group of properties which precludes calling it either a metal, a semiconductor, or a ceramic. It has the high electrical and thermal conductivities of a metal, but the artificial, poly-crystalline types show a negative thermal coefficient of electrical resistivity, generally characteristic of semiconductors. On the other hand, semiconductors, by definition, show an ever increasing resistivity as the temperature is lowered, whereas graphite approaches a finite, and, indeed, a rather low resistivity in the region of 10°K and, furthermore, a good single crystal of graphite has a positive temperature coefficient, as for a metal.' On still another hand, its porosity and brittleness at lower temperatures would put graphite in the ceramic class although, unlike most ceramics, it is readily machinable and has a high resistance to thermal shock. All things considered, it is probably more nearly appropriate to call graphite a metal than anything else. Although certainly outstanding in some ways, graphite has its peculiarities and, especially if the reader is unfamiliar with the data, it is probably valuable to review some representative property variations at high temperature. This review is meant to be mainly illustrative and no attempt has been made to be exhaustive. Review of High Temperature Properties At ordinary pressures, graphite does not melt, but sublimes directly into the gaseous phase at about 3700°C. Although the phase equilibrium diagram is still in some doubt, graphite will melt, at a slightly higher temperature, at pressures in excess of about 100 atm. The chief difficulty of using graphite in an oxidizing atmosphere is that the reaction rate becomes quite high at fairly low temperatures. If a threshold oxidation temperature2 is defined as the temperature at which graphite loses 1 pet of its weight in 24 hr, the value in air is 450°, the value in steam is 700°, and the value in carbon dioxide is 900°C. Efforts are presently being made to raise this threshold temperature either by impregnation with a retardant of some type (sodium tung-state and phosphoric acid, for example) or by a suitable metal or oxide coating. It is probably fair to say that, to date, these attempts have not shown any outstanding success in all respects. Most commercial graphites are fabricated by impregnating a carbon flour (say of coke or lampblack particles) with some type of hydrocarbon

Jan 1, 1959

By R. H. Hopkins, R. W. Kraft

X-ray and metallographic analysis reveal that the preferred cryslallograPhic relationships in direc-tionally solid~fied Pb-Sn eutectic specimens can be stated: interface growth direction, Experiments in which tin single-crystal seeds were used to nucleate the eutectic demonstrate that the normal lamellar structure observed at steady state can be forced to break down initially to a semide-generate structure when the crystallograPhic direction of the tin seed does not lie within the preferred eutectic interface plane. A normal structure eventually develops by preferred grain growth. X-ray topo-graphs and rocking curves substantiate that the perfection of eutectic samples increases as growth proceeds until steady-state conditions prevail. RECENT years have seen substantial progress made in the understanding of eutectic solidification through both intensive theoretical1'' and experimental investigations (see Ref. 7 for a review and extensive bibliography of both aspects). Several important observations concerning the nucleation and growth aspects of binary eutectic solidification have been brought to light. Briefly some of these include the nonrecipro-cal nucleation of one phase upon another,'j9 the tendency for a specific low-index direction of one or both phases of the eutectic to be aligned in the growth direction during unidirectional solidification,'0711 and the production of lamellar microstructures having a preferred interface plane between "11-13 phases. Questions quite naturally arise as to the mechanism by which preferred grain growth evolves during eutectic solidification and what relationships (if any) connect the initial nucleation of one phase upon another with the preferred growth directions and interface planes observed after a few centimeters of growth in many systems. This study was initiated in an attempt to answer these questions. An experiment was devised in which both the nucleation and growth steps in the crystallization of a binary eutectic, Pb-Sn, could be correlated with subsequently developed eutectic morphology and crystallography. This was accomplished by nucleating the eutectic upon a tin single crystal seed and then causing the eutectic to grow from the seed by directional freezing. The morphology of the structures produced in this manner was then monitored metallographically and the orientation relationships and substructural perfection determined by X-ray analysis. The information thus ob- tained was correlated to the growth history of the samples. EXPERIMENTAL DETAILS The eutectic of composition 38.1 wt pct Pb and 61.9 wt pct sn14 was prepared by accurately weighing lead and tin of 99.999+ (from ASARCO and Lytess Metals and Chemicals, respectively), melting in a clean Pyrex beaker under an argon blanket, and casting into the proper crucible for resolidification as described below. Tin seeds were grown by the method of ~halmers," saw-cut, oriented by the Laue method, and soldered to the pull rod of the Czochralski puller. All seeds were given a final electropolishing (to assure the removal of any deformed material from the cutting operation) and acetone degreasing immediately prior to the nucleation experiment in which they were to be used. Eutectic samples were unidirectionally solidified in a horizontal graphite boat1' or by pulling from the melt16 with tin (or graphite) seeds. A flowing argon atmosphere was employed in all experiments and growth rates and temperature gradients, constant for a given run, varied from 2 to 4 cm per hr and 8" to 15°C per cm over the course of all the experi-

