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By Frank Miller

THE lower cost of producing oil from naturally flowing wells compared with pro-duction costs accruing from artificial lifting methods has stimulated much research, with the joint purpose of extending the natural flowing life of wells and of increas-ing the productivity of small wells. The laboratory investigation described herein was made to determine the effect of a slotted liner on the pressure gradient in the vicinity of the wall of a flowing well. Flow restrictions caused by the liner induce energy losses between the oil-bearing for-mation and the inside of the liner, which may be reduced by improved liner design, and thereby the flow capacity of wells may be increased. These losses have been evalu-ated for rectangular slots of different sizes, and means are suggested for reducing them. The dearth of information concerning the nature of the flow of fluids from uncon-solidated sands through small openings in the walls of pipes-as represented by the flow of oil from an oil sand into a slotted liner-is acknowledged. Although the bene-fits to be realized by operators through the use of optimum liners is just beginning to be recognized generally, Coberly1 in 1937 pointed out that the functioning of screen casing is an important factor in the pro-duction of oil. From his study on the selection of size of oil strings for wells in California, Parks2 concluded, in part, that the perforated section of the oil string de-serves continued study, especially with respect to the selection of perforations. The growing use of gravel packing result-ing from certain research findings lends even more significance to the problem of selecting optimum liners, as the application of these methods usually requires slotted liners or other kinds of perforated liners. The present study was made to obtain further information for the guidance of engineers and operators in selecting slotted liners and to develop a laboratory method that may be used in analyzing possible pressure conditions surrounding most types of perforated casings used in producing oil wells, so that the present inadequate fund of knowledge on this important subject may be expanded.

Jan 1, 1940

By A. W. Gauger

For perhaps one hundred years scientists have been engaged in attempts at devising a satisfactory method of classification of coal. During this time many charts, tables and graphs have been proposed, some of which have had considerable merit, but no one system has been found to be applicable to all ranks of coal, nor has any one system received general acceptance. In many of the proposals, water eliminated between room temperature and 105" C. has been regarded as extraneous matter and calculations have been made to the air-dry or water-free basis. Such methods of calculation do not lend themselves to satisfactory grouping of the high-moisture coals.1, 2 A consideration not only of the properties of the high-moisture coals and their behavior on drying but of the generally accepted ideas of the coalification process and the role of water in this process indicates that water is an essential constituent of all coals and therefore should not be neglected. For example, in such low-rank coals as the lignites of the Northern Great Plains' deposits the inherent moisture of the lignite as mined plays a very important part in the physical properties thereof. Freshly mined lignite contains upwards of 30 per cent water and is extremely tough and resistant to shock. Upon exposure to the atmosphere, the lump loses part of its moisture and checks and splits, leaving a friable and broken up residue. So far as we have been able to determine, water is the only thing lost in this process and we are forced to the conclusion that moisture plays an extremely important part in the structural properties of the original lignite. With reference to the coalification process, Mack and Hulett3 pointed out in 1917 the important part that water played therein. They observed that water cannot be removed from peat or coal by pressure alone, but only as the result of chemical reaction, and suggested that peat in its early stages may be largely a hydrosol. Slow chemical changes occur over a long period of time until finally the mass becomes more largely a hydrogel. These views are substantiated to some extent by the experi-

Jan 1, 1932

By Walter Mathesius

The use of high blast heats on furnaces melting Mesaba ores is still the exception, the average blast temperatures carried on Mesaba stacks seldom reaching 1,100" F. Some 15 years ago, when the use of fine Mesaba ores in larger proportions to the total burden first came into practice, it was found difficult to employ even those blast heats which it had been possible ' to carry with the Old Range ores. The furnaces refused to "take" high heats, and would persistently labor with irregular stock movement, which impaired the practice and increased the coke consumption. By lowering the blast temperature, the working of the furnace became smoother, and experience taught that with the softer and more easily reduced Mesaba ores, satisfactory practice could be obtained with comparatively low blast heats. Therefore a large number of Mesaba furnaces have ever since been operated on very low blast temperatures, ranging between 800" and 1,000" F. In the face of these difficulties, furnace men were slow to recognize that furnaces could be so designed as to permit a free movement of the charges in combination with the use of higher heats. Since higher blast temperatures did not seem to offer great advantages in the smelting of Mesaba ores, investments in hot-blast stoves were not as attractive to the furnace man as labor-saving devices and means of obtaining greater tonnages. The effect of this preference is keenly felt at the present time. It has brought about the peculiar situation, that the majority of our furnace plants (among them some of the most progressive) lack modern and efficient stove equipment. The result is that, even where the proper furnace lines have been adopted and conditions are now favorable to the successful employment of higher blast temperatures, the heats required for the greatest fuel economy are not available. In an endeavor to obtain results, even with inadequate equipment, we find that, at many plants, the stoves are worked far beyond their capacity. This leads, in many instances, to a situation in which the coke saving in the

Jan 1, 1915

By W. H. Emmons

Most mineral deposits change as they are followed downward on their dips. Some of these changes are due to primary arrangement; different ores were precipitated at different depths when the deposits were formed. Other changes are due to weathering or secondary enrichment. The chief changes resulting from weathering, in the main, are understood and standard changes are recognized. The processes are relatively simple. They take place at ordinary temperatures and pressures and can be duplicated in the laboratories. Moreover, there are thousands of deposits available for study, because the processes take place near the surface where the development of mines is begun. The changes due to primary arrangement of the deposits of the metals are not so well understood. Deposition has taken place at higher temperatures and our knowledge of the chemistry of the processes leaves much to he desired. Very few experimental data are available. The deposits, moreover, offer fewer examples because many mines are not developed to depths where the changes can be studied and a change to unprofitable material usually results in stopping work. Most students of ore deposits now accept, as confirmed, the hypothesis that nearly all lodes and related deposits were formed by solutions originating in intrusive igneous masses. Outward from these masses, the deposits at many places are grouped in zones and the arrangement noted from the intrusions outward are commonly the reverse of the changes noted from the surface downward in a single lode. A study of the changes in groups of deposits, from the parent intrusion outward, will throw light on the changes to be expected in a single lode downward. Recause the changes in series of deposits from the intrusive outward may all be observed near the surface, where more data are available, it is possible to increase the number of examples many fold and to apply the statisttical method of study with greater confidence of avoiding error. It is not everywhere possible to identify the parent igneous body to which a group of ore deposits are related. Several kinds of criteria are available; certain groups are superior to others. By applying the

