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By W. C. Roberts-Austin

The subject with which the Council of the American Institute of Mining Engineers has entrusted me is one of much interest. It has been so admirably treated in America by Prof. Carl Barus* that I should have hesitated to deal with it had not the adoption of pyrometric methods in England recently occupied much attention, especially in relation to metallurgical industries and research. I shall endeavor to show what is the present state of our knowledge of practical pyrometry by briefly tracing the history of the efforts which have been made to measure high temperatures. This paper will, therefore, be limited to the consideration of those forms of appliance which have either marked distinct stages of advance, or have remained in use with more or less modification through a considerable range of time. The earliest pyrometers were essentially thermoscopes, and although their graduation presented great difficulties, their importance as affording a means for the measurement of high temperatures has been recognized for centuries. It would be difficult to illustrate this better than by a brief record of the testimony which has from time to time been offered by those who have had to apply the heat of furnaces in research or in industry, and it is mainly for the sake of the light incidentally thrown on the progress of both that the following historical notes are offered. In the eighth century, Geber, the chemist, wrote a treatise on furnaces, and showed that he was familiar with many and varied means of applying heat; but he points to the difficulties that are met with in conducting operations at high temperatures, which he attributed to inability to measure heat, his actual words being: " sed quoniam non est res ignis, quae mensuari possit." t

Jan 1, 1894

By H. W. Weart, D. J. Mack

SINCE the first recognition of eutectic solidification as the simultaneous formation of 2 solids from one liquid,1 many complex structures thus produced have been observed. Despite many attempts to ascertain it, however, the detailed mechanism by which these structures develop remains obscure. In an attempt to clarify the origin of eutectic structures, the study described in this paper was undertaken. The broad objective of the study was to investigate the effect of different solidification conditions on the structure of single eutectic grains. It was expected that the eutectic structure would thereby be isolated for study, but preliminary experiments revealed another structure within each grain. When a literature surveye revealed only 1 previous mention of the subgrain structure,' it was decided to determine the origin of the structure and to study its response to various growth conditions. Before presenting the details of the investigation, it is apropos to distinguish carefully among the 3 structures produced during eutectic solidification. This is especially desirable in view of the apparent confusion existing in the literature concerning the structures in a eutectic specimen. The confusion is due largely to the existence of the subgrain structure noted above which is easily mistaken for the grain structure. In the following paragraphs, an effort is made to distinguish the 3 structures by briefly describing their origin during solidification, even though the results are thereby anticipated slightly. The 3 structures produced during eutectic solidification are the grain structure, the colony structure, and the eutectic structure, each one contained by the one preceding it. The grain structure is analogous to the polycrystalline structure of a metal or inle-phase alloy in that each grain grows from a single nucleus. A somewhat broader interpretation is needed here, however, because of the presence of 2 phases in each grain. Since in most eutec-tics particles of 1 phase are dispersed in a matrix of the other, a grain may be taken to be the region in which the matrix phase is monocrystalline.*

Jan 1, 1959

By Eugene A. Stephenson

The writer apologizes for presenting this very elementary analysis of one aspect of proration, but a search of the literature failed to disclose any concrete illustrations of the effect of various proration formulas upon the allowable oil produced by tracts of different sizes. Many engineers have doubtless made somewhat similar calculations and are fully acquainted with the results. The various allocation formulas that are in use are based on one or more of the following factors: (1) wide-open well potential, (2) potential through an orifice, (3) uniform well allowable, (4) acreage, (5) sand thickness, (6) bottom-hole pressure, (7) productivity index, and (8) volumetric displacement. Of these, the unrestricted potential formula, or open-flow test, and the uniform well allowable are commonly regarded by engineers as those least likely to give each producer his proportionate share of the oil or gas, as represented either by acreage or by sand thickness, or both, except when the wells are located on tracts of large size. Unless the mechanical equipment that may be used during the potential test and the method of taking the test are both specified, the net result of the potential formula is to practically force the operators to use special equipment and adopt special procedures prior to and during the potential test, so as to secure the largest possible allowables. Much ingenuity and skill have been devoted to this,problem, but the general effect is to permit excessive allowables for very small tracts, and stimulate unnecessary drilling. It is interesting to compare some of the high yields from the Wilcox horizon at Oklahoma City with each other, as an illustration of the effect of an allocation factor based solely on potential (Table 5). One of the glaring instances is a well on a ½-acre lease, which had produced, as of September 1936, at the rate of almost 3,000,000 bbl. per acre. This is at least twice as many barrels as could have been present under the property if the reservoir had consisted of a tank of oil 200 ft, deep and 56 acre in area. Numerous combinations of acreage, potential, bottom-hole pressure, sand thickness, etc., have been proposed and are in use in various fields.

