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By Wilson Blake

A mathematical model based on the finite element method of stress analysis has been used to describe the behavior of the western wall of the Kimbley Pit as its slope was steepened from 45° to 57°. Theoretical stress changes because of slope modification are slight except at the toe of the modified slope. Magnitudes of stress created are small when compared with the strength of a competent rock. Resulting displacement patterns point out the need for determining the in-situ state of stress at a site prior to excavation or modification. A comparison of model results with field measurements shows that, in general, the model has described the measured behavior of the west wall of the Kimbley Pit remarkably well. The Bureau of Mines and the Kennecott Copper Corp. began joint research on open-pit slope stability at the Kimbley Pit, Ely, Nev., in 1961. The initial or planning phase of this research dealt with a detailed geologic study of the Kimbley Pit, determination of in-situ stresses in the district, laboratory and field tests to determine rock properties, and the design of a full-scale experiment to study the behavior of this pit as its western wall was steepened from 45° to 57°. Fig. 1 shows a cross-section of the original pit outline, the steepened pit outline, major geologic features, and the two instrumentation adits. After the final or slope modification phase of the research began, a laboratory research program was initiated to develop a mathematical model that would analytically describe the behavior of the pit as its western slope was steepened. This theoretical model study of the slope modification at the Kimbley Pit was conducted with the finite element method of stress analysis. The results are described in this report.

Jan 1, 1969

By H. H. Evinger, M. Muskat

Although the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.' In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was measured and an attempt was made to determine the effectiveness if sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to deter-mine the effect of tamping were performed by Snelling and IIalL2 Small charges (zo grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.~ The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.6 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

GENERAL GEOLOGICAL DESCRIPTION The uranium mineral appraisal herein described was made for an ore deposit in New Mexico. The uranium mineralization occurs as roughly tabular to lens-shaped deposits of varying thickness within the sandstone of the Jackpile formation of Jurassic age. The mineralization occurs at several horizons within the Jackpile formation, but is not always confined to specific beds. It often transgresses across stratigraphic layers, as demonstrated when attempting correlation of uranium gamma anomalies between adjacent drill holes. Preferred mineral trends have been established in some parts of the deposit, but are not always predictable when attempting to extrapolate beyond the zones defined by drill hole sampling. MANAGEMENT OF DRILL HOLE SAMPLE DATA All of the drill hole sample data used in the appraisal were obtained from interpretation of gamma-ray logs. A brief description of gamma-ray log sampling is given in Chapter 2. Two preliminary steps are involved in preparing gamma-ray logs into sample data normally acceptable for computer manipulation. 1) The gamma analog trace produced by the downhole probe must be digitized, i.e., counts-per-second (CPS) are recorded for each 0.15 m (1/2-ft) interval across the gamma-ray anomaly. The work is usually done on a "digitizer" while following the analog trace with an electronic stylus on a special tablet or table. The other alternative is to do the work manually. Some of the newest downhole logging equipment produces a magnetic tape output which can be read by a computer. 2) The gamma-ray CPS values must then be converted to equivalent U308 assay values, taking into consideration all appropriate correction factors. The US Atomic Energy Commission, now part of the Department of Energy, developed the theory and algorithm for this conversion in the 1960's, and though the work can be done manually, it is best done with the GAMRED (gamma-reduction) computer program. Fig. 14-1 illustrates a typical analog trace produced by the probe instrumentation, including gamma-ray trace (left), self-potential electric log (center), and resistivity log (right). Fig. 14-2 shows a form of the computer output after the analog data has been digitized to 0.15-m (1h-ft) intervals and converted to percentage U308 values for the same hole. The U308 grade bar graph on the right permits rapid visual inspection of anomalous values by depth and elevation. The converted U308 sample data were next processed by the SURVEY program that assigned to each assay interval [0. 15-m (1h-ft)] an X Y Z coordinate, taking into account all deviations indicated from downhole survey information. The output file of the SURVEY program was listed on the line printer for examination by project geologists, and also became the main input file for the URAN/ COMP compositing program, which is designed to group individual 0.15-m (/-ft) U308 sample values into larger intervals representing discrete anomalous zones according to a series of specified parameters entered into the program by the user. Composite U308 intervals were computed by the URAN/COMP computer program, the logic of which may be briefly described as follows: Step 1 The program searches for the highest U308 value in the hole and builds a composite by adding the highest grade interval on either side so long as the added value is greater than a minimum acceptable grade, and the total composite, after addition, meets minimum GT (grade times thickness) constraints. Step 2 The program loops back to find the next highest assay value in the hole not already included into a composite, until all anomalies above minimum cutoff grade are composited. Step 3 Individual composites are combined if they are closer than a specified minimum waste thickness, and the resultant composite grade still meets GT minimums.