Jan 1, 1924

By Robert Mehl

THE mechanical behavior of metals and alloys is presumably conditioned by two factors; namely, the crystalline symmetry and the interatomic forces. Considerable attention has been given to the first of these factors through the recent advances in X-ray .technique. It is the purpose of the present paper to call attention to the importance of the second of these factors, to point out promising methods of investigation, and to present some pertinent data. Plastic deformation takes place by-slip along atomic planes.1 This slip may be inhibited in a number of ways: by the interatomic forces of cohesion which bind the atoms rigidly in a lattice structure, which in pure metals is usually of high symmetry; by lattice distortion caused by solid ,solution formation or by mechanical strain; by the intercrystalline boundaries where slip is restrained by the non-registration of the atom planes in adjacent crystallites;2 and by the presence of small hard particles which serve to "key" the slip along the atom planes.3 In pure metals, and perhaps also in solid solutions, the atom planes, of easiest slip are those exhibiting the greatest density of atomic population and the greatest interplanar distance4 and apparently can now be predicted from the analysis of the lattices. Concerning the interatornic forces, which resist this slip by holding the atoms firmly together, little is known. Most textbooks on physical metallurgy, following the work of Bot-tone,5 correlate the hardness of the pure metals with the atomic volume;.

Jan 1, 1928

By A. D. K. Laird, John A. Putnam

This paper describes the application of x-ray theory to design procedures in connection with fluid saturation determinations during fluid flow experiments with porous media. A reliable and rapid method for calibrating the x-ray apparatuy is described. Extension of the method to fluid saturation determinations in three-fluid systems is described. INTRODUCTION In rerearch on oil production problems a method is required which will give quickly the quantity of each component of a fluid flow system present at any cross-section of a porous medium. The sample of porous medium under investigation is usually referred to as a core. The ratio of the volume of one component to the total fluid volume is defined as the saturation of the porous medium by that component. This ratio is generally given as per cent saturation. Some means of measuring saturation which have received consideration include: electrical conductivity of the fluids;1,2 emissions from radioactive tracers dissolved in the fluids; the radioactivity of silver caused by reflection of neutrons from hydrogen atoms in the fluids;' the attenuation of a microwave beam. the diminution and phase shift of ultrasonic wave trains.4,5 and the reduction in intensity of x-ray beams in passing through the fluids. X-rays have already been used with some success. Since every material has a different power to absorb x-rays, the reduction in intensity of an x-ray beam as it passes through a core depends on the fluids present. The strength of the emergent beam can be found by converting its energy into a measurable form such as heat or ionic current. or by its effect on a photographic plate or fluorescent screen. The beam strengths could be interpreted as quantities of known fluids in the core if, previously, these beam strengths had been identified with a known combination of the same fluids. With some fluid cornbinations it might be desirable to dissolve powerful x-ray absorbing materials in one or more of the fluids, to increase the differences in the beam strengths for various fluid saturations. Boyer, Morgan and Muskat6 have described a method of measuring two component fluid saturation. One component was air or water; the other. minerat seal oil in which was dissolved 25 per cent by weight of iodobenzene to increase its absorbing power. The x-ray source was a tungsten target tube operated at 43 kv potential. The beam emerging from the core was measured as ionic current flowing across an air-filled ionization chamber by means of an amplifying circuit and galvanometer. Another portion of the beam from the x-ray tube was passed through a metal plate and measured in another ionization chamber. This portion, called the monitor beam, was used as an indication of the performance of the x-ray tube. The galvanometer readings were calibrated against air-oil core saturations, gravimetrically determined. The method was apparently established by experimental means. In the present investigation the available theory of x-radia-tion was surveyed with a view to extending the usefulness of the method and to developing design procedures for its application to measurement of fluid saturation in porous media. Application of the theory permits prediction of relative meter readings to be expected for any combination of porous matrix, various saturating fluids and auxiliary filtering media. It is thus possible to calibrate the equipment in terms of fluid saturation by an indirect but rapid technique. The results of calculations based on x-ray theory indicate. and results of the saturation calibration technique confirm. that a valid measurement of the saturation of the core can be made for any two components and in some cases for three components. THEORY The strength of an x-ray beam, after it has passed through a distance. 1, of matter of density, p, and mass absorption coefficient, µ at a given wavelength, A, may be expressed by the absorption formula I = I0 e ...........(1) where I, represents the intensity of the incident x-ray beam and I is the intensity of the emergent beam. The expression e is called the transmission factor of the material. The variation of I,, with wavelength depends upon the materials through which the x-ray beam has previously passed and upon the spectral distribution of energy at the source of the x-radiation. A group of curves. called spectra. which show the variation of intensity with wavelength and x-ray tube voltage are given in Fig. 1. These curves represent the general radiation from a tungsten target tube. When the tube voltage is greater than 69.3 kv, the characteristic radiation of the tungsten is emitted and is superposed on the general radiation. At a given voltage the minimum wavelength A,,,,, at which energy can be emitted by an x-ray tube is given by the formula 12,340 xml. = ——..........(2) volts where A,.,,.. is in Angstrom units. The wavelength at which the spectra have maximum intensity a1so decreases with increasing x-ray tube voltaue. The area under each curve represents to an arbitrarv scale the total energy emerging from the x-ray tube for that voltage. The variation of µ with wavelength has been determined for many substances and may be found in such references as those by Compton and Allison7 and by Hodgman.8 The phenomenon of absorption is composed chiefly of the capture of photons by the atoms of the absorbing material with associated displacement of electrons, and of the scattering, or the deflection, of the photons by the atoms. Curves of these mass absorption coefficients show jump discontinuities. or absorption edges. at wavelengths which are short enough for the photons,