Jan 1, 1937

By Yves Dardel

INTRODUCTION SINCE the first determination of Dumas1 in 1880, many authors have tried to measure the solubility of hydrogen in solid aluminum, or at least the amount of dissolved gas in it. However, the interpretation of the results which have been obtained is still difficult. Sieverts,2 then Baukloh and Oesterlen,3 during their gassing experiments could not determine any solubility of hydrogen in solid aluminum. On the other hand, Portevin, Chaudron and Moreau,4 leaving the determination of the hydrogen solubility beyond the scope of their experiments, measured only the amount of gas that they could extract by high voltage positive ion bombardment and found up to 151 cm3 of gas per 100 g of metal. Winterhager,5 by repeated vacuum extraction during severe cold rolling, extracted up to 161 cm3 per 100 g. In both series of experiments, the extracted gas contained chiefly hydrogen with a small amount of nitrogen, carbon monoxide, carbon dioxide and methan. Later, Schmidt and von Schweinitz6 as well as Chaudron and Moreau7 showed the importance of the adsorbed layer of hydrogen, the extracted quantities being proportional to the surface and not to the weight of the sample, when its cleaning was not perfect. In earlier experiments, Steinhauser8 extracted from more massive samples nothing but a little amount (< 0. 5 cm3 per 100 g) of hydrogen, carbon monoxide and methane. Thus, according to these experiments the quantity of dissolved gas is probably very small and the effect of the surface could falsify the results of the extraction. However, owing to the care taken by Chaudron and his coworkers, it was clear that all the hydrogen extracted could not come from the superficial layer, or that the links which bound hydrogen to the surface were so strong that the usual method of cleaning could not destroy them. After the main parts of the experiments reported here had already been carried out, Eborall and Ransley9 published the results which they obtained with an analysor having an accuracy of 0.03 cm3 per 100 g, while that of the usual apparatus was only about 0.2 cm3 per 100 g. During all their experiments the adsorbed layer would have been a difficulty, for the value of the adsorbed hydrogen was approximately equal to that of the dissolved amount. [ ] Since always keeping the same adsorbed layer is very difficult, an error in the correction for the adsorption can be made when using the apparatus of Eborall and Ransley, as well as the earlier apparatus,

Jan 1, 1948

By Frank F. Aplan

In looking into the crystal-ball scene of minerals beneficiation for 1970 and beyond, an impartial observer becomes con- fused as to what has been done and what is possible in the way of improvements. The mining official must balance the burden which is being shouldered by the mineral industry for maintaining our environment in its pristine state on one hand, with the solid advancements made in technology and cost savings on the other hand. Then the official wonders if this is really the criterion for judging overall performance today. As a prospective engineer, Dave Bolles sees it this way: "Specialization has caused many engineers to subordinate everything to doing their job the cheapest and fastest way. In the future this won&apos;t be enough. The engineer in the mineral industry will be responsible not only for mining, concentrating and smelting, but also for the resultant wastes- the mine dumps, the tailing dams and the slag piles." (See Drift on page 63).

Jan 1, 1971

By R. E. Old

THROUGH the use of pressure and production records, formation properties and bottom-hole sample data, the performance of an oil reservoir may be studied analytically to define and evaluate the natural forces acting on and within the reservoir. Use is made of material-balance methods and the equations for natural water encroachment to estimate reserves. Methods for calculation of pressures are given. A study of the Jones sand, Schuler field, Arkansas, has been made and is given here to illustrate the value of the methods discussed.

Jan 1, 1942

By H. Biloni, G. F. Bolling

The microsegregation in tin specimens containing 0.2, 0.5. or 1 wt pct Pb has been studied m detail. The specimens were grown from the melt in a controlled fashion and exhibited a well-developed cellular substructure. In general, a severe microsegre-gation can be observed in all the photomicrographs presented. Some observations of special interest are: the distribution of a second phase, the presence of a eutectic in several forms, the evidence for dif- THE Smialowski or cellular substructure which forms during solidification has been extensively studied during the past decade.&apos;* Many of the im- *Most references to the cellular substructure except for the last 2 years are reviewed by Winegard.&apos; portant characteristics of this substructure, such as its occurrence and variability with growth conditions, its association with the phenomenon of constitutional supercooling, and its effect on dislocation production and mobility, have received quantitative fusion of solute in the solid, and the enhancement of segregation at a dislocation subboundary network ("striations"). On the basis of the metallographic observations, it can be deduced that the segregation observed is representative of the solute segregation produced during crystal growth. Some deductions are also made about the interplay of the two substructures, cells and striations, and about the mode of cellular growth. investigation both experimentally and theoretically. However, the concentration profile of the solute segregated during crystal growth has not been examined in detail. Tin crystals grown from melts containing various concentrations of lead have been most extensively studied. In a recent investigation of Sn-Pb alloys, Kramer et a1.2 were able to measure the effective solute distribution coefficient, k,, at the most advanced points of the solid-liquid interface, over a large range of growth conditions, finding it to approach the value of k,, the equilibrium distribution coefficient. As will be shown, this must lead to drastic segregation. Another recent study of several Sn-Pb alloys was made by Plaskett and winegard3 who investigated the variation of growth conditions

Jan 1, 1963

By F. L. Wolf

THE catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This&apos; means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a, preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of, materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though its importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation.

