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By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,' it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By T. R. Lippard

PURE gypsum may be broken down into its constituents as follows: [ ] Standard specifications (ASTM Designation C22-25) state that a material shall not be considered gypsum if it contains less than 64.5 pct by weight of CaS042H2O. Anhydrite, the second calcium sulphate mineral found in nature, may be broken into its constituents as follows: [ ] PROPERTIES OF GYPSUM AND ANHYDRITE Pure gypsum is colorless to white but various impurities change its color to shades of gray, brown, red, or pink. It has a hardness of 2 in the Mohs scale and can be scratched with the fingernail. The specific gravity of pure gypsum is 2.3 to 2.4, so that rock gypsum, free from moisture, weighs about 145 lb per cu ft. Gypsum crystallizes in the monoclinic system in tabular crystals that exhibit good cleavage

Jan 1, 1949

ASHBEL WELCH, LAMBERTVILLE, N. J.: Dr. Dudley has given the wear of steel rails under four different conditions. He arrives at the conclusion that the softer rails, or those that from their composition ought to be softer, wear better than the harder. But there is another condition which has an important bearing on the subject, and, should not be overlooked,-the weight on a wheel. With the lighter weights of the past, the softer rails may have worn best; with the heavier weights of the future, the harder may wear best. Weights will probably be increased up to the capacity of steel to bear; then doubtless the harder steel will wear best. A leaden rail with ten pounds on a wheel might carry millions of tons, but with one hundred pounds on a wheel, it would be destroyed by a few thousand tons. So in the days of iron rails, my experience was that the softer rails under light machinery stood better than some of the harder; but under heavy machinery the softer were much the most rapidly destroyed. His doubtless the same with steel. The pounding motion of the wheels loosens or spreads the particles of a thin film of steel; the pull lengthwise on the rail de- * Metallurgical Review, vol. i, page 1. † The remarks as here given, as in the previous discussion on steel rails, have all been written out or revised by the participants in the discussion, and represent, therefore, their mature views. It has been thought that this plan, when it can be carried out without doing any of the speakers injustice in debate, is much to be preferred to a strictly verbatim report. The remarks of Mr. Chanute were sent to the secretary after the. meeting, and although they did not form a part of the actual discussion, there can be no doubt of the desirability of including them in this report. The papers under discussion were “Rail Specifications and Rail Inspection in Europe,” by C. P. Sandberg ; " The Wearing Capacity of Steel Rails in Relation to the Chemical Composition and Physical Properties," by C. B. Dudley, and a Rail Patterns," by A. L. Holley. T. M. D., Secretary.

Jan 1, 1881

By Albert R. Ledoux

I AM indebted to The Kaolin Co. of West Cornwall, Conn., and particularly to its engineer, Mr. M. Wanner, for permission to make public, through the Transactions of the American Institute of Mining Engineers, the interesting results of his experiments, having in view the winning of kaolin from deep deposits without shaft-sinking or removing of the overburden. So far as I am aware, nothing like it has been accomplished heretofore, although it reminds one of the methods successfully employed in Louisiana for the winning of sulphur from deep beds by the sinking of pipes one within another, injecting superheated steam under pressure through one pipe, the heat of the steam liquefying the sulphur and the pressure forcing it up through the other pipe to bins at the surface. The kaolin-deposit at Nest Cornwall is an alteration in situ-that is, it is not sedimentary. A series of clay-veins dipping about 500 from the vertical, lie between a foot-wall of limonite and a hanging-wall of gneiss and hornblende schist. The clay-veins alternate with veins or seams of more or less broken quartz, and unaltered feldspar. The deposit, which occurs at a point about 600 ft. above the Housatonic river, was opened five years ago, and about 5,000 tons of a superior grade of washed kaolin has been extracted from open pits and sold. It soon became evident that this node of extracting the product would prove unremunerative, by reason of the dip of the vein and the intercalary strata and lenses of -quartz, and a more satisfactory method of working the deposit was sought. It is well understood, that, in the preparation of all clays for market, especially residuary kaolin, the most important as well as the most difficult step is the washing of the crude product. The difficulties increase with the percentage of foreign matter, especially quartz and mica, contained in the product, hence a sys-