Jan 1, 1969

By C. W. Mueller, P. H. Robinson

A technique was developed for depositing single -crystal films of silicon on single-crystal sapphire substrates via the pyrolytic decomposition of SiH4/H2 mixtures. Electron diffraction and X-ray Laue reflection examinations of these films revealed single-crystal patterns. These films were characterized by measuring conductivity type, thickness, resistivity, and Hall mobility. Chemical etching, dislocation staining, and electron-microscopy examination have indicated the presence of low-angle grain boundaries and microtwinning in the silicon films. The role of the sapphire substrate with respect to its quality, orientation, surface finish, and thermal and chemical treatment was investigated. Hall mobility as a function of sapphire orientation was measured. A mobility equal to 88 pct of bulk silicon mobility was attained. Insulated-gate field-effect transistors which have a transconductance of 4000 pmho at 6 ma were fabricated using these films. THE technology of the fabrication of microelectronic circuits with active and passive components directly on a single wafer of semiconductor material has attained a high degree of perfection during the last few years. One inherent difficulty with the single-wafer approach has been undesirable coupling between components arising from the common base material. Several techniques have been developed for minimizing this coupling and obtaining good electrical isolation between components; however, these result in extra capacitance being added to the circuit. The extraneous capacitance of the connecting leads, resistors, and capacitors degrade circuit performance and limit the high-frequency operation of these circuits. Recently there has been considerable interestl-3 in the deposition of silicon films upon insulating substrates. The use of silicon as the semiconductor allows the subsequent utilization of the large amount of technology which has been developed for silicon for the fabrication of good active components. A sapphire substrate supplies an excellent insulating material which at the same time gives a thermal-conductivity improvement of an order of magnitude over glass-type substrates. This paper will describe the results obtained for the deposition of single-crystal silicon layers upon single-crystal sapphire substrates as well as the characterization of these films. I) APPARATUS The 'system used for the growth of silicon films on sapphire substrates by means of the pyrolysis of SiH4/H2 mixtures is shown in Fig. 1. The all-quartz reaction chamber is water-cooled and includes a quartz optical-flat window for use in conjunction with a 5 kw, 2.5 Mc per sec constant-temperature controlled rf generator. The temperature sensor for the rf generator is a thermopile which is focused through the quartz optical flat onto the susceptor surface. With this system the rf generator will hold the temperature of the susceptor to about +0.3°C at 1200°C. The susceptor is supported on a quartz sled inclined to the gas flow to increase the uniformity of the deposition. The water jacket surrounding the reaction chamber is used to keep the quartz wall temperature low enough to limit the decomposition of the silane to the rf-heated susceptor which contains the sapphire substrates. This eliminates the reaction of silicon with the hot quartz to form SiO which deposits out on the apparatus walls, thus obscuring vision, and interferes with the optical measurements of the temperature as well as with the growth process itself. Provision is also made for "n"- and 'p"-type doping by using mixtures of either phosphine or diborane in hydrogen which are added to the silane during the growth process. The hydrogen used is the purest commercially available tank hydrogen further purified by use of a palladium diffuser. The susceptors which were used include 1) spectro-scopically pure graphite, 2) high-purity molybdenum, 3) high-resistivity silicon using a low-resistivity insert to facilitate coupling to the rf generator, 4) silicon carbide-coated graphite. The latter two susceptor materials produced silicon films on sapphire substrates with more reproducible resistivities. Prior to silicon deposition all connecting lines as well as the reaction chamber are thoroughly flushed with argon and then hydrogen. After the hydrogen flow is set, the growth temperature is adjusted to 11009 to 1150°C, and when thermal equilibrium is reached the silane flow is started. The flow rate of the hydrogen must be fast enough so that turbulent flow occurs in the size of reaction tube used, otherwise a streaked nonuniform silicon deposit occurs. After the deposition