Jan 1, 1980

By G. W. Healy, W. Craft, D. C. Hilty

By means of a theoretical extension of the Cr-C temperature relation in molten chromium steels to low chromium contents and by a correlation of the ratios of chromium to iron in the slag and metal, a method has been developed for estimating the amount of metallic oxidation during the oxidizing period of a chromium steel heat. Application of this method has indicated that due to temperature limitations metallic oxidation may be excessive for very low carbon steels charged with more than a small amount of chromium. IN the melting and refining of chromium steels the oxidation of carbon to a low level is accompanied by the oxidation of chromium and iron in considerable amounts. For the subsequent recovery of chromium and associated iron from the slag, the amounts of metal oxidized must be known for efficient reduction and control of composition. Further, in order to arrive at an accurate understanding of the process, so that chromium-bearing scrap can be used effectively, information is required on the relation between composition of the charge and weight of metal oxidized to reach the desired carbon content. Crafts and Rassbach1 recently developed an empirical relation between chromium, iron, and manganese oxidized per ton of steel charged, and final carbon content and temperature. This relation did not show any dependence on amount of chromium charged. However, it was felt that such a dependence might be present, so a further analysis of the data was undertaken. Cr-C Relation at Low Chromium Levels Crafts and Rassbach's results were based on temperatures estimated from the Cr-C relation previously established experimentally by Hilty,2 and on a single temperature observation (immersion thermocouple) on a heat made at low temperature from a charge of carbon steel scrap containing only a small amount of residual chromium. The temperatures estimated from the Cr-C relation were for heats charged with chromium-bearing scrap and which contained substantial amounts of chromium (2 to 10 pct) at the end of the oxidizing period. No data, other than that from the low temperature heat just mentioned, were available for the low and intermediate chromium ranges. In order to extend the range in which temperature may be estimated, the Cr-C relation requires further consideration. The Cr-C relation, expressed as suggests that carbon is zero at zero chromium in the bath. This is obviously absurd, because as chromium approaches zero the carbon content must approach the limit established by the Fe-C-O equilibrium. It is evident, therefore, that the Cr-C relation as defined by Eq. 1 is not valid below some minimum chromium content that may vary with temperature. On the other hand, it is probable that any such limiting chromium content is less than 4 pct at 3200°F, since the experimental data from which the Cr-C relation was derived included several observations at that level with no deviation. In any event, it is apparent that further evaluation of the results presented by Crafts and Rassbach is dependent upon a means for estimating the Cr-C temperature relation in the low chromium region. From the observations of Chen and Chipman9 and thermodynamic data given in Basic Open Hearth Steelmaking,4 the following relation can be calculated for melts containing small amounts of chromium and carbon assuming a carbon monoxide pressure of 1 atm: % Cr -21,250 K' = (%C)2; logK1 == —t— +13.88 [2] Moreover, by plotting Eq. 2 for any given temperature on cartesian coordinates, it can be extrapolated graphically to the limiting carbon content at zero chromium for the specified temperature without serious complications. By means of Eq. 2 and its extrapolation, the Cr-C temperature relations originally established experi-

Jan 1, 1954

By O. B. Buchlen, J. W. Smith

The Coal Research Bureau of the School of Mines at West Virginia University, using an experimental flotation cell designated an airlift-cyclone was able to obtain a clean coal product containing 7.64% ash with 94% yield and 97% coal recovery. This favorable performance was obtained with the experimental flotation cell operating as a simulated three-stage unit on slurry taken from the fine coal circuit of a coal preparation plant. This experimental device, consisting of a sheet metal cyclone-like unit mounted on a U-shaped uplift pipe, uses a combined flotation and cyclone action to beneficiate the minus 14 mesh partially cleaned feed product. In addition to providing comparable analytical results, the airlift-cyclone possesses other attractive features among them being a low capital expenditure, utilization of moderate plant floor space, efficient operation on high density feed slurry, and absence of moving parts. The primary shortcoming of the experimental cell is its limited capacity. The Coal Research Bureau presently has under construction a larger unit which, it is hoped, will provide the capacity and quality to establish the airlift-cyclone as a commercially feasible unit. Froth flotation of fine coal is a practice which has only recently gained wide acceptance in this country. Various explanations can be put forth for this delayed acceptance of a very selective and efficient system of coal preparation. Among these reasons would be the advent of continuous mining machines resulting in the increased production of coal fines, the change in market patterns from domestic and rail consumers who did not want fines to a predominantly utility market which normally consumes fines, and also the imposition of legal restrictions in regard to stream pollution. However, the major detriment is probably the high cost involved both in installation and operation of the flo- tation unit and auxiliary systems. These facts assume greater emphasis when considering that froth flotation installations normally process a low quality feed product. A recent estimate' of installation costs including dryers, filters, and other auxiliary equipment for a flotation system was $5000 to $7000 per ton of capacity while the operating costs, exclusive of auxiliary equipment, were estimated at 10 to 306 per ton of feed. The Coal Research Bureau of the School of Mines at West Virginia University is currently developing a simplified froth flotation cell, designated an airlift-cyclone, which may provide considerable savings in capital and operating costs without sacrificing product quality or recovery. This experimental cell consists of three primary components: 1) a vertically mounted U-shaped pipe; 2) an air injector device; and 3) an integrally mounted cyclone-like unit (Fig. 1). A feed slurry is introduced at the top of one leg of the U-pipe while compressed air is injected near the base of the other leg. The air serves both to aerate the pulp and to cause it to flow upward into the base of the cyclone unit where the floated clean coal is separated from the reject material and unfloated coal which remains in slurry. The Coal Research Bureau's experimental airlift-cyclone is somewhat similar in principle to a flotation device developed by Russian engineers in the late 1950's. In tests upon a two-stage pilot-size device, the Russians obtained very favorable cleaning efficiencies.' However, later experience with production models demonstrated that rated capacities and acceptable product quality could not always be maintained.3 Because of these limitations, Russian engineers subsequently recommended that conventional, mechanical cells be used when cleaning difficult to float slurries. Engineers at the Coal Research Bureau felt that such a device utilizing the combined actions of a cyclone and a froth flotation machine offered numerous attractive features and merited investigation. Accordingly, a small capacity experimental airlift-cyclone was designed and, with the permission of the Christopher Coal Company Div. of Consolidation Coal Co., installed in Christopher's Humphrey preparation plant near Morgantown, West Virginia.