May 1, 1906

By F. M. Lyon, F. J. Chernosky

Research efforts have not developed techniques for the complete desulfurization of coal that is needed to reduce air pollution caused by burning coal and to reduce the sulfur in metallurgical coke. Sulfur in coal occurs in three forms and of these, the pyritic sulfur occurs as discrete mineral particles and, at least theoretically, should be subject to physical rejection. Pyrite occurring in hard rock mining is concentrated by froth flotation; therefore, the possibility of removal of pyrite from coal by flotation does exist. With this possibility in mind, the flotation and adsorption characteristics of ore and coal-pyrite were compared while using potassium ethyl xanthate as the collector.

Jan 1, 1973

By Arthur Knapp

The petroleum industry is confronted with the problem of conservalion. This is not a simple problem in view of a wide difference of opinion among authorities as to whether conservation is necessary and the specific direction that it should take. Many writers accuse the petroleum industry of wasting the natural resources of the country. Others link the consuming public with the industry in this waste. Let us define our terms; agree, if possible, on where and when waste occurs in connection with either the recovery or use of petroleum and select such plans for conservation as appear most practical. A plan for conserv3tion which appears to be logical today may not meet the problem tomorrow. The conservation of petroleum is closely linked with the advancement of marly arts and sciences and as these advance, the plan of conservation has to change. The need for conservation does not necessarily rest upon the elimination of waste. There is not necessarily a fixed connection between waste and conservation. Conservation may be necessary or desirable although there is no waste. Definitions Waste: Useless or unnecessary expenditure. Conservation: The preservation of the natural resources for economical use. Both definitions contain adjectives the interpretation of which is extremely difficult. It is the determination of what expenditures are "unnecessary" or what uses are "economical" that will require study and agreement. If one lets his automobile engine run in cold weather in order to keep it hot, it is difficult to measure that necessity. If an automobile is driven two blocks, when the driver is physically capable of walking, what is the measure of necessity. This question is in the realm of one of the oldest of sociological problems, "What is a luxury?"—a problem which has not been solved. The history of society indicates that the measure of a man's wealth has been the measure of necessity. What he can afford to buy without stinting himself in some other direction, is not a luxury to him and, if it fulfills his desires, may be considered his necessity.

Jan 1, 1927

By W. C. Lilliendahl, H. W. Highriter

THE method developed and used in this laboratory for the production of metallic uranium of such purity that it is ductile and can be cold-worked to fine wire or thin sheet by rolling has already been described1. It consists, briefly, in the electrolysis of potassium uranous fluoride (KUF6) in a molten bath composed of equal parts of sodium and calcium chlorides. The bath is contained in a graphite crucible, electrically heated to about 775° C., the crucible serving as the anode for electrolysis. The uranium deposits in finely divided form mixed with salts upon a molybdenum cathode suspended axially in the crucible. Upon completion of the electrolysis the cathode is removed and cooled, the deposit broken and leached to remove salts. The metal powder is washed with water and dilute acetic acid and dried in vacuo to reduce oxidation. Suitable amounts are then pressed into pellets and heated in vacuo by high-frequency induction, using a thoria crucible. The uranium melts and flows away from the pellet, leaving a shell, which is largely oxide. In general, this method produced a satisfactory metal, although at times the uranium was not ductile. The investigations recorded here were made to find the cause of this embrittlement. It was known that the metal generally contained carbon, derived from disintegration of the graphite crucible in which electrolysis is conducted, in amounts dependent upon the thoroughness of washing the metal powder. Accordingly, analyses of several samples, both ductile and brittle, were made by combustion and absorption of CO2 in Ascarite, using air instead of oxygen to reduce the temperature and rate of oxidation. Several of these metals were made with special precautions to reduce carbon content. The results show no relationship between ductility and carbon content in the range investigated (Table 1).