Jan 1, 1967

By J. B. Dorsey, T. W. Brinkley

Performance of a high-pressure, vaporizing gas-drive project in a volatile oil reservoir is discussed. The project has been in operation for over 8 years. Present recovery from the over-all displaced portion of the reservoir is 40 percent, and an ultimate recovery of 60 percent is indicated. Calculations reflect an over-all displacement volume of 50 percent for the entire reservoir; therefore, ultimate oil recovery will be 30 percent of the entire reservoir oil originally in place. Laboratory vaporization tests conducted prior to project initiation also are presented and discussed, along with an analytical method of determining stock-tank oil production and gar injection requirements related to over-all volumetric displacement efficiency from these data. Introduction The Shoats Creek field is located in Beauregard Parish, La., in the extreme western part of the state (Fig. 1). Discovered in 1956, the field is productive in three Cockfield sand zones, ranging in depth from 8,000 to 9.000 ft. The upper two zones, 1st and 2nd Cockfield, are condensate-bearing gas reservoirs. The lowest zone, the 5th Cockfield, is a volatile-oil reservoir. Laboratory work conducted on crude oil from the 5th Cockfield zone shortly after field discovery demonstrated that, when contacted with dry gas, signidcant volumes of the oil could be vaporized at reservoir temperature and at an appropriately high reservoir pressure. Further study led to the conclusion that early initiation of a crude vaporization project in the 5th Cockfield zone would be superior economically to other methods of reservoir depletion. Consequently, the zone was unitized and gas injection operations started late in 1958. This paper discusses laboratory work performed in conjunction with the project, and project performance to the present. History of Development The 5th Cockfield zone in Shoats Creek is composed of a thin, very shaly, low-permeability sandstone. Oil accumulation is controlled by a structural trap bounded by faults along the north and west and by a water contact on the southern boundary (Fig. 2). The zone covers a productive area of 1,550 acres at an average depth of 9,000 ft. The net sand section is thin, having a maximum thickness of 10 ft and an average thickness of 5.5 ft (Fig. 3). Average reservoir rock properties, as determined from core analysis are presented in Table 1. Shaliness of the zone is illustrated by the typical electric log of the 5th Cockfield section in Fig. 4. Because of the thinness and poor quality of the sand, the 5th Cockfield was developed on a wide spacing. Eleven completions were made in the zone between 1956 and 1961 for an average density of 140 productive acres per completion, with the majority of wells being dually completed in the 2nd and 5th Cockfield. Average initial potential for producers in the 5th Cockfield was 130 BOPD. Oil from the 5th Cockfield has a stock-tank gravity of 50.5" API; with a bubble-point pressure of 3,515 psia, the oil was highly undersaturated at the original reservoir pressure of 4,675 psia. Pertinent properties of the oil as determined in the laboratory are presented in Table 2. Because of the volatile nature of the crude, laboratory studies of its susceptibility to vaporization, as well as a vapor-liquid phase study, were conducted in addition to a standard PVT analysis. The vaporization study was conducted in a visual cell; a stepwise illustration of this work and laboratory measurements are presented in Fig. 5. Field