Jan 1, 1930

By H. C. Schultz, F. K. Middleton Hunter

Certain local conditions were known to govern in large measure the successful adaptation of liquid-oxygen explosives to the large-scale blasting at Chuquicamata. The wide variation in hardness of the rock at this mine makes necessary the use of several types of explosives. A locally manufactured, relatively cheap black powder is used in blasting the softer waste and capping material, where a thorough displacement breaks the ground sufficiently. Before the introduction of L. 0. X., an ammonia dynamite of about 65 per cent. strength was being used exclusively in the harder underlying orebody, where a strong disruptive as well as a displacement effect is required for breaking the ore. The L. 0. X., as developed for quarry work in the United States, has a practically pure carbon cartridge material, and the explosive has an extremely high rate of detonation, which should therefore cause it to develop usefully its full disruptive effect in hard ground. The individual blasts at Chuquicamata arc large, black-powder shots which dislodge masses of rock averaging 250,000 tons each, and dynamite shots which dislodge masses averaging 80,000 tons each. It was desirable, therefore, to attempt to displace with L. 0. X. the faster, higher-cost ammonia dynamite used in the smaller blasts. It was not considered practical to attempt to displace the low-cost black powder with 1,. 0. X., as estimated costs showed no probable saving if this were accomplished. Since it was desirable to continue shooting relatively large blasts for effective operation, it was recognized that larger storage facilities than had been in use would be needed for the liquid oxygen. Because of the difficulty of transporting and discharging large storage containers of efficient design, the better plan appeared to be storage and discharge of the liquid at the place of manufacture, and transportation of the filled soaking boxes to the blast. Present Liquid-oxygen Plant An experimental unit with a rated capacity of 75 liters per hour was erected during the latter part of the year 1926 to prove the effectiveness of L. 0. X. at this mine, its cost, and possible efficiency of large-scale storage of the liquid. With this experimental unit 200,000 tons of ore

Jan 1, 1928

By Hsun Hu, R. S. Cline

The effect of rate of deformation on texture formatiotz has been studied with cube-oriented single crystals of 3 pct Si-Fe, compressed 80 pct at two widely different rates. Compression at a low rate (crosshead speed, 0.1 ipm) produces large orienta-tional changes and coarse deformation bands, whereas little change in orientation is observed, particularly at the surface of the crystal, when compressed at a high rate (impact velocity, -500 ips). Thin plates of mechanical twins are produced at the high rate, but their contribution to the deformation texture is practically negligible. The crystal deformed at a high rate has a lower hardness and a more uniform dislocation structure and is morc resistant to recrystallization. There is also a dilference in the recrystallization texture between the slowly and rapidly compressed crystals. These results indicate that plastic flow is less "turbulent" at high strain rates than at low strain ratcs. THE behavior of metals under high-speed deformation has been the subject of wide study in the past decade. Most of these works were concerned with mechanical properties during testing at high rates of loading, the resulting structures, and the theoretical aspects of the observed phenomena. The present status of knowledge and research activities in this field has been documented in recent publications.17&apos; There is, however, very little information available in the literature concerning the effect of high-speed deformation on the texture formation in metals. The possibility of an effect of rate of deformation on texture is suggested by the microstructural differences observed between normally and very rapidly deformed samples. Aside from the strong tendency for twinning (and phase transformation in certain metals) in high-speed deformation, the slip-line patterns and the dislocation configurations show marked differences as a result of large differences in the strain rates. For instance, in mild steel in static and dynamic compression, Campbell and co-worker3,4 observed that coarse slip occurred on several systems in specimens deformed at normal strain rates, whereas specimens deformed rapidly showed only fine slip on fewer systems, the slip-line pattern being very similar to that in specimens deformed at low temperatures and at normal strain rates. The absence of multiple slip was also noticed by Dieter5 in shock-loaded nickel. The dislocation configuration in an iron shock loaded at 70 kbar pressure was shown by Leslie et al.6 to be similar to that produced by light rolling at low temperature—the dislocation lines were mostly straight and uniformly distributed. These observations suggest that the mode of deformation at high strain rates is notably different from that at low strain rates. Consequently, the nature and the extent of lattice reori-entation during deformation should also be different. This investigation was undertaken to test this idea. MATERIAL AND METHOD The remaining part of a single-crystal ingot of a 3 pct Si-Fe alloy,* prepared for an earlier investi- gation,1 was used in the present studies. Specimens 9/16 in. square and 0.365 in. thick were cut from this ingot with (001) planes parallel to the square surfaces, and the [loo] and 1010] directions parallel to the edges of the specimen, within ±1 deg. These machined crystals were etched to remove distorted metal, and annealed at 1300°C for 24 hr in a purified helium atmosphere. The annealed crystals had a hardness of 161 Dph. The crystal orientation was rechecked with X-ray back-reflection techniques. In high-strain rate experiments the crystal was compressed in a Dynapak machine to approximately 80 pct reduction in thickness (from 0.360 to 0.070 in. with an impact velocity of -500 ips). Thus, the duration of loading was approximately 6x 10-4 sec, and the average strain rate was about 103 sec-1. As a result of this rapid, severe deformation, the specimen became a roughly circular thin disc. The original shape of the crystal, however, could still be recognized by a diffusely outlined square area in the center of the disc. For compression at a low speed, the crystal was deformed in a universal testing machine at a rate of crosshead movement of 0.1 ipm. Compared with