Jan 1, 1935

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

THE notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat- . treatment of steel. In view of the serious thought that even so simple a test as the tensile test, has evoked during the past years, it is not surprising that the notched- bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and un- predictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small- size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even mare complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be con- trolled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors. such as the com- position and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

A joint statistical report released by the U.S. Department of Commerce and U.S. Securities and Exchange Commission indicates that business investment in new plants and equipment is expected to total $81.8 billion during 1971. This figure is based on the findings of a survey conducted in late April and May and reflects about a 1 ½ % decrease in investments from the $83.1 billion projected in February. Mining, on the other hand, is still in a bullish mood and is expected to spend $1.99 billion in 1971 compared to $1.89 billion in 1970 and $1.86 billion in 1969. Based on figures quoted above, mining investment in 1971 should show a 5.2% increase over 1970. Carl E. Bagge, president of the National Coal Association, was the dedicatory speaker at the new Milton R. Young Station of the Minnkota Power Cooperative in North Dakota. This new power plant incorporates many innovations which have overcome the problems of using the low-cost lignite abundant in the area. According to Bagge, this development and President Nixon's recent request for an extra $10 million for coal gasification plants is helping the region lead the way in providing for the power needs of the future. He also maintains that gasification of coal can reconcile coal consumption with the demand for cleaner air, and also assure the nation of adequate pipeline gas.

Jan 1, 1971

By Albert R. Ledoux

I am indebted to The Kaolin Co. of West Cornwall, Conn., and particularly to its engineer, Mr. M. Wanner, for permission to make public, through the Transactions of the American Institute of Mining Engineers, the interesting results of his experiments, having in view the winning of kaolin from deep deposits without shaft-sinking or removing of the overburden. So far as I am aware, nothing like it has been accomplished heretofore, although it reminds one of the methods successfully employed in Louisiana for the winning of sulphur from deep beds by the sinking of pipes one within another, injecting superheated steam under pressure through one pipe, the heat of the steam liquefying the sulphur and the pressure forcing it up through the other pipe to bins at the surface. The kaolin-deposit at West Cornwall is an alteration in situ— that is, it is not sedimentary. A series of clay-veins, dipping about 50" from the vertical, lie between a foot-wall of' limonite and a hanging-wall of gneiss and hornblende schist. The clay-veins alternate with veins or seams of more or less broken quartz, and unaltered feldspar. The deposit, which occurs at a point about 600 ft. above the Housatonic river, was opened five years ago, and about 5,000 tons of a superior grade of washed kaolin have been extracted from open pits, and sold. It soon became evident that this mode of extracting the product would prove unremunerative, by reason of the dip of the vein and the intercalary strata and lenses of quartz, and a more satisfactory method of working the deposit was sought. It is well understood that, in the preparation of all clays for market, especially residuary kaolin, the most important as well as the most difficult step is the washing of the crude product. The dificulties increaee with the percentage of foreign matter, especially quartz and mica, contained in the product. Hence, a system

Jan 1, 1907

By Peter T. Luckie, Harold L. Lovell, E. R. Palowitch, A. W. Deurbrouck, James K. Kindig