Jan 1, 1969

By A. J. Opinsky

ThE superior performance of nonsag tungsten wire in lamps has been ascribed to the large-grained micro-structure that can be developed in it. The orientations of these large grains have been studied several times; most published data1-' appear to be similar to those plotted in Fig. 1. These new data were obtained by X-ray back-reflection Laue technique from all of the large grains occurring in thirteen different wires that had been heated at the lowest possible temperature for the formation of large grains. Here the wire axis is plotted in terms of the principal directions of the cube. Rosi decided that the preferred orientation of the large crystals could be described by a single ideal orientation, (531), being parallel to the wire axis.' Rieck2,3 and Mannerkoski' have essentially confirmed this finding. Opinsky, Orehotsky, and Seigle argued that the data suggest that (211) is parallel to the wire axis instead of a single ideal orientation.5 This {211} contains the (531) ideal orientation and would appear to be a more general case. Ahlborn and Wassermann report that their orientation data stretch from ( 110) through (531) to (311) 8 This is part of the locus of (211). All these investigators have determined the orientations of the large grains by back-reflection Laue techniques. They have all obtained essentially similar results. On the other hand, Swalin and Geisler, who obtained their data by neutron diffraction, indicated that the preferred orientation of the large grains in doped wire is (110) .7 These findings cannot presently be reconciled with the pole density data described in the previous paragraph. Rosi1 and Rieck2 have advanced arguments about how their orientations could occur. Nevertheless, the crystallographic link between the (110) (cold-worked) fiber texture and the preferred orientation of the large grains has remained missing. This link can be provided through the concept of coincidence-type boundaries. Such boundaries separate two grains that have a certain number of common lattice sites. Coincidence relationships that result from rotations about low index directions are given by Brandon et a1 .' What is desired is a calculation of those orientations that bear a coincidence relationship with the (110) fibers of the cold-worked matrix. This situation arises in the following fashion. Heating the tungsten wire for a combination of time and temperature falling short of the formation of the nonsag structure yields a structure that is still fibrous in nature and the preferred orientation remains (110). During grain growth, the growing grain is in contact with these fibers. It is hence possible that the entire process may begin by the passage of a coincidence boundary into a (110) fiber. The calculations were carried out analytically and checked graphically. Following Brandon et a1.,8 coincidence relationships from 1 in 5 to 1 in 19 have been considered. The results of the calculations are given in Fig. 2. Of the coincidences examined, some of those occurring upon rotation about ( 110) come closest to the experimental points in Fig. 1. Nineteen of the twenty-three data points in Fig. 1 can be attributed to the ideal orientations A, B, C, and D in Fig. 2. As determined analytically, three crystals lie within 4 deg of point A, four lie within 21/2 deg of point B, eleven lie within 5 deg of point C, and one lies within 1 deg of point D-a total of nineteen. The off-lying points are near the |110| point of the triangle.

