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COUNCIL The following served on Council during the year under review: Office bearers: Messrs V. C. Robinson (President), Prof D. D. Howat and Dr J. P. Hugo (Vice-Presidents), J. K. E. Douglas (Immediate Past President) and D. G. Maxwell (Honorary Treasurer). Ordinary Members of Council: Dr M. G. Atmore, Dr J. M. Bereza, H. P. Carlisle, W. W. Malan, C. E. Mavrocordatos, Prof R. P. Plewman, Dr R. E. Robinson, Dr M. D. G. Salamon, P. W. J. van Rensburg, L. W. P. van den Bosch, P. A. von Wielligh. Branch Chairmen: J. Meintjes, J. M. Meyer (Acting), J. N. Saunders (Retired). Past Presidents serving on Council: R. J. Adamson, M. Barcza, H. Britten, R. C. J. Goode, P. Lambooy, Prof J. de V. Lambrechts, Dr J. T. Mclntyre, J. F. Reid, H. Simon. Ten Council meetings were held during the year with an average attendance of eighteen and the standing committees held forty-six meetings. FINANCE The annual accounts, which are attached to this report, show an excess of income over expenditure of R5 051 compared with an excess of expenditure over income last year of R4 608. This major reversal of fortunes is due in the first instance, of course, to the increased subscriptions. There were, however, other important contributors, particularly sales of the Proceedings of the Symposium on Open Pit Mining and profits on the operation of symposia and colloquia. It would appear from a study of the accounts that there has been a substantial drop in expenditure on secretarial fees. In actual fact, however, our total expenditure on secretarial fees was higher. A portion of this expenditure was charged against the administration of the Symposium on Open Pit Mining and, in addition, the charge against the Journal accounts for secretarial fees was increased. It will be recalled that in last year's annual report it was mentioned that subsequent to the new arrangement for publication of the Journal, the expected improvement in the finances of the Journal had been slow in materialising. After a total period of 18 months there was still no sign of improvement and it was accordingly decided to end the arrangement. As a result, the drain on the finances of the Institute was considerably lessened in the second half of the year. During the course of the year Council became concerned about the rapid depletion of our accumulated funds and gave careful and detailed attention to all aspects of the Institute's financial affairs. Particular attention was given to: 1. The fact that the Institute does not have a solid financial backing and must appeal for funds every time any special event such as a symposium is held. 2. The responsibilities of the Institute to the profession and the community, with particular reference to the desirability of establishing Institute bursaries and participating in other educational activities. 3. The rapidly rising cost of living. 4. The immediate financial position of the Institute. 5. The rapidly increasing cost of publishing the Journal due to the increasing number of papers available. In the meantime the immediate financial position of the Institute has improved but as this is due largely to non-recurring or irregular items of revenue, it should not be given undue weight. After careful consideration it was decided that an appeal should be made to industry for financial assistance, which would be used to cover the cost of symposia and other unusual expenditure and also, if possible, to build up the capital resources of the Institute so that there is a solid foundation for the future. Before appealing to industry, Council wished to be quite certain that there could be no criticism of the Institute for not having done our best in a personal capacity. Furthermore, Council examined many comparative statistics, including those circulated to members, which showed that, while expenditure per member has risen at an average annual rate of 7,5% over the last fifteen years, subscription revenue per member has risen at only 3,4% per annum. It was with this background that your Council decided to raise the subscriptions. Initial approaches have been made to the big mining groups and there has been a very generous response, although the details of how financial assistance will be provided have not yet been worked out. It seems likely that some form of affiliated company membership will be the most suitable method of achieving this. When these details have been fixed, it is the intention to extend the appeal to all corners of the mining industry as well as manufacturing and metallurgical industries. It is believed that these measures will ensure that the finances of the Institute are placed on a firm foundation on which the expanding activities can be planned. The MacArthur Forrest Memorial Fund shows an excess of income over expenditure of R73 and the total fund was, therefore, increased by this amount to R4 411. The balance sheet shows that the market value of quoted shares and debentures increased during the year fron R6 540 to R9 160. The market value is now almost exactly the same as the book value. Accumulated funds now amount to R23 010 compared with R17 959 a year ago.

Page Laboratory Methods...........................127 Special Analytical Methods.......................127 Improvements in the Accuracy of the Vacuum-fusion Method for the Determination of Oxygen in Steel....................127 Quantitative Spectrochemical Analysis of Mixtures of Gases.......131 Oxygen Samples from Open-hearth Bath...............133 Rapid Analysis of Sample for Alumina.................139 Accurate Carbon Analyses in Low-carbon Steel.............139 Laboratory Technique for Study of Reactions Involving Liquid Metal. . . . 142 Rotating Liquid Crucibles......................143 Stationary Crucibles.........................145 Jones and Laughlin Experimental Furnace...............148 Vacuum Melting..........................149 Measurement of Temperature of Liquid Iron and Steel;..........149 Pouring and Teeming Temperatures..................149 Bath Temperatures.........................151 Plant Methods.............................154 Methods of Studying Slags.......................154 Sampling Slag in the Open Hearth..................155 Viscosity of Open-hearth Slags....................155 Petrographic Examination of Slag...................156 Statistical Methods Applied to Study and Control of Chemical Relations in Bath...............................166 Rapid Method of -Correlation Applicable to Study of Steelmaking Reactions............................166 INTRODUCTION On Thursday morning, Feb. 16, 1939, a round table discussion was held on the subject of Experimental Methods in the Study of Steelmaking. Dr. John Chipman, Professor of Metallurgy at the Massachusetts Institute of Technology, and chairman of the A.I.M.E. Committee on Physical Chemistry of Steelmaking, presided. In opening the meeting, the chairman said: "The purpose of this round table is to discuss methods of study by which more and better information on the fundamentals of steelmaking can be obtained. It was thought that a round table discussion rather than a symposium would furnish the best opportunity for those actually using various methods of study to get together and discuss their common problems. For this reason attention will be focused upon methods of study rather than upon their results. We want new and current and up-to-date discussion.

Jan 1, 1940

Page Laboratory Methods...........................127 Special Analytical Methods.......................127 Improvements in the Accuracy of the Vacuum-fusion Method for the Determination of Oxygen in Steel....................127 Quantitative Spectrochemical Analysis of Mixtures of Gases.......131 Oxygen Samples from Open-hearth Bath...............133 Rapid Analysis of Sample for Alumina.................139 Accurate Carbon Analyses in Low-carbon Steel.............139 Laboratory Technique for Study of Reactions Involving Liquid Metal. . . . 142 Rotating Liquid Crucibles......................143 Stationary Crucibles.........................145 Jones and Laughlin Experimental Furnace...............148 Vacuum Melting..........................149 Measurement of Temperature of Liquid Iron and Steel;..........149 Pouring and Teeming Temperatures..................149 Bath Temperatures.........................151 Plant Methods.............................154 Methods of Studying Slags.......................154 Sampling Slag in the Open Hearth..................155 Viscosity of Open-hearth Slags....................155 Petrographic Examination of Slag...................156 Statistical Methods Applied to Study and Control of Chemical Relations in Bath...............................166 Rapid Method of -Correlation Applicable to Study of Steelmaking Reactions............................166 INTRODUCTION On Thursday morning, Feb. 16, 1939, a round table discussion was held on the subject of Experimental Methods in the Study of Steelmaking. Dr. John Chipman, Professor of Metallurgy at the Massachusetts Institute of Technology, and chairman of the A.I.M.E. Committee on Physical Chemistry of Steelmaking, presided. In opening the meeting, the chairman said: "The purpose of this round table is to discuss methods of study by which more and better information on the fundamentals of steelmaking can be obtained. It was thought that a round table discussion rather than a symposium would furnish the best opportunity for those actually using various methods of study to get together and discuss their common problems. For this reason attention will be focused upon methods of study rather than upon their results. We want new and current and up-to-date discussion.