Jan 1, 1951

By John A. Putnam, A. D. K. Laird

This paper describes the application of x-ray theory to design procedures in connection with fluid saturation determinations during fluid flow experiments with porous media. A reliable and rapid method for calibrating the x-ray apparatuy is described. Extension of the method to fluid saturation determinations in three-fluid systems is described. INTRODUCTION In rerearch on oil production problems a method is required which will give quickly the quantity of each component of a fluid flow system present at any cross-section of a porous medium. The sample of porous medium under investigation is usually referred to as a core. The ratio of the volume of one component to the total fluid volume is defined as the saturation of the porous medium by that component. This ratio is generally given as per cent saturation. Some means of measuring saturation which have received consideration include: electrical conductivity of the fluids;1,2 emissions from radioactive tracers dissolved in the fluids; the radioactivity of silver caused by reflection of neutrons from hydrogen atoms in the fluids;' the attenuation of a microwave beam. the diminution and phase shift of ultrasonic wave trains.4,5 and the reduction in intensity of x-ray beams in passing through the fluids. X-rays have already been used with some success. Since every material has a different power to absorb x-rays, the reduction in intensity of an x-ray beam as it passes through a core depends on the fluids present. The strength of the emergent beam can be found by converting its energy into a measurable form such as heat or ionic current. or by its effect on a photographic plate or fluorescent screen. The beam strengths could be interpreted as quantities of known fluids in the core if, previously, these beam strengths had been identified with a known combination of the same fluids. With some fluid cornbinations it might be desirable to dissolve powerful x-ray absorbing materials in one or more of the fluids, to increase the differences in the beam strengths for various fluid saturations. Boyer, Morgan and Muskat6 have described a method of measuring two component fluid saturation. One component was air or water; the other. minerat seal oil in which was dissolved 25 per cent by weight of iodobenzene to increase its absorbing power. The x-ray source was a tungsten target tube operated at 43 kv potential. The beam emerging from the core was measured as ionic current flowing across an air-filled ionization chamber by means of an amplifying circuit and galvanometer. Another portion of the beam from the x-ray tube was passed through a metal plate and measured in another ionization chamber. This portion, called the monitor beam, was used as an indication of the performance of the x-ray tube. The galvanometer readings were calibrated against air-oil core saturations, gravimetrically determined. The method was apparently established by experimental means. In the present investigation the available theory of x-radia-tion was surveyed with a view to extending the usefulness of the method and to developing design procedures for its application to measurement of fluid saturation in porous media. Application of the theory permits prediction of relative meter readings to be expected for any combination of porous matrix, various saturating fluids and auxiliary filtering media. It is thus possible to calibrate the equipment in terms of fluid saturation by an indirect but rapid technique. The results of calculations based on x-ray theory indicate. and results of the saturation calibration technique confirm. that a valid measurement of the saturation of the core can be made for any two components and in some cases for three components. THEORY The strength of an x-ray beam, after it has passed through a distance. 1, of matter of density, p, and mass absorption coefficient, µ at a given wavelength, A, may be expressed by the absorption formula I = I0 e ...........(1) where I, represents the intensity of the incident x-ray beam and I is the intensity of the emergent beam. The expression e is called the transmission factor of the material. The variation of I,, with wavelength depends upon the materials through which the x-ray beam has previously passed and upon the spectral distribution of energy at the source of the x-radiation. A group of curves. called spectra. which show the variation of intensity with wavelength and x-ray tube voltage are given in Fig. 1. These curves represent the general radiation from a tungsten target tube. When the tube voltage is greater than 69.3 kv, the characteristic radiation of the tungsten is emitted and is superposed on the general radiation. At a given voltage the minimum wavelength A,,,,, at which energy can be emitted by an x-ray tube is given by the formula 12,340 xml. = ——..........(2) volts where A,.,,.. is in Angstrom units. The wavelength at which the spectra have maximum intensity a1so decreases with increasing x-ray tube voltaue. The area under each curve represents to an arbitrarv scale the total energy emerging from the x-ray tube for that voltage. The variation of µ with wavelength has been determined for many substances and may be found in such references as those by Compton and Allison7 and by Hodgman.8 The phenomenon of absorption is composed chiefly of the capture of photons by the atoms of the absorbing material with associated displacement of electrons, and of the scattering, or the deflection, of the photons by the atoms. Curves of these mass absorption coefficients show jump discontinuities. or absorption edges. at wavelengths which are short enough for the photons,

Jan 1, 1951

By G. E. Keller

In connection with the work of Committee D5, Coal and Coke, of the American Society for Testing and Materials in developing new standards and improving old standards, series of tests were made to check the variance of sample preparation and analysis of American coals. Table I in the "Tentative Method of Preparing Coal Samples for Analysis - 02013-62T" is rather complicated, and the tests were designed to develop data for the simplification of this table. An allowance of 20% of the total variance of sampling and analysis for the sample preparation and analysis steps was used. Also, instead of coals being grouped into ash ranges, they were grouped as washed and raw (unwashed) coals. As a result of these tests, a simplified Table I for Tentative Standard 02013 has been proposed. A standard test for laboratories to check their variance of sample preparation and analysis has been developed. Committee D5 on Coal and Coke of the American Society for Testing and Materials has been making a study of all standards applying to coal for the purpose of improving and bringing them up to date and for breaking some of the existing standards covering a number of tests into single standards. As an illustration, sample preparation is now partly covered in ASTM Designation D492-48, Sampling Coals Classified According to Ash Content, and partly in ASTM Designation D271-58, Laboratory Sampling and Analysis of Coal and Coke. The latter contains, in addition to parts of sample preparation, methods for determining Moisture, Ash, Volatile Matter, etc. Although revision of sampling methods and sample preparation methods are now assigned separately, it is possible that they may end up as one standard. One of the first new Tentative Standards developed as the result of these studies was ASTM Designation D2013, Tentative Method of Preparing Coal Samples for Analysis. Although this method is quite an im- provement over that in the old standards and gives very specific instructions, Table I (attached) is quite complicated and rather hard to understand. In order to take advantage of reduced quantities or weights, it is necessary to know the ash content within rather narrow limits before sample preparation and no distinction is made as to whether the coal is cleaned or uncleaned. No limits of accuracy are assigned to the sample preparation and analysis. The total over-all accuracy of sampling, preparation and ash determination as given in D492-48 has been specified for commercial sampling procedure as follows: "This procedure is intended for an accuracy such that if a large number of samples were taken from a single lot of coal, the test results in 95 out of 100 cases would fall within ? 10 per cent of the average ash content of the sample." Although Appendix 11, Method for Determining the Over-All Variance of Reduction and Analysis in the Tentative Methods for Mechanical Sampling of Coal, ASTM Designation D2234-63T, does give a method for determing the over-all accuracy of preparation and analysis expressed as variance and also the F test, it does not permit the determination of the variance at the various stages of reduction or of the ash determination. It was decided in 1961 to ask a number of laboratories to run a series of tests for the purpose of determining the variance at various stages of reduction and analysis with the view of simplifying Table I of the Tentative Standard D2013-62-T. This paper is a record of this series of tests with recommendations which resulted from the tests. At the same time and preceding these tests the International Organization for Standardization under Committee TC/27 WG 7 was studying the same problem. Tomlinson1 of England and Dr. paul2 of West Germany had made studies giving quite a bit of information. Also Schwerd and coryel13 published some information which was the main basis for the Mechanical Division provision in ASTM Tentative Standard D2013-62T, Table I. In checking with the various laboratories which offered to cooperate in these tests, none was found which used mechanical division through the entire preparation procedure. It was then decided to use riffles at all stages with the thought that if riffles gave satisfactory variances, approved mechanical

