Search Documents

By A. Steiner, K. L. Komarek

Activities of aluminum in solid Ni-A1 alloys have been determined between 20 and 60 at. pet Al and 1200" and 1400°K by an isopiestic method in which nickel specimens, heated in a temperature gradient, are equilibrated with aluminum vabor in a closed all-alumina system. The activity of aluminum shows a strong negative deviation from Raoult's law at low concentrations but increases by three orders of magnitude within the ß(NiAl) phase. The partial molar enthalpy and entropy of mixing are negative. Using Wagner and Schottky's theory of ordered compounds, a degree of disorder of 4 x 10 -4 for NiAl and 1.25 X 10-2 for FeAl has been calculated THE Ni-A1 system has been studied by a great number of investigators, and the results, as far as the phase diagram is concerned, have been compiled by Hansen.1 The phase boundaries from 0 to 50 at. pet Ni are well-established. At higher nickel contents the boundaries are still in dispute and an additional phase, A12Ni3, has been reported.' The phase diagram is dominated by a very stable high-melting compound, NiA1, with a relatively wide range of homogeneity. Heats of formation of solid alloys have been determined calorimetrically by Oelsen and Middel3 from 20 to 95 at. pet Ni and by Kubaschewski4 from 25 to 80 at. pet Ni. According to the most recent compilation5 no other thermodynamic investigations have been reported for the Ni-A1 system. Due to the corrosive nature and the low vapor pressure of aluminum, a method has been employed for determining activities of aluminum which was previously developed for the Fe-A1 system.= Nickel specimens, heated in a closed evacuated alumina system in a temperature gradient, were equilibrated with aluminum vapor from a source within the system kept at constant temperature. After complete equilibration the specimens were analyzed and activities calculated from the known vapor pressure of aluminum. APPARATUS AND EXPERIMENTAL PROCEDURE Materials. The nickel specimens were made from wafers of electrolytic nickel (International Nickel Corp.) of 99.99 pet purity which were rolled to a 0.001-in.-thick foil by Driver-Harris Co. and to a 0.005-in.-thick sheet in our laboratory. The aluminum (Aluminum Corp. of America) had a purity of 99.99+ pct. The alumina tubes and crucibles were made of impervious recrystallized alumina with an alumina content of 99.7 pet (Triangle RR, Mor-ganite Inc.). Experimental Procedure. Annular specimens were punched from the sheet, the punching burrs removed, and the specimens degreased in carbon tetrachloride and acetone and weighed on a micro-balance to within an accuracy of ±0.01 mg. The specimens were positioned with alumina spacers along an alumina tube, and the positions measured. Aluminum metal was machined into cylindrical shape, and placed into an alumina crucible. The tube with the specimens was then inserted into a hole drilled into the aluminum metal. An alumina tube with its closed end at the top was slipped over the specimens so that its lower end fitted snugly into the alumina crucible. The assembled reaction tube was inserted into a mullite tube with a water-cooled brass head which had an opening for a quartz thermocouple protection tube and a metal-to-glass connection to a conventional vacuum system. A Pt-Pt 10 pet Rh thermocouple could be raised and lowered in the quartz tube which was placed along the outside of the alumina reaction tube. The mullite tube was heated by two separately controlled resistance-tube furnaces so that in the experimental temperature range an over-all temperature gradient of approximately 150o to 250°C could be imposed on the reaction tube. The position of the mullite tube was adjusted so that the surface of the aluminum metal was always at the temperature minimum. The reaction tube was thoroughly evacuated before and during slowly heating the assembly up to the melting point of aluminum. A pressure of less than 2 µ (Hg) was maintained during an experiment. Once the aluminum had melted, it isolated the contents of the alumina tube from the surroundings. Several times during an experiment the temperature gradient was carefully measured. An experiment lasted from 3 to 6 weeks and it was terminated by air cooling the evacuated mullite tube. For further details of the experimental procedure the paper on the Fe-A1 system6 should be consulted.

Jan 1, 1964

By Reaves. M. J.

The title of my talk, "What Happened to the Uranium Boom?" is old news. Certainly it is for this group. All of us that make our living in uranium know that the boom of the last half of the 1970's is over. U.S. production has been exceeding consumption by more than two to one. Mines and mills are closing and yellowcake prices have been dropping for over 20 months. The gloomy outlook for the industry in the near term has been well documented by soothsayers of various descriptions, your daily newspapers, and in the Nuexco Monthly Reports. I'd like to attempt to describe the next upturn in the market (speculate, really) based upon the clues we're seeing now. In order to do that, I'd first like to go over briefly, some of the market factors that contributed to the recent price drop and resultant production cutbacks, and then hypothesize on the way these factors are changing and will change. Market prices are greatly affected (maybe even entirely determined) by buyer perceptions. This is particularly true with uranium, because of the long lead times associated with nuclear plant construction and also with conventional mine/mill development. Before the price rise (say, 1975) utility uranium buyers believed that: 1) U.S. producers would have difficulty expanding to meet U.S. demand. 2) Australian and Canadian production was essential to avoid shortages in the early 1980's. 3) Uranlum prices would continue to rise as demand exceeded supply. 4) Enrichment capacity would become inadequate. It was thought necessary, therefore, to build enriched inventory in the early 1980's for use in the late 1980's. Artificially accelerated expansion of the uranium producer industry was necessary to accommodate anticipated enrichment demand. Current perceptions are largely the opposite. These are the beliefs that were held most of this year and late last year as prices dropped. 1) U.S. production is far in excess of domestic need. Contraction of the U.S. production lndustry is necessary. 2) Canadian and Australian supply is optional and not essential. Producers in those countries are expanding mainly by displacing higher cost production and not because they fill a void, 3) Prices may be essentially stable for some time. 4) Enriched uranium is in excess supply. That is 1981. 1982 is shaping up to look like this: 1) Prices will have bottomed out. (That is not Nuexco's opinion necessarily, by the way, but it is my opinion.) 2) There will still be substantial utility inventories, but fewer spot sales. 3) Canadian and perhaps Australian sellers will have made substantial sales in the U.S. and will be aggressively seeking more. 4) U.S. production will have been dramatically curtailed. U.S. utilities that wish to con- tract long term will have difficulty in finding domestic sellers. Concern will develop about the availability of U.S. production capability. Virtually all long term con- tracts signed will be with non-U.S. sellers. 5) An awareness will begin to develop among U.S. buyers that we are approaching a period of dependence upon foreign uranium (which will be true). The history of the uranium market has been one of dramatic changes and overreaction to those changes. The rapid price rise of a few years ago generated excess U.S. production capacity and the rapid price drop of the last two years will almost certainly result in too little capacity. It will soon be difficult for U.S. buyers to buy domestic material except on the spot market. The question is, "will they care?" The lack of demand, of course, is the underlying reason for the current poor health of the uranium industry. In 1972, 1973 and 1974 collectively, there were 105 nuclear reactors ordered in the U.S. That ordering rate was expected to continue and accelerate throughout this century. In 1975, 1976, 1977, 1978, 1979, and 1980 altogether, there were 56 more reactors cancelled than ordered. The net growth of our only customer since 1974 has been a negative 56. TO put this in perspective, if these 56 reactors were operating now it would more than double present U.S. uranium consumption. Underlying lack of demand is something that is simply not going to change in this decade. Time is going to be required. The NRC indicates that the maximum feasible number of new reactors that can be licensed each year is six. That would increase uranium consumption by only 10% per year. New reactors, if ordered tomorrow, would not generate new uranium demand until after 1990. Even so, United States' consumption of uranium will rise from the 1980 level of 18 million pounds per year, to

