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By H. G. Doll

As a continuation of the earlier paper on the general subject of the SP log, a more complete analysis of certain features of the SP log in shaly sands is given. The pseudo-static SP in front of shaly sands is compared, on a theoretical basis, to the static SP in front of clean sands, as a function of the respective amount of shale and sand in the formation, and of the relative resistivities of the shale, of the uncontaminated part of the sand. and of the invaded zone of the sand. As a conclusion, the advantage of using reasonably conduc. tive mud in this case is shown. The discussion is illustrated by field examples. INTRODUCTION The discussion reported in the present paper is based on a theoretical analysis, and not on experiment. The field examples, joined to the text. are shown only as qualitative illustrations of the essential results of this analysis. Although the hypotheses made in the theoretical developments may perhaps be somewhat improved, it seems, nevertheless, that the results obtained account reasonably well for the actual phenomena, and give a fair approximation of their order of magnitude. The paper contains a mathematical analysis of a tri-dimen-sional distribution of potentials and current lines. due to spontaneous electromotive forces arising at the contact of shales and free electrolytes. as a function of the geometry and of the respective resistivities of the different media involved. It is assumed, although this hypothesis is not proven, that the emf's remain the same even if the shale occurs in very thin layers or in dispersed particles. It has already been pointed out 1,2,3 that, all other conditions being the same, the deflection of the SP log in front of a shaly sand is smaller than opposite a clean sand. When the thickness and the conductivity of a clean sand are large enough. the deflection of the SP log reaches a limiting value which is equal to the "static SP" of the clean sand. It is generally convenient to take the static SP of shale as the reference value or "base line." As a consequence, and for the sake of abbreviation, the expression. "static SP of a clean sand," is often used to designate the difference between the static SP of that sand and that of the shales, which difference is a measure of the total electromotive forces involved in the chain mud sand-shale. A similar limiting value is; also observed for the SP deflec-lion opposite a thick shaly sand, but it is smaller. just as if the total electromotive force involved were smaller in that case. This limiting value has been called the "Pseudo-Static SP" of the shaly sand. The static SP of a clean sand depends on the salinity of its connate water with respect to that of the mud, and, to a certain extent. on the differential pressure which controls the electro-filtration potentials, but it does not depend on the resistivity of the sand. On the contrary. the pseudo-static SP of a shaly sand depends not only on the salinity of its connate water and on the differential pressure, but also on the percentage of shale and on the resistivities of the shale, of the uncontaminated part of the sand, and of the zone invaded by the mud filtrate. If the three resistivities above were equal, the pseudo-static SP would be proportional to the percentage of sand in the shaly sand, and its departure from the static SP of a clean sand having the same connate water would simply be proportional to the percentage of shale. In that case, the pseudo-static SP of a shaly sand containing 10 per cent of shale would he 10 per cent less than the static SP of a clean sand. When. however. the sand is. on the average. substantially more resistive than the shale. the percentage of departure of the pseudo-static SP from the static SP of a clean sand is much larger than the percentage of shale. For that reason, the peaks of the SP log opposite shaly sands are systematically of smaller amplitude when the sands are oil-bearing than when they are water-bearing, all other conditions being the same. This feature is observed even when the sand beds are thick. and even when they do not contain a large percentage of shale. All this has already been described in all earlier publication", but mostly in a qualitative way. The present paper will analyze in more detail the action of the local SP currents which are generated inside of the shaly sands, and which are responsible for the abnormally low value of the pseudo-static SP. The quantitative computations have been extended to the general case of thin interbedded layers of sand and shale, where the resistivities of the shale and sand streaks do not have the same value: they are summarized in charts giving values of the pseudo-static SP of a shaly sand as a function of the different parameters involved. DEFINITIONS The static SP of a clean sand has been defined as the potential that would exist in the mud opposite that sand, were the SP current prevented from flowing. Such an ideal condition is represented on Fig. I-A. By analogy, the pseudo-static SP of a shaly sand can be defined as the potential that would exist in the hole, if the circuit shaly sand — surrounding shales — mud column were interrupted by the insulating plugs placed at the boundaries

Jan 1, 1950

By Richard H. Terhune

The use of water-cooled breast-jackets or cinder-tap blocks is a great convenience in lead-smelting, even when siliceous slags are made. If the charges are at all basic it is almost imperative. Jackets of riveted wrought-iron or steel are expensive; those of cast-iron are liable to crack; those of bronze are costly and not durable, being easily penetrated by tapping-bars or destroyed by streams of matte impinging against them. To overcome these objections I introduced at the Hanauer works, in April, 1886, castjackets of steel, which have been in constant use since that time and are to-day as good as new. These jackets were made for us by the Chester Steel Castings Company, of Chester, Pa., at a cost of ten cents a pound at the works of that company. The metal is 5/8-inch thick, and the jackets were cored and tapped for l1/2-inch bushings, affording two large holes for the removal of dirt and incrustations. The same holes are used for feed- and discharge-water through 3/4-inch pipe. I hope the successful introduction here of cast-jackets of steel will lead to their more extended use in all branches of metallurgy where water-cooled surfaces are severely taxed, and where the size and thickness of the castings are not unfavorable to the production of a sound article, impervious to water and of high tensile strength.