Jan 1, 1940

By F. C. Pittman, D. W. Harriman, J. C. St. John

This paper mentions briefly the history of hydraulic jetting as applied to perforating and fracture initiation. It points out the advantages of hydraulic perforation and undercutting as an aid for creating a fracture at the point desired rather than depending upon the weakest point in the formation for breakdown. It describes early experimental work with jet nozzles in search of better nozzle materials. The effect of splash-back damage and its subsequent influence on jet body and tool design during this work is discussed. A series of cutting-rate curves for jets cutting steel and steel-cement-formation combinations is presented to show the effect of hydrostatic head and the point of diminishing returns with respect to cutting time. There is a series of photographs showing various types of rock formation in which perforation and undercutting tests were made. These stones were drilled and the casing cemented in place as in an actual well. The casing was perforated and circularly cut as if preparing for a fracturing job. The conclusion reached in the paper is that hydraulic jetting with sand-laden fluid can be used for perforating and undercutting casing, cement and formation rock for the intended purpose of inducing the formation to fracture at a desired point. INTRODUCTION Hydraulic jetting as a means of cleaning a formation during acidizing has been used for many years. The acid-jet gun was used to clean formation and for drilling cement from casing with acid. This tool was dropped to a seating ring installed on the tubing and could be retrieved by reverse circulation or wire line. In this process, the fluids were directed against the formation to clean and penetrate beyond the mud-damaged area. After the development of the hydraulic fracturing process, interest in jetting the formation with abrasive-laden fluid was renewed. The cutting action of abrasive fluid on pumping equipment, which is a well known problem, has been utilized to perforate and undercut casing, tubing and formation. In this process, surface areas are provided in the formation on which the frac- turing pressures may work to produce a fracture at the location desired. EQUIPMENT The tools used consist of bodies containing two, three or four jets in a single horizontal plane equally spaced around the circumference. The body is threaded to the end of a string of tubing and run into the well. In addition, an expendable tool is available that may be left in the hole after perforating and produced through until necessary to remove the tubing. The bottom of each tool is equipped with a ball-type back-pressure valve. The ball can be reversed to the surface and recovered. This allows reverse circulation so that loose sand which accumulated below the tool while jetting may be removed before the fracturing job. The present jetting tools are of such length that, when screwed together, the jets fall on 12-in. spacing. ANALYSIS OF THE PROBLEM Early work with nozzles indicated that hardened steel was not a suitable material for jets and that more durable material would be required. Ceramics were tried and found to be superior to steel but still too shortlived for most applications. Tungsten carbide, which was tried and found to be the best material available, is now being used for jet nozzles. Analysis of the problems presented by this process indicated that the following information was needed. 1. The effect of submergence on a jet stream and the effect of submergence on the cutting rate of a jet stream. 2. The cutting rate and depth of a jet stream in steel. 3. The cutting rate in various formations and point of diminishing returns. 4. Size of hole or slot cut in a pipe by a given jet. 5. Fluids and sands used. 6. The flow of various weight fluids through the jet nozzle and the discharge coefficients. 7. The type cut formed in the formation by the jet stream. 8. The stretch and contraction of tubing due to temperature and pressure. The cutting effect of a jet stream on a target in the atmosphere is rapid and spectacular as most of the

By H. W. Schadler

The superplastic behavior of low carbon and manganese bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests are reported which indicate that high strain rate sensitivity (>0.5) and adequate elongations are achievable in ultrafine-grained steels 1 to 2 p, but at strain rates which are not commercially attractive. It has been demonstrated that the fine grain size is retained after long times and high strains if the temperature is kept within the range of the two-phase (a + ?) field. INTEREST in superplasticity has been stimulated by the desire to: 1) understand the origin of, and mechanisms responsible for, the large uniform elongations observed, and 2) exploit this property for commercial advantage in metal forming operations. Although the Zn-22 wt pct Al alloy presently being studied as a model material1-5 may find application in sheet forming and extrusion, the potential of super-plasticity should best be realized in large tonnage materials, such as steel and aluminum alloys. The degree of superplasticity in low-carbon and manganese-bearing steels has been evaluated. The results of elevated-temperature stress-strain rate and elongation tests on ultrafine grain size material are reported. Avery and Backofen6 and Hart7 have shown that geometrically stable flow leading to extensive uniform elongation in the tension test is associated with high values of the strain rate sensitivity, m, defined: Lozinsky had reported that titanium and zirconium experience permanent deformation if subjected to a constant load and cyclic heating through the temperature range of the phase transformation. Although strain rate sensitivities in excess of about 0.2 had not been reported previously for steel, permanent deformation had been observed11-13 in a wide variety of steels subjected to a constant load and cyclic heating through the temperature range of the a-? phase transformation. Thus by analogy, steel could be expected to exhibit high strain rate sensitivity but only in the a + ? condition. High strain rate sensitivity has been observed at 650°C (a + Fe3C), but not reported as such, by Bailey, Dickenson, and pearson14 in 1931 at a strain rate of about 10-9 per min. It then remained to determine whether high tensile elongations would be observed in a rate-controlled test at constant temperature and at what strain rate strain rate sensitivity values greater than 0.5 would be observed. Since previous experience8 had indicated the importance of fine grain size to realizing high m at reasonable strain rates, it was first necessary to produce an ultrafine grain size and then keep the grains from growing during the test. The results of this investigation show that fine grain size can be readily produced16 and maintained by restricting the temperature of testing to below the ? transus. Further, superplasticity (high m and large uniform elongation) is observed. However, the strain rate range is only marginally useful for commercial forming operations with the finest grain size produced. MATERIAL The material investigated initially was a 1.9 wt pct Mn, 0.42 wt pct C, hot-rolled bar previously used by Low and Turka1015 and available in the laboratory. The 0.500-in. round was cold-rolled to a 0.090-in. flat, annealed for 4 hr at 850°C in argon, air-cooled, and cold-finished to 0.050 in. Subsequently, four additional steels of the compositions given in Table I were investigated to explore the effects of manganese, carbon, and test temperature on the observed stress-strain rate behavior. These steels were melted under argon, cast to 0.75 by 2 by 5 in. slabs, hot-rolled at 850°C, surface-finished to 0.13 in., and cold-finished to 0.050 in. Sheet tensile specimens 0.200 in. x thickness with 1- or 2-in. gage length were cut parallel to the rolling direction. Table I also includes the nominal transformation temperatures for the AISI 1340 and the four experimental steels. EXPERIMENTAL PROCEDURE Production of Fine Grain Size. Ultrafine grain size (1 to 5 p) was considered essential for this studv. Grange16 has described two techniques for producing

Jan 1, 1969

By Frank Doxey

AT Dominion Steel & Coal Corp. it has long been recognized that continued mechanization of mine operations is necessary in the Pictou, Cumberland, and Sidney coal fields of Nova Scotia. The varied physical conditions in these fields call for special consideration of individual cases before planning is finalized. Because standard equipment cannot be procured which would operate successfully, many experiments have been necessary over the years to keep pace with the progress made in other countries. There are two mines, producing 2000 tpd, located in the Pictou coal field. The field is badly distorted and crossed by many faults. Seams are highly inclined and irregular and vary in thickness from 5 to 40 ft. Entries are difficult to maintain because of squeezing of the coal. ribs and movement of the roof and pavement. Output from the three operating mines in the Cumberland field is 3000 tpd. The field is highly inclined, inclination varying from 12° to 32°. Overlying beds consist of shales and massive sandstone lenses of extreme toughness and are responsible for bumps when the stresses are relieved by extraction. At greatest depth these are among the deepest coal workings in the world. Depth of cover ranges from 2300 to 4000 ft. This prohibits room-and-pillar working and necessitates longwall operation. Working of contiguous seams concurrently to maintain output increases the already difficult conditions. The Sydney field, with a frontage of about 30 miles, is the most important of the Nova Scotia coal fields. With the exception of one small area it is now wholly submarine. Output is approximately 21,000 tpd. Seams are 21/2 to 8 ft thick, and cover in the areas varies from 600 to 2300 ft, with an average of 1500 ft from sea bottom to the top of the seam. The seams dip in a seaward direction, pitches ranging from 6" to 4.0". The shoreline is the last place of entry to the seams and distance from the bank to the working faces is generally over 3½ miles, in some cases as much as 6½ miles. Ventilation is a problem and requires the construction of large permanent airways. Getting and Loading Coal: In 1925, in view of heavy pressures exerted by thickness of cover overlying the seams, roadways and pillars of the room-and-pillar system being worked began to break up and coal was lost. It was decided that a change in the method of extraction in areas with heavy cover was necessary, and experiments were made with many short walls and longwalls varying between 90 and 250 ft. Trial and error proved that the best operating length was between 400 and 500 ft, delivering all coal to the dip, with roadways to the face following a level course. The change-over was gradual, and the technique of roof control developed with the system, so that falls to the face are now very infrequent. An advantage of longwall mining is that it yields 95 pct extraction, especially important in coal seams of high quality or in seams where faults or disturbances restrict the workable areas. This percentage of extraction is based on the fact that the longwall advancing system takes development faces where pitch permits instead of driving headings and leaving roadway pillars. This system yields high tonnage during development and limits loss in extraction to duff left during operations. Accompanying disadvantages, on the other hand, are the heavy construction cost of main roadways and the necessity of driving all new flank face roadways through the gob. If the main roadways are driven through the solid, and large enough pillars are left on each side for protection against flank face weights, then the width of solid coal is approximately 1700 ft. This represents 10.6 pct of the coal available, or 89.4 pct extraction of the whole. These pillars, however, are of such size that they provide a useful pillar drawing area as a final operation of the mine. It may be that although the seam cannot be generally mined by the room-and-pillar method, it can be adapted to