Jan 1, 1964

By W. B. Wise, H. D. Attra, W. M. Black

The purpose of this paper is to illustrate a comparatively new approach for solving a problem that has plagued oil producers for many years—how to make the most money with available field production capacity. In a very basic operation such as a top-allowable one-well field, a computer and staff of engineers are not required to determine that the best operation is to produce that well at its maximum for as long a time as it will produce. However, as the problem becomes more complex and the number of wells and number of reservoirs increase, it probably will be a wise choice to devote some engineering thought and calculation time to determine the best way to operate that field on both an ultimate and day-to-day basis. Continued developments in the field broadly referred to as "operations research" have led to a number of useful engineering analyses for optimizing field operational problems. One of these techniques, termed linear programing, is parlicularly interesting because of its potential applications to the study of complex oilfield operating problems. Linear programing is concerned with the problem of planning a complex set of interde~endenl activities in the best possible (optimal) fashion. A field application of linear programing is being used to maximize daily income from a multi-reservoir producing operation. The initial results of this study indicate that the linear programing technique (I) can be applied effectively to field problems, (2) can be used to detect unsuspected avenues for improving operations and (3) can effect a significantly improved means of controlling field operations through the use of the highspeed computer. INTRODUCTION The usual approach for studying complex field operational problems has been to look in detail at several basic plans suggested by judgement and experience and, then, to choose the best plan from those investigated. This approach is entirely satisfactory provided: (1) that judgment and experience alone will reliably pick the best or near the best program as one of the plans to be investigated; and (2), and most important, that the factors which control field production will not change. This paper deals with the large group of field operations which are at least one-step removed from a satisfactory solution using the conventional method of analysis. Problems such as pipeline- and gathering-system design, transportation studies, large field development projects and multi-reservoir producing operations fall in this latter category. To find the best program for handling these problems when the best program is not obvious, a complete optimization study is required, and high-speed computers are required to continually update the program once it is selected. Operations of this type have an extremely large number of possible solutions. However, only one will result in maximum economic return and, more important, this one program must be re-evaluated and adjusted constantly to accomodate such changing field factors as the number of producing days, the price of crude, the discovery of new reserves, declining reservoir pressure with subsequent decline in production and a host of other factors which characterize specific operations. One of the most widely used, direct methods of optimization is a numerical procedure termed "linear programing", which is designed to investigate systematically each of the possible solutions involved in a given problem, determining rapidly and uniquely the optimum answer. As implied by the name, linear programing requires that all field variables be either defined or expressed in a series of interdependent linear equalities or inequalities. These relationships are solved simultaneously, using a form of matrix solutions to determine the optimum values for each producing variable that will maximize net profits. The solution techniques used in a recent field case study is termed the "simplex method" and is discussed in full detail in Ref. 1.

By D. D. Pollock, D. I. Finch

Relationships between the compositions of specially prepared manganin-type alloys and some of their electrical properties have been established. Empirical equations, based upon the electronic configurations of the alloying elements, are given which describe the resistivity, temperature coefficient, peak temperature, and thermoelectric power of Cu-Mn-Ni-Fe alloys at approximately room temperature. Calculations based upon these relationships are correlated with experimental data. SECURING suitable alloys for the construction of stable resistors, for use in precise electrical measuring devices, has been important ever since the art of electrical measurement was begun. German silver, Pt-Ag, and Platinoid are examples of some of the alloys in early use. These early alloys were un- satisfactory for one or more of the following reasons: l—insufficient stability of electrical properties with time, 2—poor reproducibility of electrical characteristics from melt to melt, 3—excessive temperature coefficients of resistance, and 4—excessive cost. Weston introduced the Cu-Mn-Fe and Cu-Mn-Ni-Fe alloys of the type now generally known as manganins. His patents are believed to represent the first disclosure of any alloy with a negative temperature coefficient of resistance. After this work, the German company, Isabellenhutte, in conjunction with Feussner and St. Lindeck, produced alloys of