Jan 1, 1982

By A. P. Svenningsen

IN the early stages of design it was not considered necessary that separate crushing plants be built for the new sulphide concentrator and smelter until sometime in the future. The plan was to use the existing crushing facilities for both oxide and sulphide ore. A few additions were contemplated for the existing plants, such as increased bin capacity, and possibly two new secondary crushing units. The more the problem was studied and discussed with the plant operators, the more it became evident that it was complex. It involved the classification of different kinds of ore from the open pit mine -sulphide, oxide and mixed-and how best to separate them so that each kind of ore was given the proper processing and treatment. It also involved the problem of keeping the different ores from being contaminated in bins, hoppers and chutes. Added to these, transportation became complicated and would involve additional handling and loading of ore from crushing plants to conveyors, to bins, and finally to railroad cars which were to be hauled to the concentrator and dumped into the fine ore bin. General In the early part of 1951 it was decided that the concentrator be constructed with ten grinding units instead of seven as originally authorized. The smelter was to be increased proportionally and naturally also the overall tonnages of ore to be handled by the new sulphide plant. Due to this increase in plant capacity and the larger tonnages involved, the difficulties which would arise by using the existing crushing plants were increased to a point where it became evident that the building of new crushing plants for sulphide ore exclusively was technically, as well as economically, advantageous. Authorization was, therefore, given by the company to construct new crushing plants to handle 30,000 tons of ore per day, and capable of reducing the run-of-open-pit ore to the proper size feed for the 10x14-ft rod mills in the concentrator. The ore, mined in the open pit, sometimes comes in pieces as large as 6 to 7 ft diam. The rod mills may call for ore crushed to 3/4 in. The large .size of ore delivered from the open pit determined that a 60-in. gyratory crusher be used as primary breaker. Such a crusher will have a capacity considerably in excess of 30,000 tons per day. The crusher will be a single discharge unit driven by a 500-hp electric motor through a tear coupling and a floating shaft. This type of drive has proven successful at a number of other crusher installations which our company has operating in the United States, Mexico and South America. The tear coupling will protect both the crusher and motor against damage in case of overload. No new features are incorporated in the design of the crusher itself, except that the, discharge chute is made the full width of the crusher with parallel sides instead of the usual converging sides. This change in detail should eliminate, a feature which has been a bottleneck in some of the operating plants and has caused loss of production due to ore hanging up and blocking the chute. The secondary crushing plants will have three 7-ft standard Symons cone crushers and six 7-ft short head Symons crushers. Between the primary and secondary crushing plants a coarse ore bin will be constructed with a nominal draw-off capacity of 30,000 tons of ore. The standard Symons and the short head Symons will be in separate buildings. All the crushing plants and the coarse ore bin are interconnected with conveyor belts for transporting the ore to the crushers at the tonnage rate desired. The final product of the new crushing plants is produced by the short head crushers. It will be delivered onto a conveyor belt leading to the top of the fines ore bin in the concentrator. A separate conveyor belt running the full length of the fines ore bin and provided with a movable tripper of rugged design will discharge the sulphide ore into the bin. The concentrator bin is planned and designed so that the installation of this additional conveyor will not interfere with the operation of the two railroad tracks on which crushed ore is brought from the existing oxide plant. Thus when completed the bin can be filled simultaneously by ore from the new crushing plant and by ore from the existing leaching plant.

Jan 1, 1952

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook's work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By Jean Howard

RECENT attempts to produce secondary recrystalli-zation in high-purity iron have given conflicting results. Coulomb and Lacombe1'2 did not find it but Dunn and Walter3,4 did. The latter workers have stated that (100) [001] and/or (110) [001] orientations develop depending on the oxygen content of the annealing atmosphere. This Technical Note records results which are in agreement with Dunn and Walter in so far as it shows that secondary recrystallization can be produced in high-purity iron, but does not confirm that both types of orientation are obtainable. Similar observations have been made on chromium-iron and molybdenum-iron, although when this technique is used on 3 1/4 pct Si-Fe, both types are obtained as in the work of Dunn and alter.' Pure iron strip was cold-rolled from sintered compacts prepared from Carbonyl Iron Powder-Grade MCP of the International Nickel Co. (Mond) Ltd. The powder contains about 0.5 pct 0, 0.01 pct C, 0.004 pct N, (0.002 pct S, $0.005 pct Mg and Si, and 0.4 pct Ni—that is, it is substantially free from metallic impurities other than nickel, which is thought to be unimportant in the present work. The iron powder was (a) pressed at 25 tons per sq in. into blocks measuring 3 by 1 by 0.3 in., (b) deoxidized in hydrogen (dewpoint -60°C) by heating first at 350°C and then at 600° C until the dewpoint returned to -60°C at each temperature and (c) sintered in hydrogen (dewpoint -40°C) at 1350°C for 24 hr. (when dewpoint is referred to in this Note, it is the value as measured on the exit side of the furnace). The sintered compacts were cold-rolled to 1/8 in., annealed in hydrogen (dewpoint -60°C) at 1050°C for 12 hr and cold-rolled to 0.004, 0.002, and 0.001 in. with inter-anneals at 900°C for 5 hr and a final reduction of 50 pct. Final annealing of strip between alumina or silica plates at 875" to 900°C in hydrogen with dewpoints of -20°, -55" and -80°C produced secondary grains with the (100) in the rolling plane; the extent of secondary recrystallization was greatest when the dewpoint was -55°C. Annealing in a vacuum of 2 x 10"5 mm Hg at the same temperature produced no secondary recrystallization at all. With strip thicker than 0.002 in. very few secondary crystals developed whatever the conditions of annealing. Using a processing schedule somewhat similar to that described above, secondary recrystallization was produced in two bcc alloys of iron, viz. 80 pct Fe + 20 pct Cr and 96 pct Fe + 4 pct Mo. The former was reduced to final thicknesses of 0.001 to 0.004 in. and the latter to final thicknesses of 0.001 to 0.016 in. With the chromium-iron, a final anneal at 1250°C (found to be the most effective temperature for developing secondary crystals in the 0.004-in material) with a dewpoint of -25°C produced a greater degree of secondary recrystallization than with dewpoints of -50°C or -20°C. Secondary crystals developed in strips of all thicknesses from 0.001 to 0.004 in. Final annealing in vacuum produced no secondary crystals at all. For the molybdenum-iron a temperature of 1200°C was most effective. It was found that a dewpoint of -50°C during the final anneal gave better results than a dewpoint of -25 "C on the 0.008 in. material. Final annealing in vacuum gave slightly worse results than annealing in hydrogen with a dew-point of -50°C. Secondary crystals were developed in strips of all thicknesses up to 0.008 in. The experiments show that the extent of secondary recrystallization is a maximum for certain critical values of oxygen content of furnace atmosphere and annealing temperature, and that these values are different for different alloys. The thinner the material, the less critical these values are. The general conclusions are that secondary recrystallization can be obtained in high-purity iron, chromium-iron, and molybdenum-iron, using a processing schedule similar to that which will cause the phenomenon to take place in high purity 3 1/4 pct Si-Fe. Unlike the silicon-iron, however, only the (100) (0011-- orientation has been produced in these alloys, irrespective of the temperature of final annealing and the oxygen content of the furnace atmosphere. The information used in this Note is published by permission of the Engineer-in-Chief of the British Post Office.

