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By Kenneth C. Vincent, A. M. Gaudin

IN a study1of the action of amyl xanthate on chalcocite in water suspension, it was found that if the xanthate is added in relatively large quantity the xanthate group can be accounted for in three forms: (1) as xanthate ion remaining in water, (2) as benzene-soluble cuprous xanthate on the chalcocite, (3) as a benzene-insoluble coating on the chalcocite. Reduction in the amount of xanthate added leads to disappearance of form 1 then of form 2. With minute quantities of added xanthate, substantially all the reagent is of the "unleachable" kind. Yet this unleachable xanthate can be dissolved by pyridine to form a soluble cuprous xanthate complex, and it is sufficient in effectiveness to make chalcocite flotable even if insufficient in quantity to form a complete monomolecular film on the mineral. In that study it was also found that chalcocite abstracts cuprous xanthate from benzene solution, in what may (or may not) be a case of molecular adsorption. It seemed desirable, therefore, to study further the "unleachable" xanthate on the chalcocite, and particularly to ascertain whether it is formed as a result of the benzene leach or is actually formed during the conditioning of chalcocite in aqueous xanthate solution. A splendid tool to make such studies has recently been perfected; that is, the use of radioactive spies or tracer atoms. With this tool, it was thought possible to answer the problem stated above, but, unfortunately, this did not prove to be true. Answer to the flotation question was clouded by the existence of rapid and selective diffusion of copper atoms in the solid mineral-a phenomenon that was totally unexpected yet remains interesting and perhaps important. METHOD OF RADIOACTIVE SPIES The method of radioactive spies is discussed in many places. Two convenient references are the article by Evans2 and the book by Pollard and Davidson.3 The method was first developed by Von Hevesy and Paneth in 1913, when only natural radioactive isotopes were available. These isotopes are few in number, and so the method remained limited in scope. Recently the synthesis of over 350 active isotopes of all the known stable chemical elements4 has opened widely expanded possibilities for the method. A fundamental tenet of the method is that a radioactive atom and a nonradioactive atom are exactly alike until disintegration of the radioactive atom. Then, by its sudden death, the spy reveals its location. The relative abundance of spies at various locations makes it possible to ascertain the relative abundance of the corresponding nonradioactive atoms at the same times and locations. A second fundamental tenet of the method of radioactive tracers is that the radioactivity lies in the nucleus of the atom: transfer of radioactivity from one

Jan 1, 1944

By Carl Lee

OXYGEN-FREE high-conductivity copper (OFHC brand) that is now being commercially offered for the first time represents a notable achievement in electro-metallurgy and is the outcome of endeavors that have extended over a long period. Its manufacture is novel in that electrolytically refined copper is melted in electric furnaces and cast into vertical water-cooled molds. The ingots show the "pipe" characteristic of sound gas-free metal and microscopic examination even at high magnification reveals no cuprous oxide in the copper. Owing to the patent situation, the United States Metals Refining Co., the producers, cannot at this time divulge the details of manufacture, but the operations are under precise control so that the castings are of great uniformity and the copper contains no residual deoxidant. Figs. 1 and 2 show photographs of cross-sections of a wirebar and a billet, both vertically cast.

Jan 1, 1933

By M. B. Kahle, A. D. Pernichele

Four types of slope failures in waste dumps are recognized debris flow, foundation failure, edge slump, and blowout. The first three types, although at times causing considerable damage to property and interfering with mine operations, are not usually dangerous to personnel because of their slow rate of movement. The fourth type, the blowout, is the most dangerous because of its explosive mode of failure and lack of forewarning. The December 1969 failure at Verona dump is presented as an example of a blowout. Data from piezometer holes indicate that the blowout was due to perched leach solutions near the face of the dump. The level of water in this zone is very closely related to the rate of leach water application on the dump. A detailed analysis of core samples indicates that the impounded water was perched on a zonal accumulation of jarosite which is associated with a buried dump surface. Drain holes proved successful in controlling perched leach solutions in the critical zone near the face of the dump. Monitoring of the water level in the perched zone is considered essential in preventing blowouts. The use of drain and piezometer holes has allowed an increase in the rate of water application on the dump while preventing additional failure.

Jan 1, 1972

By A. T. Schwennesen

(Wilkes-Barre Meeting, June, 1911.) EVERY engineer has occasion to trace or copy a map, plan, or other drawing on paper too thick for the ordinary way of using tracing-cloth or tracing-paper. When the figure is small and simple a copy may be made by holding the original against a window-pane, covering it with the paper, and tracing direct by the aid of the strong sunlight from outside. The need of utilizing this principle on a larger scale and in a more convenient position led Dr. J. C. Branner to plan the table of which the following is a description: This table was first made in the form of an adjustable glass-top table with a mirror beneath, in 1887, while Dr. Branner was State Geologist of Arkansas. Later it was modified as experience suggested until the form as here described was evolved. The device consists essentially of a drafting-table with a plate-glass top, upon which the original drawing and the paper are laid, and a mirror mounted underneath to reflect the light of the sky up through the drawing. The glass top is hinged and fitted with two arms and thumb-screws, so that it can be raised and fixed to any position, either inclined or horizontal. The mirror is pivoted and revolves about a horizontal axis, so that it may be tilted to any angle. The hood of cardboard or black cloth prevents the reflection of light from the tracing, and may or may not be attached to the table. The apparatus is set up before a window through which part of the unobstructed sky is visible. The mirror is then adjusted like the reflector of a microscope, so that the skylight is reflected up through the drawing. If the mirror can be so located that the direct rays of the sun are reflected through the drawings, thicker paper can be used. The map or drawing may be held in place by clips screwed

May 1, 1911

By Douglas Ashmead

In his paper Mr. Braley makes no mention of the bacteriological aspects of the problem. It is now quite well established that certain bacteria play a major role in formation of acid mine waters, and it is a simple matter in the laboratory to show that under sterile conditions the rate of acid production from a pyrites suspension is only about one quarter of that obtained from a similar suspension inoculated with drainage from a mine producing an acidic pit water. Under sterile conditions the oxidation is due to direct chemical action and, from the evidence just given and from much other evidence, this increase under nonsterile conditions is due to certain bacteria. Experiments recently completed, and shortly to be published, have shown that this bacteriological oxidation can be prevented by the maintenance of pH conditions above 4. It was found that to raise this pH above 4 at the beginning of the experiments was not sufficient but that, due to the continuing chemical oxidation, alkali had to be added daily to maintain the pH conditions above 4. The amount of alkali added, however, over a fixed period, was only about one quarter of the alkaline equivalent of the acid produced when pH conditions were not controlled over an equal period. The opinion expressed by Mr. Braley that sodium hydroxide has little or no effect on the rate of oxidation of pyrites is not substantiated by the above experiments. The writer does not claim that these results show a practical solution to the problems, especially in abandoned workings, but feels that the application of an alkaline coating, such as lime wash, to exposed accessible workings might be well worth trying. S. A. Braley (author's reply)—In 1919 Powell and Parrl suggested that bacteria, or some catalytic agent, hastened the oxidation of pyritic or marcastic sulfur in coal. Carpenter and Herndon (1933)' attributed the action of Thiobacillus thiooxidans. Colmer and Hinkle (1947)3 observed an organism similar to T. thiooxidans and another organism that oxidized iron. Leathen and Braley 9rst discovered this organism in 1947 in a sample of water from the overflow of the Bradenville mine (Westmoreland County, Pennsylvania). They characterized the organism in 1954" and gave it the name Ferrobacillus ferrooxidans. Although Temple and Colmer (1951)' had suggested the name Thiobacillus ferrooxidans, since they claimed it oxidized both ferrous iron and thiosulfate, we have found that pure cultures of the organism do not oxidize thiosulfate, hence the name F. ferrooxidans. In 1955 Ashmead7 isolated an organism, similar to the one called Thiobacillus ferrooxidans by Temple and Hinkle, from acid mine water in Scotland. It is probable that this organism was F. ferrooxidans. In 1954 Bryner, Beck, Davis, and Wilsonh reported microorganisms in effluents from copper mine refuse. These organisms appeared to be similar but were not in pure culture. In view of this history of bacterial investigation of acid mine water and our own ten years of experience, we do not agree with Mr. Ashmead that bacteria play a major role in acid formation. We do not find that any of these bacteria will directly oxidize pyritic material. They do, however, augment the chemical formation of sulfuric acid by atmospheric oxidation. In two papers in 1953% eathen, Braley, and McIntyre discuss the role of bacteria in acid formation and postulate the mechanism through which they operate. Mr. Ashmead in his discussion of my paper has assumed that this work was carried on in the presence of acid mine water in which bacteria would be present. This was not the case. Strictly sterile conditions were not maintained, but the organisms present in mine drainages were definitely absent in these experiments. We believe that we have demonstrated that alkalis do not inhibit the chemical oxidation of pyritic material. This is also indicated by Mr. Ashmead's discussion in which he says that alkali must be added daily due to the continuing chemical oxidation. It is interesting to note that Mr. Ashmead finds that maintenance of pH above 4.00 decreases the activity of the bacteria. We have found also that a decrease in pH below 2.8 also inhibits its activity. Table XIII of published data'" illustrates the decrease in activity with increased acidity, although pH values are not given. These values are in comparison with uninoculated controls and show the marked increase in acidity up to 22 weeks but a decline at 29 weeks, at which time the experiment was terminated. It is probable that after a longer period only chemical oxidation would have continued. From our studiesv we have postulated that the iron oxidizing bacterium (Ferrobacillus ferrooxidans) oxidizes the ferrous iron, resulting from chemical oxidation, to ferric iron. The ferric iron then aids the atmospheric oxidation of the sulfuritic material and is itself reduced to ferrous iron, which in turn acts as food for the autotrophic bacteria. Study of the physiologic properties of F. ferrooxidans shows that its preferred pH is about 3.00 and its activity decreases with variation in either direction. It is extremely inactive above pH 4.00 and below 2.5. This inactivity above 4.00 is indicated by Mr. Ashmead's observations. These properties of F. ferrooxidans then correlate perfectly with our hypothesis. Ferrous iron is oxidized very slowly by atmospheric oxygen in highly acid sohtion and since the bacteria become inactive, acid is formed only by atmospheric oxidation. At a pH of 4.00 or above iron is more readily oxidized by atmospheric oxygen, but the bacterial activity is decreased. However, with a pH above 4.00 the ferric iron is removed from the field of activity since its soluble sulfate hy-drolyzes and precipitates the iron as ferric hydroxide or a basic sulfate. As we have shown in the paper under discussion, the alkali does not inhibit the chemical oxidation, and thus the acid formation continues. This

Jan 1, 1957

By J. W. Leonard, B. A. Donahue

A method is described for incorporating coal petrography into mining and preparation plant quality control based on conventional analyses. Complete analyses are made of each of the uniform and relatively distinct petrographic bands in a coal face. With this information it is possible to develop petrographic standardization curves. These curves permit diverse coal characteristics to be rapidly monitored by application of a few standard coal tests. Single seam quality control is discussed in this paper. Inquiries continue to be made about coal petrography, and specifically, about whether coal petrography should be applied more extensively in the coal industry. Coal petrography is the study of the distinct physical, optical, and chemical increments which make up the organic rock mixture which we know as coal. Petrography can be applied by any coal company or at any coal mine where conventional coal analytical facilities are available and where additional resources can be allocated for an increased number of determinations. This first paper of a two part series includes (1) a proposed conventional approach to single seam petrography based on the development of petrographic standardization graphs and (2) some informative and supplemental interrelationships involving coal characteristics developed as a result of this research. In the second part of this series, to be published at a later date, those petrographic characteristics of bands taken from many different coal seams located over wide geographic areas which can be closely related to each other will be considered. These findings will be examined looking toward the development of a comprehensive, conventional approach to coal petrography which can be used as a common basis for multi-rank petrographic standardization graphs. Implicit to the understanding of coal petrography is the well established fact1,2 that the individual analyses of distinct petrographic bands often differ widely from the average analysis which is used to characterize a whole coal seam. In fact, a distinct and minor banded increment of coal in a high volatile seam may actually be a medium or low volatile coal with an analysis similar to the average analyses of seams located in distant coal fields. During the mining of coal, much degradation is caused which tends to randomly scatter coal bands. The degraded, scattered, and physically separated constituents of distinct petrographic bands are processed side by side in the coal preparation plant as distinct petrographic fractions with particles grouped according to a narrow size range (which derives in part from common hardness), specific gravity, and-or surface chemistry. Tile data obtained from numerous analyses made on each of the bands of any given coal seam, although diverse, can be readily interrelated. Indeed, these interrelationships can be developed into a series of nomographs or petrographic standardization graphs to serve as a basis for developing a conventional petrographic* program. Thus, by analyzing one property (for example, ash) of a selected petrographic fraction collected or separated from the flow of coal in a preparation plant, it should be possible to estimate the other physical, chemical, and thermal properties of this fraction by referring to the petrographic standardization graphs. It follows that any or all petrographic fractions in the total coal flow originating from a single coal seam can be rapidly monitored for many properties on the basis of a single analysis run on each fraction. In recent years coal petrographic research has concentrated heavily on that phase of this work which involves microscopic reflectance measurements made at many minute and selected points on a coal briquette surface.3,4 Thus, the percentage of the total number of reflectance measurements that fall into each of a consecutive series of arbitrarily chosen reflectance classes are used to characterize coal. This procedure is analagous to using the face of a coal briquette to represent the reflectance characteristics present at the face of a coal seam. Moreover, by analyzing petrographic fractions of known and uniform optical properties it is possible to closely relate reflectance to other coal characteristics. For example, reflectance has long been known to be related to such

Jan 1, 1968

By Frank Firmstone

It is proposed to consider here only comparisons made between results obtained when the materials employed are precisely the same, two furnaces at the same works for example, or the same furnace under different conditions as respects temperature of blast, method of charging, etc. With this limitation, the most important point in the comparison is the amount of fuel consumed per ton of iron. This, in fact, is the only item in the prime cost of the iron which can properly be said to vary in consequence of changes in the furnace process; for of the other principal items, the ore used per ton of iron, and also the amount of fluxing material, will depend on its richness, which, under the assumed conditions, will be practically invariable when taken over any considerable period; the labor cost also, from its nature, should be very nearly constant when estimated on the ton of iron. Moreover, as it consists principally in handling and moving material, it is greatly affected by circumstances quite independent of

By Emery C. Olsen

Most coal mining areas of the Western United States are characterized either by thick beds, steep pitches or heavy cover. Individually, each of these may present inherent safety hazards that influence mining. When all are met at one location, the combined effect is to make the safe operation of the mining property a challenge to management. These combined conditions are met in the coal mines of the Columbia-Geneva Steel Div. of the United States Steel Corp., in southeastern Utah. This coal bed measures up to 16 ft in thickness, the pitch is as much as 25 % and mining is under a cover approaching 3000 ft. The Sunnyside coal bed is found in the Book Cliff Mountains, a great escarpment extending from west of Castle Gate, Utah, some 180 miles to Grand Junction, Colo. West of Green River, Utah, the Book Cliffs swing sharply to the north because of the domelike uplift of the San Rafael Swell to the south- west. It is in this northerly extension of the Book Cliffs that the Sunnyside coal in the Blackhawk Formation of the Mesa Verde Group, Upper Cretaceous Age is found. The strata are transected by numerous faults with from a few inches to as much as a hundred feet of displacement. All of these faults have had some effect on the mining operation, either in roof control or, in the case of major faulting, the pattern of mine development.

Jan 10, 1963

By Carl Lee

WITH the modern trend toward motor drive in coal mines, more careful forethought should be given to future layouts than has usually been done in the past. Both top and bottom equipment of future new mines is likely to differ radically from those of a decade ago. No one is able to predict very far ahead, but provisions can be made to allow for uncertainty. One thing stands out: the mine of the future will be laid out for long life compared to that of the small mine of the past, where an inexpensive top plant, simple equipment, a small timbered shaft, small cars, light rail, hand loading and mule haulage all contributed to a short economical life.

Jan 1, 1933

By G. A. Beiswenger

The application of the law of supply and demand to the sale of crude oil is generally conceded, but the motives underlying the buyer's (refiner's) demands are not always obvious to the seller (producer). In some cases this obscurity has led to the conclusion that the refiner may be unnecessarily particular when he selects one crude and rejects another. This preference, however, is very largely the reflection of the refiner's product demands and the quality of the stocks obtainable from the selected crude. The purpose of this paper is to point out critical characteristies of the major classes of refined products and to show how crudes vary in their suitability for such products. With relatively few exceptions, available processing methods and addition agents make it theoretically possible to produce any type of refined product from any crude source, although it may not be economically sound to do so. The widespread application of thermal cracking for converting higher boiling stocks into gasoline is well known. More recently cracking and refining in the presence of catalysts9 have been developed, as well as various processes for polymerizing lighter hydrocarbons into gasolines having desirable characteristics.6 For several years, selective solvents have been applied commercially to refining inferior quality kerosene, Diesel fuel and lubricating oil distillates.3 Improved methods for refining lubricating oils from crude residual4 formerly suitable only for fuel, are now in use and a number of special solvent processes are available for dewaxing lubricating oils to low pour point.5 These improved refining methods have been developed not only to meet the demand for improved product quality but also to enable the refiner to obtain quality products from crude sources that would not yield such products by the older refining methods. In many cases, the utilization of these modern refining tools necessitates an appreciable expenditure for equipment as well as added manufacturing costs, and their application therefore must be justified economically. Despite the availability of such tools, the added processing costs involved and yields obtainable may render their application entirely impractical. To illustrate this point, inspections of typical cuts from various crudes

Jan 1, 1940

By Lucien Eaton

The use of filling in mines is less common in the United States than it is in Europe, where in some places it is required by law. In most cases the filling is placed by hand, and the material used for this purpose is the waste from development and that sorted from the ore in the stopes. When these sources provide an insufficient supply, additional rock must be quarried on surface or mined underground, or some other material must be used. In different parts of the world sand, clay, gravel, culm, granulated slag, mill tailings, and even ashes, have been used as filling material in place of or in conjunction with rock. Of all the materials used for filling the best is probably clean sand. Gravel, finely crushed rock, granulated slag and coarse mill tailings are almost as good, and the methods used for placing and confining sand will apply equally well to any of these. The advantages of sand are its comparatively slight compressibility and the ease, economy and convenience with which it may be placed. On account of the voids, which necessarily occur in fills made of coarse waste, such fills will compress 10 to 25 per cent before they develop their full strength, whereas clean sand seldom compresses more than 5 per cent. Sand is especially desirable when practically complete filling is required, and sand derived from mill tailings, especially when not thoroughly cleaned, has been remarkably effective in sealing off and extinguishing mine fires. When natural sand is available on surface, or when it can be obtained from the mill tailings or tailings dump, the cost of using this material for fill will probably be considerably less than that of rock. In this paper it is not proposed to discuss all methods of filling, but to describe some of the methods used for placing sand fill and to make a brief comparison of their merits. Methods of Placing Sand Sand may be transported and placed underground by several methods, which may be classified as follows: 1. By Hand.—The sand, which must be comparatively dry, is taken down the shaft in cars on cages and is distributed to its destination in these cars, or it is dumped down raises and is drawn off and distributed by means of cars, wheelbarrows or scrapers.

Jan 1, 1932

By L. Wahl, M. Allard, B. Trentini

REMOVAL of sulfur in steelmaking is presently a problem of utmost importance as requirements on final sulfur contents in finished steels become increasingly strict. This is in spite of often increased sulfur contents in the fuels used during the different stages of steel processing. According to local conditions or current economic factors, sulfur can be removed during one or more of the processing operations; for instance, in a blast furnace operated under high temperatures and with a high slag basicity ratio and also by means of high inputs of manganese into the burden. These methods of proceeding are, however, expensive and in contradiction with the acid practice which is gradually being developed owing to the fact that it allows coke and lime savings and usually permits an increase of productivity. In the melting-shop, desulfurization can proceed in the open-hearth or electric furnace with one or several very basic slags, or with special prefused slags (Perrin process) mixed with steels poured from the open-hearth, electric furnace, or converter. Liquid pig iron has also been treated separately before being used in the melting shop, in order to reduce high sulfur contents. This external desul-furization has been developed in Europe for the basic Bessemer Thomas process, which is again in favor owing to the great flexibility of such installations and to the fact that the steel produced is not polluted by impurities coming from the scrap. Since the basic Bessemer process, as usually practiced, has a low desulfurizing power, external desulfurization is generally carried out in ladles by means of alkalies such as soda ash. This method, which has the advantage of being simple and costing little, has only a medium desulfurizing power, which implies the necessity for repeating the operation several times when a substantial amount of sulfur has to be removed or when very low sulfur contents are desired. Thermal losses are high and there is a considerable decrease in output. Moreover, the resulting fluid and corrosive slag, which is extremely difficult to eliminate, attacks the refractory linings of the mixers and steel furnaces. Therefore, it seems necessary to devise a simple method for external desulfurization which would not only remove substantial quantities of sulfur from the hot metal coming from an acid blast furnace, but which would also bring the sulfur contents down to the low level required in the making of high quality steel and iron. Principle of the Process In this paper a new method will be described for desulfurizing hot metal. It has been perfected by

Jan 1, 1958

By D. J. Pye

Certain high molecular weight synthetic polymers in very dilute solutions decrease water mobility in porous media 5 to 20 times more than would be expected from the solution viscosity. This indicates that increasing water viscosity to reduce adverse mobility ratios in water floods is economically feasible in many situations. Laboratory results are consistent with accepted theory with respect to improved areal sweep, permeability distribution and displacement efficiencies as would be predicted from the solution mobility measured in the core. The laboratory results have been confirmed by field pilot floods which recovered 80 per cent and 100 per cent more oil than comparative water-flood pilots in fields containing 16 cp and 130 cp oil respectively. Economic analyses based on pilot data indicate the method to be profitable. INTRODUCTION The desirability of improving the water-oil mobility ratio in waterflood-ing operations has long been appreciated, especially for high viscosity crudes. Methods of reducing the oil viscosity by application of heat, gas resaturation and miscible drives have met with some success. Conversely, it has been generally conceded that increasing the water viscosity would also be effective, but the amount of thickening agent required to effect an appreciable increase in viscosity is discouragingly high. The use of such materials as glycerin, sugar, or glycols is completely out of the question economically, so that considerable attention has been given to the use of the much more efficient synthetic water-soluble polymers as viscosity improvers; but even these materials are not economically attractive. If increased water viscosity could be economically realized, marked improvements in areal sweep efficiency, as discussed by Caudle and Wittel and others, would be realized in field operations. Similarly, the improved mobility ratio would bring about increased recoveries by correcting permeability distribution problems as discussed by Stiles2 and Dykstra and Parsons,' and improvements in displacement efficiency would be obtained as recognized by Buckley and Leverett4 and Welge.5 LABORATORY STUDIES THE RESISTANCE EFFECT In the course of research to develop a more efficient water-soluble polymer viscosity builder, we discovered that a very few types of water-soluble polymers exhibited a most unusual and very interesting property not previously observed. Among the earliest materials showing such activity were polymers containing acry-lamide. Fig. 1 shows a typical plot of the solution viscosity vs concentration for one of these polymer solutions as determined in an Ostwald viscometer. As usual, such a plot is an approximate straight line on semi-logarithmic paper. Now, an inspection of Darcy's law, shows that a viscosity value can also be determined in a formation sample if the pressure, flow rate and permeability are known. If the core permeability is previously determined with wa- ter or brine, then the viscosity of another aqueous fluid may be determined from the equation. The viscosities so determined for glycerin (glycol or polyvinyl alcohol solutions, for example) agree with the viscometer determinations. However, in the case of the water-soluble polymer solutions in which we are interested, the viscosities measured in the formation sample depart very markedly from the viscometer values. A typical relationship for a polymer solution is also shown in Fig. 1. This unusual departure from the expected response is referred to as a resistance property of the polymer and is quantified as "resistance factor". Since the resistance factor R can best be determined in a core under study, the term has been defined on the basis of the ratio of the brine mobility to the polymer solution mobility at residual oil saturation so that:

Jan 1, 1965

By J. R. Cahoon, W. V. Youdelis

In a previous communication by one of us,1 a theory of inverse segregation was presented by which the maximum segregation and segregation distribution throughout a unidirectionally solidified, binary-alloy ingot could be calculated. The theory, which is based on the mechanism of volume contraction and interdendritic flow, quantitatively accounts for the observed maximum segregation in the A1 (rich)-CU' and Al-Zn2 alloy systems, and for the segregation distribution along the ingot lengths for the A1-Cu system.''4 One of the drawbacks to a more extensive use of the segregation equations is their complexity, particularly for the calculation of the segregation distribution throughout the length of the ingot, involving long tedious numerical calculations to obtain the segregation. Computer pro- grams, written in Fortran II for use on an IBM 1620 computer, have been developed by the authors (and are available from them), providing quick and accurate methods for the determination of the theoretical maximum segregation in any binary-alloy system, and also for the segregation distribution in any unidirectionally solidified binary-alloy ingot. The segregation distribution is controlled by the lengths of the various solidification zones'74 which are in turn controlled by the cooling rate, and are determined from temperature-distribution curves obtained during solidification. The theoretical segregation distributions shown in Fig. 1 illustrate the effect of the zone lengths on the distribution Curve 1, indicative of a slowly cooled ingot, represents an ingot having long solidification zones, while Curve 2, indicative of a rapidly cooled ingot, represents an ingot having relatively short zones. Although these distributions are calculated for an A1-10 pct Cu ingot, the shape of the distribution would be similar for any binary-alloy ingot. These curves show clearly why early workers obtained results which indicated that the maximum (chill-face) segregation approached zero at very fast cooling rates.3 Actually, the maximum segregation is independent of cooling rate,' but even at short distances from the chill face the amount of segregation drops considerably, particularly in a rapidly cooled ingot, making it very difficult to establish the amount of segregation occurring at the chill-face. The authors would like to thank Dr. J. A. Goldak for his assistance in the preparation of the programs. The financial assistance of the Steel Co. of Canada and of the National Research Council of Canada in the form of Scholarships to one of us (J. R. Cahoon) is gratefully acknowledged.

Jan 1, 1964

By T. S. Plaskett

A striated structure perpendicular to the growth axis was observed by the copper-decoration tech-nique in dislocation-free, .float-zoned silicon crystals. The striations, which were spaced about 100 p apart, fitted the relationship d = f/u , where d is the spacing, f is the growth rate, and u is the crystal rotation rate. Each stria was resolved into an UNDOPED silicon crystals pulled from quartz crucibles by the Czochralski technique usually exhibit a striated structure perpendicular to the growth axis.'-' This structure has been attributed to oxygen segregation, with the oxygen being introduced from the quartz crucible. If the crucible is rotated, the level of oxygen contamination has been reported as high as 10° atoms per cu cm.10 These striations are similar to solute striations commonly observed in doped Czochralski-grown crystals. The periodic nature of the striations is caused by a periodic variation in the growth rate",12 which is attributed mainly to thermal gradients in the melt.13 A finer striated structure14 attributed to constitutional supercooling is sometimes observed between the coarse striae. The oxygen striations have been observed by infrared transmission techniques,' by the copper-decoration technique,' by X-ray diffraction microscopy,6-8 and by 9 p absorption measurements3 on crystals pulled from the melt both with and without dislocations. In this investigation float-zoned dislocation-free crystals were examined by the copper-decoration technique. The level of oxygen for float-zone material is less than 1016 atoms per cu cm the lower limit of detection by 9 p absorption measurement. EXPERIMENTAL TECHNIQUE The crystals were grown by the float-zone process with the rf heating coil outside of the quartz envelope containing the silicon. All float zoning was done under an atmosphere of purified helium. The Dash technique15 was used to grow the crystal dislocation-free. This involves growing the crystal initially with a diameter between 2 and 3 mm and at array of starlike precipitates of copper. The strucLure was not .found at the surface tor a depth of about 1.5 mm, or in a region of similar width ahead of a dislocation network. The structure is postulated to consist of vacancy clusterings or dislocation loops. very rapid rates, about 20 mm per min, for a distance of about 3 cm. The diameter of the crystal is then increased to the diameter of the source of silicon, which in this case was about 19 mm. Because of the arrangement of the apparatus, the zone was passed downward rather than upward, contrary to the standard float-zoning practice. Also, the source was rotated rather than the seed. ziegler17 has made dislocation-free crystals by a similar technique but has passed the zone upwards. The starting material was zone-refined and had a p-type resistivity of 150 ohm-cm. The major impurity was boron; the total impurity excluding the boron was reported by the supplier (Dow-Corning) to be typically less than 2 x 1013 atoms per cu cm. The crystals were examined by the Dash copper-decoration technique18'19—a method in which about 10" atoms per cu cm of copper are diffused at a temperature between 900" and 1000°C into silicon which is then quenched to room temperature. On quenching, the copper precipitates on crystalline defects which are then visible when viewed by transmission infrared microscopy. The photomicrographs shown were taken either of the infrared image tube screen or directly on infrared film. All sections prior to decorating were chemically polished and, for some sections, given a sirtlZ0 dislocation etch-pit examination. After decorating, the samples were mechanically polished. RESULTS A photomicrograph, taken in transmission of a decorated cross section, is shown in Fig. 1. The portion of the section shown is near the surface of the crystal. The entire cross section showed no dislocation etch pits after being given a Sirtl etch treatment. It is seen that the copper precipitated randomly. Each precipitate, as has been reported by others, was found to have a starlike structure.

Jan 1, 1965

By R. S. Dean

JUST as the mineralogical name bauxite has come to include several minerals not known at the time the name was first applied, so the concept of bauxite as the one source of alumina must be enlarged during the war period to include the production of alumina from other, low-grade sources. Speaking in a narrow mineral logical sense, there is no such thing as bauxite, and similarly there is now no one source of alumina, and no one process for its extraction.

Jan 1, 1943

Jan 1, 1895

By N. G. W. Cook

When an excavation is made underground the original rock stresses are removed from the surfaces of the excavation. These surfaces converge to partially close the excavation and the superincumbent rock mass moves down towards the excavation. If the convergence of the surfaces of the excavation were controlled, energy generated by their motion against the controlling forces could be extracted. Since the total forces in the rock mass are not significantly affected by the excavation, stress concentrations arise around the excavation, which compensate exactly for those stresses no longer transmitted through the excavation. These phenomena give rise to two general principles which provide the basis for analyzing the effects of making any underground excavation. The first of these is that the total force resulting from the stresses across any plane in the rock, including any plane through the excavation, must be the same before and after the excavation is made. The second of these is that energy must necessarily be released as a result of making an underground excavation. It is instructive to consider the implications of these two principles for two extreme cases of material behavior between which the actual behavior of rock must lie, namely, the behavior of a fluid and the behavior of an elastic solid. For the purpose of analysis in this paper, an underground excavation is defined as an excavation in which the smaller horizontal dimension of any open void at a particular horizon is less than the depth of that horizon below surface. In the case of a fluid, any unsupported excavation would fill immediately, as a fluid cannot sustain shear stresses. For the same reason, stress concentrations could not arise and the forces across any plane would necessarily be the same before and after excavation. If the filling of the excavation were controlled by forces applied to the surfaces of the excavation, an amount of energy equal to the product of the fluid pressure

Jan 1, 1967

By J. W. Spretnak

It is well-established that decohesions occurring at the interface of the matrix and rigid inclusions and second-phase particles are prime causes of ductile fracture initiation. It is not clear, however, how these decohesions occur. The idea that the interface bond is broken in tension is not particularly attractive when one considers the strength of such interfaces and the fact that plastic flow is not restricted under conditions of continuing flow required to initiate and propagate ductile fracture. A suggestion as to the mechanism of decohesion arises if one takes the position that, as the dislocation density increases with plastic flow and reaches some critical range of density, the phenomenon of flow can be regarded as fluidlike instead of the crystallographic motion of dislocations. As the spacing between dislocations decreases, the matrix becomes increasingly disordered in terms of loss of periodicity. At some critical degree of reduction of the periodicity, it is suggested that flow can be regarded as hydrodynamic, rather than crystallographic. Such a state has been referred to by rheologists as the "plasticized state", or the "fourth state of matter", between the liquid and solid state. A similar argument pertains qualitatively with the increase in equilibrium vacancy concentration as the temperature approaches the melting point. Taking the viewpoint that at larger strains the flow may become hydrodynamic in nature, a mechanism of decohesion is suggested. A well-known phenomenon in boundary-layer flow is that of "separation" locally of the boundary layer from the substrate.' Under certain conditions, the flow in the immediate neighborhood of the substrate becomes reversed, causing the boundary layer to separate from it. The exact condition for separation is that the velocity gradient normal to the substrate vanishes there, or It is of interest that blunt particles such as spheres and circular cylinders are most likely to give rise to separations because of unfavorable pressure distributions behind them. The source cited gives solutions for positions of separations for various geometries. In principle, such separations can also take place when metal is flowing over a "dead zone" of stagnant metal. This may explain the initiation of fracture at the elastic-plastic boundaries of plastic enclaves under a notch.

Jan 1, 1967

By Clarence W. Balke

SMALL buttons of fused tantalum have been produced by arc fusion in a vacuum, by drawing an arc between sticks of pressed tantalum and a tantalum-faced water-cooled copper block. However, ingots of appreciable size can be produced only by the heat-treatment of bars pressed from powder. The following outline covering the production of finished bars of tantalum by the methods of powder metallurgy is also used for the production of columbium, taking into account the difference in the melting points of these two metals. PRESSING THE POWDER With possibly a few exceptions, a pressing operation is one of the essential steps in the practice of powder metallurgy. In fact, the author's experience with a number of high-melting-point metals and with numerous types of hard carbide compositions has led him to believe that this operation is often one of the most important in the entire process, and frequently one of the most difficult to carry out in a satisfactory manner. Defects due to improper pressing can readily lead to a defective finished product. It is the author's opinion that rarely is a bar or other article pressed from metal powder in such a way that all parts of the piece are uniformly pressed. The nearest approach to uniformity of pressing is possibly attained when the powder is contained in a flexible receptacle, such as rubber, and is pressed under a liquid by hydrostatic pressure. However, this method is not generally applicable. Hydraulic pressing in steel dies where one or two punches are forced into the die must usually be resorted to. As the pressure in such a die is built up, the powder begins to cling to the walls of the die with a tenacity dependent upon the nature of the powder, and this results in a bridging action, so that the layers of powder adjacent to the moving punch are pressed more heavily than those further removed in the mass. Frequently, as the pressure is carried higher, there may be a mass slippage of the powder upon itself, with the result that slip cracks are formed within the pressed

Jan 1, 1938