Jan 1, 1968

By E. W. Davis

About a year ago several carloads of magnetite ore from New York state were sent to the Mines Experiment Station at the University of Minnesota for grinding and concentration tests. The flowsheet used minus ½-in. ore as feed to a 3 by 3-ft. overflow cylindrical ball mill operating at 37 r.p.m. in closed ciruit with a vibrating screen. The screen oversize was returned to the mill for further grinding and the screen undersize was concentrated magnetically. Several different screens, between 8 and 35 mesh, were used and it was desired to determine the capacity of the ball mill operating in closed circuit with each screen. From earlier tests using this flowsheet and equipment, it was known that when comparatively coarse screens were used it was necessary to increase the grinding dilution in the mill beyond that ordinarily used when grinding in closed circuit with classifiers. It was also known that after the circulating load had passed about 100 per cent of the original feed it tended to increase rapidly in amount, and grinding conditions appeared to become unstable. These conditions may be peculiar to this small ball mill but they were very marked in this series of tests. If conditions were not right, the mill would suddenly "go dead," and it was found desirable to operate so that the occasional rattle of balls against the lining of the mill could be detected. As the test proceeded, it was found that the cure for almost any difficulty that developed in the grinding circuit was to add more water to the mill feed. To begin with, the mill was operated at pulp densities of from 60 to 65 per cent solids but gradually it was found that with higher dilutions grinding conditions were more stable and the ball-mill power per ton of screen undersize decreased. Actually, the most satisfactory operating conditions were secured with a pulp density of about 40 per cent solids. The ore was hard but it was possible to grind ½-in. feed so that all would pass an 8-mesh screen with a power expenditure in the ball mill of less than 2½ kw-hr. per ton and with a circulating load of less than 50 per cent. With so high a dilution in the feed to the mill, it was feared that steel wear would be very high. However, the mill was not noisy, and in order to find exactly the grinding conditions, a special test was made at the end of the main series of tests. After the mill had been in operation for several hours and grinding conditions had become balanced, the power to all the equipment was shut off at a given signal. The ball mill made about one revolution after the power was turned off, and just as soon as the mill stopped, a spout was placed at the discharge trunnion and all of the pulp that flowed out of the mill was caught in tanks. The manhole in the mill was then opened and the whole mill charge dumped into other tanks. Both of these products were weighed, dried, and weighed again. The balls were screened out and weighed, and the dry solids were sized. In this way it was possible to determine the nature of the pulp and the ore within the mill under actual grinding conditions.

Jan 1, 1947

By E. W. Davis

About a year ago several carloads of magnetite ore from New York state were sent to the Mines Experiment Station at the University of Minnesota for grinding and concentration tests. The flowsheet used minus ½-in. ore as feed to a 3 by 3-ft. overflow cylindrical ball mill operating at 37 r.p.m. in closed ciruit with a vibrating screen. The screen oversize was returned to the mill for further grinding and the screen undersize was concentrated magnetically. Several different screens, between 8 and 35 mesh, were used and it was desired to determine the capacity of the ball mill operating in closed circuit with each screen. From earlier tests using this flowsheet and equipment, it was known that when comparatively coarse screens were used it was necessary to increase the grinding dilution in the mill beyond that ordinarily used when grinding in closed circuit with classifiers. It was also known that after the circulating load had passed about 100 per cent of the original feed it tended to increase rapidly in amount, and grinding conditions appeared to become unstable. These conditions may be peculiar to this small ball mill but they were very marked in this series of tests. If conditions were not right, the mill would suddenly "go dead," and it was found desirable to operate so that the occasional rattle of balls against the lining of the mill could be detected. As the test proceeded, it was found that the cure for almost any difficulty that developed in the grinding circuit was to add more water to the mill feed. To begin with, the mill was operated at pulp densities of from 60 to 65 per cent solids but gradually it was found that with higher dilutions grinding conditions were more stable and the ball-mill power per ton of screen undersize decreased. Actually, the most satisfactory operating conditions were secured with a pulp density of about 40 per cent solids. The ore was hard but it was possible to grind ½-in. feed so that all would pass an 8-mesh screen with a power expenditure in the ball mill of less than 2½ kw-hr. per ton and with a circulating load of less than 50 per cent. With so high a dilution in the feed to the mill, it was feared that steel wear would be very high. However, the mill was not noisy, and in order to find exactly the grinding conditions, a special test was made at the end of the main series of tests. After the mill had been in operation for several hours and grinding conditions had become balanced, the power to all the equipment was shut off at a given signal. The ball mill made about one revolution after the power was turned off, and just as soon as the mill stopped, a spout was placed at the discharge trunnion and all of the pulp that flowed out of the mill was caught in tanks. The manhole in the mill was then opened and the whole mill charge dumped into other tanks. Both of these products were weighed, dried, and weighed again. The balls were screened out and weighed, and the dry solids were sized. In this way it was possible to determine the nature of the pulp and the ore within the mill under actual grinding conditions.