Jan 1, 1889

By Francis R. Conley, John A. Sievert, John N. Dew

A brief review is presented of the past performance of a number of large, thin, highly permeable reservoirs with low dips in the Bolivar Coastal fields of Venezuela. The performance of these reservoirs indicates that the fluids are segregated vertically within the sand section by gravity. With this assumption, equations are developed which describe the performance under pressure maintenance operations. Methods of solving these equations and results of simple example calculations are presented. Example calculations indicate that under pressure maintenance conditions injected gas tends to {tow preferentially along the top of the sands and that encroaching water has a tendency to flow preferentially along the bottom. The expected performance of segregated fluids is discussed and compared with that of fluids which are uniformly distributed in any sand section. INTRODUCTION The field performance of a number of reservoirs described herein indicates that the fluids are segregated vertically within the sand section by the force of gravity. Thus, it was felt that any method used to predict the future performance of these reservoirs should consider the effects of segregation in the sand sections. A study of the available information on some of the reservoirs suggests that increased recoveries may be expected if the reservoir pressure is maintained by either crestal gas injection or flank water injection. To predict future performance of reservoirs under pressure maintenance operations, a method of analysis was needed which would account for segregation of fluids in the sand sections. Several methods of analysis have been developed to take into account the segregation of fluids in the reservoir as a whole1,3 To our knowledge no method considers segregation of the fluids within sand sections in the manner indicated by the past performance of several reservoirs in the Mara-caibo Basin. This paper outlines part of the work done in studying some of these reservoirs and contains a description of their performance characteristics. The analysis presented is restricted to pressure maintenance conditions, since space limitations prevent a full discus- sion of the development of the mathematical relations and the various methods of solving them. Only a sketch of the development of the mathematical relations is given. The various methods of solving these relations are pointed out, but the actual determination of solutions to various problems are omitted except for one example. It is felt that these results may aid in the study of reservoirs outside the Maracaibo Basin. Some concepts on which the present analysis is based are outlined by D. N. Dietz. However, the analysis presented herein includes several factors not considered by Dietz: (1) variations in permeability and in the cross section, (2) various shapes of the cross section, and (3) the production of fluids. Also, the mathematical development presented by Dietz differs considerably from our corresponding analysis. RESERVOIR CHARACTERISTICS The reservoirs under consideration, large and thin, with low dip and high permeability, are large to the extent that they contain from 0.5 to over four billion bbl of oil initially in place. The section thicknesses vary from 100 to 400 ft and the lengths from 10,000 to 40,000 ft. Thus, a length-wise cross section of the producing formation appears to be long and thin. The dip angles vary from 0 to 6 degrees and the average permeabilities vary from 0.5 to over three darcies. The reservoirs contain from 20 to 50 per cent shale inter-laminated with the productive sands. Most shale breaks within the major sands do not correlate from one well to the next, and correlation is often difficult, even between wells drilled from the same location. However, it is often possible to correlate the shale breaks between major sands for some distance. Herein we are concerned with the performance of reservoirs containing oil of gravities over 20" API. Past reservoir performance indicates good pressure communication and, in cases where pressure sinks have developed, large amounts of fluid migration have occurred. Few of the reservoirs have had initial gas caps, but also, few have been found to be highly under-saturated. Due to gravity segregation, secondary gas caps usually form before the pressure has been reduced more than 25 per cent of its initial value. The effect of gravity has not only been apparent on a reservoir-wide basis, but has also caused segregation of the reservoir fluids in productive sections. Proof of this is found from the results of selective well tests, workovers, and electric and various other types of logs. Evidence that

By A. D. Wilkinson

A CROSS-SECTION of the converter aisle through one of the converters and reverberatories is shown in Fig. 5. The aisle is 280 ft. long by 60, ft. wide by 681 ft. to the roof trusse, which have a 63-ft. span and are us )ported by steel columns spaced at 2b-ft. centers. Two 80-ton electric trails, supplied by the Welman Smith .Owen Engineering Co., with 20-ton auxiliary lifts, serve this building. Matte shells and converter-slag shells are dumped into heavily con¬structed flat-bottom bins located on the south side of the converter aisle and 1.0 ft. above the floor. The material is broken by ball and by hand, shoveled off into ladles for unloading on to the reverberatory charge floor, and charged into the furnace as previously mentioned.