PART 1: DENSE MEDIUM SEPARATION by E. R. PALOWITCH and A. W. DEURBROUK INTRODUCTION During 1965, 64.9 percent of the 512 million tons of bituminous coal and lignite produced was cleaned mechanically, of which 95 million tons was cleaned by dense medium processes.l The percentage of bituminous coal and lignite cleaned mechanically by dense medium processes rose from 7.0 to 28.5 percent from 1938 to 1965. Dense medium separations include those coal preparation processes which clean raw coal by immersing it in a fluid having a density intermediate between clean coal and reject. As there is a general correlation between ash content and specific gravity, it is possible to achieve the required degree of removal of ash-forming impurities from a raw coal by regulating the specific gravity of the separating fluid. Dense medium processes offer the following advantages over other coal cleaning processes : 1. Ability to make sharp separations at any specific gravity within the range normally required even in the presence of high percentages of the feed in the range of e 0.1 specific gravity units. 2. Ability to maintain a separating gravity that can be controlled with ±0.005 specific gravity units. 3. Ability to handle a wide range of sizes (up to 14 inches). 4. Relatively low capital and operating costs when considered in terms of high capacity and small space requirements. 5. Ability to change specific gravity of separation to meet varying market requirements. 6. Ability to handle fluctuations in feed both in terms of quantity and quality. HISTORY Sir Henry Bessemer patented the first dense medium process in 1858. Solutions of the chlorides of iron, manganese, barium and calcium were proposed as separating liquids; the separation was made in a cone-shaped separator. One large-scale plant using calcium chloride was erected in Germany but soon was abandoned. The Chance process, using a mixture of sand and water, was first

Jan 1, 1968

By C. G. Dunn, F. Lionetti

W. G. BURGERS*—It seems almost certain that this investigation shows the way which finally, when more analogous data have been obtained, must lead to the understanding of many features of preferential growth-directions of crystals and of the occurrence of recrystallization textures. In this connection I should like to mention that Mr. Tiedema in my laboratory succeeded in developing an analogous method for preparing crystals in aluminum plates with a chosen crystal-lographic plane and direction parallel to the surface of the plate (to be published in Cryst. Ada). If such crystals were grown in high purity aluminum and test-pieces containing a few crystals such as the authors describe were prepared for this metal, it might be possible that due to the absence of growth obstructing particles, even in this low-melting point metal boundary displacements approaching equilibrium positions might be realized. With regard to the apparently marked drop in surface energy for orientation differences approaching zero degree, and orientation differences approaching those existing between twins, it seems of interest to remark that in aluminum a crystal growing at the expense of fine grained material cannot (or can only very reluctantly) absorb grains in either ap- proximately (within 5—10°) parallel or spinel twin orientation (May, Tiedema and Burgers, Nature (1948) 162, 740 and Cryst. Ada in press). Consequently with aluminum the method of preparing a crystal with a definite orientation does not succeed when the new crystal has to absorb its own texture; for example it is not possible to grow in a polycrystalline wire with a [lll]-texture a crystal with a [11 Indirection parallel to the wire axis (Tiedema: Cryst. Ada, in press). Finally I should like to mention the well-known fact (Burgers: Proc. Acad. Amsterdam (1947) 50, 723) that prolonged annealing of recrystallized nickel-iron sheet with cube-texture never succeeds in transforming this into one single crystal of the same orientation; if, by "secondary re-crystallization," large crystals are formed