Jan 1, 1955

By Donald B. Evans, Robert D. Pehlke

The solubility of nilrogen in liquid binary alloys of iron with Litanium. zivconium, columbium, vanndiurn, and tantalum was measured for alloy composiLions up to the solalbility limils of lhe alloy nitrides. All five alloying agents were found to decrease markedly the activity coefficient of nitrogen in liquid ivon. The metal/nitvogen mole ralios in the alloy nitrides formed were generally .found to be slighlly greater than 1.0, but in no case greater than 1.5. From the experimental data, the standard free energies of fortmation of titanium and zir-conium nitrides have been calculated for the Lemperaluve range 1550° to 1750 C. The solublily Products for columbium, tantalum, and vanadium nitrides are also reported. A number of research investigations have examined the effect of refractory metals on the solubility of nitrogen in liquid iron. Although data on zirconium are not available, investigators are in agreement that titanium, vanadium, columbium, and tantalum markedly increase the solubility of nitrogen in liquid iron. This fact alone makes desirable the acquisition of thermodynamic data for these elements in liquid iron. Since refractory metals are known to be stable nitride formers, they have been suggested as steel denitrifying agents, and some of their nitrides have recently been considered as containment materials for liquid iron and iron alloys. Most available thermodynamic data for these metals relate to their dilute concentrations, but effective thermodynamic treatment of these applications requires data at concentrations near the solubility limit of the alloy nitride. Although some work has been done at relatively high alloy concentrations in liquid iron (particularly for vanadium 2,3 and titanium 2,4), the results have been somewhat contradictory. Disagreement may be partly attributed to the fact that the compositions of most refractory metal nitrides have been shown to be nonstoichiometric, and to vary 2,5-8 depending on the temperature and nitrogen gas pressure with which the solid nitride phase is in equilibrium. One purpose of this study consequently has been to determine the compositions of the refractory metal nitrides precipitated from a liquid iron solution. EXPERIMENTAL PROCEDURE Rao and Parlee2 and Evans and Pehlke 9 have discussed the technique for measuring the solubility product of an alloy nitride phase in liquid iron by finding the point of departure of the nitrogen solubility from Sieverts' law. The method consists of measuring the solubility of nitrogen in a melt of iron containing a known concentration of a second metal as a function of the nitrogen gas pressure over the melt. In this study the second metal was one of the refractory metals titanium, zirconium, columbium, vanadium, or tantalum. When the nitrogen pressure at which the refractory nitride forms is reached, a deviation of the measured solubility of nitrogen in the melt from Sieverts' law is observed in the form of a "pressure halt." The concentration of nitrogen in the melt associated with this breakpoint in the nitrogen-absorption curve is then used to calculate the nitride solubility. The Sieverts method was used to measure nitrogen solubility as a function of nitrogen pressure and temperature. The experimental equipment for this technique has been previously described in detail. 1,9 Charge materials used were vacuum-melted high-purity iron (Ferrovac-E) and the best commercial grades of the refractory metals obtainable (in all cases at least 99.8+ pct pure). Recrystallized alumina crucibles were used to hold all melts except those containing zirconium, for which zirconia crucibles were necessary. Temperatures were measured by a disappearing-filament type optical pyrometer sighted vertically downward on the melt surface through a 1/4-in.-diameter sight hole in the crucible lid. By means of a technique previously described, 9 in which the refractory-metal nitride was precipitated at one temperature then redis-solved by raising the temperature 50°C and precipitated again at a higher temperature, it was possible to obtain data over a temperature range of up to 200°C on a single melt. It was found that this technique could not be used with melts containing zir-

Jan 1, 1965

By Raynor Linzey, Karl M. Busen

The formation of thin films of silicon oxide by anodic oxidation of silicon and the subsequent removal of these films by an etch is a process often used for the evaluation of concentration distributions Profiles) in silicon layers by the differential sheet conductance method. The accuracy of the resulting profile is very strongly influenced by the uniformity of the thickness of the reacted silicon. Normally, it would be expected that for a constant number of coulombs passed the thickness would be the same from oxidation to oxidation. Investigations show that in certain electrolytes, for a given number of coulombs passed through an n-type silicon sample, the thickness of the reacted silicon increased with increasing resistivity. Even for the same resistivity the thickness varied sometimes by a factor of 1.5. When an electrolyte was used which consisted of 10 pct water by volume in ethylene glycol with 4.0 g KNO per 1000 ml of solution, anodiza-tion at 5 ma per sq cm led to satisfying results. Short-time anodizations gave oxide layers of a higher apparent density than those experienced from thermally gown silicon oxides. THE functioning and the electrical characteristics of semiconductor devices are based upon the incorporation of "impurities" into a single-crystalline body of suitable material and on the concentration distribution (profile) of this impurity. The incorporation can be achieved by well-known processes as, for example, by diffusion, epitaxial growth, alloying, or ion implantation. Often the profile resulting from these processes is not known. A powerful tool to learn about a concentration distribution is given by the method of differential sheet conductance which employs successive four-probe measurements on a layer subjected to stepwise removal of thin sublayers. Differential sheet conductance vs position (or penetration depth) of a sublayer is plotted and a smooth curve is drawn through the data. From this curve the profile is then calculated. When the semiconductor material is silicon, the sublayers are removed suitably by anodic oxidation of the silicon and subsequent dissolving of the formed silicon oxide by an etch. The accuracy of the resulting profile is very strongly influenced by the uniformity of the sublayer thickness. Normally, it would be expected that, for a constant number of coulombs passed, the thickness would be constant from oxidation to oxidation. Investigations showed that for sublayers several hundred angstroms thick the reproducibility can be rather poor. Therefore, efforts were made to obtain a reliable technique for uniform removal. The present paper describes such a technique and certain phenomena which were encountered during the investigations. APPARATUS AND TECHNIQUE The first report on the investigation of concentration distributions, where for differential sheet conductance measurements thin silicon sublayers were removed from a diffused layer by anodic oxidation, was given by Tannenbaum. The author reports the removal of sublayers which for the most part were 400 thick. More advanced device designs now require much narrower layers. When it was tried in these laboratories to determine profiles within such layers, difficulties were encountered with respect to sublayers which by necessity had to be thinner than the ones reported by Tannenbaum. The apparatus used for the investigations is sketched in Fig. 1. Two cylindrical containers connected by a wide tube are filled with an electrolyte. The left container receives the cathode whereas the right container is closed at the bottom end by a sample support consisting of a Teflon base and a copper pedestal. The silicon sample (1 by 1 cm) is mounted to the pedestal embedded flush in the Teflon base using silver paint (Degussa) for electrical contact. Pyseal is applied to the edges of the sample to protect the copper pedestal from the electrolyte. The base is mounted to the container using a water-tight silicon rubber gasket. Fig. 2 gives a view of the sample support. The copper pedestal is connected to the positive side of a power supply operating at a constant current output (Kepco Model ABC 425M). The electrolyte which has been reported by Duffek et al. consisted of either 2 or 10 pct water by volume in ethylene glycol and 4.0 g KNO3 in 1000-ml solution. The electrolyte is best prepared

