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By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

Mining and Metallurgy of Lead and Zinc, AIME Vol. 121, edited by Dr. C. R. Hayward in 1936, remains a document of importance today even though 34 years have passed in the meantime. Since nothing in this world seems to be permanent, however, and progress brings new and better ways to do things, a two-volume set has just been published to bring the state of the art of 1936 up to date. This two-volume set, Mining and Concentrating of Lead and Zinc and Extractive Metallurgy of Lead and zinc, incorporates the papers to be presented during the Proceedings of the 1970 World Symposium on the Mining and Metallurgy of Lead and Zinc. The Symposium is being held October 20-24, 1970, in St. Louis, a site near to the famous Lead Belt of southeast Missouri. Some eighty papers are bound in these two volumes covering exploration, geology, mining, concentrating, roasting, smelting, electrolytic processing, residue fuming, refining, etc. All of this is laced with data on tonnages, processes, assays and efficiencies obtained, and the man-hours and equipment needed to achieve these performances.

Jan 1, 1970

By Frances Jane Cromwell, D. J. McAdam, G. W. Geil

INTRODUCTION IN a series of papers, the authors and their associates have shown that the technical cohesion limit is affected by the same four factors that affect the flow stress, namely, the stress system, plastic deformation, temperature, and the strain rate.16-28 Moreover, each of these factors affects the technical cohesion limit in the same way that it affects the flow stress.‡ The influence of any one of these factors may be represented by a curve of cohesion limits, although only one point on the curve may represent actual fracture. As the term "fracture stress" has come into use with the same significance as "technical cohesion limit," the authors are here using the shorter term with the understanding that it does not always refer to actual fracture. This paper presents the results of an investigation of the flow of notched and unnotched specimens between yield and fracture. A study has thus been made of the flow and fracture of metals as affected by the stress system, and of the ductility of metals as affected by the stress system throughout plastic deformation. Since two of the principal stresses were equal (S2 = S3), the stress systems can be represented in terms of the radial stress ratio, the ratio of the transverse radial stress S3 to the longitudinal stress Sl.* The results of the experiments are represented by a series of complete flow-stress curves for each of the metals investigated, and these diagrams have been used for the development of other diagrams of various types. Ludwik was the first to suggest that fracture occurs when the flow stress becomes equal to a technical cohesion limit. Although Ludwik was incorrect in his view that the technical cohesion limit depends only on the amount of plastic deformation and not on the stress system, he was correct in his view that the flow-stress curve for any stress system terminates at a point representing a technical cohesion limit. The authors have seen some recent references to assertions by other investigators that a point representing the fracture stress need not be on the flow-stress curve. The Ludwik principle, however, would seem to be axiomatic, provided that the flow stress and fracture stress are properly defined and that the fracture stress is properly determined. Disregard of this principle has led to some untenable theories of criteria for fracture. When a metal is very ductile, the conventional method of determining the ductility and fracture stress by dividing the breaking load by the sectional area after fracture, generally gives values that are much too high. With some metals and in some conditions, the fracture stress thus determined may be two or more times the

Jan 1, 1948

By Hugh Neill, O&apos

In previous papers,' the author has reported the results of experiments on the straining in tension of a single-crystal test piece, about 0.6 in. long, of vacuum-melted electrolytic iron containing 1.8 per cent. of silicon. The crystal was originally in the "as cast" condition, and was stressed slowly along a tetragonal axis so that slipping along conjugate gliding planes finally transformed the original cylindrical portion into a pair of fracture wedges. One of these fracture wedges was sectioned along the stress axis in a plane at right angles to the edge of the wedge. A metallographic study of this plane of section led to the conclusion that slip had taken place in the (111) direction along (112) planes making a V shape with the stress axis. The present paper describes the results of scratch-hardness tests conducted on the same section, in order to determine the distribution of strain hardness therein, followed by annealing, and considers the resulting variations in hardness. These observations supplement those made by Krivobok2 on similar material reduced 25 per cent. by hammering (i. e., by impact) in the cold. In order to investigate ageing effects, two small crystals of the same alloy were also tested. The Specimens Employed The principal specimen, A, was prepared for the metallographic examination leading to the determination of the slip planes of the crystal. Therefore the work described in this paper was conducted on metal which had been repeatedly etched and had been allowed to rest for about 30 months after straining. It consisted of a section of the fracture wedge and contiguous unstrained head of the test piece taken along a tetragonal axis parallel to the direction of stressing, the plane of section originally being not far removed from the (011). Several subsequent grindings