Jan 1, 1950

By H. J. Gluiskoter

The chlorine content of the coals in the Illinois Basin ranges from 0.00% to more than 0.60%. The chlorine content of the Herrin (No. 6) Coal has been mapped on a regional scale and, in general, increases with the depth of the coal. The depth-chlorine correlation exists because the coal is in apparent equilibrium with the composition of the ground water associated with it, and the salinity of the ground water generally increases with depth. At least part of the chlorine can be easily removed from the coal in the laboratory. In a natural weathering experiment, chlorine values decreased markedly during an 8-week period. Results to date indicate that none of the coals studied has a sufficiently high chlorine content to make it unusable in high-temperature steam boilers, although special steps may be necessary in the preparation or utilization of some of the highest chlorine coals. Investigations into the occurrence and distribution of chlorine in Illinois coals have been in progress at the Illinois State Geological Survey for over 35 years. Since 1948, chlorine analyses of face channel samples and of drill core samples of coal have been made routinely. The increased interest in chlorine and alkalies in coal in the U.S. followed that in Europe, where power plants during World War II were called upon to produce at higher levels than previously and with less down time for maintenance. Higher steam temperatures were reached, resulting in increases in the amount of fouling of external heating surfaces and in corrosion of boiler tubes when high chlorine coals were used. Early studies of the problem showed that coals with high chlorine content were more likely than those low in chlorine to cause difficulties in installations fired with powdered fuel. Crossleyl reported that the first rule of thumb developed for British coals was that coals considered to be high in chlorine (more than 0.30%) caused the most trouble, those intermediate in chlorine content (0.15% to 0.30%) were less likely to cause difficulties and those low in chlorine (less than 0.15%) generally were not associated with alkali bonded deposits and corrosion. However, this relatively simple picture was not adequate to characterize the difficulties that could be expected during the utilization of a large number of coals and Crossley1 developed another scheme for assessing the chances of superheater corrosion. This scheme took into consideration the observation that coals high in sulfur as well as chlorine are more likely to cause corrosion and fouling than coals low in sulfur and high in chlorine. Crossley also considered the ash content. When two coals had the same chlorine and sulfur contents, the one with the greater amount of ash would be the less likely to cause difficulties. Knowing only the amount of chlorine in a coal obviously will not give all the answers. Indeed, the significance of the chlorine content has been much discussed and it has been suggested that perhaps the total alkalies are a better indicator of possible troubles. The observation that the deposits that form

Jan 1, 1968

By S. Usui, I. Iwasaki

The adsorption mechanism of dodecylammonium acetate (DAA) on mercury in potassium fluoride solutions at natural, near neutral pH was investigated. Difler-ential capacity combined with electrocapillary measurements on a dropping mercury electrode were found to provide a sensitive and reliable approach. A shift in the electro capillary maximum (or the point-of-zero-charge) towards positive polarization of the surface due to the adsorption of amine indicated a specific affinity of dodecylammonium ion for mercury surfaces. The amine was shown to adsorb competitively with potassium ion on mercury. Through correlation of the adsorption density of the amine, calculated from the thermodynamic analyses of the electrocapillary curves, and of the diflerential capacity curves, the adsorbed state and the orientation of the amine at the interface were considered. The similarities and the differences in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide were evaluated. With the promise of flotation providing a cheap and large-scale process for the upgrading of low-grade ores and magnetic concentrates, the iron ore industry has made a sustained search over the years for a flotation reagent of general applicability and high selectivity. Having shelves full of commercial reagents already on hand and anticipating more, both the users and the suppliers are in need of an experimental approach sensitive enough to differentiate the individual characteristics in each group of reagents. Therefore, the adsorption behavior of various flotation reagents on mineral surfaces from aqueous solutions has been a subject of much investigation. The current view of adsorption based on the electrical double-layer theory is formulated on the assumption that certain ions in solution act as potential-determining ions. Their concentrations fix the potential drop across the double layer and their adsorptions govern the surface charge.' Two methods used to study the adsorption

Jan 1, 1971

THE story of Miami really is two stories. First, that of an excellent Porphyry Copper mine, ably managed as a business enterprise, and always among the leaders in technical progress. Concentrating its first ore in 1911, it had by 1925 paid dividends totaling $30,000,000 or $40 per share on stock that had cost the public $5 per share in March, 1908. The ore, containing 2.5 per cent copper at the start, had become progressively leaner but the recovery had tended to improve. Production costs had gone up during the World War and the early post-war period; and had come down again. In all these respects it had followed the norm. If the mine had been abandoned as exhausted and the company had been liquidated late in 1925 (a program that had been given earnest consideration in 1924), Miami would have gone down into history a first-rate mining venture; as an active and progressive participant in the great Porphyry achievement. But Miami was not liquidated in 1925; instead it started to write the record of its second and really amazing story. Near the old mine was a large body of low-grade ore containing, in place, less than 20 lb. of copper to the ton, and without, incident- ally, any considerable sweetening of gold and silver. Any method of underground mining that was cheap enough would certainly entail some dilution, so that ore as sent to the concentrator necessarily would average much less than 20 lb. As a matter of record, the average for 1929 was 16.6 lb., from which 11.726 lb. was recovered as concentrate. As already said, the exhaustion of the older orebody during 1925 was foreseen; but in 1924 the decision was reached to enlarge the concentrator and develop a new mine. An expenditure of $2,500,000 was entailed in this program. By October, 1925, the