Jan 1, 1947

By Clyde Orr

INTRODUCTION Cracks, crevices, holes, and fissures -- here collectively termed pores -- occur in all manner of substances in sizes from those evident to the unaided eye to those well below electron microscopic levels of detection. Naturally occurring materials having varying degrees of porosity are represented by wood, rock, soil, and mineral formations. Man-made materials that are porous include ceramics, sintered metals, catalysts, adsorbents, filters, and various compacted objects. The extent of their porosity greatly influences the hardness, rigidity, integrity, and general usefulness of such materials, and assessing both their pore volume and size is becoming increasingly necessary. Means by which this pore information can be obtained is the subject here. No attempt will be made to include all techniques and variations of them that have been suggested, but, hopefully, those of most general applicability will be described in sufficient detail to enable a potential user to judge their merit for a particular need. The results of pore measurements are made useful by relating them through other tests to performance criteria such as weatherability, water penetration, frost damage, oil recovery, strength, or thermal or electrical conductivity. These tests, of course, are outside the bounds for inclusion here. A pore is variously defined in dictionaries as "a minute opening", "a small interstice admitting passage of liquid", and "an interspace between particles". Clearly any object through which it is possible to find a continuous path from one side to the other either for a liquid or a gas must be regarded as porous. Passageways are not necessary for porosity to exist, however. There are so-called blind

Jan 1, 1980

By E. W. Davis

ABOUT a year ago several carloads of magnetite ore from New York state were sent to the Mines Experiment Station at the University of Minnesota for grinding and concentration tests. The flowsheet used minus ½ -in. ore as feed to a 3 by 3-ft. overflow cylindrical ball mill operating at 37 r.p.m. in closed ciruit with a vibrating screen. The screen oversize was returned to the mill for further grinding and the screen undersize was concentrated magnetically. Several different screens, between 8 and 35 mesh, were used and it was desired to determine the capacity of the ball mill operating in closed circuit with each screen. From earlier tests using this flowsheet and equipment, it was known that when comparatively coarse screens were used it was necessary to increase the grinding dilution in the mill beyond that ordinarily used when grinding in closed circuit with classifiers. It was also known that after the circulating load had passed about zoo per cent of the original feed it tended to increase rapidly in amount, and grinding conditions appeared to become unstable. These conditions may be peculiar to this small ball mill but they were very marked in this series of tests. If conditions were not right, the mill would suddenly "go dead," and it was found desirable to operate so that the occasional rattle of balls against the lining of the mill could be detected. As the test proceeded, it was found that the cure for almost any difficulty that developed in the grinding circuit was to add more water to the mill feed. To begin with, the mill was operated at pulp densities of from 60 to 65 per cent solids but gradually it was found that with higher dilutions grinding conditions were more stable and the ball-mill power per ton of screen undersize decreased. Actually, the most satisfactory operating conditions were secured with a pulp density of about 40 per cent solids. The ore was hard but it was possible to grind ½ in. feed so that all would pass an 8-mesh screen with a power expenditure in the ball mill of less than 2 1/2 kw-hr. per ton and with a circulating load of less than 50 per cent. With so high a dilution in the feed to the mill, it was feared that steel wear would be very high. However, the mill was not noisy, and in order to find exactly the grinding conditions, a special test was made at the end of the main series of tests. After the mill had been in operation for several hours and grinding conditions had become balanced, the power to all the equipment was shut off at a given signal. The ball mill made about one revolution after the power was turned off, and just as soon as the mill stopped, a spout was placed at the discharge trunnion and all of the pulp that flowed out of the mill was caught in tanks. The manhole in the mill was then opened and the whole mill charge dumped into other tanks. Both of these products were weighed, dried, and weighed again. The balls were screened out and weighed, and the dry solids were sized. In this way it was possible to determine the nature of the pulp and the ore within the mill under actual grinding conditions.