Jan 1, 1965

By Donald A. Brobst

The minerals barite (BaSO4) and witherite (BaCO3) are the chief sources of the element barium and its compounds needed for many industrial processes and products. Barite, the principal ore mineral, is found the world over and is abundant and widely distributed throughout the United States.3 Witherite is much less common than barite, though more desirable in many ways as a raw material for the production of barium chemicals. England is the chief producer of witherite. Witherite is not mined in the United States at the present time, but it has been mined with barite from a deposit at El Portal, California. Barite is also called barytes, tiff, cawk, or heavy spar. Ordinarily it is a heavy mineral that crystallizes in the orthorhombic system. It is colorless, white, or gray, and transparent to opaque. In some deposits barite is black, yellow, brown, red, green, or blue because of included impurities. The streak is white and the luster vitreous to resinous or pearly. The specific gravity of pure barite (65.7 pct BaO and 34.3 pct SO3) is calculated to be 4.5, but inclusions and impurities in natural barite may reduce this value considerably. Well-formed crystals are generally tabular and have three cleavages. The barite of many deposits, however, has an uneven fracture and an apparent cleavage caused by separation along planes between successively deposited layers. The hardness is 2.5 to 3.5 on Mohs&apos; scale. Commercially the terms "hard" and "soft" are used to refer to ease of grinding. Barite is relatively insoluble in water and acid, and thus can be used as a chemically inert material. Witherite, the natural carbonate of barium (77.7 pct BaO and 22.3 pct CO2), crystallizes in the orthorhombic system. The fracture is uneven and the luster is vitreous to resinous. The hardness is 3 to 3.5. The specific gravity of the pure mineral is calculated to be 4.29. It is transparent to opaque. The color is ordinarily white, gray, yellow, brown, or green. Geology and Distribution of Deposits Workable deposits of barite are widely distributed throughout the world in many geologic environments in sedimentary, igneous, and metamorphic rocks. Most deposits can be classified into three main types: (1) vein and cavityfilling deposits; (2) bedded deposits; and (3) residual deposits. 1. Vein and cavity-filling deposits are those in which barite and associated minerals occur along faults, gashes, joints, and bedding planes, and in breccia zones and solution channels. They also occur in various collapse and sink structures in limestone. Sharp contacts of the veins and cavity fillings with wall rocks are common. Barite cements fault and collapse breccia by replacement of the matrix or by filling voids. Large-scale replacement of the wall rocks beyond ore-controlling structures is rare. Barite in vein and cavity filling deposits is generally dense, "hard," and white to gray. Associated minerals are fluorite, calcite, ankerite, dolomite, quartz, and many sulfide minerals, especially pyrite, chalcopyrite, galena, and sphalerite. Gold, silver, and rare earth minerals occur with barite in some deposits in the western United States. Barite is also a gangue mineral in metallic ore deposits but production as a byproduct from such deposits will be affected by many economic factors. The host rocks are igneous, sedimentary, and metamorphic rocks of pre-Cambrian to

Jan 1, 1960

By W. M. Weigel

SALT production in Louisiana and Texas at the present time is entirely from salt domes of the interior and coastal groups. Before and during the Civil War salt was recovered from numerous salines and salt springs by evaporation in open &apos;kettles. The location of these in nearly every instance was near what is now known to be a salt dome, and the source of the salt in the salines and spring waters was that in the salt core. The tops of many of the shallower domes have been subjected to erosion1. The discovery that the salt occurred as large masses of rock salt in the form of domes was made in May, 1802, at Avery Island, La., by John Marsh Avery, grandson of the original owner, John C. Marsh, who built the old salt works in 18122. The first shaft for mining was sunk on the Avery dome in 1867 by Chouteau and Price. It was 90 ft. deep, about 58 ft. being in solid salt. It was abandoned in 1870. There are three general groups or fields of salt domes; interior Louisiana in northern Louisiana, interior Texas in northeastern Texas, and the coastal domes nearer the Gulf Coast and extending from the Mississippi River to the Rio Grande. This last group contains by far the greatest number of domes. As many of the coastal domes especially are prolific producers of petroleum and a few of sulfur, their geology has been intensively studied and fully covered in the literature. The depth to the top of the salt varies from near the surface, where shallow ground waters have dissolved the salt to just below recent deposits, to several thousand feet, where the depth has been estimated only by geophysical methods. The diameter of the salt core varies from less than ½ mile to over 2 miles. Only domes where the salt is compara-tively near the surface have been developed for commercial salt. Three deeper domes, which will be described later, have recently been developed or are in process of development, as a source of brine for chemical use.