Jan 1, 1962

By M. D. Arnold, H. J. Gonzalez, P. B. Crawford

A method is presented for estimating the effective directional permeability ratio and the direction of maximum and minimum permeabilities in anisotropic oil reservoirs. The method is based on the principle that production from a well in an anisotropic reservoir results in elliptical isopo-tentials about the well, rather than circular. Bottom-hole pressure data from three observation wells surrounding a producing well are required to apply the method. The method involves fitting field pressure data to a set of general charts of isopotentials and making a few simple calculations until a solution is found. The method is based on a steady-state equation for homogeneorrs fluid pow. In addition to the method, a brief discussion of the theory underlying it is presented. INTRODUCTION The existence of a different permeability in one direction than another in oil reservoirs has been mentioned in several papers. Hutchinson' reported laboratory tests on 10 limestone cores and pointed out that one-half of them showed significant, preferential, directional permeability ratios, the average being about 16:1. Johnson and Hughesz reported a permeability trend in the Bradford field in the northeast-southwest direction with flow being 25 to 30 per cent greater in that direction. Barfield, Jordan and Moore -eported an effective permeability ratio of 144:1 in the Spraberry. Crawford and Landrum4 showed that sweep efficiencies could often vary by a factor of two to four, and sometimes considerably more, due to variations in flooding direction and patterns in anisotropic media. These findings indicate that the poss'bility of anisotropy may be worthy of consideration in the development of an oil field. In considering this, it should first be determined if anisotropy exists. If it does, the direction of the maximum and minimum permeabilities and the ratio of their magnitudes are quantities which can be of value in planning the most efficient well-spacing patterns. Past methods of determining these quantities have included analysis of oriented cores and analysis of flooding performance of pilot injection patterns. In recent work, Elkins and Skov5 resented an analysis of the pressure behavior in the Spraberry which accounted for anisotropic permeability. This work was based on the transient pres- sure distribution in a porous and permeable medium, with the solution expressed as an exponential integral function involving rock and fluid properties. The purpose of this study is to provide a method, based on steady-state equations, of estimating the direction and relative magnitude of permeabilities in an oil reservoir from field pressure data and well locations only. The method presented is based on work by Muskat6 which shows that Laplace's equation represents the steady-state pressure distribution for homogeneous fluid flow in homogeneous, anisotropic media if the co-ordinates of the system are shrunk or expanded by replacing x with it is desirable that data be obtained early in the history of a field because knowledge of an anisotropic condition would allow new wells to be spaced in such a manner that reservoir development and subsequent secondary recovery programs could be planned more efficiently. THEORETICAL CONSIDERATIONS A brief discussion of the theoretical basis on which the graphical solution was developed is presented in this section. Muskat's two-dimensional6 olution for the pressure distribution in an homogeneous, anisotropic medium with an homogeneous fluid flowing can be algebraically manipulated to show that the isobaric lines are perfect ellipses. The ratio of the major axis to the minor axis, a/b, is related to the permeability ratio, k,/k,, as follows. alb = dk,/k,--...........(1) It can also be shown that the pressure varies linearly with the logarithm of the radial distance from the producing well. However, the gradient along any ray is a function of the orientation of that ray, and a ..xiable is present when anisotropy exists which cancels out for a radial (isotropic) system. For a system such as that described, a dimensionless pressure-drop ratio was developed which is completely independent of the actual magnitude of the pressures. This was done by arranging Muskat's solution in such a way that aIl variables cancelled out except k,/k, and well positions. However, this solution depends on having a co-ordinate system with axes coinciding with the major and minor axes of the elliptical isobars. Thus, it was necessary to introduce a co-ordinate system rotation factor. The two unknown variables are then k,/k. and 0, and the two measured dimensionless pressure-drop ratios are related to the unknown variables as follows.

By G. P. Tiwari

Recrystallization and grain growth in thoria dispersed nickel and nichrome were recently studied by Webster as a function of temperature and deformation. The unexpected part of these results was that specimens which had received heavier deformation developed greater resistance to recrystallization. Retardation of recrystallization was accompanied by the formation of voids around thoria dispersion. To explain these results, Webster suggested that the formation of void around the particles increased the effective size of thoria particles. This resulted in greater impediment to the grain-boundary migration and as a consequence the recrystallization of the matrix is retarded. In the present note an alternative and more probable explanation for the effect of voids on recrystallization is presented. The exact mechanism of void formation in thoria dispersed nickel or nichrome is not known. However, it is reasonably certain that it must be preceded by the stress concentration in the matrix around thoria dispersion during the deformation.'' The resulting stress concentration must be sufficient enough to supply the surface energy for the new surfaces created. Further, the decrease in the strain energy of the matrix surrounding the potential void nucleus must be larger than the surface energy of the newly created surface. The release of strain energy due to formation of crack results in a strain free cylinder of the material around the voids.13 If the void formation is not localized, at few points only (as is the case here), this process may lead to considerable amount of release of strain energy of the matrix. The pattern of recrystallization behavior of single phase homogeneous matrix as well as the matrix having a second phase dispersion is same except for the fact recovery and recrystallization are more clearly delineated.14 In general, the recrystallization temperature is lowered (i.e., recrystallization is easier) with increase in the amount of cold work. This is due to the increase in stored energy in the matrix with increasing amount of deformation. If somehow there is a relaxation of strain energy in the matrix, the recrystallization should become difficult because of the decrease in the amount of stored energy available for recrystallization. Since the formation of voids leads to a decrease in the strain energy of matrix, the recrystallization of the matrix would be inhibited due to the formation of voids during deformation prior to recrystallization. It has been observed by earlier workers15'16 that the presence of preexisting voids in a matrix retards the recrystallization. The essential issue here is how do the voids act to produce this effect. If the voids influence recrystallization only by blocking the grain boundary migration, then the effect should be maximum when they are present almost exclusively along grain boundary. These conditions are obtained during high temperature deformation. However, the voids produced due to creep along grain boundary are not able to prevent recrystallization17 suggesting that they are not effective in blocking grain boundary movement. Recently it was shown by Davies and Williams that the voids can act as sinks for vacancies." As a result the processes dependent on vacancy diffusion like recovery, recrystallization, dislocation climb, and so forth, will be hindered. This fact may be responsible for inhibition of recrystallization during subsequent deformation and annealing cycles. It is to be noted here that there is a large difference between the density of voids in creep experiments and the other experiments where retarding effect of voids on recrystallization is seen. The voids in former may number up to l04 to l05 per sq cm whereas in latter cases the voids density is typically around 1010 to 1013 per sq cm. It appears that the decrease in supply of vacancies in creep is insufficient to adversely affect the recrystallization due to low void population. The author is grateful to P. Das Gupta and S. P. Ray for helpful discussions. Author's Reply D. Webster Tiwari appears to have misunderstood the nature of grain boundary-particle interactions. Tiwari (quoting Cahn) states that second phase particles become more effective as they become smaller, therefore as the voids in TDNiC make the thoria particles effectively bigger their ability to resist grain boundary movement is impaired. This particle size argument was originally proposed in the form of an equation by Zener 20 years agol9 and is not necessarily valid as is discussed below. However, assuming it is valid, it predicts a greater boundary restraining effect by smaller particles simply because their combined cross sectional area is greater at a constant volume. If the number of particles remains the same and their effective size increases, as in the present case, Zener's equation predicts a greatly reduced grain size. This is because the effect

Jan 1, 1970

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.' The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.' Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By D. A. Dukelow, K. Li, G. C. Smith