Jan 1, 1957

By M. Muskat, H. H. Evinger

Although the shooting of oil wells for the purpose of increasing production has been practiced since 1866, present-day shooting technique has been arrived at almost wholly by a process of trial and error. The difficulties attending either a theoretical analysis of the problem or an experimental attack become apparent when one actually embarks on a theoretical investigation or attempts to formulate an intelligent experimental program. The literature on the subject consists mainly of descriptions of current practice, scattered eye-witness accounts of events following the shooting of a well, and vague speculations on the mechanical processes involved. In contrast to quarry blasting, the results of oil-well shooting cannot be determined by means of visual inspection, and it is perhaps for this reason that only one attempt at what approaches a direct experimental attack has been reported in the literature.' In these experiments, charges of liquid nitroglycerin were exploded in holes drilled in a sandstone outcrop. In order to observe the character and extent of the resulting fractures, the rock was blasted away so as to expose the original shot holes. After all this had been done it was found impossible to distinguish the fracturing due to the original shots from that due to the subsequent blasting. The enlargement of the holes due to the pulverizing action of the shots was measured and an attempt was made to determine the effectiveness if sand tamping. Only five shots were made and few definite conclusions could be drawn. Some small-scale experiments to deter-mine the effect of tamping were performed by Snelling and IIalL2 Small charges (zo grams) of dynamite were detonated at the bottom of a cylindrical hole in a lead block and the resulting enlargement of the hole was taken as a measure of the effectiveness of the explosion. It was found that when the shot was tamped with a sufficient amount of sand or clay, the volume enlargement was approximately double that found when no stemming had been used. The properties of the explosives have been the subject of much study by the manufacturers, the U. S. Bureau of Mines, and various other agencies. For example, velocities of detonation for many commercial explosives are to be found in the Blasters' Handbook, issued by the Du Pont company. Many other properties are given in a treatise on the subject by Naoum.~ The shock wave that accompanies the detonation of high explosives has been studied photographically by Payman4 and others. The hydrodynamical theory of the shock wave has received much attention, and an extended theoretical treatment is given by Bateman.6 Two aspects of the well-shooting problem will be considered in this paper; namely, the fracturing of subsurface strata, and possible damage to casing. With respect to the former of these, several calculations have been made giving the stresses in the rocks surrounding the shot. In order to arrive at numerical results at all, however, it is necessary to introduce a great many simplifying

Jan 1, 1941

By Gregoire Gutzeit

THE development reported in this paper was begun by the author a number of years ago, while he was a lecturer on complex chemistry and metallurgy at the University of Geneva, Switzerland, and in charge of that institution's research laboratory. Completion of the development and reduction to practice did not occur until last year at the Westport mill, laboratories and testing plant of the Dorr Company, where this method is now in general use for identifying and localizing the mineral constituents of both metallic and nonmetallic ores. It has proved to be a practical tool of the metallurgical staff at the Westport mill, devising unusual milling flowsheets for complex and refractory ore bodies. In a number of instances the findings have been successfully used as fundamental factors in the design and specification of complete metallurgical plants. Seven examples of the use of this method in solving practical milling problems are included in this paper. GENERAL OUTLINE The microscopic study of an ore, at first only of scientific interest, has proved extremely useful both in practical geology and in ore dressing. The binocular magnifying lenses for rough observation of the products of an ore-dressing plant have been in use for a long time; but only within the last few years has a systematic microscopical examination of ore samples become a normal tool of any research laboratory dealing with ore-dressing problems. Such an investigation avoids considerable loss of time as well as empirical trials and useless experimentation. It will generally indicate the correct grinding and often will suggest the proper method of treatment. The petrographic determination of transparent minerals in thin sections, or even in grains, has been perfected, and very accurate methods have been devised to meet any requirement, such as Feodorof's rotating stage on the petrographic microscope. Almost all transparent minerals can be positively identified by their optical properties; i.e., isotropism, anisotropism, color, pleochroism, refractory index, cleavage, crystal form, birefringence, and others. The identification of opaque minerals is a much more difficult problem and can be done only by using polished specimens. Unfortunately, most of the valuable metallic ores, and even some of the nonmetallic ones, are not transparent; therefore it has been necessary to develop a special technique for the determination of these minerals. Some optical properties-for instance, isotropism, anisotropism, color, cleavage, reflecting power-are often adequate in roughly classifying the mineral. Only "reflecting power" is a measurable value, provided special photometric equipment (ocular photometer or Orcel's photoelectric cell) is available. The other optical properties mentioned are more or less relative,

Jan 1, 1942

By C. W. EICHRODT

NUMEROUS requests for the suspension of publicity make difficult the preparation of the annual review of copper metallurgy for 1934. In the United States, sales allocations indirectly have set restrictions on the scope of activities of producers and refiners, and necessitated closer cooperation between secondary and primary producers. However, the feeling exists that preparations for a return of intense competition should not he neglected, and careful investigations are being conducted for ways and means of improving industrial positions and production methods. In all probability, efficiency in technique and equipment will prove of far greater importance in the near future than production capacity, and many important developments in copper metallurgy later will be found to have been born during the current year.