Jan 1, 1935

By Richard I. Petritz

A brief review of today&apos;s processing of integvated circuits is given. The major trends in the development of advanced integvated electronics are identified as 1) the broadening of the integvated circuit concept to a large class of circuit function, 2) the processing of more complex circuits within relatively small chips of silicon, and 3) the processing of very large electronic functions on complete slices of silicon. This latter trend, called array technology, is then developed in detail. Emphasis is given to defining the key tech-nological problems. Current progress being made is illustrated. THIS paper will endeavor to identify the major trends in advanced integrated electronics technology. One of these, array technology, will be developed in some detail. The array technology discussion will identify the key problem areas. Since it is the scope of the entire meeting&apos; to present specific progress in the science and technology of integrated electronics, we shall indicate general directions being explored rather than discuss comprehensively solutions to the problems. In order to set the stage for the discussion of future trends in integrated-electronics technology, let us briefly compare the processes by which circuits are fabricated through discrete-device technology with that of integrated circuits technology. The reader is referred to the December 1964 issue of Proceedings of IEEE2 for a comprehensive review of integrated electronics. The article3 by Jay Lathrop is an excellent discussion of integrated-circuits technology. A discussion of the history of semiconductor technology is contained in Ref. 4. A) Current Status of Integrated Electronics. Fig. 1 (top) shows the process by which circuits are constructed from discrete devices. Key points are: 1) Slices containing large numbers of transistors or diodes are processed separately. 2) The slices are scribed into small chips (on the order of 15 mils on a side is about as small as can be conveniently handled) each chip containing one transistor. 3) Each device is specified separately—circuit -function specs are derived largely from device specs. 4) Circuits are formed by connecting together the discrete devices. 5) The number of circuit connections required is approximately equal to the number of devices. 6) There are potentially many more discrete devices per inch2 of semiconductor—only our lack of ability to handle them in discrete form prevents us from going to several orders of magnitude higher density iin Fig. 1, 400,000 transistors are discussed at 1.5 mils on a side). The bottom part of Fig. 1 illustrates the integrated circuit process. Key points are: 1) On the same slice of silicon, transistors, diodes, and resistors are processed grouped to do a complete circuit function. 2) While still in slice form, the components are interconnected into circuit functions by an evaporation process, eliminating the need for separate interconnection steps later. Dramatic improvements in cost and reliability are realized. With a simple flash of metalization thousands of interconnections are reliably made. 3) The slices are scribed into chips which contain complete circuit functions. 4) The circuit functions are specified-not each component in the circuit. This important point was missed by some of the early opponents to integrated circuitry. They argued that, with device yields at x pct, integrated circuit yields would be pct, where n is the required number of devices to make a circuit. This argument leads to extremely low yields for integrated circuits. The fallacy of the argument is that in integrated circuits each device is not specified separately. Furthermore, since a device is forever integrated into a specific circuit function, it need meet only the requirements for that particular function. Discrete devices, on the other hand, are tightly specified so that they can be applied to a variety of circuit functions. 5) Extremely high packing densities are achievable because one need only make the basic devices as large as the circuit demands. Their size is not dictated by handling requirements. A current example

Jan 1, 1967

By G. W. Brock

Experiments in the form of aging of overstrained tension specimens and elevated temperature tension testing, have been carried out on recrystallized arc-cast molybdenum. The aging behavior of molybdenum was found to be strongly dependent on the degree of plastic strain present in the lattice: the reason for this being the low solid solubility for the common interstitial elements in molybdenum. GEORGE W. BROCK, formerly Research Associate, Department of Theoretical and Applied Mechanics, University of Illinois, Urbana, III., is Research Associate, Department of Engineering Sciences, IBM Research Center, Yorktown Heights, N. Y. Manuscript submitted January 19, 1961. IMD THE term strain aging is familiar in connection with the recovery of the yield point in mild steel after tensile overstraining, and there are other instances where it is known to exert an appreciable effect on mechanical properties. For example, steel exhibits a greater tensile strength at mildly elevated temperatures than at room temperature and serrated stress-strain flow curves occur under certain conditions. It has been known for a number of years that the phenomenon of strain aging is directly connected with the presence of carbon and nitrogen in the lattice; and extremely small amounts of either element are sufficient to produce the effect. In this study, the aging behavior of overstrained tensile specimens of recrystallized molybdenum has

Jan 1, 1962

By H. A. Lesser, H. L. Stone, G. H. Bruce

ESSO PRODUCTION RESEARCH CO., HOUSTON, TEX. A mathematical model that represents the conduction heating of a rock formation of limited permeability is formulated. Heat is introduced by the injection of a hot condensing gas into horizontal fractures through the formation. The fractures are assumed to be equally spaced; the flow of fluid is linear. The model consists of three coupled partial differential equations and two functional relationships. Temperature histories for both fractures and formation are obtained by numerical procedures. Application of the model in predicting in situ heating of oil shale is illustrated with four sample cases. Influences of shale thermal diffusivity, fluid pressure in the fracture and fracture spacing upon heating rate are demonstrated. In all cases considered, several years were required to heat all the formation to 700F with 1,000F steam. Less than 32 per cent of the injected heat was utilized for heating the shale. To facilitate extensive calculations of this type, a set of seven dimension-less quantities are derived. With this dimensionless system, the effect of controllable parameters on economics can be explored. INTRODUCTION Vast deposits of hydrocarbons are contained in oil shale formations in the western United States and in other countries. These hydrocarbons, known as kerogen, are difficult to recover because they are immobile solids and because the rock formations in which they are found have very limited permeability. The kerogen can be converted through pyrolysis to recoverable liquids and gases if the formation temperature is elevated to the range 600 to 800F. To accomplish this heating, the formation might be artificially fractured and a hot fluid injected into the fractures. If the injection and production wells are vertical and the fractures horizontal, interwell communication will be established and the hot fluid will flow from an injection well to a production well. In this process, some of the heat in the fluid will be given up and conducted into the formation. Products of pyrolysis will flow from the heated rock matrix into the fractures and be produced, commingled with the injected fluid. The practicality of such a process is strongly influenced by the rate at which heat can be transferred from the hot fluids to the formation. An analysis of this heat conduction problem is the subject of this paper. Linear flow of a condensing gas through a set of horizontal, equally spaced fractures is considered. Temperature histories for both fractures and formation are obtained from numerical procedures. The analysis also applies to formations containing streaks of natural permeability instead of fractures. Heat flow problems similar to the one treated here have been studied by other workers. Thomas1 has solved a radial problem in which he considers the injection of a noncondensing gas into a single, horizontal fracture and approximates the temperature profile in the fracture by a step function. The solutions to other problems, which are less similar to the present problem than the one treated by Thomas, have been reviewed by Spillette.2 In addition to these mathematical studies, a field test of an in situ shale oil recovery process using hot natural gas as the injected fluid has been reported.3 The first part of this paper is concerned with the mathematical development of the problem. The differential equations, boundary conditions and functional relationships which describe the physical model are formulated and the equations are cast into finite difference form. The method of solution of the difference equations is discussed (Appendix B). The second part of this paper presents results computed for a typical oil shale formation for which steam at 1,000F is the injected fluid. Fracture spacing, horizontal and vertical thermal diffusivities

Jan 1, 1967

By G. J. Heuer, J. N. Dew, G. C. Clark

The effect on well behavior of partial permeability barriers, changes in producing rates and well spacings have been calculated through use of a radial, unsteady-state, two-phase-flow mathematical model. This model allows for variations in permeabilities and porosities with distance from the wellbore. The numerical methods necessary to solve the problem require use of a highspeed digital computer, in this case an IBM 704. In each instance, pressure and saturation gradients, gas-oil ratios and recoveries around a well producing by solution-gas drive have been calculated as a function of time and distance from the wellbore. Comparisons are made to show the effect of changes in producing rate and of varying permeability near the wellbore and out in the formation on the production and pressure history of the well. The effect of different well spacings on producing rate and ultimate recovery is considered. Although the mathematical description of the reservoir is simplified in comparison to an actual reservoir, the results do give some insight into the difficult problem of spacing and proration in a heterogeneous solution-gas-drive reservoir. Results show that for the cases considered spacing has little effect on ultimate recovery and that permeability barriers removed from the well decrease producing rate for a period of time but have only a small effect on ultimate production. INTRODUCTION The effect of spacing and producing rate on the production characteristics and ultimate recovery of a well producing by the solution-gas-drive mechanism have been topics of interest to the oil industry for many years and the subject of many hearings before state regulatory bodies. The problem is very complicated because of the difficulty of simulating in the laboratory a reservoir producing by the solution-gas-drive mechanism under anything like normal field conditions. This paper gives the initial results of a study aimed at determining the effect of these factors on production from reservoirs simulated by a mathematical model. Two-phase, unsteady-state equations are used to calculate pressures, saturations, and rates of oil and gas flow as a function of time and distance from the wellbore. The model is radial, and reservoir properties may be varied with distance from the wellbore. A decrease in permeability at a given distance results in a low-permeability ring concentric with the wellbore through which all the fluids from more distant portions of the reservoir must flow. The current mathematical model allows for variation of permeability, porosity and saturations as a function of distance from the well. Any desired drainage radius for the well may be selected. Drainage radii of 745 and 1,053 ft, which correspond to 40- and 80-acre spacing, were chosen for the calculations which follow. A large amount of the input data has been held constant. No investigation was made into the effect of changes in fluid properties and relative permeability characteristics on oil and gas production behavior. Fluid properties and relative permeabilities are essentially those of the White Mesa portion of the Greater Aneth area in southeastern Utah. A recently concluded hearing before the Utah Oil and Gas Conservation Commission to determine spacing for the field aroused interest in the possible effect of permeability constrictions located some distance from the well on production and recovery. This interest stimulated the present study. In this paper, no attempt has been made to simulate any field production characteristics exactly. Only the solution-gas-drive mechanism has been investigated, and production by liquid expansion has not been considered. This investigation is exploratory in nature but does give some insight into the problems of spacing and proration in a solution-gas-drive field having permeability variations. THE MATHEMATICAL MODEL The mathematical model is similar to that proposed by West, Garvin and Sheldon.&apos; Approximately the same techniques have been used in arriving at a solution. The equations are nonlinear, partial differential equations which have been known for some time. The particular equations used for this study neglect the effects of capillary pressure and gravitational forces. The advent of modern digital computing equipment has made their solution practical. Basically, the method solves for pressure, saturations, and oil and gas flow rates as a function of distance and time. In our model, distance to the

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900&apos; to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.&apos; Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,&apos; the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-&apos;9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.&apos; In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970

