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By J. J. Gilvarry

Recently, Gilvarry1,2 has given a rigorous derivation of the proper distribution function for fragment size in single fracture, based on a closely defined physical model and deduced strictly by the laws of probability. The physical point of departure is Griffith's theory of brittle strength, identifying sub-microscopic flaws as the cause of the low strength of a solid in comparison with values implied by cohesive energies. Gilvarry and Bergstrom,4-7 and Gilvarry8 have compared the predictions of the theory with experiment, and have found excellent agreement, in general. The purpose of this communication is to sketch the extension of the theory to the case of comminution, and to indicate the applications to some examples in nature. The present treatment represents an amplification of a brief discussion appearing elsewhere. 9 Although the basic ideas of the Griffith theory are perfectly general for rupture of brittle solids, it was originally formulated with very brittle materials such as glass in mind. Moreover, Griffith's original experimental work was carried out on glass specimens. Recently, however, the theory has been extended by race" to apply directly to rocks. This extension makes the theory immediately applicable to the materials generally of interest from the standpoint of comminution. GENERAL CASE To obtain the distribution function for fragment size in single fracture, three assumptions are made, that: 1) Fracture proceeds by activation of preex-istent Griffith flaws in the volume, faces, and edges of a fragment; 2) the distributions of flaws of these three types are independent of each other; and 3) activated flaws of a particular type are distributed at random, individually and collectively, in the sense of Fry.11 The last assumption implies that each distribution is separately of Poisson type.

Jan 1, 1964

By Alwyn Birchmore Cox, Ian William Wark

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By Ian William Wark, Alwyn Birchmore Cox

Different parts of the world in which mineral separation by flotation is practiced experience vastly different natural temperatures, and in some districts there is a big difference between summer and winter temperatures. It will be shown in this paper that the temperature is of considerable importance where it is desired to separate pyrite or arsenopyrite from other minerals. It is probable that some of the differences obtained in the flotation of these minerals at plants working under otherwise similar conditions are due to temperature variations. The influence of temperature on the flotation of galena, chalcopyrite and sphalerite by xanthates is less marked than its influence on pyrite flotation. Experimental Method The methods used have been described previously.l-4 In each test the clean mineral specimen was immersed in a solution prepared by adding the reagents in the following order: (1) sodium carbonate and hydrochloric acid as necessary to buffer the solution and to give approximately the pH value desired, (2) sodium cyanide, (3) copper sulphate, (4) ethyl xanthate, followed by (5) a final adjustment of pH value. After ½ hr. the mineral was tested for a xanthate film by bringing a bubble of air into apparent contact with the submerged polished surface. If true contact (spreading) was not obtained within ½ min. and after cleaning the surface by wiping with a small linen pad, it was concluded that the adsorption of a xanthate film had been prevented. Following the method already described (ref. 2), curves have been constructed such that for a solution composition corresponding to any point below the curve, contact between mineral and air is possible, whereas for a solution composition corresponding to any point above the curve, contact is impossible.

Jan 1, 1939

By C. A. Stetefeldt

It will be of interest to compare the statistics of the gas-producer plant at Aspen, Colorado (recorded by Mr. W. S. Morse in a paper read at the Montreal Meeting, February, 1893*), with those at the Marsac mill, Park City, Utah, where such a plant was first introduced by the writer in July, 1890. In both mills a Stetefeldt furnace is used for roasting; but the Marsac mill has the old-fidsdshioned revolving dryers, while at Aspen, shelf-dryers are at hand. At Aspen, separate Taylor-producers are provided for the Stetefeldt furnace and the shelf-dryers; at the Marsac mill one 7-foot producer supplies gas to both the furnace and the dryers. Hence, in the latter case, the quantity of coal consumed for each apparatus can only be estimated, based upon the relative consumption of wood before gas was introduced. According to Mr. Wilson's statement, the relative consumption of wood in the Stetefeldt furnace and the revolving dryers was as 3 to 2. In the year 1892 the Marsac mill put through the dryers and the Stetefeldt furnace the following quantities of ore and salt (approximate dry weights) : ore, 22,800 tons; salt, 2262 tons. There were consumed in the Taylor-producer 2,714 tons of Rock Springs coal. We may thus make the comparative estimate as follows: Table Showing the Consumption of Coal per Ton Of Ore and Salt at the Marsac and Aspen Mills. Marsac. Aspen. Difference. Pounds. Pounds. Pounds. Drying ore and salt,.... 86.63 72.22 14.41 Roasting ore,.....142.40 117.44 24.96 Total,.....229.03 189.66 39.37 In making a just comparison a number of items must be taken

Jan 1, 1894

By R. V. Vines, E. M. Wise

It is known qualitatively that the recrystallization behavior of platinum is dependent upon the amount and particularly the nature of impurities present, the amount of prior cold-work and the annealing time and temperature, but published data are limited. A study of the effects of cold-work and annealing temperature on the hardness of a sample of very pure platinum was undertaken to supply part of this information. Conclusions 1. The platinum used in the experiments had a probable platinum content of 99.99+ per cent, and had the following mechanical properties in the completely softened condition: Vickers hardness number, 39.4; ultimate tensile strength, 19,340 lb. per sq. in.; proportioilal limit, very low; elongation, 37.5 per cent in 2 inclles. 2. The effect of cold-rolling on the hardness is shown in Fig. 1. The hardness increases rapidly up to 10 to 15 per cent reduction and more slowly up to about 75 per cent reduction, beyond which it increases more rapidly. 3. The recrystallization temperatures for a 15-min. anneal, after cold-rolling 19, 39.5, 50.8, 66, 80.5 and 89.5 per cent reduction in thickness, are approximately 765°, 700°, 635°, 600°, 545' and 425°C., respectively. 4. The recrystallized grain size of this platinum is a function of the percentage of cold reduction, being larger the lower the percentage of cold-work. 5. Little or 110 grain grourtll resulted from subjecting recrystallized samples to higher temperatures or annealing for longer times. Prior Work As already mentioned, data on the recrystallization of platinum are scarce. Gmelin'sl handbook, which summarizes data published earlier than August 1938, lists values ranging from 400' to 810°C. for the minimum temperature of recrystallization of samples with rather indefinite

Jan 1, 1940

By E. M. Wise, R. V. Vines

It is known qualitatively that the recrystallization behavior of platinum is dependent upon the amount and particularly the nature of impurities present, the amount of prior cold-work and the annealing time and temperature, but published data are limited. A study of the effects of cold-work and annealing temperature on the hardness of a sample of very pure platinum was undertaken to supply part of this information. Conclusions 1. The platinum used in the experiments had a probable platinum content of 99.99+ per cent, and had the following mechanical properties in the completely softened condition: Vickers hardness number, 39.4; ultimate tensile strength, 19,340 lb. per sq. in.; proportioilal limit, very low; elongation, 37.5 per cent in 2 inclles. 2. The effect of cold-rolling on the hardness is shown in Fig. 1. The hardness increases rapidly up to 10 to 15 per cent reduction and more slowly up to about 75 per cent reduction, beyond which it increases more rapidly. 3. The recrystallization temperatures for a 15-min. anneal, after cold-rolling 19, 39.5, 50.8, 66, 80.5 and 89.5 per cent reduction in thickness, are approximately 765°, 700°, 635°, 600°, 545' and 425°C., respectively. 4. The recrystallized grain size of this platinum is a function of the percentage of cold reduction, being larger the lower the percentage of cold-work. 5. Little or 110 grain grourtll resulted from subjecting recrystallized samples to higher temperatures or annealing for longer times. Prior Work As already mentioned, data on the recrystallization of platinum are scarce. Gmelin'sl handbook, which summarizes data published earlier than August 1938, lists values ranging from 400' to 810°C. for the minimum temperature of recrystallization of samples with rather indefinite

Jan 1, 1940

By D. Mills, G. B. Craig

ZIRCONIUM has been float-zone-refined in an electron-beam furnace and the redistribution of oxygen, iron, and tungsten has been measured. The iodide zirconium used in the present experiments initially contained both oxygen and iron in the range 100 to 200 ppm by weight, and tungsten in amounts less than 10 ppm. Float-zone refining of zirconium, using induction heating, has previously been attempted by Kneip and Betterton1 and Langeron.2 Kneip and Betterton were primarily interested in the removal of iron and nickel. They achieved some purification, with respect to both these elements, in material given up to six passes at 150 mm per hr under an argon atmosphere. Langeron reported purification for a large number of elements after four completed passes in a static vacuum system operating at pressures less than 10-6 mm of Hg and with rates of zone travel between 30 and 40 mm per hr. He did not report oxygen concentrations, but stated that there was inverse segregation of this element. westlake5 has also used a minimum of four zone passes to remove iron from zirconium. No rates or conditions were given. Belk6 has shown that tungsten contamination can occur during electron-beam melting. He reported an increase from 0.01 to 0.05 pct by weight tungsten in molybdenum after four complete zone passes. The vacuum system for the electron-beam unit used in the present investigation consisted of a single-stage rotary pump backing a liquid-air-trapped oil-diffusion pump. A pressure of less than 10-8 mm of Hg was obtained with Dow-Corning 705 fluid in the diffusion pump. In order to avoid contamination of the zirconium by evaporation from the tungsten filament, a special focusing cage4 was employed. Three rates of zone travel, 114, 38, and 4 mm per hr, were investigated, with the liquid zone moving from the bottom to the top of the bar. The bars used were 3 mm diam and the total melted length was 130 mm. Oxygen was analyzed by neutron-activation analysis using a neutron flux of 10' neutrons per sq cm per sec to form the isotope N16 by the 016 (n,p) N16 reaction. The standard deviation is quoted for each oxygen determination. The iron and tungsten analyses were performed spectrographically, and the precision is estimated to be ±6 pct. Analyses for tungsten were all below the detectable limit of 10 ppm, confirming the protection given by the focusing cage. No significant redistribution of oxygen was found at the two higher rates of zone travel. The redistribution of oxygen and iron obtained after five passes at a rate of zone travel of 4 mm per hr (1.1 x 10-4 cm per sec) is recorded in Tables I and 11. Burris, Stockman, and Dillon3 have estimated the distribution of solutes during multipass zone refining. Using their curves for an effective distribution coefficient of Keff = 1.5 and 2 for oxygen and Keff = 0.3 for iron, the expected concentrations were estimated for the present material. These are shown in Tables I and 11, along with the experimentally measured values. The calculated concentrations are based on a molten-zone length of 10 pct of the total melted length, whereas in the present experiments the molten zone was approximately 5 pct of the total melted length. The effect of zone length on solute redistribution is most pronounced after a large number of zone passes. Comparison with Pfann's published data8 for solute redistribution for various Keff's and zone lengths indicates only small differences at low numbers of completed zone passes. It is evident that the expected distribution has not been realized in the case of iron. Scrapings of material deposited on the inner surfaces of the electron-focusing cage were found to be magnetic. It is, therefore, concluded that redistribution of iron is masked by evaporation. Deposition of iron inside the focusing cage was observed at all rates of zone travel. The results of the investigation may be summarized as follows: 1) Segregation of oxygen is typical for a solute with a distribution coefficient, Keff > 1. 2) No redistribution of oxygen takes place at high rates of zone travel. 3) The distribution coefficient for oxygen lies between 1.5 and 2.0. 4) Purification with respect to iron occurs mainly by evaporation. 5) The focusing cage is effective in preventing tungsten contamination.

Jan 1, 1967

By Charles C. Fatino, Joel S. Hirschhorn

Loose compacts of strained and annealed stainless-steel powders were sintered at various temperatures and times to determine the effect of residual strains on the sintering behavior. The atomized powders were prepared by annealing, ball milling, and rean-nealing. The residual strains and domain size were determined by a Fourier analysis of X-ray diffvaction dala. The specimens were prepared by siwzultaneously sintering cylinders of both strained and unstrained powder. The evaluation of the sintered compacts included density measurements, metallographic examinations, and analyses of X- ray diffraction data. The results of these studies reveal a definite increase in sintered density and sintering rate for the strained powders. THE pressure compacting of metal powders causes deformation of the particles, mechanical interlocking, and increased contact area. After the deformation, severe residual strains remain in these particles. The subsequent contributions of these strains to the sintering process have been considered to be negligible, since the recovery and recrystallization temperatures usually occur prior to the temperature required for the sintering process. Sintering is con-sidered to be the process by which the powders are transformed into solid compacts at temperatures below their melting points. The sintering operation for stainless steel usually takes place in the range of 2050" to 2400°F (0.84 to 0.95 T,, where T, is the absolute melting point or liquidus temperature) while the temperature required for recovery is approximately 1800°F (0.75 T,). However, it has been shown for several metal powders that densification becomes significant in the range of 0.35 to 0.45 T,.' It is the purpose of this study to determine what effect residual strains have upon the sintering behavior of stainless-steel compacts. Loose compacts were selected for study in order to isolate the strain contributions and eliminate the variables inherent in sintering of pressure-formed compacts. Additional variables were minimized by using only one mesh size, one composition, one particle shape, and also by simultaneously sintering both types of powder. Very little work has been carried out previous to the present study to delineate the effect of strains on sintering behavior. Lenel et 01.2 observed that residual stresses in copper compacts caused shrinkage at comparatively low temperatures. Delisle3 loose-sintered ball-milled electrolytic iron and observed that bonding among particles began at a lower temperature as compared to the behavior of annealed powder. Increased densification of ball-milled oxide powders has also been noted.4'5 EXPERIMENTAL PROCEDURES Powder Preparation. The powder used for this study was a commercial-type 316L stainless steel made by the atomization process. A typical chemical analysis is: C- 0.025 pct Mo- 2.2 pct Cr-18.6 pct Ni-12.5 pct Fe—Balance The atomizing process is essentially the rapid freezing of liquid droplets. This nonequilibrium cooling causes coring to occur and two distinct phases are present within the solid particle, the austenitic phase and the ferritic phase. Due to the presence of this ferritic phase, the particles tended to fracture as well as become cold-worked during the subsequent ball-milling operation. (It was also found that this type of cooling produced a broadened and shifted

Jan 1, 1968

By N. Albon, J. F. Miller, R. W. Coutant

The deposition of nickel from nickel carbonyl onto amorphous substrates has been studied, with attention being paid to the specific effects of the physical and chemical nature of the substrate and to the effect of oxygen on the crystal morphology. With substrates having microscratches or etch lines, nu-cleation was observed to occur preferentially at these surface features. Flame polishing of the substrate surfaces was found to remove any regularity in preferred nucleation sites. Nucleation was observed to occur less readily on substrates having relatively low surface energies, e.g., Teflon and carbon, than on materials having relatively high surface energies such as fused silica. At low oxygen concentrations [Ni(CO)4/O2 > 54 x 1031, apparently pure and well-formed nickel crystals were observed to nucleate and grow irrespective of the presence of oxygen. At higher concentrations of oxygen, a secondary growth process, dependent upon oxygen concentration and resulting in a gradual change in crystal morphology, was observed. It is concluded that the influence of oxygen on the nucleation and growth of nickel is determined by the relative kinetics of the various possible reactions, and that under the experimental conditions employed the 0-Ni interaction occurs at some nucleation or prenuclea-tion stage. THE purpose of the research on crystal nucleation in chemical vapor deposition as described in this paper has been twofold: 1) to examine some effects arising from the use of amorphous substrates, and 2) to study the specific effects of oxygen on the nucleation and growth of nickel in a nickel carbonyl-carbon monoxide system. The nickel-nickel carbonyl system was chosen for study for several reasons: 1) nickel films are of potential interest in electronic technology, and 2) the deposition can be carried out at moderate temperatures, thus making possible detailed study of the processes occurring and the use of a variety of substrate materials (including some which melt at relatively low temperatures). Fairly well-characterized chemical kinetics and a broad background of information are available on the py-rolysis reactions and on the mechanisms of Ni-O interactions. NUCLEATION AND GROWTH THEORY The theoretical background for the analysis of nucleation and growth by vapor deposition for a one-component system (physical vapor deposition) and the problems encountered therein have been reviewed by Hirth and pound.' More recently Mande12 has indicated the difficulties of applying such theory to chemical systems. One of the major problems involved is the possible multiplicity of chemical reactions and deposition routes. For example, those reactions which are probably of significance in a discussion of the pyrolytic deposition of nickel from nickel carbonyl under the conditions of the present experimental work are illustrated in Fig. 1. As is true with most cases of chemical deposition, many of the quantitative data necessary for a complete analysis of the system are either not available or not directly measurable. However, with the present system, sufficient data are available for a discussion of nucleation and growth on a qualitative basis. Classically, the rate of nucleation of a monatomic species being deposited from a vapor phase is given by

Jan 1, 1965

By T. Leffers, A. Grum-Jensen

The development of texture in copper and brass (15 pct Zn by weight) rolled at room temperature and in copper rolled at -196°C has been followed by determination of pole figures for various degrees of reduction. The concurrent development in microstructure has been investigated by transmission electron microscopy. For low deformations, the texture in brass, and in copper rolled at -196°C, is the same as the texture in copper rolled at room temperature. The difference in texture does not show until 50 pct reduction. At the same reduction at which the difference in texture appears, mechanical twinning starts in brass and low-temperature rolled copper. Nevertheless, Wassermann's twinning theory is found to be incompatible with the present resulls. All fcc metals and alloys develop, by heavy rolling, one or the other of two types of texture, classified for convenience as copper type and brass type, or possibly a '(mixed" texture representing an intermediate stage between the two types. The pure fcc metals, except silver, develop copper-type texture by rolling at room temperature. Silver and many alloys, including brass with more than 10 pct Zn, develop brass-type texture.' By rolling at low temperatures a transition in texture from copper type to brass type has been observed for copper of commercial purity.2'3 It is generally accepted that there is a correlation between the type of texture developed and the stacking fault energy. Metals and alloys having fcc structure develop brass-type texture when rolled at room temperature if the stacking fault energy is low, whereas those with higher stacking fault energies have copper-type texture.2 Thus, the difference in stacking fault energy must cause a difference in deformation mechanism responsible for the difference in texture. Of the numerous theories advanced concerning the nature of this difference in deformation mechanism, four seem to be of current interest. Smallman and Greeen,2 Dillamore and Roberts,4 and Dillamore5 refer to the fact that cross slip more easily takes place in a material with a higher stacking fault energy and suggest that the copper-type texture is developed by deformation with extensive cross slip whereas the brass-type texture is developed by deformation without cross slip. Haessner6 has advanced the theory that the copper-tye texture is developed by a combination of normal {111} slip and slip on other planes, mainly 1100). Thus his theory, like the theory above, proposes an additional deformation mode for the formation of the copper-type texture. Contrary to this, wassermann7 and Ahlborn et al.8 believe that the copper-type texture is obtained by normal slip. In their opinion mechanical twins will change a copper texture into a brass texture. For this reason it is suggested that the brass-type texture is developed when, in addition to normal {111}(110) slip, mechanical twinning is present. None of these theories are, however, supported by direct experimental evidence. In a recent experiment Hu et al.9 have followed the development of rolling texture in copper and brass. The texture of copper and brass was found to be es-

Jan 1, 1969

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice Chairman for Production of the Petroleurn Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive, locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert 2; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are deter-minable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir.

Jan 1, 1936

By James Terry Duce

In order to facilitate interpretation of the data in this chapter, we print the following excerpts from circulars to authors, compiled by Mr. Frank A. Herald when he was Vice Chairman for Production of the Petroleurn Division: Generally in Table 1 the unit for presentation of data is a field. For our purposes a field is defined as the whole of a surface area wherein productive, locations are continuous. Such unit commonly includes and surrounds nonproductive areas. Such unit commonly includes a great variety of geologic conditions-—several units of continuous productive reservoirs of distinctly different structure and of distinctly different stratigraphy. Therefore it is hoped that our authors will subdivide "field" so as to enable students to make analyses that may have scientific and/or commercial value. As to each space in the tabulation, it is either (1) not applicable, (2) the proper entry is not determinable, (3) the proper entry is determinable, but not determinable from data available to the author, (4) the proper entry is determinable by the author. In spaces not applicable, the author will please draw horizontal lines; in spaces where the proper entries are not determinable, the author will please insert 2; in spaces where the proper entries are determinable but not determinable from data available to the author, the author will please insert y; in spaces where the proper entries are deter-minable by the author he will, of course, make such entries. Generally, y implies a hope that in some future year a definite figure will be available. Inability to determine precisely the correct entry for a particular space should not lead the author to insert merely y. Contributions of great value may be made by the author in many cases where entries are not subject to precise determination. In such cases the author should use his good judgment and make the best entry possible under the circumstances. For many spaces, the correct entries represent the opinion of the author (for example, "Area Proved") and in such cases the entries need not be hedged to such extent as in cases where the quantities are definite yet can be ascertained only approximately by the author. In cases under definite headings but where figures are only approximate, the author may use 2. For example, if the total production of a field is known to be between 1,800,000 and 1,850,000, the author may report 1,8xx,xxx; or if the production is between 1,850,000 and 1,900,000, the author may report 1,9xx,xxx. Where a numeral is immediately to the left of x or y, such numeral represents the nearest known number in that position. As to quantity of gas produced from many fields the question will arise as to whether the figures should include merely the gas marketed or should include also estimates of gas used in operations and gas wasted. Although rough approximations may be involved, our figures should represent as nearly as possible the total quantity of gas removed from the reservoir.

Jan 1, 1936

By M. H. Gaskell, D. M. Kehn, G. T. Pyndus

A correlation of the bubble point pressure for black oil systems is developed using the standard physical-chemical equations of soiutions. The correlation is based on 158 experimentally measured bubble point pressures of 137 independent systems and is expressed in terins of the usually measured field pnrameters— flash separation gm-oil ratio, rank oil gravity, total gas gravity, and reservoir temperature. The data were obtained on systems produced in Canada, Western and Mid-Continent01 United States, and South America. The average error (algebraic) in the representation is 3.8 per cent, and the maximum error encountered is 14.7 per cent. INTRODUCTION In the absence of experimentally measured properties of reservoir fluids, it is often necessary for the field engineer to make estimates regarding the fluid properties based on the usually measured producing parameters. To aid in these estimations, various correlations have appeared in the literature in recent years. Among the pertinent properties of interest is the bubble point pressure. A correlation for this parameter has been reported by Standing'. However, this correlation was based essentially on California produced crudes and this limitation was pointed out with its presentation. The correlation presented in this paper utilized data on crude oil systems from Canada, Wes- tern and Mid-Continental United States, and South America. CORRELATION DEVELOPMENT The basic assumption used in this development is the same as employed by Standing', There is a wide variety of ways to combine these parameters; however, in this instance the combination was made on the basis of Henry's law2. Accordingly, the relationship proposed is Although Eq. 2 defines an individual system, it is of limited value since H' is a function of gas-phase composition and the system temperature. It was observed that for the systems where the bubble point was measured at several temperatures that the ratio of the bubble point pressures and the ratio of the corresponding absolute temperatures (R) were practically identical. Thus, for correlation purposes the bubble point pressure may be taken as a direct function of the absolute temperature. This relation is valid only for those systems that are not near the critical point. Accordingly, this correlation will be inadequate for systems in the region of the critical point. The solubility of the various hydrocarbons found in the gas phase increases with the molecular weight. Thus, the saturation pressure should be inversely related to the gas gravity. Applying these principles to Eq. 2 and rearranging terms gives: The variables 02 the left side of Eq. 3 were designated as the "hubble point pressure factor". The number of mols of tank oil per barrel is a function of the "mclecular weight" of the tank oil. Although the tank oil is a complex mixture, it was assumed for the purposes of this correlation that a unique molecular weight could be assigned to a given oil. This was designated as the "effective molecular weight", and was related to the oil gravity, This empirical relationship was developed simultaneously with the correlation by assuming values of M,. and working to obtain a smooth curve for both the correlation and the effective molecular weight. The relationship between the oil gravity and the effective molecular weight used in this correlation is shown in Fig. 1. The effective molecular weight is somewhat higher than the molecular weight of the C fraction. The difference between these values is largest for the low-gravity systems. It is noted that this effective molecular

By K. G. Davis

Dilute alloys of silzer in tilz haz been solidzjzed a1 controlled rules, in lzorizontal tubes 2 mrz and 0.5 rn in diam. Radioactive; tracer techniques we?-e used to study solute distvihutions along llze specimens and irmpurity substructures, as functions of the conditions growth. The results have heen mzalyzed using Burton, Prim, and Slichter's tnodel for the solute disty-ihution in the liquid ahead of an advancing solid-liquid interface. DECANTING techniques have been used to establish criteria for the formation of impurity substructure during solidification in several alloy systems An analysis equating the appearance of impurity substructure with the incidence of constitutional supercooling was developed,= in which diffusion was assumed to be the predominant mode of solute mixing in the liquid. Substitution of experimental data into the equations derived from the diffusion analysis gave reasonable values for solute diffusivity in the liquid. However, in these investigations solidification rates of 10 cm per hr and over were used, to minimize the effect of natural conection, whereas for crystals of high perfection lower solidification rates are needed, usually between 1 and 5 cm per hr. A knowledge of the conditions under which impurity substructures will be formed at low growth rates, and the degree of segregation to be expected, is therefore of interest. In the present investigation, radioactive-tracer techniques have been used to study the effect of growth rate, initial solute concentration, and size of specimen on the formation of substructure in uni- directionally solidified rods of dilute silver in tin alloys, over a range of growth rate between 0.5 and 10 cm per hr. Criteria for the formation of substructure were established by auto radiography. This was believed preferable to the decanting technique, for the relationship of the structure on a decanted interface with that of the freezing interface is not clear, since a layer of liquid is left on the surface following decanting.' The effect of substructure on the distribution of solute along the rods was also investigated. EXPERIMENTAL The procedure for sample preparation has been described in detail by einber. Alloys were prepared from tin of 99.999 pct purity and silver of 99.99 pct purity. A"', an emitter of both y and 0 radiation, was used as tracer. Samples of the alloys were drawn up into silica tubes with inside diameters 0.5 or 2 mm, remelted in a horizontal furnace, and solidified at controlled rates. A few centimeters of the samples were left unmelted for a measure of the initial concentration. Total sample length was approximately 20 cm. The temperature gradient in the furnace was kept constant at 36°C per cm in the region corresponding to the melting point for tin. To find how well this corresponded to the actual temperature gradient in the melt, a thermocouple of 38-gage wire was electrically insulated with a thin layer of Sauereisen cement and placed within one of the 2-mm-diam tubes, which was then filled with tin. The maximum diameter of the coated wire was 0.5 mm, the bead of the thermocouple junction being no larger than the diameter of the wire. A plot of temperature vs distance traveled by the furnace is given in Fig. 1 for a rate of furnace travel of 1 cm per hr. The temperature gradient in the liquid

Jan 1, 1967

By J. F. Havard

Gypsum is a useful industrial mineral found abundantly on the earth's crust. It is inexpensive to mine and process, and its calcined products have a wide range of readily controllable properties such as strength, density and setting time. It has proven to be such a useful material indeed, that ten American companies, operating some 57 calcining plants in 25 states in 1958, produced or imported in that year a total of 13,649,000 tons of the crude mineral valued at $39,361,000, which they then converted into manufactured products with a value of $329,070,000. Gypsum (CaSO4.2H2O) is calcium sulfate with two molecules of combined water, which are responsible for most of its useful properties. It is closely associated in most deposits with anhydrite (CaSO4), which contains no combined water and has limited commercial value in the United States. Man has long recognized the useful qualities of gypsum. It was utilized by the Egyptians in the construction of the pyramids and, later, by the Romans for important structures. Many of the ancient peoples prized gypsum for artistic and ornamental purposes, carving statuary from alabaster and making casts with plaster. The tabular variety, selenite, was used for windows, and the light transmitted through these windows reminded people of light from the moon (selene), hence the name selenite. The use of gypsum continued through the Middle Ages and into modem times. Benjamin Franklin was a famed exponent of gypsum because he applied ground gypsum to clover fields in the form of large letters which later read, in the more luxuriant growth, "land plaster used here." Gypsum is still used as an effective conditioner for some soils, but in recent decades, particularly in North America and Europe, it has become much more important as a major material for the building industry. Description Gypsum and anhydrite are closely associated minerals. Gypsum is found in a number of forms: massive rock gypsum, alabaster, selenite, satin spar, and gypsite. Anhydrite is found as massive rock or as smaller bodies or isolated crystals included in gypsum. Massive Rock Gypsum comprises most of the commercial gypsum and occurs as a sedimentary rock, interbedded in most places with shale, limestone or dolomite. This rock is soft and crystalline. Its color is white or shades of gray, pink, yellow, brown or other colors. Alabaster is a pure, compact and fine-grained variety suitable for use in sculpture or turning into artistic forms; it may be white or selected for attractive coloration. Selenite is gypsum crystallized in flat, transparent, flexible foliated plates, found in clays or in surface vugs in gypsum. Satin Spar is a fine silky fibrous variety with the axes of the crystalline fibers perpendicular to the vein or joint in which it has formed. Gypsite is an earthy mixture of gypsum with clay and sand in secondary formations; it is sometimes useful as a soil conditioner and has been used in making base-coat plasters. Pure gypsum contains 20.9 pct combined water, 46.6 pct sulfur trioxide (SO3) and 32.5 pct lime (CaO). Standard specifications (American Society for Testing Materials Designation C 22-50) read that minimum purity for material to be called gypsum is 70 pct CaSO4.2H20. Most of the commercial gypsum is 85 to 95 pct pure as produced. Impurities in

Jan 1, 1960

By Ramesh Malhotra, Hubert E. (Deceased) Risser

THE WORLD Coal, as a source of energy and as a source of coke for the smelting of iron ore, has contributed significantly to the development of every major industrial nation of the world A number of other materials-oil, natural gas, wood, waste materials, water, and, in some applications, nuclear materials -can be used satisfactorily for the generation of heat and energy, but no generally acceptable and economic substitute has been found to supplant coke in iron ore smelting in conventional blast furnaces. In the development of many nations, coal provided the initial source of energy for industrialization Although coal provided more than 60% of the world's energy each year between 1902 and 1929, oil and natural gas have surpassed it as a source of energy in more recent years (Ref. 38, pp. 439, 441). Despite the rapid rise in importance of other fuels, a considerable amount of the total energy consumed is still supplied by coal. In 1972, coal supplied 32.1 % of the total world energy (Ref. 49, pp. 2-3). To produce this energy, 2.4 billion metric tons of coal were consumed-a 16.0% increase over the amount consumed in 1962. A further worldwide increase in the amount of coal used to supply energy is projected. According to Dr. Karlheinz Bund (Ref. 37, p 145), by the year 2000 world coal consumption could amount to 5 billion mt. Coal Resources and Production The world's coal resources are estimated to be about 10,872 billion mt. Of this amount, 1,297 billion mt are classified as measured reserves (Ref. 50, p. 57). In Table 13.A.1 the estimates of measured reserves and total resources, recent production, and the ratio of measured reserves to production of major coal-producing countries are shown. About 90% of the world's total coal resources are estimated to be in the USSR, the United States, and China. The United States ranks second in the world in coal resources, but in measured reserves, it ranks first. Because of the difference in rate at which available coal resources are being exploited, the ratio of measured reserves to actual production varies widely among areas and countries. France and East Germany have the lowest reserve to production ratios, 49.5 and 60.1, respectively. In Mexico, where currently less than 5 million mtpy of coal are produced, the ratio is 1257 For all countries producing more than 200 million mtpy of coal (except East Germany), the ratio ranges from 350 to 670. For the United States, the ratio is 669.7. In Table 13.A.2, distribution of the world's coal resources by area is shown. More than 97% of the total resources lie in the northern hemisphere, with Asia, including European USSR, having 63.4%. Only 1.9% of the total coal resources are estimat-

Jan 1, 1976

By T. W. Smoot

Bentonites are composed chiefly of montmorillonites which are clay minerals generally distinguished from other clay minerals by their surface activity and extremely fine particle sizes. The uses of bentonite are many and varied, depending principally on one or more of the following characteristics: 1) Thixotropy, 2) Dispersion, 3) Plasticity, 4) Swelling, 5) Surface area, activity, ab- and adsorbtive properties. Some of the major uses of bentonite are briefly reviewed as are the mineralogical and physical properties. The uses of X-ray diffraction, differential thermal analysis and other tests for physical properties are reviewed as to their uses in evaluation. In the past 40 years, the industrial uses of bentonite have grown to include many applications. The physical and chemical properties of bentonites are such that they can be used as catalysts, adsorbants, plasticizers, binders, drilling muds, and pelletizers. Not all bentonites, however, can be used for all of these purposes and some are probably of little or no value for any use. The purpose of this paper is to briefly review the mineralogical, physical, and chemical characteristics and variations of bentonites. The determination of these characteristics and their uses in industry are also reviewed so that these determinations can be used as guides for evaluation. DEFINITION OF BENTONITE The word bentonite, as used in this paper, refers to a clay material, usually (but not necessarily) the result of the in-place-weathering of volcanic ash. Its mineralogical composition is dominated by the clay mineral montmorillonite and generally carries other clay minerals and silica minerals as the major 'impurities'. For this discussion, such a definition is justified since most of the economic uses of bentonite~ depend upon the physical and chemical characteristics of the montmorillonite minerals involved. The terms montmorillonite and bentonite have been used almost interchangeably in industry although the latter is much more commonly used. Therefore, where montmorillonite is discussed, it should be understood that the major feature of a bentonite is the subject. STRUCTIJRE OF MONTMORILLONlTE The economic importance of bentonites is generally based on one or more of the following characteristics of montmorillonite: 1) high-thixotropy and easy dispersion in water, 2) high-plasticity, 3) swelling properties, 4) large surface area/unit mass, 5) high surface activity, and 6) adsorptive properties. To understand these properties, an appreciation of the structural scheme of montmorillonite is helpful. Montmorillonite IS one of the three-layer clay minerals composed essentially of hydrous aluminum silicates. The essential building blocks of these layered silicate:; are: 1) silica tetrahedron composed of a silicon atom surrounded by four oxygen atoms, and 2) aluminun (iron, magnesium, etc.) octahedral unit that, ideally, has one of these atoms surrounded by six hydroxal units. Fig. 1 is a diagrammatic sketch of the montmorillonite structure. In the montmorillonite structure, the tetrahedron are pointed inward and attached to the octahedral units so that the O= atoms replace the hydroxal units where they are bonded; hence two-thirds of the hydroxal units

Jan 1, 1962

By Toshimi Yamane

The internal friction of cold-worked titanium iso-thermally annealed at temperature below the recrystallization temperature was measured. The internal friction was calculated from the half width of a resonance curve of the specimen which was vibrated transversally by the electromagnetic method. The experimental results were as follows: 1) The specimens annealed for a long time at temperature below the re crystallization temperature after cold working have the strain-amplitude dependent internal friction. 2) The internal friction increased by the cold working was decreased during the isothermal annealing. The reason of decrease of the internal friction is considered to be caused by the annihi-lation of lattice defects. 3) There is a linear relation between logQt-1/Q0-1 and (1/T)2/3 below the recrys-tallization temperature, where Q0-1 is the internal friction standing 24 hr at the room temperature after cold rolling, Qt-1 is the internal friction annealed at T°K for t min. 4) The hardness of the cold-worked titanium does not change by the annealing at 300°C for a long time but decreases by annealing at 400ºand 460°C. METALS, when cold worked, show sharp changes in physical and mechanical properties' The internal friction of cold-worked metals increases sharply and has a maximum value1,2 connected with working de- grees. The increased internal friction of cold-worked metals is recovered by annealing. This phenomenon is the well known effect called Köster effect. The recovery of the internal friction occurs earlier than the changes in tensile properties, hardness, or X-ray diffraction, and is very sensitive to the structure of a metal. The mechanism of the recovery at a temperature lower than the recrystallization temperature is being considered variously by many investigators: there are such views as the annihilation of dislocations by smith,' the rearrangement of dislocations mentioned by Nowick,4 and interaction of dislocation with point defects.5 Smith and Nowick also considered the interaction but it is so difficult for them to explain the rearrangement mechanism systematically, it being not considered a special model; therefore, we do not explain it quantitatively. Experiments measuring the recovery of the internal friction of cold-worked metals were performed by Gordon and Nowick6 on NaCl, and by Smith on copper. In addition, there are many studies, particularly those of measurements on copper by other investigators. There are comparatively many investigations on aluminum and iron which are the cubic system,'-' but only a few on metals of the hexagonal system.10 In view of this, I investigated cph titanium at room temperature and measured the internal friction after annealing isothermally at temperature lower than the recrystallization temperature. SAMPLES AND EXPERIMENTAL METHOD samples for the experiment were cut from a 6-mm titanium plate. The long direction of samples was

Jan 1, 1963

By P. A. Tucker, C. R. Hudgens, D. E. Etter, D. L. Roesch, D. B. Martin

The equilibrium phase diagram of the Pu-Cd system is presented based on data obtained by differential thermal analysis, metallography, and electron-microprobe X-ray analysis. Liquidus temperatures range from 320° to 934°C. The system contains one congruently melting compound, PuCd, (945°C), and three incongruently melting compounds, PuCd, (800°C), PuCd, (730°C), and PuCd11 (410°C). A liquid-miscibility gap extends from 2 to 60 at. pet Cd with the monotectic reaction isotherm at 910°C. INTEREST in the potential use of plutonium alloys as reactor-fuel materials has prompted investigation of the phase equilibria in plutonium binary systems. A cursory investigation of the phase equilibria in the Pu-Cd binary system was conducted by differential thermal analysis (DTA), metallography, and electron-microprobe X-ray analysis (EMX). Extensive solid solubility of cadmium in both e and 6 plutonium was predicted1 based on atomic radii and electronegativities. Liquid immiscibility between these two elements was also predicted based on Mott's extension of Hildebrand's method. In the only previous investigation of the Pu-Cd system,2 two intermetallic compounds, PuCd11 (incon-gruent melting point 406°C) and PuCd8, were identified. EXPERIMENTAL The plutonium metal used in this work had a total impurity content of 500 ppm; the major impurities were: carbon (215 pprn), silicon (75 ppm), iron (60 ppm), nickel (40 ppm), and aluminum (25 ppm). The cadmium was reagent grade with a purity of 99.99 pet. The DTA technique for the study of plutonium alloys was previously described in detail.3 The alloys to be studied were prepared in tantalum DTA specimen capsules which were sealed by inert-gas welding. The alloys were homogenized in the liquid state in these sealed capsules which prevented the loss of cadmium by vaporization. Only the thermal arrests in the DTA heating curves were used to define the transformation temperatures of the system since supercooling affected many of the results during cooling. After the alloys were analyzed by DTA, the same alloys were used for the metallographic studies. Metallographic examinations were conducted in the manner described for plutonium alloys., No reaction was detected between the alloys and the tantalum capsules. Alloys for EMX analysis were placed in metallographic mounts together with specimens of unalloyed plutonium and cadmium which served as standards. The samples were highly polished but unetched. No protective coatings were applied to the surfaces of these radioactive specimens. Such coatings are detrimental to the excitation conditions and have been found to be unnecessary for the control of radioactive contamination. RESULTS The results of the DTA studies are presented in Table I. The phase diagram, constructed from these data plus the metallographic and EMX results, is presented in Fig. 1. The congruently melting compound, PuCd2, was identified by the occurrence of a maximum melting point (945°C) at 33.3 at. pet Pu-66.7 at. pet Cd and by the presence of a single phase in this composition.

Jan 1, 1965

By James Norman

BARITE (BaSO4) is the most important industrial barium mineral from the standpoint of quantity consumed. In 1938 the amount was 365,000 tons. Its uses are numerous, some of the more important being in the production of pigments, as an inert filler in a wide variety of products, as a weighting material in oil-well drilling muds, in the manufacture of some kinds of glass, and in the production of barium chemicals. The barite studied in this investigation occurs as the massive variety in a shale replacement formation near Magnet Cove, Ark. It is intimately mixed with quartz and small amounts of iron oxide and residual shale. Complete liberation of barite and quartz is not obtained when the rock is ground to loo per cent through 325 mesh. The crude rock with which all test work was done assayed 85.1 per cent BaSO4, 11.11 per cent SiO2, and 2.85 per cent R2O3. Its specific gravity was 4.03. It was found in the course of the investigation that the barite contained a small amount of uniformly distributed carbonaceous material, so intimately dispersed that it could not be seen with the microscope, but gave a definite gray cast to the barite concentrates. The color of the barite in polished sections of the crude rock ranged from gray to almost black, while finely ground powder was a reddish gray. The reddish hue was due to the iron oxide present. In 1939, under the supervision of Oliver C. Ralston,* the Bureau of Mines, in cooperation with the Milwhite Company, of Houston, Texas, undertook to study the flotation of barite from Magnet Cove, Ark. Flotation of several southern barite ores had already been investigated by the Bureau of Mines.' The Magnet Cove barite was unique, however, in that it had to be ground to such an extremely small particle size for liberation. The flotation of nonmetallic minerals in the presence of a large amount of slime is usually very difficult and when done is an innovation calling for conditions different from those under which granular material is separated. LABORATORY FLOTATION WORK Preliminary investigation showed that the flotation reagents recommended by O'Meara and Coe1 for separating barite and siliceous material were suitable, but much larger quantities of reagents were required to separate such finely divided material. Moreover, it was found that careful control of the frothing was necessary. When oleic acid and sodium silicate were used a voluminous froth was observed at the beginning of a test, and toward the end there was not enough froth to effect complete recovery of barite. The addition of pine oil as a frother gave proper frothing for the duration of the test, and the substitution of coconut fatty acid (crude lauric acid) for oleic acid produced a more heavily burdened froth. Two different paper-mill fatty-acid products were tested

Jan 1, 1941