Jan 1, 1935

By W. L. Prehn, Adele Chambers, R. L. Slobod

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By R. L. Slobod, W. L. Prehn, Adele Chambers

The centrifuge has been found to be an extremely useful tool for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. The use of the centrifuge for determining the properties of small core plugs has been discussed in the literature,',' but practically no experimental evidence has been presented justifying the use of this method in preference to other methods (mainly disc method) now in use. Data have been accumulated and are now presented demonstrating the advantages of the centrifugal method, some of which are: (1) rapid establishment of equilibrium, (2) excellent precision yielding very reproducible results, (3) availability of high pressure differences between phases, (4) simple operational procedure, and (5) ability to establish connate water, residual oil, or to obtain complete capillary pressure curve in one day or less. A commercially available centrifuge capable of speeds up to 3,800 rpm, and a high speed attachment providing a maximum rate of rotation of 18,000 rpm were used in this work in conjunction with core holding tubes designed specifically for this application. In view of the outstanding advantages associated with the use of the centrifuge the conclusion has been drawn that this method should be used in place of the more tedious, slower, and less reliable disc method for determining capillary pressure curves and for establishing connate water and residual oil in small core plugs. INTRODUCTION The need for accurate values of connate water, residual oil, and capillary pressure curves in reservoir engineering has been recognized for many years, and the extent of the effort devoted toward solving these problems is reflected in the large number of papers3-" which have appeared in the literature during the past decade. Most of the methods discussed in the recent literature employ a porous disc as a semi-permeable membrane to separate two immiscible phases and make pos-ible the application of an explicit difference in pressure between two phases in the core. Thus, in the determination of the capillary pressure curve the wetting phase (water) is displaced by the non-wetting phase (air or oil). Several investigators1,2 have used centrifugal forces to develop pressure differences between phases. As a result of the first work' in this field the conclusion was reached that "the more rapid centrifugal method for measuring irreducible saturation may have equal value, (compared to use of discs) but more work is required to establish this point." This work was followed in 1945 by a more detailed study2 in which the concepts of this experimental work were more clearly enunciated. A method for calculating saturation for any given speed of rotation based on the observed volume of water displaced was developed and a wider application of the method was suggested. The absence of any subsequent pertinent literature on this subject is interpreted as indicating that no additional work has been completed to substantiate or deny the earlier claims and suggestions of promise contained in the original papers on this subject. One purpose of this report is to provide evidence designed to establish the practical value of centrifugal methods in determining core properties such as connate water and capillary pressure curves. It is also our purpose to suggest a broadening of the scope of this tool to include determinations of residual oil by gas or water drives. THEORY AND PRACTICE IN USE OF CENTRIFUGE Hassler and Brunner2 have clearly presented the basic concepts involved in the use of the centrifuge by relating the performance of a small core in a field of high acceleration to the

Jan 1, 1951

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats of Formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 and the heats of solution of tellurium and selenium in liquid bismuth have been measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides have been measured in a constant temperature gradient calorimeter. The thermo-dynamic quantities are interpreted in relation to the stability of the compounds and the nature of the solid-liquid transition. THE selenides and tellurides of several elements of Group VB of the periodic system are of interest because of their electronic properties. The compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 are semi- conductors; they also have gained prominence in the fields of thermoelectricity and photoconductivity. However, little is known about their thermody-namic properties. As part of a research program on the thermo-dynamic properties of intermetallic compounds, the heats of formation of the compounds Sb2Se3, Bi2Se3, Sb2Te3, and Bi2Te3 were measured in a liquid metal solution calorimeter. The heat capacities near the melting point, the heats of fusion, and the melting points of the two tellurides were measured in a constant temperature gradient calorimeter. The results, in addition to their intrinsic interest as thermodynamic quantities, contribute to an understanding of the stability of the compounds and the nature of the solid-liquid transition. 1) EXPERIMENTAL 1.1) Materials. Samples of the compounds SbzSe3 and Bi2Se3 were prepared by melting the elements in stoichiometric proportions in evacuated Vycor capsules followed by quenchinn in water. They- were then annealed in vacuum for 12 hr at 550°C. A sample of Sb2Te3, consisting mainly of one large grain, supplied by the Lincoln Laboratory,

Jan 1, 1964

By E. H. Rennhack

Phase equilibria of the zinc-rich portion of the Zn-Fe-A1 system containing up to 20.0 wt pct Fe and Al have been investigated at 600°C (1112°F), 450°C (842°F), and room temperature by metallographic and X-ray diffraction techniques. The phase relationships were found to involve only those phases present in the three binary systems. THE presence of small quantities of aluminum (approx. 0.2 wt pct*) in zinc galvanizing baths is known to suppress the formation of Zn-Fe alloy layers within the coating.' As part of an extended investigation of this suppression effect and the alloy reactions involved, the zinc-rich corner of the Zn-Fe-A1 equilibrium system containing up to 20.0 pct Fe and Al was determined at 600°C (1112°F), 450° F (842° F), and room temperature. The present paper reports the findings of this study. The constitution of the Zn-Fe system has been reported by Raynor2 based mainly on the work of Schramm3-3 and Truesdale et a1.6 The solid solubility of iron in zinc is extremely small and lies between 0.0009 and 0.0028 pct in the range 150° to 400°C (302°to752°F). Within the temperature and composition range of interest, a eutectic reaction involving nearly pure zinc, liquid = Zn+FeZn13, is observed at about 419°C (786° F) and 0.018 pct Fe along with a peritectic reaction, FeZn7+ liquid e FeZn13, at 530°C (986° F) and 6.2 pct Fe. The latter reaction is sluggish due to the large proportipn of solid phase involved in the transformation. Halla et al.,7 identified the compound FeZn13 as monoclinic with a = 13.68, b = 7.63, c = 5.07, and B = 128°44'. The structure of FeZn7 was reported by Bablik, et al.,8 to be of hexagonal symmetry, belonging to either the C6v = C6/m mc or D46h = C6/mc space group. Divensions of the unit cell are a = 12.81A and c = 57.6a. The Zn-A1 diagram as composed by Raynor9 and later Gebhardt10 is characterized by a eutectic decomposition, liquid 382°C (720°F) and 95.0 pct Zn and a eutectoid decomposition, at 275° (527°F) and 78.0 pct Zn. The eutectoid reaction cannot be suppressed permanently by quenching. Above 275° (527° F), a and a' co-exist in a closed miscibility gap between 31.6 and 78.0 pct Zn. Both phases are fcc and have nearly the same lattice parameter. The maximum solubility of aluminum in zinc (B) is approximately 1.0 pct at the eutectic temperature. PROCEDURE Materials. The experimental alloys were prepared from both massive and powdered material. Cast alloys were composed from three zinc-base master alloys containing 8.0 pct Fe, 16.0 pct Fe, and 50.0 pct Al which were made from C.P. zinc, Armco iron, and