By J. Brett, L. Seigle, L. Castleman, T. Montelbano

Impurity-induced low-temperature recrystallization of cold-worked tungsten was inuestigated with emphasis on the influence of nickel on the reaction. Palladium, nickel, aluminum, manganese, platinum, and iron greatly lower the recrystallization temperature of doped tungsten, which zs normally very high, but the recrystallization temperature of electron-be am zone-refined tungsten wzre is slightly raised by conlacl with nickel. Recrystallization can be induced at low temperature by the presence of solid nickel on the surface of doped tungsten wire, but apparently not by exposure to nickel vapors alone. Approximately 200 ppm of Ni dijjused into 10-mil wires at 1200 from a deposit of nickel on the surface produced total recrystallization, whereas more than 600 ppm of Ni could be absorbed frotn a vapor source without altering the fibrous structure of cold-worked tungsten. Once initiated, nickel-induced recrystallization required a continued source of&apos; nickel for propagation of the recrystallization front. The solubility of nickel in fibrous 10-mil W wire was approximalely 500 ppm at 1150&apos; C, and the activation energy for penetration of the recrystallization front was 52 kcal per mole. In many applications the usefulness of tungsten depends on critical control of its structure. Cold-worked tungsten with the fibrous structure developed by suitable thermo-mechanical treatment has a low, but technologically significant, ductility. It has long been known1 that traces of nickel, and perhaps other metals, are profoundly deleterious in doped tungsten, because they induce recrystallization at low temperature, which produces a brittle, equiaxed grain structure. This effect appears to be an exception to the general observation that recrystallization is impeded and the recrystallization temperature raised by the presence of impurities.2"9 Previous studies7-&apos;&apos; of the annealing and recrystallization of tungsten wire have divided the phenomenon into prior recovery stages, primary recrystallization and secondary recrystallization. The present investigation is concerned principally with primary recrystallization which is defined here as the replacement of the fibrous structure of deformed tungsten by equiaxed grains. The objective of this study was to explore the nickel-induced recrystallization reaction in tungsten and attempt to elucidate its mechanism. As well, an effort to define which other elements give rise to low-temperature-induced recrystallization was carried out. EXPERIMENTAL PROCEDURE The procedure adopted for these experiments was essentially to bring nickel and other elements into diffusive contact with cold-worked tungsten wires. The process of recrystallization was followed as a function of time and temperature by light and electron microscopic observations. First the influence of nickel on the recrystallization temperature of arc-melted, zone-refined, and variously doped tungsten wire was determined by electroplating a deposit of nickel on the surface of the wire and annealing at a variety of temperatures for 3 hr. The chemical analyses of the tungsten wires used in this investigation are given in Table I. The surface of the tungsten wire was etched with Murakami&apos;s slution&apos; and approximately 0.005 in, of Ni was deposited from a Watts-type low pH bath14 for the conditions of these experiments. Variations in plating thickness from about 0.001 to 0.005 in. had no discernible influence on the resulting structures. The wires were then annealed in an atmosphere of dry hydrogen to establish the recrystallization temperature. Concurrently, un-plated specimens were annealed to establish the recrystallization characteristics of nickel-free wire. The criterion of recrystallization was that the fibrous structure be completely replaced by equiaxed grains after a 3-hr treatment of temperature. This provided more reproducible results than use of the first recrystallized grain or a fixed proportion of re-crystallized structure as the critical observation. The structures encountered in longitudinal and transverse sections were examined by both light and electron microscopy at magnifications up to X32,000 using parlo-dion-carbon replicas shadowed with platinum for the latter method. Second, the influence of a variety of metals on the recrystallization temperature of 0.010 in. D alumina-silica doped tungsten wire, AW136-64, was determined. The elements were applied by electroplating whenever possible. Alternatively, they were vapor-plated on the tungsten wire and a greater thickness built up by coating with a dispersion of metal powder in nitrocellulose lacquer. Elements not amenable to either of these procedures were merely slurry coated on the tungsten. The recrystallization temperature was determined as above. Third, the nickel-induced recrystallization process in doped wire was studied more closely by electroplating 8 mils of Ni on 65-mil alumina-silica doped tungsten wire, AW153-NS10, and exposing the wire to temperatures of llOO°, 1200°, or 1300°C for various times in a hydrogen atmosphere. A circular recrystallization front, &apos;Onsisting of equiaxed grains, developed at the periphery Of the coated tungsten wire, and the advance of this front into the fibrous interior was studied. These experiments employed relatively coarse 0.065 in. D wire because the 0.010 in. D wire recrystallized too quickly to permit observation of the pene-