Jan 1, 1934

By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By John P. Dolan, Charles A. Einarsen, GiIman A. Hill

his paper discusses how the following formation characteristics can be determined mathematically from drill-stem test pressure charts: true formation pressures, effective permeability of the entire section tested, well productivities, wellbore damage, and possible detection of barriers (faults, pinchouts, etc.). This paper also presents a practical method for im-mediate determination of eflective permeability and well-bore damage from successful double shut-in pressure tests. A list of recommendations for improving the reliability of drill-stem rest pressures is also presented. INTRODUCTION A drill-stem test is a temporary completion designed to sample the formation fluid and to establish the possibility of commercial production. Early pressure recording devices were used merely to verify proper operation of the testing tool. Until recently the accuracy of the pressure gauges has been insufficient for any reliable quantitative use of the recorded pressures. In view of the need for more reliable formation evaluation and as a result of the recent interest in exploration work employing the concept of hydrodynamic en-trapment,1,2,3,4 better pressure recording gauges are now in use. These devices can record pressure within 1 per cent above 1,000 psig and can detect differential pressures as low as 1/2 psig. In addition to formation pressure, several other reservoir characteristics can be determined from DST charts; namely, well productivity, formation permeability, wellbore damage, and the possible existence of bar- riers (faults, pinchouts, changes in permeability, etc.). This paper presents a practical method to interpret DST pressure charts for formation pressures and many other reservoir properties, a method that has been developed in analyzing approximately 4,000 DST charts during the last five years. The techniques used are a composite of published articles on drill-stem testing5,6, together with well-known pressure build-up analysis methods. THEORY It has been shown7,8 that the following equation may be used for analysis of pressure build-up curves: Po - Pw = 162.6 qu/kh log ( to + ?/?) .....(1) When this equation is applied to the curves obtained in drill-stem testing, the assumptions and boundary con-ditions are more nearly realized than in conventional flow and build-up tests on producing wells. Zak and Griffen9 have recently discussed in detail the use of this equation in analyzing DST charts. One of the problems with DST curves is the lack of reservoir data for precise analysis. Therefore, it is necessary to develop empirical rules and field methods for analyzing DST charts in quantity. For this reason, the empirical methods presented in this paper have been developed, and their derivation is found in Appendices A and B. METHOD USED FOR ACCURATE READING OF DRILL-STEM TEST CHARTS In order to apply the pressure build-up theory to DST charts, it is necessary to obtain a digitized expression for the pressure and time data recorded by the pressure gauge. These data may be either provided by the service company or interpolated by projecting a

Jan 1, 1958

By C. W. Sherman, J. Chipman, H. I. Elvander

J. F. Elliott—This is an excellent piece of work and makes a chemical metallurgist more enthusiastic than ever about what can be done with multicomponent systems, if we have satisfactory data. I have a remark to make on the interpretation of fig. 5. First, I will comment on the problem of activities in solutions. The iron-sulphur system has in its phase diagram an intermediate solid phase FeS. The occurrence of an intermediate phase is normally associated with negative departures from Raoult's law over a portion of the activity curves in the liquid. (Perhaps it would be better to reserve the phrase "departure from ideality" to departures from Raoult's law line rather than to departures from Henry's law line). Fig. 5 indicates that the deviation of the sulphur activity curve from the Henry's law line is negative;