Jan 1, 1962

By Kurt Kennedy

A method is described by which three elements can be condensed simirltaneously on a common substrate in such a way that the composition varies with position on the substrate. Almost all possible combinations of three solid elements can be formed in a single evaporation. The three elements are heated by magnetically deflected electron beams. The alloys and cornpounds formed by this method generally correspond to those trade by other methods; however, many exceptions exist. Simple symmetric crystallographic phases tend to form in preference to more complex phases. The Nb-Sn. Cr-Fe-Nt, and other systems of alloys made by this method will be discussed. Phases that form very slowly, such as the o phase in Cr-Fe alloys, may be formed rapidly by this method when certain substrate temperatures are used. STUDYING all the mixtures and compounds of two or more elements by the preparation of individual samples forces the investigator to make sampling sufficiently close together so that the properties of the intermediate compositions can be inferred. A completely unknown system will require a dis c our aging ly large number of preparations in order to fully know all its properties. For the purpose of expediting this type of investigation, methods have been devised to prepare samples that have a continuous variation in composition over some predefined area. The code-position of two elements onto suitable substrates has been used to produce alloys or compounds that have variable compositions depending on their positions on the substrates Composition gradients have been formed by depositing a wedge-shaped layer of one element and then depositing a second wedge-shaped layer on top of it such that the total film thickness is kept constant. Concentration equilibrium perpendicular to the surface is then established by annealing.4 This paper describes a method for the simultaneous condensation of three volatile components on a substrate such that there is a regular variation of composition with position on the substrate. The arrangement of the evaporation sources and the substrate is shown schematically in Fig. 1. Materials to be evaporated are placed in three water-cooled crucibles located at the corners of a 10-in. equilateral triangle. Electron beams from cathodes located below the crucibles are bent 180 deg by magnetic fields and focused on the material to be evaporated. The cathodes are connected in parallel to a constant-current 12-kv power supply. The distribution of emission current from each cathode is controlled by filament temperature. When materials that sublime are to be evaporated, the electron beam is deflected by an auxiliary ac magnetic field so that the beam moves over the surface of the evaporating material rather than digging a hole in one spot. The substrate is a 10-in. triangle of 2-mil stainless steel or molybdenum which is stretched against a slightly curved heat sink by a frame as shown in Fig. 2. This frame and heat sink are located so that each corner is directly above an evaporation source. The heat sink has three radiant heaters at each corner that can be separately controlled permitting the

Jan 1, 1967

By C. P. Lawhon, J. P. Simpson, W. M. Evans

Recent efforts to design drilling fluids for increased drifting rates have confirmed some laboratory results of other investigators, but have also produced additional data that should be considered. These data were obtained under controlled test conditions using a microbit drilling machine. Clays and some polymers have previously been reported to cause reduction in drilling rate. Recent data have shown that under laboratory conditions, suspensions of a single day or polymer have sometimes given faster drilling rates than when water was used. Measurements have been made of clay suspensions and polymer suspensions comparing filtration (I) under API conditions, (2) while drilling with temperature of 150F and differential pressure of 1,000 psi and (3) under dynamic conditions after drilling. Some correlation between instanraneous filtration (white drilling) and drilling rate has been observed. INTRODUCTION Several papers have been presented that related drilling fluids to penetration rate. Generally, it was found that a decrease in the solids concentration resulted in significant increases in the drilling rate. Of course, this change also resulted in a decrease in the viscosity of the drilling fluid.' Conclusions from investigations by this laboratory are in agreement. Data have shown that of the simple mud measurements commonly made at the drilling rig (density, plastic viscosity. yield point, API filtrate and total solids), only the density and total solids have a significant relationship to the drilling rate in Berea sandstone when attempting to correlate a single mud property individually.' More recent drilling rate experiments have been designed to study (1) effects of individual clays and polymers on drilling rates in Berea sandstone and Lueders limestone, (2) the relationship between drilling rate and dynamic filtration as measured after drilling and (3) the relationship between drilling rate and dynamic filtration as measured during drilling. Data show that drilling rates are dependent upon type and concentration of particles, type of formation and filtration of the individual fluids while drilling. Mud pressure: pressure of drilling fluid as measured after leaving the drilling chamber (Fig. 1). This is taken to be approximately the mud pressure just past the bit and at the face of the formation. Terrastatic pressure: pressure representing weight of overburden. Formation pressure: pressure of formation fluid as measured at outlet of drilling chamber (Fig. 1). This is taken to be approximately the pressure of fluid in the interstices of the formation. Differential pressure: difference between the mud pressure and formation pressure. LABORATORY EQUIPMENT AND TESTING PROCEDURE The drilling equipment was described in two previous publications."' Main components are a drilling chamber, filter-heater, rotary drive and variable-speed circulating pump. Auxiliary pumps supply pressure boosts for the mud, terrastatic and formation pressures. All equipment is designed for 15,000 psi and 500F. Capacity of the circulating system is approximately 7 gal. The mechanical design was facilitated by moving the rock down onto the bit. Data collected with this design should not differ from that obtained by a normal design where the bit moves into the rock. Drilling fluid is pumped through 50 ft of ID pipe coiled in an oil bath, enters the rotary shaft at a right angle and is pumped through the jets on the bit (Fig. 1). Most of the drilled solids are extracted by a screen mounted in the circulating system on the suction side of the pump. Data reported in this paper were obtained by controlling these parameters: mud pressure, 5,000 psi; formation pressure, 4,000 psi; terrastatic pressure, 5,000 psi; force on bit, 1,000 Ib; formation, Berea sandstone and Lueders limestone; flow rate, 7 gal/rnin; bit, 11/4-in. diameter with two 0.078-in jets; mud temperature. 150F; and rotary speed, 60 rpm. Mud pressure was controlled at 5,000 psi, thus giving a differential pressure of 1,000 psi even though the fluid densities varied. Cores of 3%;-in. diameter and 8 in. long were selected from quarry blocks to provide some control of grain size distribution, permeability and porosity. A 2-in. section was cut off each core and a I -in. diameter plug was taken from this section. Permeability to 5 percent by weight sodium chloride solution was determined and the large cores were

By Robert L. Akre

When Marco Polo visited China in the 13th century, no one knew what black powder was except the Chinese; they knew enough to make dazzling fireworks with it. But the realization that black powder could also do useful work came much later and, like all important discoveries, it altered the course of history. It was in the 14th century that black powder was first used to break rock in a very crude way; there were no drills and the powder was simply poured into cracks and exploded by setting it afire. Because its energy value was pretty low, the need for something more powerful was felt when the industrial revolution began. In the 1850s, miners began experimenting with liquid nitroglycerine on a limited scale. This was a very sensitive and dangerous explosive. Fortunately in the 1860s, Alfred Nobel succeeded in stabilizing nitroglycerine by absorbing it in kieselguhr-and a new product, dynamite, was born. With it, miners were able to unleash the great energy of nitroglycerine for blasting purposes. But dynamite was still a very sensitive explosive. In subsequent years, other explosives of various strengths and characteristics were developed, such as blasting gelatin, gelatin dynamite, ammonia dynamites, (all containing some nitroglycerine or nitrostarch), and liquid oxygen explosives. These products and their variations supplied the blasting trade for many years. A grained ammonium nitrate product containing some carbonaceous material entered the market in the 1930s. This explosive had below-zero sensitivity-meaning: a No. 6 blasting cap imbedded in it would not detonate it. A more sensitive initiator, called a primer, was needed to detonate this mixture. From Rags to Primacord to Solid-State The first initiator for an explosive charge was probably a rag slowly burning its way to the charge; this method was quite unreliable. Then came the burning fuse, which was an improvement. Next was the nonelectric blasting cap initiated by a fuse. With these initiators, a miner needed quick reflexes and good legs; upon lighting the fuse, he had to run immediately for cover. Development of the electric blasting cap that allowed for accurate timing eliminated this hazard; the electric cap, however, introduced other safety problems because of its susceptibility to extraneous electricity, e.g., ground currents, lightning, and static electricity. These caps also became available in millisecond delays. Development in the mid-1930s of Primacord, a detonating fuse insensitive to electrical currents or impact, further reduced blasting hazards, and is generally acknowledged as the safest known means of initiation. Eventually, Primacord millisecond connectors also became available for delay patterns in blasting. In the mid-1960s, the Primadet delay was introduced; it is a practical nonelectric detonator system that offers the precise timing of electric blasting caps-and is immune to the hazards or effects of extraneous electricity. Recently, Research Energy of Ohio, Inc. introduced a new type of solid-state blasting machine that combines a sequential timer and delay caps. It enables the efficient breakage of rock with a minimum amount of shock, ground vibration, and noise. Improvements in Blast-Hole Drilling World War II created an enormous demand for coal and other minerals in the U.S. and elsewhere. Great efforts and large amounts of capital were spent to find new mineral deposits and develop better mining methods. But while mechanization in mining proceeded at a rapid pace particularly in open-cut work, there was a definite lag in developing new or improved machines for drilling blast holes. The industry continued to depend largely on horizontal, churn, and pneumatic drills. No better machine was available for large scale production. The need for improvement in this phase of mining became more acute in the post-war years. Despite efforts toward further mechanization, mining costs rose rapidly because of mounting inflation and increasingly high wages. In most operations, drilling and blasting the overburden became the principal item of cost. Therefore, whatever size holes were being drilled, the holes had to be spaced so that any foot of the bore hole could be loaded with the maximum load required for the number of cubic yards of material that each foot of the hole was carrying. With the smaller holes that were being drilled, the proportion of drilling cost to the total drilling and shooting cost was much higher than it would have been with larger holes (because of the closer spacing required by smal-