Jan 1, 1969

By A. U. Seybolt

Experiments on both suljidation and hot corrosion have been carried out using ternary Ni-Cr-X alloys and commercial nickel-base superalloys. It has been shown that lhere are certain micro structural similarities between sulfidation using H,S/H2 mixtures and hot corvosion using Na,S04 in "crucible" experiments or hot corrosion tests using a flame tunnel apparatus. It is proposed that two key processes in the hot cowosion process are: 1) formation of chromium sulfides which deplete the alloy matrix, and 2) oxidation which can be accelerated because of chromium depletion. Other processes play an important role in the hot corrosion process, such as accelerated oxidation attack due to the presence of a N& S04 or N&SO,- NaC2 film which inhibits the formation of a protective external oxide scale. However, this latter phenomenon was not studied in this work. THE term hot corrosion has come to mean a combination of sulfur and oxygen attack on nickel-base or cobalt-base superalloys used as gas turbine blades or partitions. This attack can be initiated by any combustion process in air involving fuel containing sulfur if the sulfur level is sufficiently high. Levels of 5 pet SO2l for example, in the combusting gas have been observed to produce hot corrosion attack on nickel-base alloys. The important immediate corroding medium in aircraft gas turbines, however, has been established to be Na2S04, formed from reaction between NaCl from sea air and sulfur in the fuel.&apos; The Na2S04 concentrates the sulfur sufficiently so that superalloy parts heated in the range 1400" to 1900°F can become sulfided by reducing the Na2S04 film which forms on the parts, and this reaction allows sulfur to gain access to the alloy. The sulfur thus released diffuses into the superalloy and forms primarily chromium sulfides of various compositions, but frequently Cr2S, has been identified. Figs. 1 and 2 show the morphology typical of hot corrosion of a cobalt-base superalloy X-45 (25 Cr, 10 Ni, 7.5 W, 0.25 C) and a nickel-base alloy, Udimet 500 (19 Cr, 19 Co, 4 Mo, 3 Ti, 2.9 Al, 0.07 C). Both alloy samples were subjected to the same hot corrosion conditions: 616 hr at 1600°F in a combusted 2.9 pct S distillate oil containing 125 ppm Na as NaC1. It will be noted at once that the nickel-base alloy is much more severely attacked. The depth of corrosion is much greater and the number and size of the sulfides present are much greater. Both alloys show a duplex oxide scale, which is more noticeable in the X-45 alloy. The external scale is probably a spinel in both cases, with CrQ3 lying next to the alloy. Many investigators1 -"ve been concerned with hot corrosion phenomena, but there has been a lack of unanimity of opinion as to the details of the hot corrosion mechanism. More than one definition of hot corrosion is possible. Some investigators con- sider as a measure of hot corrosion only the weight gain due to an accelerated oxidation. However another point of view is that the total depth of affected alloy may be used as a measure. While it is recognized that surface oxidation attack is greatly accelerated by the presence of salts like Na2S04 or Na2S04-NaC1 mixtures, sulfur penetration into the alloy also undoubtedly produces very important effects. The region of sul-fide penetration which is so prominent in Fig. 2 is one of the outstanding characteristics of hot corrosion. For highly stressed parts, such as first-stage buckets, this sulfur-penetrated region can be more significant in mechanical property loss than the reduction of cross section produced by the formation of the massive external scale. In addition, evidence will be presented that this sulfided region can be less resistant to subsequent oxidation attack. Since it appears that the sulfided region below the surface oxide scale plays an important role in the overall corrosion process,

Jan 1, 1969

By A. R. Kaufman, P. Gordon

THE large-scale manufacture and use of uranium in conjunction with the atomic energy development during the war led to a need for knowing the equilibrium diagrams of uranium with various other metals. The alloys of uranium with aluminum and with iron were among the first that were studied for this purpose. Much of the work was done in the manner of a survey since it was necessary to determine the important features of the phase diagrams rather than to obtain completely detailed results. For this reason no attempt was made to locate exactly such features as liquidus lines, solid solubility limits and compound and eutectic compositions. It is believed, however, that there are no great inaccuracies in the diagrams reported here and that no important points were overlooked. Earlier work on alloys of uranium with aluminum and iron is almost nonexistent and in each case is considered to have been of little value by M. Hansen. It is interesting to note, however, that the compound UAl3 was first reported in 1902 by L. Guillet. Experimental Procedure Materials: The uranium used for making most of the aluminum alloys was obtained from material prepared by Metal Hydrides, Inc., and melted in vacuum at M.I.T. Because of the lack of an adequate supply of metal, it was necessary to use material from several different batches and hence it is impossible to state an exact analysis. However, a few results indicated about 0.01 to 0.03 pct iron and probably about 0.03 to 0.05 pct carbon. Toward the end of the work a small amount of metal was obtained from Brown University and from Iowa State College and this was used in determining the transformations in pure metal and in some dilute alloys. All of the aluminum used in this investigation came from a supply of high purity metal (greater than 99.9 pct aluminum) which was obtained through the courtesy of Dr. Mehl of the Carnegie Institute of Technology. The uranium used for making the alloys with iron was produced by the bomb reduction process which has been described by J. Chipman.² This metal, after vacuum melting, contained about 99.9 pct uranium by weight with carbon and iron as the chief impurities. Electrolytic iron containing about 0.012 pct carbon, 0.020 pct nickel and 0.009 pct copper was used in making the melts. Melting Equipment: The melting of the alloys went through a stage of development which culminated in the use of beryllia or beryllia-lined crucibles and in the use of high frequency heating in either vacuum or in an atmosphere of argon. It was found that uranium at a few hundred degrees above its melting point would pick up aluminum and to a lesser extent silicon from an alundum thimble while aluminum above 1000°C would extract silicon from the impure alundum. No reaction of either metal with beryllia was noted at temperatures as high as 1800°C. The distillation of aluminum from the aluminum-rich alloys was quite troublesome at temperatures above about 1300°C and was only partially avoided by the use of argon instead of vacuum. Melting in resistance furnaces,

Jan 1, 1951