Jan 1, 1965

By R. D. Stover, F. O. Shuck

The variation of binary-diffusion coefficients with composition in the liquid Bi-Sn system at 300°C was measured using the capillary-reservoir technique. The experimental coefficients did not exhibit a simple composition dependence. A number of tests were also made to determine the effect of variation of density with composition on convection within the capillaries. These tests indicate that the density changes arising from composition duferences may give rise to high diffusion coefficients unless care is taken to maintain a stable configuration. In recent years there has been considerable interest in diffusion in liquid metals. However, the bulk of the work done to date has involved measurements of self-diffusion or diffusion of dilute concentrations of "solute" metals. Because there are possible applications to liquid phase processing of metal alloys and since additional data may help to clarify the nature of diffusion in liquid metals, investigations of the concentration variation of diffusion coefficients in binary alloys have been undertaken. Of past studies only two have covered large ranges of binary composition. Niwa et al.' investigated the Pb-Sn, Bi-Pb, and Bi-Sn systems and Grace and Derge2 investigated the Bi-Pb system. Because of the discrepancy between the data of these investigators, it was deemed desirable to check the possibility of convection arising from the variation of density with composition. The capillary-reservoir technique of Anderson and saddington3 was chosen for the present investigation since it has been widely used for measurements involving dilute solute concentrations and it was the technique used by Grace and Derge.2 It was necessary, however, to modify the normal procedure of using a pure metal bath to avoid measurement of integral diffusion coefficients over large concentration ranges. The alloy system chosen for study was the Bi-Sn system for which there are some data available.' EXPERIMENTAL PROCEDURE In order to utilize the capillary-reservoir technique for measurements of diffusion coefficients as a function of composition, it was necessary to modify the normal procedure slightly. This modification consisted of using a reservoir composition which was only slightly different from that in the set of capillaries, in order that the integral coefficients measured might be taken over a small composition range and might thereby be assumed to approximate the differential coefficient at some average composition between that of the capillary and that of the bath. It was found that a composition difference of approximately 0.10 mass fraction provided a satisfactory compromise between a small increment in composition and reasonable accuracy in measuring changes of composition. The alloys were prepared from tin and bismuth of 99.999 pct purity. The materials were first cleaned of surface oxides, then weighed and melted to form a homogeneous alloy in a Pyrex filling apparatus. The capillaries used were of precision bore Pyrex tubing 1.000 *0.005 mm bore. Capillaries of various lengths (from 2.85 to 5.85 cm) were cut and sealed at one end by fusing a 3-mm Pyrex rod to the end. The capillaries were filled by inserting them into the filling chamber, evacuating the chamber, submerging the capillaries, and pressurizing the chamber with argon. Two sets of capillaries were prepared for each run. One set contained an alloy more dense than the bath alloy and one set a less dense alloy. This procedure was followed so that the effect of density difference on the measurement could be determined. After filling one set of capillaries, these were placed open end up in a capillary holder and transferred to the diffusion chamber which consisted of a Pyrex tube inserted into a graphite block. The second set of capillaries was then filled and placed into the diffusion chamber. The reservoir alloy, which had been melted in a separate crucible, then was poured carefully into the diffusion chamber. Sufficient reservoir alloy was used to cover all capillaries to a depth of several centimeters. All of these operations: capillary filling, melting of alloys, and diffusion anneal, were carried out in a fused-salt bath which maintained a temperature of 300"*1°C. All capillaries were permitted to diffuse for approximately 48 hr. At the end of the diffusion period the capillary holder was removed from the bath and