Jan 1, 1951

By N. M. Levine, W. M. Fassell

In this laboratory study the problem of aerative conditioning to separate chalcopyrite and pyrite from cobaltite was simply effected with a sulfy-drate collector and pH by proper choice of mixing variables. It was shown that for a given impeller type and geometry, selectivity is governed by a relation between the Froude number and a modified power number multiplied by impeller tank-diameter ratio wherein the power factor is expressed as power intensity or horsepower per unit volume of contained pulp. In applying this approach to other systems, other criteria would be used in place of selectivity. The purpose of this paper is to show how solutions to problems of aerative conditioning of pulps may be enhanced by development of mixing parameters in a given system through application of a fundamental approach to agitation. The term aerative conditioning refers to a combination of processes which include mechanical gas dispersion, gas solution in the liquid phase, transport of dissolved gases and other reactants to the reaction zone, physico-chemico interaction within the liquid phase and/or at the solid surface, and, finally transport of products away from the reaction zone. Important elements of these processes are: 1) Air-Liquid Contact Area: This area limits the rate at which a given gas may dissolve in a given liquid. Thus, an aerative conditioning system should be designed for optimum gas dispersion. 2) Diffusional Factors: Such factors as concentration gradient, diffusion film thickness, and diffusivity may govern the rate at which dissolved constituents are transferred to the zone of interaction at a particle surface and the rate at which reaction products are transported therefrom. Thus, such systems would be designed for maximum turbulence to effect good mixing and to minimize diffusion film thickness. 3) Solids-Turbulent Liquid Contact Time: Sufficient time should be provided for interactions to take place at solid-liquid interfaces. The region of maximum turbulence for mechanical systems being in the impeller zone, it is important that the number of passes through this zone be optimized. This means that a proper balance should be struck be- tween flow and turbulent power to achieve optimum conditioning time. Too high a flow rate and insufficient turbulence may be improper if the reactions are diffusion limited. On the other hand, too much turbulent power and too little time in the reaction zone due to insufficient flow power may also be limiting. 4) Geometry and Impeller Design: The design of the conditioning vessel and the type of impeller employed are important factors in determining the relative distribution between flow and turbulent power and the degree of gas dispersion. Maximization of power input would be to no avail if the distribution between flow and turbulent power were improper or gas dispersion insufficient. 5. Physical Chemistry: The reactions between dissolved gases and solid surfaces may be limiting if gas solubility, activation energies and/or free energies are not favorable. J. H. Rushton, E. W. Costich, and H. J. Everett' have summarized the mechanical elements of the combination of processes listed in a fundamental mixing equation. This equation was derived by dimensional analysis and relates the physical variables for a single impeller, centered in a cylindrical, vertical axis, flat-bottomed tank. It is, where T is tank diameter in feet; H is liquid depth in feet; C is height of impeller off tank bottom in feet; S is pitch of impeller; L is length of impeller blades; W is width of impeller blades; R is number of baffles; D is impeller diameter in feet; Np is the power number, pg/dN3D5; P is power in foot-pounds per second; g is the gravitational constant, feet per second; J is width of baffles; B is number of im-

Jan 1, 1961

By Edwin R. Phelps

In the year 1900 about 212 million tons of bituminous coal were produced in the United States. Almost none of this was produced by surface mines (Fig. 1), because there was no large equipment suitable for stripping overburden at that time. By 1915 the surface mines had built up their capability largely through use of the steam shovel to the point that they produced 2.8 million tons of the nation's total production of 443 million tons. Over the intervening years between 1915 and 1970 surface mining provided a continually increasing percentage of the nation's bituminous coal, stimulated by the growing availability of giant surface mining machines, some of which are presently capable of removing 220 cu yd of earth with one bite of their mighty buckets. In 1970 the nation's surface mines produced 244 million tons of bituminous coal, over 40% of the total national production. On the other hand, the nation's underground mines hit a peak of 560 million tons in 1920, dropped to a low of 273 million tons in 1961, and are presently on a very slow rise. Environmental pressures generally oppose surface mining, and have forced coal companies to consider more underground mining in future planning. Also, since strippable reserves are decreasing in the eastern states, an increase in underground mining is expected over the coming years. However, in the western states there are enormous reserves to be extracted by surface methods. Why has surface mining increased, while underground mining has decreased? It's largely a matter of economics. The cost per ton is greatly reduced by surface mining because of the relative ease of obtaining the coal. Also, there is a much greater percentage of coal recovery-nearly 85% in surface mines within the minable area, as compared to an average of about 50% in underground mines. Much surface mining recovers coal that could not be extracted by underground methods because of coal bed thinness, or multiple beds close together, split seams, the nature of the roof, and other geologic conditions. What are some of the limitations of surface mining? First of all, with presently available machinery it is difficult to surface mine at depths

Jan 1, 1973

By William P. Prof. Blake

THE occurrence of siderite in beds of considerable thickness in the clay formations of Martha's Vineyard, Mass., may have some economical importance, and is at least interesting in a scientific point of view.

Jan 1, 1876

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

By B. M. Bird

ONE of the problems studied by the U. S. Bureau of Mines in cooperation with the University of Washington has been the re-treatment of table middlings. Hydraulic classification has given the best results. Instead of using the classifier to prepare the feed to the tables, as has been the practise for many years in ore dressing, it is used to separate part of a middling product that cannot be re-treated successfully on the table. Middlings are desirable in a table plant because the separation according to specific gravity is incomplete; that is, in the products of the table there is always an overlapping of free particles of coal and refuse that can be distinguished with heavy liquids such as are used in the float-and-sink test. The causes of this overlapping may be divided into two groups, those outside the table separation itself and those inherent in the table separation. The first of these groups includes, among other causes, the following: (1) poor adjustments of the table, (2) overloading or underloading the table, (3) irregularities in the quantity and quality of the feed, (4) irregularities in the power and water supply, and (5) a vertical danc-ing motion of the table deck due to weak foundations. These causes of overlapping are largely unnecessary in a properly designed and constructed plant; but whenever they are present they materially affect the character of the middling product, and hence the problem of re-treatment. The other group includes three additional causes: (6) small differences in specific gravity between coal and impurities, (7) a size-specific-gravity relationship of the coal and refuse particles in the table feed such that the sizing action of the table opposes the separation according to the specific gravity, and (8) shapes of particles that prevent a separation. The sixth, small differences in specific gravity, may be a very important reason for an incomplete separation. The change in specific gravity from coal to shale is always gradual and the designation of one part as coal and another part as refuse is arbitrary. If some specific gravity, such as 1.45, is chosen as the dividing point between washed coal and refuse,

Jan 1, 1928

By J. Moore Samuel

INTRODUCTORY BEFORE the year 1909, no measurements of dust losses and flue gases had been made at the Copper Queen Reduction Works, at Douglas, Ariz. At that time the "unaccounted" loss of the smelter had reached a figure, that drew attention to the possibility of large stack losses. The measurement of dust losses had not been studied much at that time, and estimates of dust losses, with a few exceptions, were the results of tests by what has been termed "chemical methods," that is, the aspiration and filtration through cotton, wool or some similar medium of a few liters of gas, the dust being weighed on a chemical balance, and the volume of gas computed from the volume of aspirator water. The possible error of this method is enormous, and the probable error much too large for reliable results. Since the object of these tests was to discover not only the extent of the dust losses, but also the possibility of profitably reducing the same, it was decided that the method adopted must have the following characteristics: 1. The sample of gas taken for filtration must be representative of the whole volume of gas, that is to say, it must have the same dust content. This condition will be fulfilled in all cases if the gas sample is drawn off without change of rate of flow. Then it will contain the same proportion of entrained or suspended particles of dust as the original gas. In the case of flue gases which contain only fume, at a temperature above or near the sublimation point, this condition need not be adhered to since the fume will not behave as entrained particles, but more nearly as a true gas. Consequently the gas sample in this case only may be drawn off at any rate of flow. 2. The gas sample taken must be large enough (a) to yield sufficient dust to permit of accurate chemical and physical examination; (b) so that the ratio of the total volume of gas passing through the flue to the volume of gas sample taken shall not be too large.

Jan 6, 1916

DURING the past year the Committee on Coal and Coke has been collecting data concerning various points in the bituminous industry about which a large amount of misinformation circulates through the press and, in some cases, through the coal trade papers. The data presented have been compiled by various members, from the most authentic sources available, and where possible cover the period 1913-1924. They will enable comparisons to be made within the industry, and of this and other industries, and will explain some of the differences between conditions existing now and in the prewar period. CAPACITY AND OVER-DEVELOPMENT The capacity of bituminous mines is frequently stated at figures ranging between 800,000,000 to 1,400,000,000 tons per year. Table 1 shows statistics for the industry, mainly from U. S. Geological Survey sources but partly from U. S. Coal Commission reports. Column 3 gives the mine capacity with equipment and labor as of given date, as estimated from the data published by the U. S. Geological Survey. This is calculated for each State by obtaining the total man days worked as. reported by the operators (multiplying average men employed by total days worked at each mine) and dividing this figure into the total production, getting the production per man day; this figure times number of men employed times 308 (a theoretical full working year) equals estimated- full-time capacity. Two major objections are made to this method-one that the total number of men employed is used, instead of the number actually working, and the other that the number of days used only deducts Sundays and five holidays. The first objection is answered by the fact that the same number of men is used in estimating capacity as is used in actual production, and while this number is always from 12 to 20 per cent. more than are actually working, this condition exists at all times, although it is worse at times of maximum output. Few coal men will agree with the conclusion that the use of 308 days is correct, as it is practically impossible to keep any mine working full time at the same

Jan 2, 1926

By J. E. Sandor, P. F. Schmidt

A general review of the present knowledge of the semiconductor/oxide interface is given, with emphasis on silicon and germanium. The electrical properties of clean surfaces and the changes that occur upon oxidation are described. A brief disczcssion of the methods and mechanisms of oxidation of silicon is given, and the interaction between the semiconductor substrate and the oxide phase is considered. Physical properties of the oxide film, charge storage effects due to the dielectric, and some device applications of oxide films on semiconductors are discussed. THIS paper will be heavily preoccupied with the elemental semiconductors germanium and silicon. Undoubtedly some injustice is done thereby to other semiconductor-oxide systems, but it is not readily possible to cover all aspects of so vast a field in the present review. In considering the semiconductor/oxide interface, we may start out by discussing briefly an idealized clean semiconductor surface, and may then follow the changes brought about by oxidation, as the oxide is allowed to grow progressively thicker. The references given are not a complete list, but are to be taken as guides to the literature. Tamml suggested in 1933, based upon the study of a one-dimensional asymmetrical potential model, that localized surface states may appear at the surface of a crystalline lattice; it was pointed out by Fowler that these states should occur in pairs. shockley3 examined the origin of such surface states on the basis of a more general one-dimensional model and found that surface states may appear in the forbidden region between the highest filled and the lowest vacant band. This happens when the two bands overlap, as, for instance, the "s" and ('p" bands of the diamond structure. In a three-dimensional model these levels would produce a surface band which is half-filled for diamond, and the number of surface states should be approximately equal to the number of surface atoms. This picture of the surface has been refined by more recent theoretical work, like Handler's4 and Koutecky and Tomasek's~ without introducing essential modifications. When these concepts were applied to semiconduc-

Jan 1, 1965

By W. E. Bergman, P. G. Carpenter, H. B. Fisher

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By P. G. Carpenter, H. B. Fisher, W. E. Bergman

The conditions under which barium carbonate can be used to remove sulfates from drilling muds are limited The amount of sulfate remaining in solution in the system after treatment with barium carbonate is shown to be a function of the concentration of the carbonate and barium ions and the concentration of other electrolytes. Barium hydroxide may advantageously replace barium carbonate when the contamination is not entirely due to anhydrite (calcium in the system is then stoichiometrically less than sulfate) or when the carbonate concentration is high. The effect of substances such as quebracho, phosphates, and chromates, which form complexes or precipitates with barium, is discussed. INTRODUCTION As the complexity of the operations in drilling for oil has increased, more attention has of necessity been directed to the problems pertaining to the maintenance of good drilling mud properties. As a result, chemical treatment of muds has become an important factor in recent years. Some of these treatments have been designed to eliminate the deleterious effects of contaminants in aqueous mud systems by precipitation or other means. The most common of substances encountered during drilling include sodium chloride, cement, and calcium sulfate while various other contaminants: usually in small amounts, may be introduced from the water, clays, and other materials used in preparation of the mud. In certain cases, for example where continued salt-water flow is encountered or massive anhydrite is drilled, special muds may be used so that the physical properties of the mud will remain satisfactory for drilling. In other cases, it is desirable to remove the contaminants so that soluble electrolytes in the system are maintained at low values. For sulfate contamination, the conlmon practice in the field is to add barium carbonate to precipitate the sulfate as barium sulfate Ordinarily such a procedure gives satisfactory results. There have been important instances, however, where addition of barium carbonate was not effective in removal of soluble sulfates from drilling muds. and it is to these cases that the present paper is directed. While it is generally known that barium carbonate is not always effective in removing soluble sulfates from drilling muds, certain inconsistencies appear in the literature as to the limitations of its use, and little explanation for the limitations are given. Varnell and Kimbrel state that "the treatment (with barium carbonate for removal of sulfate) is simple and consists in maintaining a pH of 9 with caustic soda and quebracho." They caution that concentrations of quebracho greater than 1 lb./bbl. may inhibit the reaction. In another publication', a pH of 10.5 is considered "the maximum desirable," and the indication is that as much as 2.5 lb. quebracho per barrel may be present in the particular mud under discussion. Lancaster and Mitchell5 state that appreciable amounts of phosphates in the mud will inhibit the reaction with barium carbonate and that the phosphate treatment should be discontinued at least 24 hours before addition of the carbonate. Experimental work was initiated to ascertain the factors involved in using barium carbonate for the removal of sulfate contamination in drilling muds. While the experimental data herein reported are limited, they focus attention on the pertinent factors which must be considered for successful treatment. These factors are discussed from a practical and a theoretical view, the latter being supported by equilibrium data found in the literature. Further, it will be appreciated that the factors involved in this specific study will be closely analogous to those in certain of the other chemical treatments which involve a precipitation of the soluble contaminant. A thorough comprehension of these factors should result in a more fruitful application of this type of chemical reaction to the treatment of drilling muds. EXPERIMENTAL A. Reagents Two muds were used during this investigation. For one series of tests, bentonite suspensions were prepared by dilution of a stock suspension containing 8 per cent by weight of bentonite (Aquagel). For another series, a 6.4 per cent ben-tonitic mud weighted to 9.7 lb./gal. with barium sulfate (Mag-cobar) was used. Distilled water was used in all preparations. The quebracho (72% tannin extract) was obtained from the Thompson-Hayward Co. of Tulsa and contained 11.4 per cent moisture (105 C.). All other materials were reagent grade, and concentrations were corrected for water of crystallization, if any. All concentrations are expressed in pounds per barrel (42 gallons). B. Technique The systems — either mud or water — were contaminated with either sodium or calcium sulfate after treatment with the desired amounts of sodium hydroxide and quebracbo. For treatments with barium carbonate an approximately 3-fold excess (5 lb./bbl.) was used over that computed to be required to precipitate all the sulfate as barium sulfate. Barium hydroxide was used in concentrations of 2 lb./bbl. — about