Jan 1, 1945

By D. J. Weintritt, R. G. Hughes

Statistics show arz increase in the average depth of wells drilled in recent years. As a corollary to this trend, drilling fluids have been improved in an effort to meet the problems inherent at temperatures approaching 500°F. Of importance are (1) deterioration of mud components and (2) the effect of solids on filtration and rheological properties. High-temperature, stable water-base and oil-bare muds are discussed. Those areas in which differences exist are pointed out. Results are based on data taken from the Fann consistotneter, rheometer and shear-strength measurements, static and dynamic filtration tests, methy-lene blue test for bentonite solids and specific heat measLrrenlents of muds. INTRODUCTION Higher well temperatures go along with the fact that the average depth of wells continues to increase. Recent data by Gardner' lists 137 completions deeper than 15,000 ft for the first half of 1964 with a record second-half total of 167 wells drilling or proposed. In addition, there has been an increase in drilling for steam for power production or mineral recovery. In this application the depths are modest, but the mud may approach the critical pressure and temperature of water. Scearce and Magnon' report drilling mud used at temperatures of about 700°F in the Salton Sea area of California. Most deep wells have been drilled with water-base muds. In recent years, however, there has been a substantial increase in the use of oil-base muds because of technological advances in effective additives. The significance of this development was dealt with in considerable detail by Simpson and his co-workers.3 Additiona1 field data have now been obtained to indicate that oil muds are competitive in control, performance and cost with the best types of water muds for use at high temperaturc. This parallel offer of two very different fluid systems, each offering a similar variability in performance, cost and convenience, has created the need to evaluate the merits of these fluids under specified conditions so that the advantages and disadvantages of each can be weighed in relation to the over-all drilling program. This paper is not intended as a review of all the factors. Rather, it attempts to emphasize: (1) important condltions and facts peculiar to high-temperature drilling muds, (2) that more than one imposed test condition or testing method is necessary to describe the quality of a mud at high temperature and (3) that elaborate experimental precautions are necessary whenever laboratory data are used in selection of a mud for field use. WHAT IS A HIGH-TEMPERATURE DRILLING FLUID? For the purpose of this discussion, a high-temperature drilling fluid is any system so formulated or treated to economically minimize the effects of temperature on the properties of the fluid. Our experience in drilling fluids suggests that these effects become obvious for many mud materials at temperatures of 300F or higher. It is understood that hydrolysis of starches, depoly-merization of certain organic thinners, or irreversible chemical reactions (such as that of clay and lime) can affect filtration, viscosity and shear strength at less than 300F. However, the temperature level is not a serious point and in no way affects the precautions and techniques used in this study. An up-to-date review of the literature on high-temperature drilling fluids and the many variations was treated by Rogers'in 1963. EXPERIMENTAL REQUIREMENTS TESTING EQUIPMENT AND PROCEDURES With the advent of deeper drilling and increased demand for temperature-stable drilling fluids, new testing equipment and laboratory techniques were devised for the evaluation of drilling fluids subjected to elevated temperature and pressure. While the equipment has not been standardized, it is in widespread use. Milligan et al. Qescribe a filtration cell for determining the filtration properties of drilling fluids at temperatures in excess of 300F. They showed the effect of variations in temperature and pressure on oil and water muds filtered in the 300 to 400F range. The dynamic filtration apparatus described by Simpson6 permits the study of the filtration properties to temperatures of 350F for drilling fluids circulated over sandstone cores. Watkins et al.' describe the use of pressure bombs for studying the effect of prolonged periods of elevated temperature upon the gelation or solidification of drilling fluids. Chisholm et a1.' describe the use of a modified cement consistometer adapted for use in drilling fluid evaluations. A similar consistometer is used in this study, although the application and data-recording method have been changed. The consistency of a mud sample is measured by timing the movement of a soft iron bob which is magnetically moved up and down in the sample container.* Changer in the time of travel and the temperature of the mud at that moment are plotted with a two-point Brown Elec-tronik Recorder. A 10-in. chart with a speed of 4-in./hr is used. Fia.- 1 is a generalized internretation of the data ob-

Jan 1, 1966

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963