Jan 1, 1969

By G. E. Keller, G. D. Coe

Several methods have been devised for rapid determination of sulfur in coal using a high-temperature combustion furnace. The fundamental principles of the various methods are similar but the techniques vary widely. The method described herein is no different in principle from some of its predecessors but varies considerably in technique. Originally devised to overcome the low-accuracy criticism leveled against the others, the tube-furnace method has proved successful for limited applications. Work is being done to widen the applicability of the technique. Subsequent to the work of A. Vita1 in 1920, a number of investigators have published data dealing with the rapid determination of sulfur in coal using a high-temperature combustion furnace.2-5 These, together with several unpublished methods, involve wide differences in technique although they are all similar in principle. Investigation of typical details of procedure showed that poor precision or accuracy could be attributed to one or more of the following: 1) inadequate quantity of sample to be representative, 2) a delivery tube temperature too low to confine condensation to a washable area of the tube, 3) no provision for back washing the delivery tube, 4) incomplete absorption of the sulfur compounds due to inadequate bubbler, and 5) the false assumption that all of the sulfur is evolved as sulfur dixoide. The method herein discussed is no different in principle from some of its predecessors; the differences are in technique. Although the method is rapid—a determination can be completed in 5 min— accuracy has riot been sacrificed in order to achieve speed. MATERIALS AND EXPERIMENTAL WORK Fig. 1 shows the arrangement of the equipment. A metered volume of oxygen is passed through calcium chloride for removal of moisture, then through Ascarite for removal of carbon dioxide, and thence through a glass tee to the feed end of the combustion tube. Connected to the side arm of the glass tee is a rubber tube that is closed with a pinch clamp during combustion of a sample. The products of combustion are expelled through a Vycor bubbler, the end of which is submerged 3 cm below the surface of a 1 pct hydrogen peroxide solution contained in a 300 ml high-form beaker. At the completion of the 4-min combustion period the contents of the beaker are titrated to a yellow end point, using a methyl red indicator, with 0.05 N sodium hydroxide (or sodium tetraborate). The pinch clamp on the tube leading from the tee in the oxygen line is then opened and mouth suction applied to draw the hydrogen peroxide up into the bubbler past the ell, almost to the rubber tube connecting the bubbler to the combustion tube. This washing of the bubbler is repeated until no further acid reaction with the indicator is obtained. The hydrogen peroxide-sul-furic acid solution is then titrated to the final yellow end point. Test work conducted at the Robena Laboratory disclosed the following critical conditions that had important bearing on the precision of the method: Weight of Sample: Several series of tests wherein the sample weight ranged from 0.1 to 0.5 g of -60 mesh coal showed that the lowest variance (standard deviation squared) resulted from the use of 0.5-g samples; the variance was slightly greater when 0.3-g samples were used, and with less than a 0.3-g sample weight the variance increased rapidly with decrease in weight. Although the use of a 0.5-g sample invariably resulted in a very slight explosion as soon as the sample entered the hot zone of the combustion tube, this did not detract from the precision of the method. Temperatures: Mott and Wilkinson5 found that a combination of low temperature (1250°C) and low oxygen flow rate (less than 700 ml per min) tended to give high results due to formation of oxides of nitrogen. Although the method herein employs a much higher oxygen rate than 700 ml per min, as an additional precaution to assure accurate results, 1315°C (2400° F) is recommended as the most desirable furnace temperature. The temperature of the elbow of the bubbler should be at least 75°C to minimize condensation

Jan 1, 1961

By D. A. Elgillani, M. C. Fuerstenau

With either sulfonate or oleate as collector, quartz responds to flotation with moderate additions of calcium only at moderately high pH, where some portion of the activator has hydrolyzed to caOH+ . Calculations of the concentrations of various ionic and precipitated species of calcium and collectors suggest that the products of [(CaOH+) (RSO3)] and [(CaOH+)(01-)] determine whether flotation is obtained under specific conditions. Ion products on the order of 10-12 were calculated for both the sulfonate and oleate systems. The activating effect of calcium ion in nonmetallic flotation systems is of considerable interest because of the normal presence of calcium in natural water. As a result, this phenomenon has received quite some attention in the past. Kraeber and Boppel1 showed that quartz could be activated by calcium above pH 10 with sulfonate as collector. The feasibility of selectively separating quartz from hematite with calcium activation at relatively high pH was demonstrated by Clemmer, Clemmons, Rampacek, Williams, and stacy.2 Cooke and Digre3 showed with a bubble pick-up method that the minimum quantity of calcium ion required as activator for complete pick-up of particles occurs at pH 11.5 for an addition of 20 mg per liter sodium oleate. They also showed that larger additions of calcium (10-fold increase per unit decrease of pH) must be added for complete bubble pick-up as the pH is reduced. Schuhmann and Prakash,4 using a vacuum flotation technique, found that quartz could be floated with moderate additions of calcium chloride and oleic acid at neutral pH, providing the metal ion was present in stoichiometric excess over the quantity needed to form the normal soap with oleic acid. They also reported that calcium will function as an activator only in basic media. More recently, Eigeles and volova5 have shown that essentially complete flotation of quartz is obtained with 6 x 10-4 mole per liter calcium chloride and 1.7 x 10-5 mole per liter sodium oleate at pH 11.6. while no flotation is obtained at about pH 10.9 and below. The importance of adsorption of activator and collector at the air-liquid interface is also demonstrated in these systems. The important role that metal ion hydrolysis assumes in quartz activation systems was also demonstrated recently.6-8 A detailed investigation of metal activation in sulfonate flotation of quartz was undertaken in one system7 and yielded a number of interesting and important observations. Quantification of the data of this system7 to the extent desired was not possible, though, because certain species could neither be ignored nor accounted for accurately. These difficulties can be circumvented when calcium is involved as activator. This detailed analysis was undertaken to obtain a more quantitative explanation of calcium and metal ion activation in quartz flotation. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate9 mol wt 450, and pure potassium oleate were used as collectors. All other reagents used were reagent grade in quality, i.e., n-amyl alcohol as frother, KOH for pH adjustment, and calcium chloride. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. The experimental equipment and procedure were the same as that described previously.6,10 EXPERIMENTAL RESULTS As the presence of precipitates was noted in all of the systems to which ca++ and collector were added, experiments were undertaken to determine the solubility products of calcium sulfonate and calcium oleate using a nephelometer. With this technique, collector is titrated into a known solution, which in this case was 5 x 10-5 mole per liter CaCl2 at pH 5.5. Upon precipitation of the calcium-col lector salt, e.g., calcium oleate, light is scattered and detected