Jan 1, 1933

By Werner Ostertag

A series of rare earth cobalt compounds of the composition RCoa (r = Ce, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Ev, Tm, Lu) has been prepared. The compounds crystallize in space gvoup R3m and are isomorphous with PuNi3. Except for CeCo3 and PrCo, the series shows decreasing- values of a. and co. The relalively small parameters of CeCo, and PrCo, are explained by valencies of cerium or praseodymium which exceed the usual rare earth valency of three. The structure of the compounds is discussed as in-fillings of kagome nets in direct and staggered superposition. In the course of a systematic investigation of rare earth cobalt compounds"2 and their magnetic properties,, a series of alloys corresponding to the formula Rco3 has been prepared. The investigation of the Rco3 series was stimulated by our investigation of the yttrium cobalt system2 as well as by reports in the literature: Smith and Hansen4 reported the structure of YcO3 and Van vucht5 that of GdCo3; ceco3,6 Gdco3,7 and DyCo3 7 have been found to be single-phase during phase diagram studies. It was the purpose of this work to report crystallographic data on the entire Rco3 series and to interpret the structure of these compounds on the basis of general principles as discussed by Frank and Kasper.8 At the time this work was terminated, it was learned that a similar investigation has been carried out independently by Bertaut, Lemaire, and schweizer.9 Except for CeCo3 (ao = 4.952, co = 24.73') and NdCo3 (a0 = 5.067, co = 24.76') data of this work are in satisfactory agreement with their investigation. EXPERIMENTAL TECHNIQUES A series of samples having the composition Rc03 was prepared from stoichiometric amounts of the rare

Jan 1, 1968

By Josef Intrater

A dilatometric determination of the a + ß region temperature limits was performed on vacuum melted Zircaloy-2. The temperature of transformation for a-a+ß and a+ß — ß on heating and cooling as a function of rate of heating and heat treating history was studied. The limits were found to be 815° to 830°C to 975° to 995°C on heating and from 960° to 930°C to 785° to 770°C on cooling. A 5° to 15°C increase was observed for a- a + ß with increased rate of heating and a 20° to 30°C decrease for ß - a + ß with increased rate of cooling. 1 HE transformation temperature for pure zirconium has been determined by many investigators1-5 using metallography, electrical resistivity measurements, and dilatometry. The effect of the rate of cooling on the transformation temperature of zirconium has been studied by Hayes and Kaufmann6 and Duwez,7 and the effect of alloying elements by pfei18 and McGeary.13 Since the development of Zircaloy-2, the limits of the a + ß region for that alloy have been also determined. The first reported temperature for the a — a + a transformation in Zircaloy-2 was 900°C and for a + ß - ß 1000C Subsequent studies by Picklesimer and damson" indicated the beginning of the transformation at 810°C, and the metallographic study by the Technology Group of the Special Materials Section at the Westinghouse Bettis plant1' suggested that 820°to 830°C is the temperature of transformation. The dilatometric investigation by the latter group yielded 830°C for the beginning of the transformation. Thomas and Forscher12 set the beginning of the transformation at 900 °C on heating and the end of the transformation at 870°C on cooling. The above investigators stated in their paper that the dilatometric curve exhibits features caused by a eutectoid reac-

Jan 1, 1962

"Acta Metallurgica" Dennis Carney, '59 Alfred Noble Joint Prize Committee F B Foley, Dec '61 American Association for the Advancement of Science F T Agthe, Dec '59, William L Fink, Dec '60 American Geological Institute Arthur Montgomery, Oct , '59, F C Kruger, Oct '60 American Power Conference J P Weir, T D Hess American Society for Testing Materials

Jan 1, 1959

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase