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By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

By Magnus Troilius

INTRODUCTION BY C. P. SANDBERG. SINCE the discussion On steel rails in America has forcibly drawn attention to the value of chemical analysis, if not as a necessary stipulation, at least as a guide to control the usual mechanical tests, some doubt has been thrown upon the accuracy of the analytical results Obtained by different chemists. To any One having the least acquaintance with chemistry., it is quite clear that if exactly similar results are to be obtained from the same borings of steel, exactly the same methods must be used by the different analysts. Hence the necessity (if complications are to be avoided) of establishing what I may call standard or normal methods, to be used both by the inspectors and by the chemists at the works. Remembering that the application' of chemistry to steel-rail inspection is yet in its infancy, it is of great importance to possess a perfect acquaintance with the best methods in use. Being myself a grateful pupil of Professor Eggertz, of the School of Mines in Sweden, it Occurred to me, two. years ago, that I could not do better than start a laboratory of my. own, and engage One of his pupils, Mr. Troilius, for the purpose of analyzing the steel borings from mechanically-tested rails, so that I might thus Obtain without delay thoroughly accurate determinations. Moreover, in Order to carry on the, operations in perfect accordance with the methods used at the steel works in England and Germany, where I had to control the manufacture, I deemed it desirable to allow Mr. Troilius to go through a course of training at these works; and I gladly seize this opportunity of expressing my grateful acknowledgments to several works in England and in Germany for affording every facility for such an exchange of information as was found necessary in arriving at the best analytical methods to be used.

Jan 1, 1882

By L. L. Karafiath, S. G. Vick, E. A. Nowatzki

Computer analyses of the trafficability of copper mine tailings by four different commercially available BWEs were performed. A mathematical model incorporating the tailings' Coulomb strength parameters and the vehicles' geometry and operational characteristics was used to study the vehicle terrain interaction. The computer output provides the maximum tractive force (net drawbar pull) that each BWE can develop for given tailings conditions without bnngzng about a state of plastic failure in the tailings. Estimates of sinkage are also provided. The theoretical results for the BWEs and tailings studied compare favorably with the operating experience of similar BWEs used for remining gold tailings in South Africa. This lends some confidence to the validity of the mathematical model. The results of such analyses may be wed to evaluate, on a relative basis, which of a number of different machines would perform better than others under given conditions of a tailings deposit.

Jan 1, 1982

By H. M. Day, C. H. Mathewson

THE constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy' in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were confirmed and supplemented through X-ray analyses by Preston2 and Stenbeck.3 According to Murphy, at 276° C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower temperatures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in. the right region. PREPARATION OF ALLOYS The silver used in the present investigation was supplied by the United States Metals Refining Co. through the courtesy of the Committee on Industrial Uses of Silver and, since a complete spectrographic and chemical analysis was furnished, no attempt was made to purify it or to further establish the impurities present. The analyses reported by the company are shown in Table 1. Milligan4 has found that the magnesium content is probably less than 0.0005 per cent.

Jan 1, 1938

By H. E. Ellis, O. L. Patterson, Granville Dutton

A large-scale water-injection program for the Holt Bryant reservoir of the Delhi field has been established by means of the new automatic multi-pool analyzer. The objectives of this program were to increase reservoir pressure and eliminate a cross-dip gradient of 200 psi. Pressure increases during the first 15 months of operation have allowed for increased oil production rates of 2,600 BID or 25 per cent. To determine the required water injection it was necessary to predict natural water influx ram. Elimination of the pressure gradients required the water-injection program to account for the fluid migration and pressure interaction between segments of the reservoir. An integral part of the ana1ysis included the determination of in-place volumes of oil and gas. The operation of the automatic multi-pool analyzer in determining the water-injection program is described. New features of the analyzer inc1ude an automatic maferial balance analog and a leart-squares computer for determination of unknown reservoir properties. Operational procedures are sufficiently simple to allow direct use by reservoir engineers on a routine basis. The rapidity and accuracy with which problems may be solved permit repeated ana1yses as a check upon reservoir performance. INTRODUCTION This paper describes the use of a new analog com- puter in determining the optimum injection program for a complex reservoir. The Holt-Bryant (Fig. 1) is the major reservoir in the Delhi field of Louisiana. Production is from the Tuscaloosa at subsea depths of 2,970 to 3,286 ft. The sand dips to the south and southwest from three to five degrees. The reservoir is approximately 12 miles long and varies in width from 1/2 to 2 miles. Various calculations have placed the initial volume of oil in-place in the wide range of 275 to 355 million STB. Two small gas caps were initially present in the reservoir. The Holt-Bryant reservoir was discovered in Dec.. 1944, and was fully developed with 188 producing wells by 1948. After development was completed, an east-west pressure gradient began to establish itself. This

Jan 1, 1957

By A. L. Galpin

INTRODUCTION For many tailings ponds, particularly those having substantial watershed areas, the control of pond water levels will be a major factor influencing the operation of the pond and the design and construction of the dam retaining the pond. This paper summarizes the basic factors affecting the control of water in tailings ponds, methods of water control, and methods of estimating the variables involved. The influences that pond water levels can have on the design, construction, and stability of tailings dams are explained in order to emphasize the importance of water control in the overall planning of mine tailings disposal systems. Two examples of pond water control planning conclude the paper. BASIC FACTORS The principal factors influencing the control of water in tailings ponds are illustrated on Fig. 1. Fig. 1 (a) shows the general disposition of the tailings solids and water in the pond; the solids settle from the slurry to form "slimes", deposits sloping down into the pond from the points of discharge; these slimes hold volumes of water in the voids between solid particles; water in excess of this "retained" water forms a pool of "free" water laying over the slimes deposits. In some cases, tailings solids (and water) go to the tailings dam for its construction. Fig. 1 (b) indicates those ways additional to tailings disposal in which the pond gains or loses water. These include surface and sub-surface runoff from the pond watershed, water reclaimed from the pond for ore processing, evaporation, and seepage. Seepage losses sometimes include water draining from tailings sand placed in the dam, but a portion of the total seepage flow is often collected and returned to the pond in order to avoid downstream pollution and to recover water for re-use. PRINCIPAL REQUIREMENTS In relation to the control of water in a tailings pond, the first requirement is usually to maintain a pool sufficiently large to ensure adequate clarification of the free water prior to its reclaim for use in the mill, or its discharge from the pond.

Jan 1, 1972

By Herbert Johnson

DURING the past 10 or 12 years very little information has been made generally available concerning the commercial possibilities of separating materials by means of static electricity; and yet during that same period important improvements have been made in various branches of the science of electricity, which, when taken together, and applied to electro-static separation, have resulted in important improvements in that art as well. For example, much improvement has been made in high-voltage electrical equipment such as full-wave vacuum-tube rectification and improved mechanical rectification. Great strides have likewise been made in the development of insulators for high-voltage work, not only in the materials used but also in the design of the insulators themselves. Again, in another field, the development of air-conditioning equipment has improved the technique of controlling the surface condition, through drying or humidifying, of the various materials that are passed through the electrostatic separator. In many authoritative publications and textbooks, the electrostatic separation process is declared to require a balance far too sensitive for general commercial application. For example, one publication1 in the past has referred to an unfavorable effect on the process caused by varying atmospheric conditions such as humidity. Some2 have even gone so far as to state that sunlight and shadows may seriously affect the separating efficiency of the process. Such statements may have been true in the early development of the art, when the source of static elec-tricity was derived from a friction disk machine, such as the Wimshurst. The Blake Mosher equipment and the work of Huff in applying motor-generator sets, transformers and mechanical rectification overcame much of this kind of objection to the commercial application of the elec-trostatic separating process.

Jan 1, 1938

By Charles Barrett

THE orientation of metal crystals and grains, both large and small,. can be determined conveniently and accurately without the use of X-ray apparatus. This seems to be appreciated by so few metallurgists that it may be useful to explain in detail the method we have found most satis-factory in the laboratory the reflection of light from crystallographic etch pits. This note includes a description of a suitable inexpensive instrument and instructions for etching various metals and for plotting the data. As the stereographic projection is used to facilitate handling the data, this note may be considered as an appendix to an earlier review of the metallurgical uses of the stereographic projection.1 Various methods involving etch pits have been used by other investi-gators, Bridgman's method2 consists of attaching the specimen to a sphere (a transparent sphere is convenient4), holding it at arm's length, and marking a spot on it when it has been turned so that the etch pits reflect light into the eye of the observer from a lamp standing behind him. It has an accuracy of about 2° and is extremely rapid. A greater accuracy can be obtained by having the reflected light fall on a screen, as has been done by Czoehralski, 5 Chalmers,6 and Schubnikov.7 All of these methods have been intended for undeformed single crystals. Tammann and his coworkers"' developed a method for estimating the number of grains in a polycrystalline aggregate having orientations in a given region of the stereographic triangle and thus obtained statistical information about deformation and recrystallization textures. While the method has had some use in recent years,9 it is not applicable to the majority of problems in physical metallurgy. Smith and Mehl10 determined orientations by plotting the directions of the sides of individual etch pits on a stereo-

Jan 1, 1940

AT the meeting of the Board of Directors held on June 25, 1926, and in response to numerous in-dividual suggestions for changes, a committee on Re-vision of the Constitution and By-Laws of the Insti-tute was appointed, consisting of C. F. Rand, Archi-bald Douglas and H. Foster Bain. Various confer-ences were held, much correspondence conducted and a preliminary draft was prepared. It proved imprac-ticable to complete the work in time to submit the matter to the membership for approval or disapproval at the annual meeting in 1927, and the Committee was continued with instructions to prepare a report as a basis of action in 1928. After Mr. Rand's death George Otis Smith was appointed in his place and the tentative draft herewith submitted has been pre-pared in its present form by Messrs. Smith, Douglas and Bain, though not differing in any material mat-ter from an earlier draft approved by Mr. Rand. In preparing this the Committee has kept in mind primarily the desirability of simplification and of making the By-Laws conform to the actual practice of the Institute as worked out through experience. The Constitution and By-Laws adopted in 1912, and which with minor amendments only still govern the Insti-tute, are full of specific provisions regarding pro-cedure; such as that laid down for guidance of the Papers and Publications Committee. Many of these have proved unworkable and in practice have not been always strictly followed. It now seems wise to write into the Constitution and By-Laws only the general fun-damental principles to he followed and to provide for such easy change in methods of following them out as will permit efficient conduct of the business. It is this thought that has guided the Committee in rewrit-ing many of the sections. With this in view also the Constitution, as such, has been shortened to the brief-est feasible statement of fundamentals. All matters relating to means of making these principles effec-tive have been put into the By-Laws or in the hands of committees whose work is subject to control and whose rules are subject to approval or disapproval by the Board of Directors. Many suggestions for changes have come to the Committee that have not been incorporated in this draft. Some of these are in themselves excellent but have not been incorporated here because the Commit-tee discovered no sentiment for them such as would be likely to secure their approval, or found them out of harmony with the general plan followed herein.

Jan 9, 1927

By Guy W. Jordan, David P. Hale

High-iRon cements have a number of advantages over cements carrying little or no iron. The presence of iron in Portland cement aids in the manufacture of the cement and also imparts certain advantageous physical properties to the finished product. In manufacture, the presence of iron lowers the fuel consumption, increases the ease of proper"burning, and lessens the destructive action of the charge on the kiln refractories. In the finished cement the presence of iron reduces the expansion and contraction, adds strength, adds increased resistance to"freezing and thawing, and increases the resistance of the cement to sea "or sulphate waters. [" During the past few years the construction of numerous dams through- "out the Southeast by the Tennessee Valley Authority has stimulated the "production of high-iron cements. At present a great number of specifica- "tions call for an iron cement, and the industry is supplying this demand "with a Portland cement carrying approximately 5 per cent iron oxide. "Several manufacturers are now making practically all of their cement "of this type and a number of others manufacture it as a special cement "over short periods to meet demands from the Tennessee Valley Authority "and other buyers. " The recent increase in the use of iron in Portland cement has created "a market for iron products that previously was nonexistent. The chief "sources of supply for the cement manufacturers at present are iron sand, "iron sinter and slag, and ocher. The Copperhill mining district, Ten- "nessee, supplies both iron sinter and slag for use in cement. The Carters- "ville district supplies iron sand, ocher, and some iron resulting from the "magnetic separation of iron from barite. The advantages of these "products vary according to the chemical properties of the raw materials "and the methods of handling used by the different manufacturers. Where "the iron is to be handled by conveying belts and in hopper cars, the iron"sand and sinter and slag are preferable. Where the silica content must "be raised, the iron sand is doubly advantageous because it supplies both

Jan 1, 1942

By David P. Hale, Guy W. Jordan

High-iRon cements have a number of advantages over cements carrying little or no iron. The presence of iron in Portland cement aids in the manufacture of the cement and also imparts certain advantageous physical properties to the finished product. In manufacture, the presence of iron lowers the fuel consumption, increases the ease of proper"burning, and lessens the destructive action of the charge on the kiln refractories. In the finished cement the presence of iron reduces the expansion and contraction, adds strength, adds increased resistance to"freezing and thawing, and increases the resistance of the cement to sea "or sulphate waters. [" During the past few years the construction of numerous dams through- "out the Southeast by the Tennessee Valley Authority has stimulated the "production of high-iron cements. At present a great number of specifica- "tions call for an iron cement, and the industry is supplying this demand "with a Portland cement carrying approximately 5 per cent iron oxide. "Several manufacturers are now making practically all of their cement "of this type and a number of others manufacture it as a special cement "over short periods to meet demands from the Tennessee Valley Authority "and other buyers. " The recent increase in the use of iron in Portland cement has created "a market for iron products that previously was nonexistent. The chief "sources of supply for the cement manufacturers at present are iron sand, "iron sinter and slag, and ocher. The Copperhill mining district, Ten- "nessee, supplies both iron sinter and slag for use in cement. The Carters- "ville district supplies iron sand, ocher, and some iron resulting from the "magnetic separation of iron from barite. The advantages of these "products vary according to the chemical properties of the raw materials "and the methods of handling used by the different manufacturers. Where "the iron is to be handled by conveying belts and in hopper cars, the iron"sand and sinter and slag are preferable. Where the silica content must "be raised, the iron sand is doubly advantageous because it supplies both

Jan 1, 1942

By Arthur Knapp

The petroleum industry is confronted with the problem of conservalion. This is not a simple problem in view of a wide difference of opinion among authorities as to whether conservation is necessary and the specific direction that it should take. Many writers accuse the petroleum industry of wasting the natural resources of the country. Others link the consuming public with the industry in this waste. Let us define our terms; agree, if possible, on where and when waste occurs in connection with either the recovery or use of petroleum and select such plans for conservation as appear most practical. A plan for conserv3tion which appears to be logical today may not meet the problem tomorrow. The conservation of petroleum is closely linked with the advancement of marly arts and sciences and as these advance, the plan of conservation has to change. The need for conservation does not necessarily rest upon the elimination of waste. There is not necessarily a fixed connection between waste and conservation. Conservation may be necessary or desirable although there is no waste. Definitions Waste: Useless or unnecessary expenditure. Conservation: The preservation of the natural resources for economical use. Both definitions contain adjectives the interpretation of which is extremely difficult. It is the determination of what expenditures are "unnecessary" or what uses are "economical" that will require study and agreement. If one lets his automobile engine run in cold weather in order to keep it hot, it is difficult to measure that necessity. If an automobile is driven two blocks, when the driver is physically capable of walking, what is the measure of necessity. This question is in the realm of one of the oldest of sociological problems, "What is a luxury?"—a problem which has not been solved. The history of society indicates that the measure of a man's wealth has been the measure of necessity. What he can afford to buy without stinting himself in some other direction, is not a luxury to him and, if it fulfills his desires, may be considered his necessity.

Jan 1, 1927

By S. Leber, R. F. Hehemann

This investigation describes the kinetics of alloying in a (Cb-15 wt pct W. 5 wt pct Mo, 1 wt pct Zr) powder-metallurgy alloy. The degree of homogeneity obtained in hydrostatic ally pressed and vacuum-sintered samples is described by composition distributions resulting from analysis of X-ray dvfraction line profiles. Sintering variables and degvee of powder dispersion were evaluated. The utility of single-value parameters obtained from composition distributions is disaissed. The spatial distribution of composition, as revealed by anodically tinted metallographic sarrzples, was used to provide diffision models based on a concentric-sphere geometry. Diffusion equations developed from these models were found to be in general agreement with experimental results. The powder-metallurgy method for the production of refractory metal alloys has the ability to produce an inherently fine-grained, fabricable structure. The more general use of this method is inhibited, in part, by the presumed difficulty in obtaining homogeneity on a microscale. The degree of homogeneity therefore is an important, but usually neglected, variable in specifying the quality of a powder-metallurgy alloy. Convenient techniques for measuring the degree of homogeneity are now available,' and have been used to develop a model describing the process of alloying in a simple binary mixture.' In this investigation, the process of alloy formation has been studied in a more complex system. PROCEDURE The columbium-based F-48 mixture was prepared from the constituent powders shown in Table I. The particle sizes tabulated were provided by the vendors of the individual powders. Standard laboratory techniques utilizing a jar mill were employed for blending. The blended powders were hydro-pressed into 1-in. diam rods which were then sliced into thin discs for vacuum sintering. All samples were given a preliminary treatment at 1700°C for 2 hr. Varying degrees of homogeneity were obtained using additional treatments at higher temperatures. The degree of homogeneity obtained by a specific sintering treatment was evaluated metallographi-cally using the anodic-tinting technique described by olff,' and quantitatively by the analysis of X-ray diffraction line profiles using the X-ray diffraction technique developed by udman.' The diffraction technique is strictly valid only for binary systems. However, the relatively small difference between the lattice parameters of tungsten and molvbdenum when compared with columbium permitted the treatment of the complex composition of F-48 as a (W, Mo)-Cb pseudobinary. Calculations were weighted in accord with the W-Mo ratio in the F-48 composition. The contribution of the 1 pct Zr was ignored since it could not even be detected in the blended powder. Two factors are required to convert an X-ray line profile into a composition distribution. The variation of these factors with composition is shown in Fig. 1. Curve A was used to convert angular posi-

Jan 1, 1964

By Leon W. Dupuy

Many articles have been written describing peculiar and particular types of drilling. Little correlation has been made between the character of ground to be drilled and sampled and the type of drilling most desirable for procuring satisfactory samples. In development work, the engineer and metallurgist often desire the recovery of a sample in as physically natural a condition as possible, particularly when the sample must provide material for process tests as well as chemical and physical analyses. This paper describes the results of experimentation in drilling unconsoli-dated materials carrying titanium minerals in the Magnet Cove area, Ark. The drilling was most difficult in that the ground varied much in consistency, and it was vitally necessary to recover a physically natural sample. Ordinary churn drilling recovered a sample that could be analyzed chemically, but the sample was not in its natural state. The problem was successfully solved by utilizing and further developing methods used in the oil and clay industries. In the Magnet Cove area of Hot Spring County, Ark., the titanium minerals include rutile, brookite, ana- tase, leucoxene, and others. They occur in soil, clays, and altered rocks adjacent to novaculite in contact meta-morphic deposits. In preparing titanium minerals for use in the industry, it is necessary to know the physical characteristics of the ore. Also it is believed that the particular physical character of the titanium mineral used is just as important as the chemical character. Brookite and rutile, for example, are the same chemically but differ in crystalline structure. In preparing titanium minerals for market, beneficia-tion is necessary. For the millman to make a satisfactory laboratory test, the sample he uses must be as nearly of the same physical character as he would have from mine run ore. In the past at Magnet Cove, churn drilling had been done on the properties, and assays of total titania had been obtained. It was found, however, that the total titania was indicative merely of the presence of titania but did not tell the metallurgist the character of the material or even give him the slightest indication of what he might expect to recover. When the Bureau of Mines entered the field in the winter of 1947 and 1948, it was therefore necessary that a natural sample be recovered. LIMITATlONS IN ORDINARY PRACTICE The churn drilling that had previously been done had shown that the occurrence of titanium-bearing mineral was somewhat widespread. The samples were, however, completely beaten up and in a finely powdered state. The minerals had been slimed, and such ore dressing tests as were made from the churn-drill samples were found to be worthless. Test pitting and outcrop sampling had provided satisfactory samples of surface ore but did not represent the entire ore body. A quantity of rutile had been produced from the surface residual concentrations in the westerly part of the cove, but production ran into metallurgical trouble as depth was attained. Representative deep samples upon which ore dressing research might depend were needed.

Jan 1, 1950

By J. H. Brophy, A. L. Prill, H. W. Hayden

An error lzas been found in the conventional way of determining the time exponent of linear shrinkage for the solution-precipitation stage of liquid-phase sintering. Large amounts of shrinkage due to initial rearrangenzent result in erroneously low exponents and tni si dentification of the rate-controlling process. Two alternative, mathematically correct, methods of calculation are applied to existing data on Fe-Cu, WC-Co, and Tic-Ni-Mo. This results in reidentifi-cation of the rate-controlling process and somewhat better agreement with related data. In each case the solution-precipitation process is solution-controlled and not diffusion-controlled. THE liquid-phase sintering process has been the object of a considerable amount of research for many years. Linear shrinkage vs time data at various sintering temperatures have been used recently in an attempt to identify the prevailing mass-transport processes in a number of metallic and nonmetallic systems. There is an analytical error inherent in the methods previously used for handling data during the "solution-precipitation" stage of shrinkage which must be recognized before the correct rate-controlling processes can be determined. It is the purpose of this paper to show how the error has affected previous conclusions and to suggest corrections. A number of mechanisms have been proposed to explain experimental observations during sintering in the presence of a liquid phase. The earliest of these is due to Price, Smithells, and williamsl who attributed the observed growth of the solid phase to the simultaneous solution of smaller particles and growth of larger particles. From the work of Lenel et al.2,3 and Gurland and Norton4 has come the suggestion that the liquid-phase sintering process may be divided for analysis into three steps: 1) rearrangement upon formation of the liquid phase; 2) solution and reprecipitation of the solid phase in the liquid; and 3) "coalescence" or a final stage of sintering, characteristically slower than the solution-precipitation process. The sequence of steps is shown schematically in Fig. 1. Kingery5 presented a thermodynamic and kinetic analysis of the first two "stages" of the liquid-phase sintering process in which the functional dependence of lineal shrink- age on time at temperature was used to identify the rate-controlling mass-transport process. Table I summarizes the time dependences and processes considered by Kingery.5 This method of data presentation has been employed by Kingery and coworkers for Fe-CU,6 WC-Co, and a number of nonmetallic systems," and bv Whalen and Humenik for Tic-Ni-Mo and Fe-cu.8 In each of these studies, the rate-controlling step during the "solution-precipitation" stage was identified from the slope of the curve in that stage on a logarithmic plot such as Fig. 1. However, in all of the previous studies, at a certain composition, relatively large amounts of shrinkage due to rearrangement preceded the solution-precipitation stage. Under these conditions, the larger the amount of rearrangement shrinkage the

Jan 1, 1965

By M. C. Fuerstenau, J. D. Miller

The response of calcite to flotation with saturated fatty acids and alkyl sulfonates of various chain lengths is presented. The amount of collector re-quired for flotation is shown to decrease systemati-cally with increasing carbon content from 8 to 12-carbon atoms per molecule. This systematic flotation response is correlated with the solubilities of the calcium-collector salts, which were established with a nephelometer. The 14-carbon collectors deviate from this systematic behavior, and no flotation is possible with the 16-carbon homologs. As determined by infrared analysis, the mechanism of collector adsorption involves a specific chemical reaction be-tween the collector and the surface. A reaction of the form CaCO3(s)+ 2 RCOO"=*=Ca(RCOO)2(s) + C03= is suggested. The pH of the system is also shown to be a most important parameter as it controls the carbonate, calcium, and collector ion concentrations in solution and thus controls flotation response. The importance of hydrocarbon chain length of collectors was recognized early, and various studies have been made on this aspect of flotation. Wilkinson, ' for example, noted that as the chain length of alkyl xanthates is increased, the amount of collector required for flotation of sphalerite is decreased. The same effect has been shown in the flotation of galena.2 Similar results were obtained when malachite3 and calcite4 were floated with various fatty acids. DeBruyn5 has shown that a similar phenomenon occurs when quartz is floated with amines at constant pH. Recently, Fuerstenau, Healy, and Somasundaran6 correlated this phenomenon with the van der Waals cohesive free energy of association of the hydrocarbon chains. It seems unlikely, however, that chain association could be involved in the sulfide and carbonate systems with the collector additions employed, especially with the short-chain xanthates. Rather, it would seem that the decrease in collector concentration with increase in chain length noted for flotation is related to the solubility of the metal-collector salt. The purpose of this investigation is to verify this premise and also quantify this phenomenon if possible. Calcite was selected for study with both alkyl sulfonates and saturated fatty acids as collectors. EXPERIMENTAL MATERIALS AND METHODS The collectors used in this investigation ranged from 8 through 14 carbon atoms per molecule. The fatty acids had a reported purity of greater than 99%. The sodium alkyl sulfonates were provided by the Marathon Oil Cot, Littleton, Colorado, and had the

Jan 1, 1968

By C. G. Dunn

NUCLEI that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,1 that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclassesf of the 36 third- order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of de- formation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a {110} plane in a < 100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is notparticularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1946

By J. P. Pritchard, J. T. Pierce, O. G. Slay

This paper discusses the results of a technology-evaluation program to ascertain the feasibility of a piotornask-photoresist technology developed for fabrication of multiple-layer thin-film superconductive circuitry. The uehicle selected for this evaluation was a 120-bil associative data processor requiring a set of nine photomasks to define a similar number of patterned material layers of lead, tin, and polymer insulation. A total circuit area of 4 sq in. involved 2500 actitle and 12,000 passive crossings. Several short-free, electrically continuous specimens were satisfactorily completed under this program. Problems encountered in the preparation and use of the requi-ed set of Photomasks are discussed, as also are the problets of providing suitable external connections. A major retarding factor in the development of the superconducting thin-film cryotron technology for many years was the absence of batch fabrication means yielding necessary device density and count per substrate for practical applications. Early workers in the field desired only limited numbers of devices to permit careful study of discrete devices and representative circuitry integrating logic and memory capabilities. For these purposes mask stencils could be formed to selectively control the placement of materials, sequentially vapor-deposited in vacuum, to form the multilayer structure. In general a distinct pattern was required for each material layer; therefore, mechanical provisions were required to change not only the material source, but the patterning mask as well, before each deposition. All deposition steps were preferably performed in a single evacuation of the deposition chamber. Thus the means for storing, transporting, and registering masks and sources with respect to the substrate existed and were operated within the vacuum environment. In the authors&apos; experience, the approach was and remains serviceable for preliminary device study, but was not extensible to an economical manufacturing method by virtue of the difficulties inherent in mask stencil preparation and use, and the capital investment implicit in the mechanization requirements. Since the commercial attraction of the cryotron technology stems principally from its potential for economical batch fabrication, the authors&apos; program has placed major emphasis on fabrication methods. A highly useful method has evolved through adaptation

Jan 1, 1967

By James Norman, Benjamin S. Lindsey

Barite (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some binds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to I00 per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaS04, II.II. per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.&apos; The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of non-metallic minerals in the presence of a large amount of slime is usually very difficult, and when done is an innovation calling for conditions different from those under which granular material is separated. Laboratory Flotation Work Preliminary investigation showed that the flotation reagents recommended by O&apos;Meara and Coel for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1943

L. C. UREn,* BerkelEy, Cal. (written discussion).—I heartily concur with Rlr. .Fobs concerning the need for advanced courses on various phases of Petroleum Engineering. I think that his criticism is probably true of most of the engineering schools that are specializing at all in Petroleum Engineering, that is, that most of their so-called graduate courses are not of graduate caliber but are merely more specialized aspects of undergraduate subjects. It would undoubtedly be to the advantage of the petroleum profession if more advanced work could be offered in a few of the leading engineering institutions so that there would be something substantial to offer graduate students wishing to return after a period of undergraduate work, for additional training. There is no doubt but that a better trained engineer, more useful to the oil industry, could be secured from schools offering such advanced training. The problem of adpting our instruction to fit the needs of engineers trained along other lines who wish, after completion of their undergraduate work, to enter thc petroleum engineering field, is a more difficult one. It has been my experience that such men are usually sadly deficient along certain lines and that they are really not prepared for the more advanced work in Petroleum Production Engineering until they have gone back over the work which they have missed in their undergraduate training. I note that Mr. Fohs suggests that other eastern and western colleges not now stressing Petrolelim Engineering, should be encouraged to take up advanced work of this character. With this, however, I cannot agree unless the institutions arc also prepared to offer a full sequence of undergraduate work on which the more advanced courses may be superimposed. Whether or not there is a need for additional engi-ncering colleges entering the petroleum engineering field is an open qucstion. I believe that we arc turning out enough petroleum engineers at the present time and that none of the six institutions now specializing in this field arc overcrowded. Morc-ovcr, they are fairly well distributed over the country, though there may be room for an additional school in the field in the eastcrn section of the United States. F. W. Padgett, Norman, Okla. (written tliscussion).—Assuming that the stnclcnt has the proper fundamentals, that is, general science and a knowledge of the technology of the industry, then the problem is: What courses should be offered from the graduate standpoint? (a) Course Work.—His knowledge of the technology of the industry can be extended advantagcously by means of one and two-hour courses, which consist in a more detailed survey of the various branches of the industry. (b) Lilerdure.—This work may, or may not, be connected directly with his research problem. The student should become familiar with methods of locating articles in the 1iterature; should also become familiar with all the important original

Jan 1, 1928