Jan 1, 1967

By Lyman Johnson

Single crystals qf copper in "single slip" orientatiorzs have been deformed in compression. During defortnation all of the independent deformation parameters have been measured. These parameters consist of thefive strain components and three components descrihing the lattice rotation. By a finite strain analysis these pararmeters , forrming a deformation gradient martrix, are related to the amounts of slip on each of the twelve slip systems. The results show that the amount of secondary slip is about equal to the amount of primary slip. This is an order of magnitude larger than has been believed previoutsly. ACCORDING to early theory and experiments, when a single crystal of a fcc metal is deformed in tension or compression it should deform by slip on only one slip system until the stress axis reaches a symmetrical orientation.' However. the observation of a large increase in the secondary dislocation density during ..single slip" makes it clear that some slip does occur on secondary systems. Knowledge of the amount and distribution of this secondary slip is essential to a complete understanding of the mechanisms of single-crystal deformation. Ahlers and Haasen 2 and Mitchell and Thornton1 have tried to detect the amount of secondary slip in single crystals of silver and copper, respectively. Each simultaneously measured the angle A, between the tensile axis and the primary slip direction and the length 1 of a gage section of the specimen after incremental amounts of deformation in tension. The measured A, was then compared with the theoretical single slip angle hp. given by sin Ap = j sin . hO where ?o was the initial angle between the tensile axis and the primary slip direction and lo was the initial gage length. In both sets of experiments a small but systematic difference between ?e and ?p was found. This difference must be due to the occurrence of secondary slip. However, as Mitchell and Thornton1 pointed out. nothing quantitative can be said about the amount and distribution of this secondary slip from the measurements that they made. The reason that no quantitative conclusions could be made is because no unique solution for the distribution of slip on the twelve fcc slip systems can be determined from only two measured deformation parameters such as A and 1. There are, in fact, eight independent macroscopic deformation parameters that can be measured when a single crystal undergoes a homogeneous deformation. Physically these can be thought of as the five finite strain components and the three angles describing the crystal lattice rotation. All eight of these parameters were measured by Taylor4,5 for aluminum deformed in tension and compression. At that time the concern was to show that slip occurs on {111 (110) systems in fcc metals, and the mathematics were not available to determine what slip distributions were compatible with the measurements. In this paper the mathematics6,7 are developed that allow the slip distribution to be determined from these measurable macroscopic deformation parameters. The analysis is applied to the measurements of the strain and lattice rotation of copper single crystals deformed in compression. The results show that the amount of secondary slip is an order of magnitude larger than had previously been thought. CRYSTALLOGRAPHIC DESCRIPTION OF A HOMOGENEOUS DEFORMATION The deformation of a solid body can be represented by a transformation matrix F that transforms the un-deformed state into the deformed state. Consider a vector X connecting two material points in the unde-formed material and the vector x connecting the same two material points after deformation, where both vectors are referred to the same set of Cartesian axes. The final vector x is related to the initial vector X by the equation: X = FS. [2] Eq. [2] can be considered as the equation defining F, which is called the deformation gradient matrix. Its components are: If the deformation is homogeneous, the transformation is linear and the components of F are constants. Using subscript notation, if P is the unit vector in the initial direction of a material line, the components of the unit vector p in the direction of the same material line after deformation are given by:

Jan 1, 1970

By T. W. Guy

DURING recent years, tremendous strides have been made in the economical use of coal. This has resulted in, and to some extent has been a result of, making the fuel specifications more and more rigid. For this reason, all producers have found it necessary to improve their preparation materially, both as to sizing and the elimination of impurities, either by more effective preparation underground or at the tipple and cleaning plant, or both. This cause and its effect in all producing fields seem likely to continue for several years-at least. The splendid inherent qualities of the Pocahontas and New River coals are known all over the world, but their good reputation is only partly due to inherent qualities, and to natural conditions which generally favor loading coal comparatively free from impurities; it is due in large measure to the care and skill used, either with or without the aid of mechanical devices, to ship products consistently low in ash. The first coal from the West Virginia smokeless fields was mined and shipped near Quinnimont, on New River, in 1871, while the first shipments from the Pocahontas field were in 1883. The development of both fields progressed rapidly. At first activities followed the main lines of the Chesapeake & Ohio and Norfolk & Western railroads, and were extended later as branch lines were built from these roads. The Virginian R. R., about 1907, opened up the Winding Gulf territory, which has since become a large producer of smokeless coals from the Pocahontas and the New River measures.

Jan 1, 1931

By Milton H. Ward

INTRODUCTION Historically, planning a mine involved the economic decision of whether to mine by open-pit methods or underground methods. The method selected was influenced by a number of factors, including size, tenor, and location of the deposit. If the project could not be justified by either underground or open-pit practices, it remained in fallow until economic conditions changed or technology advanced. Technology has advanced and the mining industry now has another option, that of in situ leaching. This method is on the threshold of becoming a commonly used alternative for production in many types of metal and mineral deposits. It will be utilized as the primary method for developing an ore body or as an adjunct to open-pit or underground operations. The following considers application of the technique to a deposit that had been partially exploited by open-pit methods. HISTORY The Big Mike Copper Mine is located approximately 30 miles south of Winnemucca, in Pershing County, Nevada. Interest in the property dates from the turn of the century, but little exploration was undertaken until the mid '60s. In 1967 Cerro Corporation acquired the property and initiated a major drilling effort. Ranchers Exploration obtained the property after this exploration program in late 1969 and confirmation drilling was undertaken. The deposit was delineated and it was determined that reserves amounted to about 100,000 tons of 10.0% massive copper sulfide ore and 700,000 tons of 2 .O% mixed oxide-sulfide ore. The ore body was a lenticular deposit, dipping at 50°. The massive sulfide mineralization was chalcocite and

Jan 1, 1974

By Hiroshi Oikawa, R. G. Blake, A. G. Guy

An equatzon has been derivedfor conveniently calculatzng the couvse of homogenzzation in a three-corviDonent solid solutiorz. The necessary assumptions are that the initial distributions of concentration are sinusoidal and that the four interdiffusion coefficients are constant. Employed in the deriuation were the Laplace transform and the fouter Fourier sine transfovwz. The final equation is shown to be in good agveetnent with the experimental results of Kirkaldyet al. on Cu-Sn-Zn alloys. COMMON boundary conditions for representing physical problems are those of the finite solid and of the infinite solid. Many metallurgical phenomena, however, have the geometrical form of a finite pattern reproduced throughout an infinite solid. Precipitation within a uniform matrix and segregation during solidification are examples. The purpose of this treatment is to show that a convenient and useful mathematical analysis is possible in those cases in which the finite pattern can be approximated by a sine function. The particular topic to be considered here is the elimination of segregation by diffusion, but the mathematical model has applicability in many other areas. It should be recalled that the mathematical solution of a typical problem involving a finite solid, such as diffusion into a thin layer, is quite involved.' Various types of solutions are used depending on the degree of advancement of the diffusion process and on the initial conditions. A step function is the simplest initial condition, but even in this case the general solution has the form of an infinite series. Kirkaldy et a1.2 have