Jan 1, 1967

By J. L. Dumanoir, Maurice Martin

The induction-electrical log is a combination of a SP curve, a short normal curve, and an induction log; all three logs being recorded simultaneously in a single run. The spacing of the short normal is 16 in. The induction log is designated as 5FF40, which means that the sonde involves five coils and a focusing system, and that the distance between the main coils is 40 in. Examples of induction-electrical logs are shown in Figs. 13 and 15. The right-hand track contains the induction conductivity curve. The scale of this curve is linear with the units of conductivity, i.e., mhos/m or millimhos/m (mmhos/m), increasing from right to left. The same curve can be read in the reverse direction as a resistivity log, with a hyperbolic scale. In the middle track, the solid curve represents the short normal. (An amplified short normal is also shown in Fig. 15). The dotted curve is the resistivity curve of the induction log, i.e., the reciprocal of the conductivity curve, recorded with the same linear scale as the short normal. The SP is in the left-hand track. In this combination, the SP curve and the 16-in. normal are the essential correlation curves, as in the conventional electrical log. The induction log provides a more accurate and detailed record of formation boundaries than the conventional log, especially in hard rock territories. Furthermore, the induction-electrical log makes possible the determination of fluid content, particularly in thin beds—at least qualitatively and very often quantitatively. In such thin beds, because of the adverse effect of the adjacent formations, the responses of the conventional devices are generally doubtful and/or incom-plete. Another advantage of the new combination is that the induction log is little affected by the presence of thin hard streaks interbedded within the permeable sections, whereas such occurrences are the cause of serious distortions of the long normal and lateral curves. The evaluation of saturation from any resistivity log implies the knowledge of the true resistivity R, of the bed and of the resistivity R.. of the flushed zone, or at least of the ratio Rxo/Rc. With the induction-electrical log run in fresh mud, the 16-in. nor-mal has a smaller radius of investigation than the induction log, so that the former reads closer to R.. and the latter closer to Rt. Thus, it has been observed that the ratio of the 16-in. normal to the induction log readings can be used as a basis for the interpretation in terms of saturation, with the help of appropriate charts. The purpose of the present paper is essentially to explain this procedure and to provide the corresponding charts. On the other hand, when a formation is deeply invaded, the response of any log (in particular the induction log) depends upon the radial distribution of formation resistivities behind the wall of the hole, which itself is a function of the arrangement of the fluids saturating the formation pore spaces. This paper, accordingly, will begin with a schematic description of the distribution of fluids and resistivities in the invaded zone. Next, some essential characteristics of the induction log will be reviewed. Finally, the determination of the interpretation charts and their application will be explained. The discussion will be confined to the case of fresh muds, i.e., muds whose resistivity is at least five times as great as that of the formation waters. With the present equipment the induction log is not well adapted for logging in salty mud. The Laterolog and guard electrode log are at their best under conditions of low resistivity mud. Accordingly, when these tools were introduced a few years ago, the use of salty mud was recommended. Now, with the introduction of induction logging, spe-

Jan 1, 1958

By C. R. Ramachandra, C. C. Patel

Flotation of chalcopyrite from a low grade ore was studied by using different xanthates and dixanthogens as collectors and by conditioning the flotation pulp with oxidizing gaseous systems. The improvement in the recovery of chalcopyrite with the oxidizing systems was mainly due to the auto-activation of chalcopyrite, leading to the enhanced adsorption of xanthates and dixanthogens even when the latter were formed by oxidation of the xanthates. With air or oxygen as oxidizing system, the amount of ethyl xanthate required at pH 8.5 was much less than normally employed in the industry, the recovery being 97-99% of chalcopyrite with a concentrate of 24% copper. With isopropyl and isoamyl xanthates, the recovery was improved but the grade was lowered. By conditioning the pulp with air-CO2 or oxygen-CO2 mixture, the recovery was lowered with ethyl xanthate only, mainly due to the depressant action of bicarbonate formed. Flotation with dixanthogens gave cleaner concentrates of chalcopyrite. because iron pyrite did not float with these collectors. Of the dixanthogens tried, diisopropyl dixanthogen gave the highest recovery, 99% chalcopyrite with a concentrate containing 28.5 to 30% copper, when the pulp at pH 8.5 was condi-tioned with air. Isopropyl dixanthogen was found to be the best collector of all the xanthates and dixanthogens studied. It was found that the adsorbed ethyl, isopropyl and isoamyl xanthates at chalcopyrite surface, activated by cupric sulfate, and at iron pyrite surface were oxidized to the corresponding dixanthogens to different degrees in presence of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture.' The dixanthogen formed at chalcopyrite surface was, however, firmly adsorbed while that at iron pyrite surface was easily desorbed. Since dixanthogens formed have greater hydrophobicity than the corresponding xanthates, as revealed by contact angles,1,2 the former were expected to improve the flotation results. It was, therefore, thought desirable to find out the effect of air, oxygen, air-carbon dioxide mixture and oxygen-carbon dioxide mixture on the selective flotation of chalcopyrite when individual xanthates were used as collectors. The effect of direct use of dixanthogens as collectors on the selective flotation of chalcopyrite was also investigated. For these studies, low grade chalcopyrite ore, received from the Indian Copper Corp., Ltd. (I.C.C.), Ghatsila, Bihar, was employed. At the milling plant of the I.C.C., chalcopyrite is floated at a pH of 8.5, employing ethyl xanthate as collector. EXPERIMENTAL Materials Employed: XANTHATES - Ethyl, isopropyl and isoamyl xanthates of potassium were prepared in a pure state by the methods described earlier.4 A 0.03% aqueous solution of a xanthate was freshly prepared in air-free distilled water for flotation studies. DIXANTHOGENS - Diethyl, diisopropyl and diisoamyl dixanthogens were prepared by the oxidation of xanthates by iodine and purified by extraction with petroleum ether. A 0.03% alcoholic solution of dixanthogen was used as a collector. FROTHER - A 0.2% solution of pine oil in ethyl alcohol was employed. SODIUM CARBONATE - A 0.4 N solution was used. ORE - The composition of the -100 +200-mesh size (Tyler standard) powdered ore, as determined by standard methods of analysis, was: copper 1.57%, iron 10.29%, sulfur 3.15% and acid insolubles 66.10%. Iron present as chalcopyrite (CuFeS2) was 1.38%, while that present as iron pyrite (FeS,) was 1.37%. Both chalcopyrite and iron pyrite were found to be liberated from the gangue minerals and from each other, as observed under a microscope. Flotation of Chalcopyrite with Xanthates in Presence of Different Gaseous Systems: Fifteen grams of -100 + 200-mesh size ore were shaken well with 100 ml of distilled water. The pH of the pulp was adjusted to 8.5 by the addition of sodium carbonate solution. Then 0.1 ml of xanthate solution (0.005 lb xanthate per ton of the ore) was mixed with the pulp, and the latter together with washings transferred to a

Jan 1, 1963

Jan 1, 1924

By J. W. Spretnak, D. A. Chatfield, G. W. Powell, J. R. Eifert

In nzost cases, the driving force for a lattice transformation is produced by supercooling below the equilibriunz transformation temperature. The interfnce reaction in isothermally annealed, multiphase diffusion couples may involve a luttice transformation which also requires a driving force. Direct experinzental evidence has been obtained for the existence of the driring force in the form of a supersaturated phase at the aocc)-0@cc) interface in Cu:Cu-12.5 ult pct A1 couples; the super saturation is equivalent to an excess free energy of approximately 3 cal per mol at 905. A tentatiue interpretation of the dynanzic situation a1 the interface based on the free energy-composition diagram is proposed. THE presently accepted theory of diffusion in multiphase couples1 states that there will be a phase layer in the diffusion zone for every region which has three degrees of freedom and which is crossed by the diffusion path in the equilibrium phase diagram. For binary systems, this restriction excludes all but single-phase fields and, for ternary systems, only one- and two-phase fields are included. In addition, Rhines"~ as well as other investigators3 6 have reported that the compositions of the various phases adjacent to the interfaces are, for all practical purposes, the compositions given by the intersections of the diffusion path with the solubility limits of the single-phase fields of the equilibrium phase diagram. Some studies of the rate of thickening of these intermediate diffusion layers indicate that the thickness of the layer changes para-bolically with time, or: where x is the position of the interface relative to an origin xo, t is the diffusion time, and k is a temperature-dependent factor. crank7 shows mathematically that, if the compositions at an interface are independent of time and the motion of the interface is controlled by the diffusion of the elements to and from the interface, then the segments of the concentration penetration curve for a semi-infinite step-function couple will be described by an equation of the form: hence, Eq. [l] follows from Eq. (21 if the interface compositions are fixed and if the motion of the interface is diffusion-controlled. Although the concept of local equilibrium being attained at interfaces has assumed a prominent role in the theory of diffusion in multiphase couples, experimental evidence and theoretical discussions which challenge the general validity of this concept have been reported in the literature. arkeen' has stated that strict obedience to the conditions set by the equilibrium phase diagram cannot be expected in any system in which diffusion is occurring because diffusion takes place only in the presence of an activity gradient. Darken also noted that it is usually assumed that equilibrium is attained locally at the interface although the system as a whole is not at equilibrium, the implication being that the transformation at the interface is rapid in comparison with the rate of supply of the elements by diffusion. ISirkaldy3 indicates agreement with Darken in that he believes the concept of local equilibrium is at best an approximation because the motion of the phase boundary requires that there be a free-energy difference and, hence, a departure from the equilibrium composition at the interface. Seebold and Birks9 have stated that diffusion couples cannot be in true equilibrium, but the results obtained are often in good agreement with the phase diagram. The initial deviation from equilibrium in a diffusion couple will be quite large because alloys of significantly different compositions are usually joined together. Kirkaldy feels that the transition time for the attainment of constant interface compositions (essentially the equilibrium values) will be small, although in some cases finite. Castleman and sieglelo observed such transition times in multiphase A1-Ni couples, but at low annealing temperatures these times were quite long. Similarly, ~asing" found departures, which persisted for more than 20 hr, at phase interfaces in Au-Ni and Fe-Mo diffusion couples. Braun and Powell's12 measurements of the solubility limits of the intermediate phases in the Au-In system as determined by microprobe analysis of diffusion couples do not agree with the limits reported by Hiscocks and Hume-Rothery13 who used equilibrated samples. Finally, Borovskii and ~archukova'~ have stated that the determination of the solubility limits of phase diagrams using high-resolution micro-analyzer measurements at the interfaces of multiphase couples is not an accurate technique because of deviations from the equilibrium compositions at a moving interface; diffusion couples may be used to map out the phase boundaries in the equilibrium diagram, but the final determination of the solubility iimits should be made with equilibrated samples. The purpose of this work was to investigate the conditions prevailing at an interface in a multiphase diffusion couple and to compare the interface compositions with those associated with true thermodynamic equilibrium between the two phases. Microanalyzer techniques were used to measure interface compositions in two-phase Cu-A1 diffusion couples annealed at 80@, 905", and 1000°C for various times.