Jan 1, 1949

By Hobart M. Kraner, E. B. Snyder

THIS paper shows that volume stability, low porosity and decreased pyroplasticity are desirable for blast-furnace linings, particularly for the hearth. It shows further that a hot load test is a valuable means of testing the fusion or softening behavior of a refractory at operating temperatures. The effect of carbon monoxide on commercial blast-furnace refractories in their as-received condition and after refiring is reported, showing that many commercial blast-furnace refractories disintegrate badly but that refiring decreases the effect and certain special refractories are now available which are almost free of the tendency. FACTORS AFFECTING CHOICE OF REFRACTORIES If one were to depend entirely upon experience or trial in the selection of clay refractories, the solution of a problem would be a slow process. Furnace campaigns are so long and attended by so many variables that it is difficult to draw fine distinctions within a reasonable period of time in regard to the quality of refractories used. It could be said, of course, that if service results do not yield the proper information for intelligent choice, there is no difference in the quality of brick being considered, but this is not necessarily true. Conventional ceramic tests are designed to give the ceramic engineer information as to the refractoriness and firing temperature, which he in turn interprets in terms of volume stability, ability to withstand load at high temperature (pyroplasticity), permeability, chemical stability and resistance to the action of slag. In most refractory applications several of these factors are involved. In a particular instance, one requirement may be predominant, while in others some other factors may be of primary importance. In this country, clay refractories are generally made from mixtures of plastic and flint fire clays. The process of firing a clay refractory is one of slowly melting the constituents, and during this operation its porosity is gradually reduced. The process is arrested, of course, in its incipient stages and the progress is determined by measuring slight changes in. porosity, volume, bulk gravity, etc., that have taken place. Often the temperatures to which clay refractories are exposed in service are higher than those employed in their firing. However, if the manufacturer were to fire them at such high temperatures the brick would distort. Therefore it would be difficult for the manufacturer to fire all of his clay refractories to temperatures . at which they are to be used, although in many cases it would be desirable from the user's point of view if he would do so. The porosity of clay refractories decreases by firing, to a minimum limit, after which a further increase in the temperature causes expansion in certain clay constituents and bloating in others. -Both may occur in the same refractory containing two such clays.

Jan 1, 1944

By R. H. Maes, R. E. de Strycker, J. J. Jacobs

A simple method, based upow density measurements, has been perfected in order to determine the critical temperature of liquid miscibility gaps. Applied to the Pb-Cu system, it yielded a value of 980"C for the critical tempevature of the miscibility gap in this system. In the Pb-Cu-As system, the immiscibility between lead and coppev evolves towards a miscibility gap be-tween lead and copper arsenides; the liquation temperatures were determined joy different avsenic contents and values up to 1065°C were found. Combining these results with those given by the clzemical analysis of liquid samples taken at dqj.event temperatures, it has been possible to make a cowzplete determination of the liquid miscibility gap in this ternary system. In the Pb-Cu-Fe-As system, a ternary miscibility gap has been discovered; for some compositions, the molten and slowly cooled alloys separated into three layers: an Fe-As alloy, a Cu-As alloy, and a lead-rich layer. ThE Pb-Cu-Fe-As system is of interest for the study of the behavior of speiss or arsenical alloys in the lead blast furnace. The speisses produced in lead metallurgy generally have complex compositions, but they may be considered, in a simplified way, as a mixture of copper, iron, nickel, and cobalt arsenides; there is often an excess of metallic constituants, and lead is also present. Speisses liquate from lead at various temperatures according to their composition; according to industrial experience, iron speisses are already distinctly separated from lead bullion at temperatures of the order of 1100°C, whereas copper speisses only begin to liquate from lead at much lower temperatures, near their solidification points, which were never accurately determined until now. Besides these considerations of practical interest, the present study is of importance for the knowledge of liquid miscibility gaps. Particularly the data of the literature about critical temperatures of liquation are incomplete and present sometimes considerable disparities; a method has been perfected in the present work to determine these temperatures with accuracy. MISCIBILITY GAP OF THE LEAD-COPPER SYSTEM Review of Literature. The generally admitted outline of the Pb-Cu equilibrium diagram is shown by Fig. 1. This figure, with its numerical indications, is taken from the review of Hansen and ~nderko;' compositions are given in weight percent, as will be the case in the remainder of this paper. Between 36 and 87 pct Pb, Pb-Cu alloys separate into two layers, in the liquid state. The critical temperature of liquation has been much disputed in earlier studies, where values up to 1500°C were claimed; but a reliable study of ~ohnen,' based upon differential thermal analysis, gave a value of 990°C; this rather low value was verified by a recent study of Schiirmann and Kaune? based upon thermodynamical properties of the Pb-Cu alloys, which predicted a value of 1002°C. Liquid miscibility gaps were also studied by means of chemical analyses. Satisfactory results were generally obtained with the method consisting in taking samples of the two liquid layers in equilibrium and submitting them to chemical analysis; however, this method becomes delicate near the critical temperature. With this technique, Friedrich and waehlerts ob-