Jan 1, 1968

By L. H. Marshall

MALLEABLE-IRON castings frequently are made brittle by hot-dip galvanizing. The castings may be and usually are perfectly normal before the hot-dip treatment, in that they will stand a remarkable amount of distortion and punishment before fracturing, yet, after galvanizing, a single blow with a hammer will often cause a break. One such casting broke when accidentally dropped on a concrete floor. Such weakness causes galvanizers to view malleable cast iron with misgivings, and, in turn, is a source of worry to the manufacturer of the castings. It is felt, therefore, that a practical method of overcoming this embrittlement, a method that has already been used on several thousand tons of castings, will be of general interest. The purpose of this paper is to describe this immunizing process. DEVELOPMENT OF THE PROBLEM In the early days the trade was not much concerned with the finish of the castings and in most cases the only protection given to the parts placed in service was a coat of paint. It was soon found that this form of protection was inadequate and the user demanded a better type of rustproofing. In compliance with this demand, the use of zinc for coating gradually spread until it became general practice. More than half of all the zinc produced today is used for coating iron and steel, and, in spite of the recent use of cadmium and chromium, zinc coatings are still recognized as among the best general rust inhibitors for atmospheric exposure.

Jan 2, 1926

By Frederick Laist

IN the course of the past 75 years the treatment of copper ores has undergone the most profound changes. To a lesser degree, this is true of all the nonferrous metals, but the rapid increase in the demand for copper due to the phenomenal growth of the electrical industry, and the discovery of vast new ore deposits in Michigan, Montana and Arizona, provided an exceptional incentive for improvements in smelting practice and for large-scale operations. Because these must perforce be carried on in regions where labor was scarce and wages high, the need for mechanization and larger smelting units soon became apparent. At a later date the porphyry coppers were discovered, with ores so low in grade that enormous tonnages had to be treated daily if they were to be made to pay at all. In some instances these ores were associated with, or overlain by, oxidized ores, which could not be concentrated mechanically and, of course, could not be smelted directly. This led to the development of the copper-leaching process. While the principles of the various smelting and leaching processes are for the most part of European origin, and have long been known, modern practice is essentially American and was evolved on this side of the Atlantic. The ores of copper may be divided into three general classes; viz, native copper, sulphide and oxidized ores. By far the greater number of commercially important ore deposits come under the classification of sulphides. Commercial deposits of native copper are limited to the Lake Superior

Jan 1, 1947

By Charles L. Mantell, George Ferment

This investigation determined the jeasibility of current-potential curves as an analytical tool for monitoving manganese electroicinning solutions for metallic impurities. Nine metallic impurities were studied: trickel, cobalt, silver, copper, zinc, molybdenum, catlmiun magnesium, and sodium. The individual effect of each metallic irzplrl,iLy on the standard point-izatiorr was determined for a range of 'concentration. Not all of Ihe impurities affected the polarization curve; correlation between transition current and cotrcetztration of impurity. Molybdenum had an uncorrelated effect on the polarization curie. The effects of binary mixtures of impurities were studied to see if the transition current of the mixture could be predicted. Interactions occurred between impurities which prei'etzted the pvecliction the transition current of tile rrlisLitr.e by additive laws. The polarization curve was shown to be sensitive to metallic impurities which affect the current efficiency of a manganese cell. THE application of current-potential curves in manganese electrowinning is not new but played an important part in the conversion of an inoperative large-scale pilot plant into a continuous comnercial operation.1"" The effects of trace metallic impurities in manganese electrowinning solutions on cathode current-potential curves,5-19 specifically nine impurities (nickel, cobalt, silver, copper, zinc, molybdenum, cadmium, magnesium, and sodium) were studied for a range of concentrations. Cadmium, magnesium, and sodium had no effect. Nickel, cobalt, silver, copper, and zinc yielded a correlation between transition current and concentration of impurity: molybdenum had an uncorrelated effect. Binary mixtures of impurities were studied to de-termine if the transition current could be predicted from the values for the individual constituents. Interactions between impurities prevented the prediction of the transition current of the mixtures by an additive law. The polarization curve was shown to be sensitive to metallic impurities which affected the rurrent efficiency of a manganese cell. The electrowinning of manganese relies upon maintaining a high-purity electrolyte. Purification schemes were developed to remove all of the heavy metals, the magnesium and calcium. Concentration limits have been established for single impurities. With high-purity electrolytes, favorable cell efficiencies are consistently obtained; but with impure solutions there is a reduction in efficiency. With the rapid rise to commercial prominence of electrochemical processes, there has been a lag in developing rapid methods for determining whether an electrolyte is sufficiently pure for efficient electrolysis. The most sensitive test for impurities is the behavior of the electrochemical cell. Impure electrolytes will cause a serious reduction in cell efficiency, and in many cases metal deposition will be prevented or reversed. The effects of impurities are not usually evident until after long periods of electrolysis, resulting in a disruption of the process. A method which could predict the behavior of an electrolyte in terms of cell efficiency prior to reaching the commercial cell is needed. Van Arsdale and Maier," Allmand and Campbell,a1'22 and others attempted to develop an electrochemical process for manganese,"3"29 but all met with some degree of difficulty. Jacobs et a studied the effects of metallic impurities in manganese electrowinning. Plant methods were based on a 2-hr plating in a small electrolytic cell. The final method was based on a 24-hr plating run, performed in a relatively large test cell. Here, current efficiencies were calculated with and without impurities in the electrolyte, and the critical concentration was established as the maximum amount of impurity that the electrolyte could tolerate before there was a serious loss in efficiency. The amount of impurity that could be tolerated decreased as the plating time increased, indicating deposition of the impurity. This test duplicated the conditions of commercial practire, and was sensitive to impurities. Small amounts of impurities significantly affect the hydrogen overvoltage at a metal surface, increasing or decreasing it depending upon the nature of the impurity. ockris established the limit for the onset of poisoning at 10-l moles per liter. The effects of impurities were studied by potential-time curves at a constant current density. The technique did not lend itself to rapid analysis in that several hours were needed to establish stable potential-time curves. Serfass and coworkers3' developed calorimetric and spectrophotometric techniques for analyzing for trace impurities. Our method4'" is based on current-cathode potential curves produced by continuously changing the cell voltage at a programmed rate. Starting with a clean stainless-steel cathode, the cell voltage was initially adjusted to yield zero current: the program was then started and the current was plotted as a function of the cathode potential. Fig. 1 is a typical current-potential curve. In initial region A the hydrogen-evolution reaction predominates and the polarization curve