Decarburization in the Fe-C system by oxygen top blowing has been studied in laboratory -scale experiments. It is shown that equilibrium models fail to explain or predict either the course of refining or endpoint conditions, giving results which either are incompatible with the chemistry of the system or do not satisfy material balance requirements. Also the path of decarburization was found to vary even for heats made under apparently identica1 conditions. A promising approach to analyzing the decarburization results is to relate oxygen efficiency fm carbon removal to bath carbon content. This relationship for Fe-C heats shows the same range of oxygen efficiencies as is obtained in pilot-plant and commercial heats using hot metal-scrap charges. This implies that oxygen transfer is primarily controlled by the decarburization reaction itself, independent of other refining reactions. Therefore, it should be possible to study separately decarburization and slag-metal reactions. DECARBURIZATION is probably the most important reaction in steelmaking. Not only is it a main reaction in the refining of iron to steel but it also provides the stirring action in the bath necessary for the diffusion processes to proceed at reasonable rates so as to make a steelmaking process practical. Kinetics of decarburization in the open-hearth process has been a subject of investigation for many years.&apos;-B It is generally accepted that at steelmaking temperatures the rate of homogeneous C-0 reaction is extremely high and cannot constitute a rate-controlling step. Diffusion of oxygen through a boundary film in the metal phase has been suggested by arken&apos; as rate-determining. Recently, Larsen and sordah16 concluded from experiments in a laboratory furnace that, with oxygen supplied from air or combustion gases, the rate of "steady-state" carbon boil is controlled essentially by a diffusion process of O2, Co2, or H2O through a film of nitrogen above the slag surface. Displacing this diffusion film by a stream of nearly pure oxygen produced a ten-fold increase in the rate of carbon boil with the rates of slag-metal oxygen transfer, bubble nucle-ation, and other steps all apparently able to keep pace. In the top-blown basic oxygen process, however, the transport of oxygen takes a more direct route. and the state of bath agitation is much more turbulent than in the open-hearth process. In addition, direct contact of the gas with the metal phase provides opportunity for direct oxidation of carbon. It is likely that the rate-limiting factor for the decarburization reaction will be different. However, only a few descriptive discussions of the subject have been reported in the literature.10-l2 Studies of the decarburization kinetics based on plant or pilot-plant data are necessarily complicated and are influenced by other refining reactions which occur simultaneously. In order to investigate the mechanism of decarburization, experiments have been conducted in which carbon-saturated iron melts were top-blown with pure oxygen over a range of conditions. It is hoped that this study will form a foundation on which a more basic understanding of this important reaction may be built. EXPERIMENTS One group of blowing experiments was made in a standard 200-lb induction furnace and another group in a 500-lb induction furnace. The furnaces were modified to the general shape of a basic oxygen furnace by adding a rammed refractory cone section to the regular crucible body. Crucible and cone were of high MgO (95 pct) material. A water-cooled lance, 1/2 in. in diam and threaded at one end to take a nozzle, was used for blowing oxygen. The lance with its water and oxygen lines was supported on a cantilever arrangement so that it could be moved up, down, or sideways. Oxygen of 99.5 pct purity was supplied from a cylinder and metered through a rotameter equipped with pressure and temperature gages. Another pressure gage was located at the top of the lance. A schematic diagram of the assembly is shown in Fig. 1. Before each experiment, a weighed amount of ingot iron, containing 0.02 pct C, < 0.01 pct Si, 0.10 pct Mn, 0.019 pct P, and 0.015 pct S, was charged in the furnace and melted down by induction heating. Graphite was then added to the molten charge until it became saturated. When the temperature of the charge reached the desired level, the lance was lowered to a predetermined height above the bath

Jan 1, 1964

By G. A. Swanquist, E. M. Morales

INTRODUCTION The idea of water management and control at the Church Rock Mill operations began to take shape in February 1979. At that time, we were already investigating the feasibility of decreasing the fresh water requirements so that the solids would become the limiting factor in tailings impoundment utilization. The area for solution evaporation could be kept at a fraction of the normal requirements under the standard process of full water usage. The Church Rock Mill is an acid leach circuit followed by solids/liquid separation with thickeners in counter current decantation, and solvent extraction. Following the normal design of acid leach circuits, reuse of tailings solution was not incorporated in the original mill process design. INITIAL WATER CONTROL INVESTIGATIONS The investigations to decrease the fresh water requirements centered around modifying the grinding circuit from the present semi-autogenous grinding (SAG) mill in closed circuit with hydrocyclones, to open circuit grinding with a rod mill. The open circuit grinding with the SAG mill and rod mill in series had the potential of decreasing the water requirements for grinding and leach dilution by approximately 50% or 1.4 m3/min (300 gpm). The grinding pulp density would be maintained at 70 to 72% solids, and the leach dilution to 50% solids would be accomplished with acid tailings liquor recycle. In such a grinding circuit arrangement, the SAG mill would provide the primary or coarse grind, and the rod mill would be used for the fine grind. By the SAG mill and rod mill series grinding method of water control and other secondary water controls in various places downstream from the grinding circuit, the required necessary evaporation area was estimated at 120 acres of liquid surface. A second method of water control at grinding was investigated. A two-stage cyclone classification circuit appeared to have a good potential of achieving the same water reduction at a much lower capital and operating cost. However, in retrospect, this would not have been a viable method since a high slime recycle load would have been established hindering classification. The use of reagents to neutralize the acid tailings solution was not considered seriously at that time, since it would have materially increased operating costs, although it would have also allowed more tailings solution recycle and consequently, less fresh water usage. However, with the tailings solution deposition area available at that time, it was not then necessary to incur the high cost of neutralization. The control expected by the series grinding of semiautogenous and rod mills would have been sufficient to maintain a water consumption/evaporation equilibrium well in line with the available land area. IMPLEMENTATION OF NEUTRALIZATION OPERATIONS During the summer of 1979, the UNC Church Rock Mill experienced a tailings dam breach which resulted in a prolonged mill shutdown. Upon resumption of operations at the end of October 1979, tailings deposition was restricted to a small portion of the tailings impoundment area. Figure 1 shows the general tailings area and the limits of the present deposition area in the central part including the borrow pits. These borrow pits had been excavated to provide materials for tailings dam construction. Immediately after resumption of operations, it became evident that it would be necessary to control the quantity of liquid to be evaporated because of the small confined area available for tailings solution deposition and to maximize the deposition time in the tailings area. The water control required had to be exercised on a large scale, and to be in operation as quickly as possible. An obvious solution was to reuse the tailings liquor in mill process. Immediate steps were taken to install the necessary equipment for tailings neutralization on an interim basis. Anhydrous ammonia was selected as the primary neutralization reagent since it was the quickest system that could be placed in operation. Previous laboratory tests indicated fair results with ammonia neutralization. Such a system required a minimum of installed equipment and handling. INITIAL NEUTRALIZATION OPERATIONS Actual neutralization operations began on November 26, 1979. The raffinate solution which normally would have been discarded was pumped to a 3.7 m (12ft) diam by 4.3 m (14ft) tank for reagent contact, see Figure 2. At this tank, anhydrous ammonia was added directly from the tanker trailers and controlled at pH 7.0 nominally. Agitation was provided by air sparging. The neutralized product formed a highly viscous slurry in the grinding circuit which resulted in pumping and cyclone classification problems.

Jan 1, 1982

By T. A. Read, M. S. Wechsler, D. S. Lieberman

A theoretical analysis of the austenite-martensite transformation is presented which predicts the habit plane, orientation relationships, and macroscopic distortions from a knowledge only of the crystal structures of the initial and final phases. THIS paper presents a new theory of the formation of martensite. This theory makes possible the calculation of the austenite planes on which the martensite plates form, the orientation relationship between the austenite and martensite crystal axes, and the macroscopic distortions which are observed. The only input data needed are the crystal structures and lattice parameters of the austenite and martensite. Considerable effort has been devoted over the past thirty years to the development of an understanding of the crystallographic features of martensite reactions. Much of this work has been done on steels and iron-nickel alloys, for which a great deal of data has been accumulated concerning the shape and orientation of the martensite plates, the relative orientations of the austenite and martensite crystal axes, and the observable distortions which result from transformation. These observations are reviewed in refs. 1, 2, and 3. The first major step toward an understanding of these phenomena was made in 1924 by Bain,&apos; who showed that the a body-centered cubic structure can be produced from the 7 face-centered cubic structure by a contraction of about 17 pct in the direction of one of the austenite cube axes and an expansion of 12 pct in all directions perpendicular to it. Since that time, most of the efforts at further interpretation have been made by investigators who have worked from the phenomenological data, incorporating some of the information from the lattice properties, and have sought an analysis into likely deformations which would produce the observed results."- "11 but the three most recent papers on the subject have already been reviewed in some detail." Machlin and Cohenl0 measured the components of the distortion matrix and verified that the habit plane is a plane of zero distortion and rotation for the (259) case. They showed that the measured distortion matrix, when applied to the parent lattice, does not yield the product lattice and hence some inhomogeneous distortion must occur. Frank,u working from the lattice properties and taking some clues from the observations, considered the correspondence of close-packed rows and planes in the austenite and martensite. He predicted substantially the observed lattice relationship and habit plane for certain steels which have a (225) habit. Geisler12 suggested that there is a natural tendency for the habit plane to be a (111) and postulated certain slip processes to account for the fact that the experimentally observed habit plane is irrational and deviates from the assumed one. The present work differs from previous treatments of martensite formation in that it permits calculation of all the major manifestations of the process. Habit plane indices, orientation relationships, and observable distortions are all calculated from a knowledge of the crystal structures of the initial and final phases alone. The calculations contain no adjustable parameters. The agreement found between calculated results and the observations reported in the literature constitutes powerful evidence in favor of the mechanism of martensite formation proposed. The theory is applicable to systems other than steel (as is discussed later in this paper) which exhibit a diffusionless phase change but because of the wide-spread interest in the austenite-martensite transformation, particular attention will be given to the iron-base alloys. For other systems which undergo a similar face-centered cubic to face-centered tetragonal transformation, the mathematical treatment is identical with that presented here. Hence the theory successfully describes the transformation in the indium-thallium alloy.&apos;" Homogeneous Transformation to Martensite The distortion which any homogeneously transforming volume of austenite undergoes in order to become martensite is shown in Fig. 1, as was first suggested by Bain.&apos; (This distortion will hereafter be referred to as the "Bain distortion.") This specification of a contraction along one cube axis ;ombined with an expansion in all directions perpendicular to this axis describes what is properly called the "pure" distortion associated with this transformation. The distinction between a "pure" and an "impure" distortion plays an important part in the discussion which follows. A "pure" distortion is characterized by the existence of at least one set of orthogonal axes fixed in the body which are not rotated by the distortion. (These are called the "principal axes" of the distortion.) No such set of axes exists in the case of an "impure" distortion. On the other hand, an impure distortion can always be represented as the result of a pure distortion combined with the rotation of the specimen as a rigid body. For a given impure distortion the corresponding pure distortion

Jan 1, 1954

By N. S. Stoloff, K. R. Jordan

The temperatwe and grain size dependence of the mechanical avoperties of ordered and disordered Fe-49 pct Co-2 Pct V were investigated. The yield and flow stresses obeyed the Hall-Petch relationship u = ai + kd-&apos;I2. Ohdering reduced the intercept stress cjj and raised the Petch slope, k, at all temperatures. Ordering also increased the temperatwe dependence of k. The ductile to brittle transition temperature increased with order and grair~ size. Cleavage fracture was nucleation limited and the fracture stress did not zlary linearly with d-&apos;". A quantitative test of the Cottrell-Petch fracture theory (and recent modifications which consider the influence of slip mode), demonstvated that this theory is not applicable to FeCo-V. COTTRELL&apos; and etch&apos; independently suggested that a criterion for cleavage failure at the yield point, a,, based on dislocation pileups at a grain boundary or other obstacle to dislocat.ion motion, is: aYYkd&apos;I2 1 opy [ll or, equivalently, aikz,d112 +k:)bpy [2] where a, and ky are the Hall-Petch intercept and slope, respectively, 2d is the grain diameter, P is a geometric factor dependent on the macroscopic ratio between shear and tensile stress, p is the shear modulus, and y is the true elastic surface energy. When the product of quantities on the left side of the equation is equal to or exceeds that on the right, cracks should be able to nucleate and propagate at the yield stress, as shown schematically in Fig. 1. Therefore a high intercept stress, high Petch slope, or coarse grain size favors brittleness. petch3 associated the existence of a ductile to brittle transition in ferrous alloys with the temperature dependence of ai. One of the earliest modifications of the Cottrell-Petch theory was presented by ~rmstrong,~ who derived an expression for transition temperature in terms of several measurable flow and fracture parameters. The latter paper was able to rationalize situations in which the transition temperature increases with decl-easing grain size, as in the case of molybdenum,&apos; and also suggested that Ppy should be a function of grain size as well as temperature. More recently Johnston et a1.6 and Smith and worthington7 have suggested that the temperature or composition dependence ol&apos; ky must also be taken into account if there is any cha.nge in deformation mode, as from wavy to planar slip, or wavy slip to twinning, with change in temperature or solute content. Armstrong %as suggested that for hcp metals changes in o;k,dw> o;k,d1/2< / is / ^^^^ / / y_______________________________________ d-"2 Fig. l—Schematic representation of grain size dependence of yield stress, cry, and fracture stress, CTF. Intersection defined by Cottrell-Petch equation. slip mode should be incorporated in the theory through changes in the critical resolved shear stress for the slip system which controls ky. The purpose of the present investigation was to critically test the modified677 Cottrell-Petch theory of fracture in the superlattice alloy Fe-49 pct Co-2 pct V, by studying the grain size dependence of the yield and fracture stresses over a range of temperatures, in conjunction with an investigation of slip mode and fracture behavior. Previous work has shown that long range order results in a sharp decrease in flow stress, a small increase in work hardening rate and a drastic upward shift in the ductile-brittle transition temperature of F~CO-V.~&apos;~ The only comprehensive study of slip character in this alloy has been reported in a preliminary account of the present investigation.10 EXPERIMENTAL PROCEDURE The experimental work was carried out on material produced from a 10 lb vacuum melted ingot, of composition 49.32 wt pct Co, 2.09 wt pct V, balance Fe. 30-mil thick sheet samples with a 1; in. gage section were machined from cold rolled stock. The degree of cold work ranged from 85 pct for the finest grained samples to 5 pct for the coarsest grain size. Details of ingot fabrication are reported elsewhere." Equi-axed grain sizes in the range 12.7 to 75.4 p were obtained by annealing for varying times at 850°C. (Re-crystallization annealing time, rather than temperature , was varied to control grain size to insure that samples of all grain sizes contained equivalent quenched-in vacancy and interstitial concentrations.) Grain sizes were measured by the line intercept method on several specimens of each grain size. Following recrystallization, all samples were disordered by quenching into iced brine.

Jan 1, 1970

By A. U. Seybolt

The solubility limit of oxygen in columbium has been determined in the range between 775&apos; and 1100°C by means of lattice parameter measurements and microscopic examination. The solubility is a function of temperature and varies, in the range given above, from 0.25 to 1.0 pct O, respectively. BECAUSE of the marked deleterious effect of oxygen upon the mechanical properties of some of the transition metals, it is desirable to know something about the solubility of oxygen in these metals. The brittleness caused by oxygen in solution is particularly marked in the case of the group VA elements, vanadium, columbium, and tantalum. The solubility of oxygen in vanadium has already been reported in an earlier paper,&apos; and Wasilewski2 has given a value (0.9 wt pct) for the solid solubility of oxygen in tantalum at 1050°C. Brauer3 in 1941 investigated the Cb-0 system up to Cb2O5, but made no real effort to investigate the extent of oxygen solubility in the metal. He made the observation, however, that this solubility must be less than 4.76 atom pct (0.86 wt pct) oxygen. This estimate was made from X-ray diffraction results on the alloys CbO, CbO, and CbO; all alloys consisted of the terminal (Cb) solid solution plus CbO, but the last alloy containing 4.76 atom pct 0 showed only three very weak CbO lines. It is surprising that Brauer, by examining only three alloys, arrived at an estimate of the solubility which agrees very well with the results to be reported herein. Experimental Procedure A columbium strip obtained from Fansteel Metallurgical Products was cut into strips, 0.020x1/2x2 in. Two holes, about 3/16 in. in diameter, were made near the ends of the strips in order to hold them against a flat steel block for mounting in a General Electric X-ray spectrometer for lattice parameter measurements. The same holes were used to hang the specimens inside a fused silica vacuum furnace tube which was part of a Sieverts&apos; gas absorption apparatus. The apparatus and method of adding oxygen gas has been previously described.1 According to the supplier, the columbium obtained had the analysis given in Table I. After degreasing the samples, approximately 0.001 in. was etched from each side of the samples in order to remove possible surface impurities from the last rolling operation. For this purpose the following cold acid pickle was found satisfactory: 8 parts HNO3, 2 parts H2O2 and 1 part HF. Various Cb-O compositions were obtained up to 0.75 wt pct O by the gas absorption and diffusion technique. After the sample had absorbed all the oxygen gas added at 1000°C, an additional 24 hr was allowed for homogenization. This treatment appeared to be adequate, as shown by the linearity of the lattice parameter-composition plot. More concentrated alloys were prepared by arc melting mixtures of Cb and Cb2O5 since it was very time-consuming to make Cb-0 alloys in the neighborhood of 1 pct O, or over, by the diffusion method. When the flat strip specimens were used, they were ready for the X-ray spectrometer after cooling from the Sieverts&apos; apparatus. The cooling rate obtained by merely allowing the hot fused silica furnace tube to radiate to the atmosphere (when the furnace was lowered) was sufficiently fast to keep the dissolved oxygen in solution. Arc-melted alloys were reduced to —200 mesh powder in a diamond mortar, wrapped in tantalum foil, sealed off in evacuated fused silica tubes, and then heat treated as indicated in Table 11. The fused silica tubes were quickly immersed in cold water without breaking the tubes after the heat treatments. The tantalum foil prevented reaction between the fused silica and the sample; there was no reaction between the powdered samples and the foil at 1000°C, but some trouble was experienced at 1100°C. At this temperature level a reaction between the sample and the foil was sometimes observed, which resulted in erroneous parameter values. Experimental Results Hardness Tests: Since most of the X-ray samples were in the form of flat strip, it was convenient to obtain Vickers hardness numbers as a function of oxygen content. Compared to the V-O case,&apos; oxygen hardens columbium much more slowly, presumably because of the larger octahedral volume in colum-bium (about 12.0 compared to 9.3Å3 in vanadium), hence, requiring less lattice strain for solution. The plot of VHN vs wt pct O is shown in Fig. 1.

Jan 1, 1955

By H. C. Gatos, J. T. A. Pollock

It is well known that the superconducting critical current densities of many alloy superconductors may be increased by cold working and in some cases further enhanced by a short heat treatment. This latter enhancement has been attributed to the redistribution of dislocations into cell-like networks&apos; and to the precipitation of second phase particles,2&apos;3 which act as flux pinning centers. In a manner analogous to dislocation pinning in precipitation hardening alloys,4 it is expected that here also a critical distribution of the pinning centers should result in maximum pinning effect. Concentration inhomogeneities exist in most or all commercial alloys yet there have been only a few attempts made to determine their effect on critical current capacity in the absence of cold working. Sutton and Baker,5 and Kramer and Rhodes6 have found that the complex precipitation processes occurring during the aging of Ti-Nb alloys can result in critical current density enhancement. Livingston7-10 has clearly shown, for lead and indium based alloys, that the distribution of precipitated second phase particles is of critical importance in determining magnetization characteristics. However, these &apos;(soft" alloys age at room temperature and the time involved in specimen preparation prevents metallographic examination in the state in which the superconducting measurements are made. Thus results with such alloys are expected to be biased towards larger precipitates and interpar-ticle spacing. The present study of Ta-Zr alloys was undertaken to examine the influence of second phase precipitation, as controlled by heat treatment, on the critical current capacity of well annealed polycrystalline material. A study of the published phase diagram11 indicated that annealing supersaturated samples containing up to 9 at. pct Zr at suitable temperatures would result in the precipitation of a zirconium-rich second phase. It was MATERIALS AND PROCEDURE The alloys were prepared from spectrochemically pure tantalum and zirconium. Analysis was carried out by the supplier. Major impurities in the tantalum were: 12 pprn of 02, 17 pprn of N2, 19 pprn of C, and less than 10 ppm each of Mo, Nb, Al, Cr, Ni, Si, Ti. The crystal bar zirconium was pure except for the following concentrations: 15 pprn of 02, 17 ppm of C, 23 ppm of Fe, 11 ppm of Cu, and less than 10 pprn each of Al, Ca, N2, Ti, and Sn. Samples were prepared in the form of 8 to 10 g but-tons by arc melting using a nonconsumable electrode on a water-cooled copper hearth in a high purity ar-gon atmosphere. Each button was inverted and re-melted three times to ensure an even distribution of the component elements. The samples were then homogenized at temperatures close to their melting points for 3 days in a vacuum furnace maintained at 5 x 10-7 mm Hg. After this treatment the buttons were cold rolled to sheets approximately 0.020 in. thick from which specimens were cut, 0.040 in, wide and 1 in. long suitable for critical current density (J,) and critical temperature (T,) measurements. These strips were then recrystallized and further grain growth was allowed by an additional vacuum heat treatment at 1800°C for 60 hr. Some second phase precipitation occurred during cooling of the furnace and a solution treatment was necessary to produce single phase supersaturated samples. This treatment was successfully carried out by sealing the samples together with some zirconium chips in quartz tubes under a vacuum of 5 x 10-7 mm Hg, heating at 1000°C for 5 hr and then quenching into water or liquid nitrogen. The samples were then heat treated at either 350" or 550°C and quenched into water or liquid nitrogen. All samples which were heat treated at 350°C were quenched in both cases by cracking the capsules in liquid nitrogen. The samples treated at 550°C were quenched by dropping the capsules into water. Analysis for oxygen in randomly selected samples indicated that the oxygen content was in the range of 175 to 225 ppm. Values of Tc were determined by employing a self-inductance technique. Jc measurements were made at 4.2oK by increasing the direct current through the wire in a perpendicularly applied field until a voltage of 1 pv was detected with a null meter. The risk of resistive heating at the soldered joints during these latter measurements was reduced by first plating the ends of the wires with indium and then soldering to the copper current leads using tin. Metallographic examinations were performed after mechanical polishing of the same samples and etching in a 4H20:3HN03 (conc):lHF(conc) solution.