Jan 1, 1969

By Rollyn P. Jacobson

THE town of Pacific, in Jefferson County, Mo., is 127 miles west of St. Louis. Since the area lies entirely on the flood plain of a cutoff meander of the Meramac River, it was considered a likely environment for accumulation of commercial quantities of sand and gravel. Excellent transportation facilities are afforded by two major railways to St. Louis, and ample water supply for washing and separation is assured by the proximity of the river. As a large washing and separation plant was planned, the property was evaluated in detail to justify the high initial expenditure. An intensive testing program using both geophysical and drilling methods was designed and carried out. The prospect was surveyed topographically and a 200-ft grid staked on which electrical resistivity depth profiles were observed at 130 points. The Wenner 4-electrode configuration and earth resistivity apparatus" were used. In all but a few cases, the electrode spacing, A, was increased in increments of 11/2 ft to a spread of 30 ft and in increments of 3 ft thereafter. Initial drilling was done with a rig designated as the California Earth Boring Machine, which uses a bucket-shaped bit and produces a hole 3 ft in diam. Because of excessive water conditions and lack of consolidation in the gravel there was considerable loss of hole with this type of equipment. A standard churn drill was employed, therefore, to penetrate to bedrock. Eighteen bucket-drill holes and eight churn-drill holes were drilled at widely scattered locations on the grill. The depth to bedrock and the configuration will not be discussed, as this parameter is not the primary concern. Thickness of overburden overlying the gravel beds or lenses became the important economic criterion of the prospect.** The wide variety and gradational character of the geologic conditions prevailing in this area are illustrated by sample sections on Fig. 2. Depth profiles at stations E-3 and J-7 are very similar in shape and numerical range, but as shown by drilling, they are measures of very different geologic sequences. At 5-7 the gravel is overlain by 15 ft of overburden, but at E-3 bedrock is overlain by about 5 ft of soil and mantle. Stations L-8 and H-18 are representative of areas where gravel lies within 10 ft of surface. In most profiles of this type it was very difficult to locate the resistivity breaks denoting the overburden-gravel interface. In a number of cases, as shown by stations M-4 and H-18, the anomaly produced by the water table or the moisture line often obscured the anomaly due to gravel or was mistaken for it. In any case, the precise determination of depth to gravel was prevented by the gradual transition from sand to sandy gravel to gravel. In spite of these difficulties, errors involved in the interpretation were not greatly out of order. However, results indicated that the prospect was very nearly marginal from an economic point of view, and to justify expenditures for plant facilities a more precise evaluation was undertaken. The most favorable sections of the property were tested with hand augers. The original grid was followed. In all, 46 hand auger holes were drilled to gravel or refusal and the results made available to the writer for further analysis and interpretation. When data for this survey was studied, it immediately became apparent that a very definite correlation existed between the numerical value of the apparent resistivity at some constant depth and the thickness of the overburden. Such a correlation is seldom regarded in interpretation in more than a very qualitative way, except in the various theoretical methods developed by Hummel, Tagg (Ref. 1, pp. 136-139), Roman (Ref. 2, pp. 6-12), Rosenzweig (Ref. 3, pp. 408-417), and Wilcox (Ref. 4, pp. 36-46). Various statistical procedures were used to place this relationship on a quantitative basis. The large amount of drilling information available made such an approach feasible. The thickness of overburden was plotted against the apparent resistivity at a constant depth less than the depth of bedrock for the 65 stations where drilling information was available. A curve of best fit was drawn through these points and the equation of the curve determined. For this relationship the curve was found to be of the form p = b D where p is the apparent resistivity, D the thickness of overburden, and b a constant. The equation is of the power type and plots as a straight line on log-log paper. The statistical validity of this equation was analyzed by computation of a parameter called Pearson's correlation coefficient for several different depths of measurements, see Ref. 5, pp. 196-241. In all but those measurements taken at relatively shallow depths, the correlation as given by this general equation was found to have a high order of validity on the basis of statistical theory.

Jan 1, 1956

By E. Douglas Sethness

The uranium industry is booming. In Texas alone, there are about 22 different companies with active exploration programs. Twelve solution mines have been permitted; three surface mines have been authorized; and two mills are currently in operation. However, the industry also has a problem, and that is the disposal of radioactive wastes. Over the past several years, stories concerning nuclear wastes have appeared frequently in the news. One of the most frequently cited cases occurred in Grand Junction, Colorado. In 1966, after ten years of investigations, the U. S. Public Health Service (PHS) discovered that tailings from a uranium mill were being used as fill material and aggregate for local construction purposes. It was estimated that between 150,000 and 200,000 tons of material had been removed and used under streets, driveways, swimming pools, and sewer lines. In addition, tailings had been used under concrete slabs and around foundations of occupiable structures. Further studies prompted the Surgeon General to warn that the risk of leukemia and lung cancer could be doubled at the measured radiation levels. More recently, the L. B. Foster Company discovered that its building site in Washington, West Virginia, was radioactive. While digging a foundation, the ground erupted and a ball of fire 30 feet high shot out. Evidently, the dirt was laced with radioactive thorium and zirconium, a potentially explosive mixture contained in a Nigerian sand which had been used by the previous site owners in the manufacture of nuclear fuel rods. Just this month we have read about legal suits to stop exploration for a nuclear waste disposal site in Randall County, Texas. The U. S. Department of Energy is trying to locate a deep underground nuclear waste depository for final burial of over 76 million gallons of high-level wastes. The problem is acute, the wastes are accumulating at a rate of about 300,000 gallons per year. Nor do these numbers include the spent fuel elements from nuclear power plants that are in temporary storage facilities. Fortunately, public awareness of these and other related issues is high. Unfortunately, the differences in the waste products from the nuclear fuel cycle are not always apparent to the general public. There are two distinct types of radioactive wastes: "high-level", which consist of spent fuel or wastes from the reprocessing of spent fuel; and "low-level", which, in general, are by-product wastes. There are numerous non-technical definitions that can be applied to help the layman differentiate between high-level and low-level wastes. For this latter purpose, it is best to think of them in terms of what we can see and feel. In general, high-level wastes are physically hot and can cause acute radiation sickness in a short period of time. Low-level wastes are not hot, but may cause chronic health effects after long exposure. The wastes which we are concerned with in the uranium mining and milling industry are low-level wastes. As recently as ten years ago, there were very few controls or regulations governing tailings disposal methods. At the same time, mine reclamation was not enforced through either state or Federal laws and the long-term viability of abandoned tailings ponds was not assured. The regulatory climate has changed significantly in the last decade, however. The low-level radioactive wastes generated by uranium mining and milling are generally contained in a tailings pond. Approximately 85-97% of the total radioactivity contained in uranium ore is present in the mill waste that goes to such tailings ponds. The isotope Radium-226 is probably the most potentially harmful radioactive parameter in the ponds. Radium emits gamma radiation and is also an alpha particle emitter. Because gamma radiation is very penetrating, it presents a potential health problem when a source is located external to the body. Gamma radiation will go through the body, causing damage to each cell encountered on the way. Although alpha particles have very little penetration capability, they can cause extensive cell damage. For this reason, alpha particles are a problem after inhalation or ingestion. Radium creates a health hazard by both of these mechanisms. Radium decays to radon gas which can be inhaled and serve as an alpha particle emitter. Additionally, radium is very soluble and readily enters the natural hydrologic cycle if allowed to leach from a tailings pond. With a half-life of 1620 years, radium has plenty of time to be taken into the food chain and end up in our bodies, emitting alpha particles. Because the potential health problems are better understood today than ten years ago, and because the Nuclear Regulatory Commission (NRC) has developed increasingly stringent government regulations, the uranium mining industry applies a high level of technology to the disposal of nuclear wastes. In most cases, low-level radioactive wastes are disposed of at or near the site where they are produced. There are six commercial burial grounds for low-level wastes, but it would not be economical to ship all mine or milling wastes to these sites. The on-site disposal methods most often used are ponding