Jan 1, 1967

By B. J. Kochanowsky

To improve blasting methods it is necessary to know how the explosive force acts and how rock resists this force. Because of the tremendous power developed within milliseconds and the great number of other factors directly affecting the technical and economic results, an analysis of the fundamentals of blasting theory is difficult. But since the rules used for layout design and for calculations of size of explosive charges are based on theoretical assumptions, complete knowledge of blasting theory has great practical importance in mining. Analysis of Blasting Theory: It is interesting to note the opinion of blasting experts with respect to contemporary blasting theories. F. Stussi,' Professor of the University of Zurich, stated: "We do not have enough experience yet to change our army engineering regulations in blasting and base it on new fundamentals. It is our duty to collect more practical data and to do more research in blasting to close this gap." K. H. Fraenkel,' editor of the Manual on Rock Blasting published in 1953 in Sweden and written by well-known Swedish, German, Swiss, and French blasting and explosive experts, said: "To the best of our knowledge no suitable formulas for civil blasting work are to be found in the American, French or German literature."

Sep 1, 1955

By R. E. Ogilvie, N. L. Peterson

Diffi-lsion measurements were conducted at all compositims in the bcc solid solution of the U-Nb system employing incremental couples at composition intemals of 10 at. pct. Diffusion coefficients were determined by the Matano method from concentration gradients obtained with the electron-probe microanalyzer. The activation energy for inter-diffi-lsion as a function of compositim shows three distinct regions: 1) 80 to 100 pct U.6= 30 kcal per mole; 2) 20 to 80 pct U, $ - 70 kcal per mole; 3) Oto 20 pet U, Q = i40 kcal per mole. The frequency factor, fi0 and the activation energy $ were found to be roughly related by the following equation: log Do ^9.7 X IO-5Q -6,6. The Kirkendall marker movement indicates that DU is larger than DNb between 16 and 100 pct U and DNb is larger than DU from 0 to 4 pct U. FOR practical as well as fundamental reasons, the rates of diffusion in alloys are of considerable consequence. Most solid-state reactions are largely dependent upon the diffusion of atoms through the lattice structure and along grain boundaries. The high-temperature strength and reasonable nuclear properties of niobium have prompted its use as a reactor material in contact with uranium fuel. Hence, diffusion data for the U-Nb system are of considerable importance. In the previous diffusion study1 on the U-Nb system using pure element couples, reliable data were obtained only in the range of 0 to 10 at. pct Nb due to the large variance of the diffusion coefficient with composition. Also, a large Kirkendall effect and considerable porosity in the uranium-rich areas of the specimen were reported, which suggests that the true diffusion coefficients are somewhat larger. The purpose of the present study was to obtain reliable diffusion coefficients at all compositions using incremental diffusion couples with intervals of 10 at. pct. In view of the abnormal self-diffusion be- havior of y uranium2-4 and some other bcc transition elements,&apos;-&apos; it was felt that a comparison of the interdiffusion coefficients in the bcc U-Nb system with those of Reynolds et al.9 for the fcc gold-nickel system might shed some light on the diffusion mechanism involved. Both systems have similar phase diagrams, in that complete solid solubility exists above a miscibility gap. EXPERIMENTAL PROCEDURE The uranium used in this investigation was obtained through the courtesy of Argonne National Laboratory. An analysis of this material detected only Si-30, A1-7, C-6, N < 10 and 0-18 ppm. The niobium was electron-beam melted material obtained from Stauffer-Temescal. The gaseous impurities were less than 50 ppm, and the spec troc hemical analysis showed Ta-500 and W-200 ppm. U-Nb alloys were prepared at composition intervals of 10 at. pct by melting the appropriate amounts of the pure elements in an arc furnace. The buttons were inverted and remelted 6 times to assure complete mixing. The buttons were then wrapped in molybdenum foil, canned in Zircaloy-2 or stainless steel, and hot rolled 30 pct reduction in thickness at temperatures between 850" and 1100°C. Alloys with 10, 20, 30, 40, and 90 at. pct Nb rolled quite easily under these conditions, but the 50, 60, 70, and 80 pct alloys remained brittle. After melting and rolling (when possible), the alloys were annealed for 24 hr at a temperature within 100°C of their melting point in a dynamic vacuum of better than 4 x 10-8 mm Hg. These treatments produced alloys which were homogeneous on a 1 p scale within the detectability limits of the electron probe. During fabrication, the alloys picked up as much as 100 ppm Mo and 100 ppm Zr. Other elements checked for but not found were Co, Cr, Fe, Mn, Ni, and Ti. The grain size of the annealed samples ranged from 3 mm for the uranium-rich alloys to 0.3 mm for the niobium-rich alloys. This permitted measurements of the concentration gradients in the diffusion samples without crossing more than one or two grains, thereby eliminating any grain boundary effects. The specimens were bonded by theU&apos;picture frame" technique as reported by Kittel.10 Specimens of composition b)U + (100 - x)Nb were sandwiched between two specimens of composition (x + 10)U + (90 - x)Nb after they were ground flat and parallel

Jan 1, 1963