Jan 1, 1968

By Winston A. Wong, John J. Jonas

Commercial purity aluminum was deformed by extrusion over the temperature range 320° to 616°C and the strain rate range 0.1 to 10 per sec. Flow stresses and strain rates were calculated from the experimenLa1 ram pressures and speeds. The stress-strain rate-lemperature relationship in extrusion was found to be similar to that in creep. Extrusion, torsion, compression, and creep data extending over ten orders of magnitude of strain rate and over two orders of magnitude of stress were correlated by a single creep equation. It was concluded that hot-working is a thermally activated process, in which the rate-controlling mechanism is either the climb of edge dislocations or [he motion of jogged screw dislocations. The microstructural changes observed during extrusion were consistent with the proposed deformation mechanisms. ALTHOUGH great progress has been made in understanding the technology of extrusion, very little is known about the actual deformation mechanisms operating during flow. Previous accounts describing extrusion have indicated that the relationship between ram speed (V), pressure (P), and temperature (T) can be given as follows:1 V = apb and P = A' exp(-AT). In these equations, a and b are constants which depend on temperature, A' is a constant which depends on ram speed, and A is a "coefficient" with a different value for each metal. Although these equations have fairly wide application, they do not contribute much to a fundamental understanding of the deformation. Furthermore, extrusion has not hitherto been considered as a thermally activated rate process. This lacuna is surprising because hot-working is similar to high-temperature creep in several respects. There is, in fact, a fair body of experimental evidence suggesting that the material response under hot-working conditions is similar to that occurring under creep conditions, in spite of the many orders of magnitude difference in strain rate.2"4 Since creep has been extensively analyzed in terms of dislocation mechanisms, the comparison of hot-working to creep is useful, for it can suggest the possible deformation mechanisms operating during hot-working. In this paper, the hot extrusion of aluminum will be examined from the point of view of thermally activated deformation mechanisms, such as operate during creep. EXPERIMENTAL PROCEDURE The experimental procedure consisted of extruding commercial purity aluminum* over a range of ram velocities and temperatures at constant die reduction by the direct method. Details of the experimental equipment have been published elsewhere.5 Extrusion was carried out at each of the following billet temperatures: 320°, 376°, 445°, 490°, 555°, and 616°C at the following constant ram speeds: 0.002, 0.008, 0.02, 0.1, and 0.2 in. per sec.* All results were obtained using a square-shouldered die with an extrusion ratio of 40:1, giving a reduction in area of 97.5 pct. The ram force was the dependent variable, and was measured by means of strain gages on the ram and was plotted as a function of ram travel. The sequence of events before making an extrusion was duplicated before each run so as to minimize as much as possible variations in experimental conditions. For example, after the equipment had been assembled, the billet was allowed to heat up to temperature inside the insulated container. Once the container attained the desired temperature, a period of 1/2 hr was allowed to elapse before the extrusion was made. This time was found to be required to allow the billet to reach a steady-state temperature, as determined from previous tests. When all was ready, extrusion was carried out without interruption; that is, the billet was upset and extruded in one operation. EXPERIMENTAL RESULTS AND DISCUSSION The two usual experimental approaches for investigating high-temperature deformation exhibit an important common feature. In the first approach, which corresponds to creep, a constant stress (or load) is applied to the material at constant temperature and the resultant strain is recorded against time. After an initial transient stage, a state of constant strain rate exists (secondary creep), in which a steady-state condition is established which is sensitive to variation in either applied stress or temperature. In the second approach, a constant strain rate is applied and the resultant flow stress is recorded. This corresponds to the situation in hot torsion or hot compression, where it is observed that, for a constant test temperature, there is an initial rise in stress to a steady value which is maintained up to very high strains. In tests of this type, a steady-state region is also established in which the stress is sensitive to variation in either the strain rate or the temperature.3,4,6-16 In both types of tests, therefore, a steady-state region is established after an initial transient. In the case of hot-working this region may be called steady-state hot-working, and it is analogous to steady-state creep with which it has many common features. Stress Dependence of the strain Rate in Extrusion. In order to assess the stress dependence of the strain rate under extrusion conditions, and to compare it to that of creep, as well as of hot torsion and hot compression, the extrusion data were analyzed according to power, exponential and hyperbolic sine creep equations.

Jan 1, 1969