Jan 1, 1970

By D. W. Lillie

It has been demonstrated that considerable bend ductility exists in bulk specimens of polycrystalline high-purity silicon. The possibility of hot-forming at 1200°C is suggested. EXCELLENT corrosion resistance in many media and low cross section for absorption of thermal neutrons (0.13 barn) would make silicon of interest to nuclear engineers were it not for extreme brittle-ness and the difficulty of fabrication by any reasonable means. The use of silicon for structural purposes also has been considered in view of its light weight and oxidation resistance. Johnson and Han-sen&apos; have investigated the properties of silicon-base alloys and concluded that there was no way of making pure silicon or silicon-rich alloys ductile at room temperature. In view of reports of appreciable ductility in germanium single crystals above 550°C&apos;." and some plastic deformation in single-crystal silicon above 900oC,&apos; the present investigation was undertaken to define more precisely the limits of high-temperature ductility in pure silicon. After this investigation was begun torsion ductility in both germanium and silicon was reported by Greiner." Through the courtesy of F. H. Horn, a small bar of cast extra high-purity silicon was obtained and small bend specimens were made from it by careful machining and grinding. All of the reported tests results were obtained from samples from this bar (bar No. 1) and one other of similar source (bar No. 2). No complete analysis was obtained but, based on analysis of similar semi-conductor grade material, metallic impurities were under 0.01 pct total. Vacuum-fusion analysis for oxygen showed a value of 0.0018 2 0.0003 pct for the first bar tested and metallographic analysis showed no evidence of a second phase. Bend tests were carried out on an Instron tensile machine using a bend fixture with a 1 -in. span loaded at the center. Supporting and loading bars were 0.250 in. round and the load was applied by downward motion of the pulling crosshead of the machine. Specimen thickness and width were approximately 0.10 in. and % in. respectively. Loading rate was controlled by holding crosshead motion constant at 0.02 ipm. In some cases a smaller specimen was used on a 5/8-in. span with a 0.129-in.-diam loading bar. The entire bend fixture was surrounded by a hinged furnace and all heating was done in air atmosphere. Temperature measurement was made with thermocouples fastened directly to the bend fixture within less than 1 in. from the specimen. Autographic stress-strain curves were recorded during each test, and breaking load, total deflection, and plastic strain could be obtained from these curves. Stress was calculated from the beam formula S = 3PL/2bh2, where P is the load in pounds, L the span in inches, b the specimen width in inches, and h the specimen thickness in inches. This formula is strictly correct only in the elastic range but has been used to calculate a nominal stress for convenience in the plastic range. The stress given is the maximum stress in the specimen. Results The results of the complete series of tests are shown in Table I. The first group of tests (specimens Nos. 1-6) showed the beginning of plastic flow at a test temperature of 900°C, so two additional tests (Nos. 8 and 9) were made at 950°C on small-size specimens from bar No. 2. Specimen No. 8 was tested in the as-machined condition, and No. 9 was heat-treated in hydrogen at 1300°C for 2 hr, cooled to 1200°C and held 1 hr, cooled to 1000°C and held 1 hr, cooled to 900°C and held 1 hr, and finally cooled to a low temperature before removal from the hydrogen. It is apparent that the heat-treatment had a significant effect on yield strength and ductility. In addition, the magnitude of the yield point was conslderably reduced in the heat-treated specimen as is shown m Fig. 1 by tracings of the stress-strain curves. After obtaining a furnace capable of reaching higher temperatures specimens Nos. 10 to 13 were tested at 1100 and 1200°C. Strain rate was increased by up to a factor of 10 to see whether the ductility observed was excessively strain sensitive. Specimen NO. 10, strained at 0.02 ipm and 1100oC, was still bending at a deflection of 0.322 in. when the load rate was increased to 0.2 ipm, resulting in immediate

Jan 1, 1959

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.&apos; The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.&apos; Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By E. F. Thomas

THE late George S. Rice was active in the inves--I- tigation of bumps, particularly in the last ten years of his career as chief mining engineer of the U. S. Bureau of Mines. Since most of his investigation was carried out in Great Britain, continental Europe, and—to a lesser extent—Canada, his thinking on prevention was influenced considerably by the experience of those countries. It is not surprising, therefore, that when he was called upon a few years before his retirement to investigate bumps in the U. S. and suggest ways to prevent them, he turned to longwall mining. A longwall method had been most successful in combating the bump hazard in mining coal under deep cover, especially in Great Britain, but the prevailing method there at the time was advancing longwall mining, which he knew was uneconomical under U. S. mining conditions. For this reason he proposed a modified retreating longwall system that he believed included the best features of the advancing method. As brought out by Rice,&apos; if the cover is 2000 ft and 50 pct of the coal is extracted, the static load on the remaining pillars will be about 4000 psi, which exceeds the ultimate crushing strength in most instances. If the pillar coal is overloaded before a pillar line is established, then the abutment zone preceding a line of extraction is no place to split pillars or extract them by any method other than an open-end system. Rice therefore advocated open-end mining, preferably by longwall, but he was willing to compromise with long-face mining if the longwall method was not acceptable. Rice&apos;s system was put into operation in a mine in Harlan County, Kentucky,3 but subsequent experience has shown that it did not take into account two important factors—avoidance of pillar-line points and maintenance of adequate development in advance of the pillar-line abutment area. For ten years after Rice&apos;s retirement the USBM did little investigation and research on bumps, chiefly because so few were occurring that there was not much cause for alarm. But in 1951 there were three occurrences involving fatal injuries, and the Bureau began a statistical survey in that year. C. T. Holland, head of the department of mines at Virginia Polytechnic Institute, was retained as a consultant. The resulting study&apos; of 117 case histories brought out these important conclusions: 1) Almost invariably the bump occurred in a locality affected by the abutment zones of one or more pillar lines. 2) In most cases the locality of the bump was influenced by the abutment zones of more than one pillar line. The term pillar-line point has been used for many years in the Appalachian region for such a situation. Point is used in the geographical rather than the mathematical sense. 3) In pillar-line extraction the following practices are safest in preventing bumps: a. The mine layout should provide for pillars of uniform size and shape along the extraction line. b. The mine layout should be planned so that no development need be done in the abutment zone of a pillar line. c. The layout should permit open-end extraction of pillar lines from the next goaf, so that it will not be necessary to resort to pocket mining, splitting pillars, or any practice that will involve driving in the direction of the goaf within the abutment zone. d. Pillars should be large enough to support area without undue roof and floor convergence before establishment of a pillar line. These are, of course, generalities, and while they are useful in laying out areas where bumps can be expected, they are of limited help in many mines that were committed to a system of mining before it was realized that they were subject to bumps. Under such conditions it becomes necessary to choose between the following alternatives: 1) Abandon the territory, except for pillars that offer no extraction problems. 2) Through experience select the pillars that are most heavily loaded, and, by augering, induce bumps from a safe vantage point so that impinged loads are relieved. This method was first developed at the Gary, W. Va. mines of U. S. Steel Corp. and later adapted to mining thick coal beds at Kaiser Steel&apos;s Sunnyside mine in Utah. No scientific method is available to determine where to drill within a loaded pillar. Although this method of unloading has worked very successfully at Gary—with one exception—

Jan 1, 1959

By G. M. Willis, F. L. Hennessy

The oxygen pressure in equilibrium with silver and Ag2O-B2O3 melts has been measured between 800&apos; and 900°C, to obtain the thermodynamic properties of the liquid. The compound Ag20. 4B20:1 appears to exist in the liquid, which shows marked heat content and entropy effects. A KNOWLEDGE of the thermodynamic properties of binary liquid silicates, borates, and phosphates would be of considerable assistance in the interpretation of the behavior of multi-component metallurgical slags. However, the literature contains comparatively few studies of the thermodynamics of binary slags. The system Ag20-B,O, attracted our attention as it was known to give a single liquid phase,&apos;,&apos; in which high contents of silver could be obtained (up to 61 pct Ag according to Foex2). Further, it would be expected that the partial pressure of oxygen over melts in equilibrium with metallic silver could be used to determine the activity of Ag2O in the Ag,O-B,O, system. In many respects, it may be expected that the reaction of a basic oxide with boric oxide would be analogous to its reaction with silica. Liquid immiscibility frequently occurs in both borate and silicate systems. With B2O3 and SiO reaction with a basic oxide presumably involves a breakdown of the three-dimensional network of the acid oxide by reaction with oxygen atoms common to more than one silicon or boron atom. Ag2O-B2O3 was therefore investigated as a model of a slag system in the hope that its thermodynamic properties would assist in understanding those of other systems. Several methods for determining the activity of a component in a slag have been described in the literature. Chang and Derge" used high temperature electromotive force measurements to obtain the activity of SiO2 in CaO-SiO2 and Ca0-Al203-Si02 slags, but the cell reaction in their work is not clear. low has used rate of volatilization and vapor pressure measurements combined with phase diagrams to obtain activities in the systems KO-SiO,, Na,O-SiO, and Li,O-SiO," and PbO-SiO26 Taylor and Chipman7 extrapolated their results for the distribution of FeO between liquid iron and CaO (+Mg0)-FeO-SiOl slags to obtain the activity of FeO in the binary FeO-SiO2 system. In principle, one of the most direct methods for obtaining the activity of a metallic oxide in a phase is by comparison of the equilibrium oxygen pressure for the system metal-pure oxide with that of metal oxide-containing phase. Schenck and othersa have studied the stabilization of Ag2O on combination with other oxides (MO,) in the solid state by measurements of the oxygen pressure in systems of the type Ag-Ag,O-xM0,-MOy-0, (gas). Schuhmann and Ensio" have determined the activity of FeO in iron silicate slags in equilibrium with solid iron, using CO/CO2 mixtures to establish known partial pressure of oxygen. Although the method gives the activity of FeO without ambiguity, the slag is not a binary system, and interpretation of the results in terms of the hypothetical binary system FeO-SiO, is not possible. If a metal is solid at temperatures at which the properties of the slag containing its oxide are to be studied, this method has the considerable experimental advantage that the metal can be used as the container for the slag, and contamination by contact with refractories is avoided. In this work, crucibles for Ag2-B,O, melts were made from silver, and the liquid brought to equilibrium with definite pressures of oxygen gas. The oxygen pressure PO, thus fixes the activity of Ag20 in the liquid silver borate. For the reaction at a given temperature. is substantially constant, is directly proportional to the square root of the equilibrium oxygen pressure. Varying the oxygen pressure changed the silver oxide content of the liquid and it was possible to obtain the activity of Ag2O over a range of composition. Experimental Procedure In principle, the method consisted of bringing melts in silver crucibles or boats to equilibrium at a fixed temperature under a definite pressure of oxygen and analyzing the glass after solidification. Materials: B2O3 glass was prepared from A.R. quality boric acid by fusion in platinum. The silver

Jan 1, 1954

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,&apos; and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,&apos; the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,&apos; who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By H. L. Bilhartz, H. F. Dunlap, C. R. Bailey, Ellis Shuler

Data are presented which indicate that the saturation exponent, n, in the equation, R. = R100S-11, relating core resistivity, I:,. to the resistivity at 100 per cent saturation. R100. and to the saturation, S. may vary appreciably from the value of two which is usually assumed for this exponent when interpret ing well logs. Values ranging from one to two and one-half have been found on (.ore sample investigated to date. Attempts to correlate this saturation exponent with porosity or permeability of the core have not been successful. The saturation exponent is apparently not a function of the interfacial tension between the brine and the displacing fluid. Some evidence is given indicating that the resistance of the core is not a unique function of the saturation but depends upon the manner in which this saturation was achieved. Equipment and technique are discussed for measurement of resistivities in core plugs in which water saturation can be varied. lNTRODUCTION A number of investigations of the resistivity-saturation relationship for un-c~~nsolidated sands and consolidated (.ore samples have been reported in the literature. According to most of these: R. = R¹ººS², where R² = the resistivity of a formation at saturation S, and R¹ºº= the resistivity of the formation at 100 per cent water saturation. Much of this work was (lone on unconsolidated sands desaturated by gas or oil. Hen-clerson and Ynster worked exclusively with dynamic systems, flowing oil or gas through consolidated cores. There is some doubt as to how well this reproduces static reservoir conditions. Jakosky and Hopper³ onsidered also the case of consolidated core plugs, but the oil-water distribution in the emulsions which they used to saturate their cores is almost certainly different from that occurring in reservoirs. Recently Guyod quotes the results of some Russian work which indicates that n may vary from 1.7 to 4.3. No experimental details of this work are available. In connection with electric log interpretation it is important to know the value of the saturation exponent. For example, if in a given reservoir it is found that the resistivity is three time.; the resistivity observed when the reservoir is 100 pel. cent &apos;saturated with water, this fact would be interpreted as indicating a water saturation of 33 per cent if the saturation exponent were 1 and a water saturation of 6-1 per cent if the saturation exponent were 2.5. EXPERIMENTAL METHOD In the work to be described it was assumed that reservoir conditions are most nearly obtained when core plugs are desaturated by the capillary pressure technique referred to in numerous places in the literature, as for example. in Bruce and Welge&apos;s paper.&apos; In this technique the core. saturated 100 per cent with brine, is placed in contact with a ceramic disc permeable to brine but not to the displacing medium for the displacement pressures used. Pres-ure is then applied to the displacing medium and brine forced out of the core through the ceramic disc. Fig. 1 shows the core plug in place in the cell in which resistivity and saturation measurements are made. Fig. 2 shows the schematic electrical diagram wed to make resistivity measurements on the core plug. A four-electrode type circuit is used, employing a Hewlett-Packard model 400A. AC vacnum tube voltmeter. The 60-cycle AC current througli the core is adjusted to 1 milliampere and measured by noting the voltage drop across the calibrated 100-ohm resistor. The vo1tages appearing at probes 1, 2, 3, and 4 are then successively measured. Voltage drops across the top, center, and bottom portions of the core are obtained by sublracting the voltages appearing at successive probes. This technique avoids any polarization or other high contact resistance phenomena which may develop at the current input electrodes. Resistances which may develop between the core and the probes, and which are small compared to the 1-megoam input impedance 01&apos; the vacuum tube voltmeter will (obviously not affect the measurements allpreciably. Any very appreciable resistallces which may develop at any of the probe wires are detected and allowed for by inserting a 1-megohm resistor in series with the voltage measuring probe. If the probe resistance is actually zero, the new voltage measured after insertion of the I-megolim resistor will be approximately one-half of that previously measured. since the input impedance of the vacuum tube voltmeter is itself 1 megohm. If an! appreciable probe resistance has developed, the new voltage is found to be appreciably greater than one-half of the previously measured voltage. Such probe resistance; have been found to develop only occasionally and usually can be traced to poor connections betwern the core

Jan 1, 1949