Jan 1, 1979

By K. E. Brown, A. R. Hagedorn

Continuous, two phase flow tests have been conducted during which four liquids of widely differing viscosities were produced by means of air-lift through 1%-in. tubing in a 1,500-ft. experimental well. The purpose of these tests was to determine the effect of liquid viscosity on two-phase flowing pressure gradients. The experimental test well was equipped with two gas-lift valves and four Maihak electronic pressure transmitters as well as instruments to accurately measure the liquid production, air injection rate, temperatures, and surface pressures. The tests were conducted for liquid flow rates ranging from 30 to 1,680 BID at gas-liquid ratios from 0 to 3,-270 scf/bbl. From these data, accurate pressure-depth traverses have been constructed for a wide range of test conditions. As a result of these tests, it is concluded that viscous effects are negligible for liquid viscosities less than 12 cp, but must be taken into account when the liquid viscosity is greater than this value. A correlation based on the method proposed by Poettmann and Carpenter and extended by Fan-cher and Brown has been developed for 1¼-in. tubing, which accounts for the effects of liquid viscosity where these effects are important. INTRODUCTION Numerous attempts have been made to determine the effect of viscosity in two-phase vertical flow. Previous attempts have all utilized laboratory experimeneal models of relatively short length. One of the initial investigators of viscous effects was Uren1 with later work being done by Moore et al.2,3 and more recently by Ros.4 However, the present investigation represents the fist attempt to study the influence of liquid viscosity on the pressure gradients occurring in two-phase vertical flow through a 1¼-in., 1,500 ft vertical tube. The approach of some authors has been to assume that all vertical two-phase flow occurs in a highly turbulent manner with the result that viscous effects are negligible. This has been a logical approach since most practical oil-well flow problems have liquid flow rates and gas-liquid ratios of such magnitudes that both phases will be in turbulent flow. It has also been noted, however, that in cases where this assumption has been made, serious discrepancies occur when the resulting correlation is applied to low production wells or wells producing very viscous crudes. Both conditions suggest that perhaps viscous effects may be the cause of these discrepancies. In the first case, the increased energy losses may be due to increased slippage between the gas and liquid phases as the liquid viscosity increases. This is contrary to what one might expect from Stokes law of friction,' but the same observations were made by ROS4 who attributed this behavior to the velocity distribution in the liquid as affected by the presence of the pipe wall. In the second case, the increased energy losses may be due to increased friction within the liquid itself as a result of the higher viscosities. The problem of determining the li- quid viscosity at which viscous effects becomes significant is a difficult one. Ros4 has indicated that liquid viscosity has no noticeable effect on the pressure gradient so long as it remains less than 6 cstk. Our tests have shown that viscous effects are practically negligible for liquid viscosities less than approximately 12 cp. Actually there is no single viscosity at which these effects become important. These effects are not only a function of the viscosities of the liquids and of the gas but are also a function of the velocities of the two phases. The velocities in turn are a function of the in situ gas-liquid ratio and liquid flow rate. Furthermore, the role of fluid viscosities in either slippage or friction losses will depend on the mechanism of flow of the gas and liquid, i.e., whether the flow is annular. as a mist, or as bubbles of gas through the liquid. These mechanisms are also a function of the in situ gas-liquid ratios and the flow rates. It would thus seem that the best one could hope for is to determine a transition region wherein the viscous effects may become significant for gas-liquid ratios and liquid production rates normally encountered in the field. The viscous effects might then be neglected for liquid viscosities less than those in the transition region but would have to be taken into account when higher viscosities are encountered. There are numerous instances where crude oils of high viscosity must be produced. The purpose of this study has been to evaluate the effects of liquid viscosities on twephase vertical flow by producing four liquids of widely differing viscosities through a 1 % -in. tube by means of air-lift. The approach used in this study was as follows:

Jan 1, 1965

By M. R. Yalamanchili, J. D. Miller

Discussion by M.R. Yalamanchili and J.D. Miller The authors, M. S. Celik et al., should be recognized for their efforts to describe the flotation behavior of boron minerals. In the case of borax and other soluble salt minerals, analysis of the flotation chemistry has been difficult because of the high ionic strengths associated with these soluble salt systems. However, considerable progress has been made in this area, and recently a surface charge/collector colloid adsorption model was proposed by Miller and his coworkers to explain the collector adsorption phenomena observed in soluble salt flotation systems (Milleret al, 1992; Yalamanchili et al., 1993; Miller and Yalamanchili, 1994; Yalamanchili and Miller, 1994a: Yalamanchili and Miller, 1994b). In this work, the sign of the surface charge of alkali halides in their saturated brines was established on the basis of nonequilibrium electrophoretic mobility measurements by laser-Doppler electrophoresis (Miller et al., 1992). Generally, these results are what would be expected from the simplified lattice-ionhydration theory. This electrokinetic information coupled with the stability and prevalence of collector colloids in such soluble salt flotation systems indicates that the selective flotation of alkali halides is due to the adsorption of oppositely charged collector colloids by heterocoagulation. Experimental flotation/bubble attachment results for 21 different alkali halides (Yalamanchili et al., 1993; Yalamanchili and Miller, I994b) confirmed that the flotation response of soluble salt minerals with weak electrolyte collectors can best be explained by the adsorption of oppositely charged collector colloids rather than by the adsorption collector ions and/or neutral molecular dipoles as originally suggested by many researchers (Fuerstenau and Fuerstenau, 1957; Schubert, 1967; Roman et al., 1968). In addition, the flotation of certain alkali oxyanions (Pizarro et al., 1993) and double salts such as schoenite and kainite can be explained by the same collector colloid adsorption mechanism (Miller and Yalamanchili, 1994). The borax flotation results reported by Celik et al. need to be examined in terms of the above mentioned surface charge/ collector colloid adsorption model. Unfortunately, the authors seem to be unaware of this recent work that nicely describes soluble salt flotation with weak electrolyte type collectors such as amines and carboxylates. In view of our past work, the flotation characteristics of borax were of particular interest, and, in this regard, the results of dodecyl amine flotation of borax reported by Celik et al. have been examined in further detail in the light of experimental results from our laboratory. In our research, a vacuum flotation technique was used to study the flotation response of borax (Na2B407.10H20), which has a solubility of 39 g/L at 25 °C) with dodecyl amine hydrochloride as collector. These chemicals were purchased from Eastman Kodak and used as received. Saturated solutions of borax at desired pH values were prepared by continuously stirring the salt solutions over a period of about 10 hrs. It should be mentioned that the conditioning time to achieve equilibrium is an important variable and can significantly change the flotation response of some soluble salts (Yalamanchili et al., 1993). Collector was added to the saturated borax solutions containing about one gram of 100x 150 mesh borax particles, and conditioning was done for about 20 minutes prior to flotation. The borax flotation recoveries from saturated brine are presented in Fig. 1 as a function of collector addition at the natural pH of 9.3, as reported both by Celik et al. and as measured in our laboratory. In addition, the region of precipitation for the dodecyl amine hydroborate is included in Fig. 1. It can be seen in Fig. 1 that the flotation response curves are separated by about one order of magnitude in R12NH3CI collector addition. The flotation results of Celik et al. show that the maximum borax recoveries can be obtained below the solubility limit of the dodecyl amine hydroborate collector. However, in our experiments borax flotation seems to occur only after the precipitation of the dodecyl amine hydroborate collector as might be expected from the collector colloid adsorption model (Yalamanchili et al., 1993) if borax were negatively charged. Further analysis by nonequilibrium and equilibrium electrophoretic mobility measurements for borax indicates that borax is negatively charged at the natural pH of 9.3, as discussed below. The reliability of the nonequilibrium electrophoretic measurements has been demonstrated previously for alkali halides and alkali oxyanions (Miller et al., 1992; Miller and Yalamanchili, 1994). The equilibrium and nonequlibrium electrophoretic measurements for borax were found to be consistent and are presented in Table 1. These results provide clear evidence that borax carries a negative surface charge in its saturated brine (pH 9.3), and the sign of the surface charge of borax reverses and becomes positive if the pH is reduced to 8.6. The equilibrium between borax and its saturated brine can be described by the following reaction: [2Na2B407.1OH2O-4Na++B407=+HB4O7 +OH+19H20] It appears that the oxyanions of the borax lattice provide

Jan 1, 1995

By John Henderson

FOR some time now the most commonly accepted description of liquid silicate structure has been the "discrete ion" theory, proposed originally by Bockris and owe.' This theory is that when certain metal oxides and silica are melted together, the continuous three dimensional silica lattice is broken down into large anionic groups, such as sheets, chains, and rings, to form a liquid containing these complex anions and simple cations. Each composition is characterized by "an equilibrium mixture of two or more of the discrete ions",' and increasing metal oxide content causes a decrease in ion size. The implication is, and this implication has received tacit approval from subsequent workers, that these anions are rigid structures and that once formed they are quite stable. The discrete ion theory has been found to fit the results of the great majority of structural studies, but in a few areas it is not entirely satisfactory. For example it does not explain clearly the effect of temperature on melt structure,3 nor does it allow for free oxygen ions over wide composition ranges, the occurrence of which has been postulated to explain sulfur4 and water5 solubility in liquid silicates. In lime-silica-alumina melts the discrete ion theory is even less satisfactory, and in particular the apparent difference in the mechanism of transport of calcium in electrical conduction8 and self-diffusion,' and the mechanism of the self-diffusion of oxygen8 are very difficult to explain on this basis. By looking at melt structure in a slightly different way, however, a model emerges that does not pose these problems. It has been suggested5" that at each composition in a liquid silicate, there is a distribution of anion sizes; thus the dominant anionic species might be Si3,O9 but as well as these anions the melt may contain say sis0:i anions. Decreasing silica content and increasing temperature are said9 to reduce the size of the dominant species. Taking this concept further, it is now suggested that these complexes are not the rigid, stable entities originally envisaged, but rather that they exist on a time-average basis. In this way large groups are continually decaying to smaller groups and small groups reforming to larger groups. The most complete transport data 8-10 available are for a melt containing 40 wt pct CaO, 40 wt pct SiO2, and 20 wt pct Al2O3. Recalculating this composition in terms of ion fractions and bearing in mind the relative sizes of the constituent ions, Table I, it seems reasonable to regard this liquid as almost close packed oxygens, containing the other ions interstitially, in which regions of local order exist. On this basis, all oxygen positions are equivalent and, since an oxygen is always adjacent to other oxygens, its diffusion occurs by successive small movements, in a cooperative manner, in accord with modern liquid theories." Silicon diffusion is much less favorable, firstly because there are fewer positions into which it can move and secondly, because it has the rather rigid restriction that it always tends to be co-ordinated with four oxygens. Silicon self-diffusion is therefore probably best regarded as being effected by the decay and reformation of anionic groups or, in other words, by the redistribution of regions of local order. Calcium self-diffusion should occur more readily than silicon, because its co-ordination requirements are not as stringent, but not as readily as oxygen, because there are fewer positions into which it can move. There is the further restriction that electrical neutrality must be maintained, hence calcium diffusion should be regarded as the process providing for electrical neutrality in the redistribution of regions of local order. That is, silicon and calcium self-diffusion occur, basically, by the same process. Aluminum self-diffusivity should be somewhere between calcium and silicon because, for reasons discussed elsewhere,' part of the aluminum is equivalent to calcium and part equivalent to silicon. Consider now self-diffusion as a rate process. The simplest equation is: D = Do exp (-E/RT) [I] This equation can be restated in much more explicit forms but neither the accuracy of the available data, nor the present state of knowledge of rate theory as applied to liquids justifies any degree of sophistication. Nevertheless the terms of Eq. [I] do have significance;12 Do is related, however loose this relationship may be, to the frequency with which reacting species are in favorable positions to diffuse, and E is an indication of the energy barrier that must be overcome to allow diffusion to proceed. For the 40 wt pct CaO, 40 wt pct SiO2, 20 wt pct Al2O3, melt, the apparent activation energies for self-diffusion of calcium, silicon, and aluminum are not significantly different from 70 kcal per mole of diffusate,' in agreement with the postulate that these elements diffuse by the same process. For oxygen self-diffusion E is about 85 kcal per mole,' again in agreement with the idea that oxygen is transported,

Jan 1, 1963

By E. R. Russell, N. E. Richards

The current ejyiciency of aluminum cells was derived from the metal produced over a period of time and the theoretical faradaic yield. The difference in the actual amount of aluminum in the cathode at the beginning and end of the period must be determined. The weight of aluminum in the cathode was calculated from the dilution of an added quantity of impurity metal. Use of multiple indicator metals, copper, manganese, and titanium, demonstrated that the weight of aluminum in cells can be determined to within 1 pct with routine but careful chemical analyses. Over intervals of the order of 30 days, current efficiencies reliable to within 1 pct can be obtained. INVESTIGATIONS beginning with those of Pearson and waddington ,' through the most recent published work of Georgievskii,9-11 illustrate the direct relationship between the composition of the anode gas and the applicability of analysis of anode gases to the control of alumina reduction cells. McMinn12 noted the lack of an independent method for measuring cell production efficiency over the short term. There is no doubt that changes in the current efficiency are immediately reflected in the composition of anode gases. However, the accuracy of faradaic yields calculated from gas analyses depends upon the degree of interaction between primary anode gas and Carbon.6 A conventional industrial practice of obtaining long-term current efficiency for production units from mass balances and quantity of electricity is generally insensitive to the impact of planned control of any one or more of the influential reduction cell parameters such as temperature, alumina concentration, and mean interelectrode distance. Consequently, there is a real need in the aluminum industry for a procedure to obtain the absolute cell current efficiency over a short term—10 to 30 days—both for the calibration of values obtained from gas analysis6 and for evaluating the effect of controlling specific parameters in the reduction process. The amount of aluminum produced may be determined by considering the cathode pool as a reduction of an impurity metal in aluminum. Analyses over a period will show a decreasing concentration of the impurity due to the accumulation of aluminum solvent. The increase in aluminum inferred from analyses is the amount produced by the cell during the period. Combining weights of the cell aluminum in the cathode at the beginning and end of a specific period, weights of aluminum tapped and the quantity of electricity passed during the interval will yield the current efficiency. Smart,I3 Lange;4 Rempel,15 Beletskii and Mashovets,16 and winkhaus17 have used dilution techniques to determine aluminum inventory in alumina reduction cells. A technique for determining the weight of aluminum in production cells by addition of small amounts of copper to the aluminum cathode was described by smart.13 The precision in values of the aluminum reservoir through dilution of copper in the cathode ranged from about 1 to 3 pct depending upon the quantity of copper added in the range 0.2 to 0.01 wt pct, respectively. Because the method appears so direct and apparently simple, one would not anticipate difficulties in application to industrial cells. The objective of this study was to resolve this problem associated with the trace metal dilution technique for determining the amount of aluminum in a cell. The approach in evaluating trace metal dilution as a basic factor in determining the weight of aluminum in the cell reservoir, and the absolute current efficiency of the Hall-Heroult cell, was to dilute more than one trace metal in the aluminum cathode so that we could discriminate among complications arising from physical mixing, the possibility of separation of intermetallic compounds, loss of the added elements, and chemical detection. EXPERIMENTAL METHODS These experiments are not complex but require standardized procedures. The technique involves addition of the trace metals to the cathode, knowing when these metals are homogeneously distributed in the liquid cathode, timing of the sampling, employing accurate and precise analytical methods, using reliable procedures for monitoring the amount of electricity passed through the cell, and accurate weighing of aluminum removed from the cell during the particular period. More accurate results might be obtained if the increment in concentration of the added indicator metals were of the order of 0.1 to 0.2 wt pct. The method must be applicable to production units and, hence, the contamination of the aluminum minimized. For this reason, the concentration of trace metals in the cathode was kept below 0.07 wt pct and generally at 0.04 wt pct level. Trace quantities of copper, manganese, titanium, and silicon are already present in virgin aluminum and are suitable as additives from electrochemical and analytical points of view. Concentration of silicon is quite dependent upon the characteristics of the raw materials and was not used extensively in this work. Chemical Analyses. All instrumental analyses require calibration against an absolute technique such as a gravimetric, volumetric, or spectrophotometric method which represents the ultimate in sensitivity, precision, and accuracy. On review, the best methods for copper appeared to be optical absorption without

Jan 1, 1969

By Ian M. Loomis, Keith G. Wallace

The Waste Isolation Pilot Plant (WIPP) is a U.S. Department of Energy research and development facility designed to demonstrate the permanent, safe disposal of U.S. defense-generated transuranic waste. The waste storage horizon is 655 m (2150 ft) below surface in bedded salt. To date the WIPP project has not emplaced any waste. There are three intake shafts used to supply air to the underground. All air is exhausted though a single return shaft. The total design airflow during normal operations is 200 m3/s (424,000 cfm). The ventilation system is designed to provide separate air splits to construction, experimental, and storage activities. Separation is achieved by isolating the storage circuit from the construction or experimental circuits with bulkheads. Any air leakage must be towards the storage area of the facility. Field studies have shown that the pressure differential necessary to maintain the correct leakage direction is susceptible to the effects of natural ventilation; therefore, extensive studies and analyses have been conducted to quantity the natural ventilation effects on the WIPP underground airflow system. A component of this work is a monitoring system designed to measure the air properties necessary for calculation of the natural ventilation pressure (NVP). This monitoring system consists of measuring dry bulb temperature, relative humidity, and barometric pressure at strategic locations on surface and underground. The psychrometric parameters of the air are measured every fifteen minutes. From these data, trends can be determined showing the impact of NVP on the ventilation system during diurnal variations in surface climate. Both summer and winter conditions have been studied. To the author's knowledge this is the first reported instance of automatic and continuous production of time and temperature variant NVPs. This paper describes the results of the initial monitoring study. INTRODUCTION The ventilation system at the Waste Isolation Pilot Plant (WIPP) in Carlsbad, New Mexico, is designed to perform two distinct functions. First, it supports normal mine ventilation requirements complying with all state and federal mine regulations. Second, the system is designed to prevent an uncontrolled release of radioactive contaminants from the storage and transportation areas of the facility. Although a nuclear radiation release in the facility is considered unlikely, many special features are implemented in the ventilation system to prevent the possible spread of contamination. The facility is constructed with the waste transportation and storage areas separated from the mining and non-radioactive experimental areas. The ventilation system is designed such that air leakage is from the mining and experimental areas to the storage areas. Furthermore, radiation detectors are located throughout the storage and waste transportation areas underground and an exhaust filtration building is installed on surface to prevent the possible release of radiation to the environment. For over two years the underground ventilation system has been rigorously tested and balanced. It was during this period that the adverse effects of NVP were noticed and subsequently quantified. From extensive field studies and computer models, several mitigating features were designed and constructed and special operational procedures were implemented to control the impacts of NVP. To quantify more accurately the NVP at the WIPP, a continuous monitoring system was installed. This monitoring system consists of measuring dry bulb temperature, relative humidity, and barometric pressure every fifteen minutes at strategic locations on surface and underground. From this psychrometric data, the NVP is calculated. Fan operating pressures and flows and strategic differential pressures are recorded from the site Continuous Monitoring System (CMS). The monitoring system provides a means of evaluating how the ventilation system behaves in regard to climatic conditions and to judge the efficacy of the mitigating features and operational procedures. To the author's knowledge, continuous calculation of NVP as a function of time and surface temperature has not been previously reported. Overview of the Waste Isolation Pilot Plant The U.S. Department of Energy determined that the plastic nature of bedded salt may provide the best solution to isolate transuranic (TRU) waste from the biosphere. Initial evaluations at the WIPP site began in 1974. In 1979, the United States Congress enacted Public Law 96-164 for the construction and development of the WIPP project. The mission of the WIPP is to demonstrate the safe, long-term disposal of TRU waste generated by the national defense programs of the United States. TRU waste is classified as a low to medium level waste. The waste is stored in drums and does not produce significant heat (not greater than 1 W per drum). The WIPP site is located approximately 47 km (29 miles) east of Carlsbad, New Mexico in the Chihuahuan Desert. The repository is located in the 630 m (2000 ft) thick Salado Formation. This Permian Basin salt deposit is about 225 million years old and appears to have been minimally disturbed by earthquake, faulting, and ground water activity since it was deposited. The underground facility is 660 m

Jan 1, 1993

By Willard L. Hunter

Four solvent extraction systems were studied to determine their efficiency jor extraction and separation of tantalum and columbium. Aqueous feed solutions of varying HF-HCl concentrations and metal content were contacted with equal volumes of cyclohexanone, 3-methyl-2-butanone, and 2-pentanone and solutions of varying HF-H2S04 concentrations were contacted with equal volumes of 2-pentanone. One multistage continuous test was made in a polyethylene pulse column using cy clohexanone as the organic phase. In each system studied, columbium and tantalum purities in excess of 95 pct with respect to each other were obtained in single-stage tests at low acidities in the feed solution. Separation factors ranging from 1700 to 2400 were obtained when rising HF-HCl mixtures in the aqueous phase. Best results were obtained when a solution of HF-H2S04 was used as the aqueous phase and 2-pentanone as the organic phase. A separation factor in excess of 6000 was obtained in one stage with aqueous solution concentrations of 2 _N HF and 2N H2S0,. When acid concentrations were increaszd to 52 HF and 10 _N H2S0,, 99.9 pct of the tantalum and 98.2 pct of the columbium initially present in the feed solution were transferred to the organic phase. The separation of columnbium and tantalum obtainable by means of the solvent extraction systems presented in this paper was found to corn -pare favorably with other systems, including the HF-H2SO4-methyl isobutyl ketone system currently used by most producers for the extraction and separation of these metals. TANTALUM and columbium are always found together in minerals of commercial significance, although the proportion of the two metals in ores varies within broad limits. Columbium is estimated to be 13 times more abundant than tantalum. Five methods generally employed for the separat:ion of these metals are: 1) fractional crystallization (the Marignac process),2 2) solvent separation, 3) fractional distillation of their chlorides, 4) ion exchange, and 5) selective reduction. Of these methods, the one currently used by industry to the greatest extent is that of solvent separation. One of the early technical developments in solvent separation of tantalum from columbium was reported by the Bureau of Mines: the HF-HC1-methyl isobutyl ketone system; data were presented for both laboratory and pilot-plant experimentation.3 Of twenty-eight organic solvents tested for their ability to extract tantalum from an HF-HC1 solution of columbium and tantalum, 3-pentanone (diethyl ke-tone), cyclohexanone, 2-pentanone, and 3-methyl-2-butanone were chosen for further study. Data on the HF-HC1-diethyl ketone system has been published4 and data describing the use of cy clohexanone, 2-pentanone, and 3-methyl-2-butanone as the organic phase are included in this report. RAW MATERIAL The source of tantalum and columbium oxides for this study was ('Geomines" tin slag from the Manono Smelter, Cie Geomines, Gelges, S.A., Congo. In order to extract the valuable Ta-Cb content, the slags were carbided, chlorinated, and the sublimate from chlo-rination was hydrolized and washed free of chloride with water. The washed material was air-dried and stored in a stoppered container. Throughout the paper, "feed material" refers to this mixture of hydrated oxides which was employed because of its high solubility in aqueous solutions. Typical analysis of the hydrated oxides is shown in Table I. I) HF-HC1-CYCLOHEXANONE SYSTEM Batch Separation. Effect of Acid Concentration. To determine the effect of varying the acid concentration upon the transfer of tantalum and columbium, a series of tests was made in which approximately 2.5 g of feed material was added to 25 ml solutions of 2, 4, 6, 8, and 10 N HF and 0 through 5 N HC1. Tantalum pentoxide concentration of the solu%ons was approximately 21 g per liter and columbium pentoxide was 14 g per liter. These starting solutions were shaken with equal volumes of cyclohexanone in 100 ml polyethylene bottles for 30 min. The phases were carefully separated in 125 ml glass separatory funnels. The time of contact of the solutions with the separatory funnels was kept at a minimum to reduce silica contamination. The measured phases were separated into 400 ml polyethylene beakers and the metal contents of each were precipitated by addition of an excess of ammonium hydroxide. Precipitate from each phase was filtered on ashless filter paper, ignited at 800" to 1000°C for 45 min, weighed, and analyzed by X-ray fluorescence.5 Data tabulated in Table I1 and illustrated in Fig. 1, show that maximum separation of tantalum from columbium for each HF concentration was obtained with no HCl present. The purest tantalum product was obtained with some HCl present. The highest separation factor was obtained at 2 N HF and

Jan 1, 1970