Jan 1, 1977

By J. B. Clemmer, P. E. Churchward, C. Rampacek

A cyclic method for processing manganese ores using sodium sulphate as the basic reagent is described. Sodium sulphate is electrolyzed in a diaphragm cell to give an anolyte-containing agentisdescribed.Sodiumsulphuric acid and a catholyte-containing iselectrolyzedincaustic soda, a part of which is carbonated in a cyclic manner to form soda ash. The reduced ore is leached with the anolyte to dissolve the manganese and the impurities are precipitated by addition of catholyte. Manganese in the pregnant todissolvethemanganeseandtheimpuritiessolution is precipitated as synthetic rhodochrosite with a carbonated catholyte, and sodium sulphate is regenerated. Calcining the manganese carbonate gives a high grade product and the carbon dioxide is returned to the carbonation step. The results of laboratory tests using cells equipped with synthetic-fiber diaphragms and permselective membranes, which permit transfer of anions or cations during electrolysis, are described. A METHOD which has been considered for pro-cessing manganese ores under emergency conditions to recover a product suitable for smelting to ferromanganese involves reductive roasting of the ore for leaching with dilute sulphuric acid followed by precipitation of the manganese from the purified pregnant solution with sodium carbonate. Although the process is operable and involves no novel or untried steps, it is noncyclic in regard to reagents. Research seemed warranted to determine if a cyclic process could be developed by electrolyzing the sodium sulphate formed during precipitation of the manganese with soda ash to regenerate sulphuric acid and sodium hydroxide. Reduced ore would be leached with acid anolyte to dissolve the manganese. The iron, alumina, and other dissolved impurities would be precipitated with the caustic catholyte, and the manganese in the purified pregnant solution would be precipitated as artificial rhodochrosite with carbonated catholyte to regenerate simultaneously sodium sulphate for electrolysis. Waste boiler gas and CO, from calcining the manganese precipitate would be recycled for carbonation of the caustic catholyte. There is a surprising lack of data in the technical literature on diaphragm electrolysis of sodium sulphate. One of the more comprehensive papers, by Atwell and Fuwa, describes the problem involved in electrolyzing byproduct sodium sulphate from the viscose process with particular regard to the design and operation of asbestos diaphragm cells. Frisk' also investigated electrolysis of sodium sulphate from viscose-spinning baths to recover caustic soda and sulphuric acid. The objective in these investigations was to produce, by electrolysis and evaporation, a concentrated caustic-soda solution and a sulphuric-acid solution low in sodium sulphate. Because of these requirements, the process was not too attractive despite a favorable yield of caustic and acid with a reasonable power consumption. Because strong acid and base are not required for processing manganese ores and nonelectrolyzed sodium sulphate is not objectionable in either reagent, the present problem was somewhat simpler than that of these investigators. The purpose of this report is to summarize briefly the results of laboratory electrolysis of commercial sodium sulphate in diaphragm cells of different types and the application of the acid and caustic for processing manganese ores in a cyclic manner. Electrolysis in Permeable Diaphragm Cells The principal problem in electrolyzing sodium sulphate in a permeable diaphragm cell is to prevent mixing of the acid and base formed in the anode and cathode compartments. It is not enough to separate the anolyte and catholyte by a single diaphragm. A three-compartment cell in which the sodium-sulphate solution is fed to the center compartment and flows through the permeable diaphragms to the anode and cathode compartments is more efficient electrically. Diaphragms should be porous enough to allow flow of solution to outer compartments but tight enough to prevent gross mixing of the anolyte and catholyte. In addition to being resistant to acid and alkali, the diaphragms should offer minimum resistance to the flow of current. It is also important that the electrolyte contain a high concentration of sodium sulphate to furnish an abundance of sodium and sulphate ions and thereby decrease the current carried by hydrogen and hydroxyl ions. A practical limitation of sodium-sulphate concentration is imposed by the decreased solubility of sodium sulphate with decreasing temperature. At 20°C, a concentration of 200 g per liter sodium sulphate can be maintained. Little is gained in conductivity by using a concentration greater than 200 g per liter. The small-scale continuous electrolysis tests were made in a 12x12 in. open-top bakelite cell equipped

Jan 1, 1956

By P. R. Bradley

NO thought had been given to deep level mining at the Alaska Juneau mine prior to 1930, but in that year a prospect winze was started and continued for 1000 ft. vertically below the main haulage or adit level. The point at which this winze was started was selected entirely by the prevailing physical conditions, such as proximity to established workings, convenience, and the presence overhead of a substantial pillar of dimensions sufficient to lo¬cate the sheave wheel and loading pocket. It was, therefore, with some surprise that the unusually high-grade ore found just below the collar of the winze persisted, with certain vari¬ations, to a full depth of 1000 ft. vertically. Likewise this unusually high-grade ore was found to persist on the various crosscuts driven on levels at 200-ft. vertical intervals. To be brief, this deep level work found richer ore than any yet found in the mine over like areas, and inasmuch as the area was sufficient to plan for extensive deep level mining, plans for such work were given extended consideration.

Jan 1, 1936