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKD 1895

Jan 1, 1923

By R. W. Ph. D. Raymond, Anton Filers, O. H. Hahn

THIS paper will treat of such works only as beneficiate ores directly in the mining districts. And when it is said that more than twenty furnaces exist in Utah, about as many in Nevada, five in Montana, and four in Cerro Gordo, Inyo County, California, it is obvious that a business so extended deserves attention. Wide apart as these different works are located, they have nevertheless to deal in nearly every case with the same or very similar circumstances and conditions, so that, with very few exceptions, virtually the same system of smelting is followed in all these establishments. This is the so-called method of reduction and precipitation in blast-furnaces. As the principal reasons for the employment of a blast-furnace process are to be considered : the low percentage of lead in the ores, the high price of the only available fuel, charcoal, and the exorbitant rates demanded for labor. The reasons why the reduction and precipitation process is preferred to a roasting, reduction, and precipitation process are the high prices of labor and materials, and the preponderance of oxidized ores over sulphurets, though in some cases the latter are quite abundant. The weight of these reasons will be better understood when the character of the ores to be treated and the object of the smelting are more minutely stated. The ores are in nearly all cases a preponderating mass of oxidized lead ores, such as cerussite, anglesite, and leadhillite, in which nests and nodules of undecomposed galena occur. Associated with these are : in Eureka, Nevada, arseniate of iron and arsenical pyrites, hydrated oxide of iron, quartz, and calcareous clay ; in Little Cottonwood Canyon and American Fork, Utah, iron oxide, and in some cases a combination of antimony, the nature of which I have not ascertained; also dolomite and quartz in widely varying proportions; in Bingham Canyon, Utah, only quartz and comparatively little oxide of iron, or iron sulphurets; in Cerro Gordo, California, oxide of iron, iron pyrites, antimonial compounds, copper ores, and, as gangue, carbonate of lime and quartz. In Argenta, Montana, occur, besides the above-named lead ores, pyromorphite, and molybdate of lead. The preponderating gangue of the Argenta ores is quartz, and there is here a larger proportion of galena than elsewhere in the West. In most of the localities named, the lead ores themselves contain sufficient silver to render its separation from the ore the main object of the smelting; but in some of the districts, and especially in Montana, the lead ores serve only to furnish the extracting agent for the silver of true quartzose silver ores, which at the same time contain a sufficient percentage of lead to make amalgamation impracticable. They are therefore beneficiated by smelting, although the lead itself has no market value.

Jan 1, 1873

By J. L. Bray

LEAD has often been suggested as a protective coating for iron and steel. Such a protective coating should possess: (1) good adhesion, (2) durability, (3) ease of application, (4) freedom from pinholes, (5) good appearance and (6) low cost, but, unfortunately, lead coatings so far produced do not have all of these characteristics. Because of the necessity of carrying out the coating process cheaply, and because lead solutions have poor plating characteristics, most of the efforts have been directed toward the hot-dipping process rather than electroplating. The hot-clipping processes using lead have not been successful chiefly because of the lack of adherence between iron and lead. In any coating process involving iron a bond can be obtained only by the formation of an intermetallic compound, the formation of a solid solution, or mechanical means. Lead forms with iron two immiscible liquid solu-tions, and in the solid state no intermetallic compounds or solutions. It is necessary, therefore, to employ some other element or elements as a binding agent. Tin may be used as in terneplate, or copper in the form of a thin film of electrolytically deposited metal to which the lead will adhere. Because of its physical and chemical properties, lead as a coating medium would undoubtedly be limited in its use to sheet and wire and then only when the article is not subject to abrasion or wear. A very large tonnage of these products are being used under such conditions and a successful lead-coating process should be a valuable contribution to the science. Two other difficulties stand in the way of successful lead coating-that of poor appearance of the weathered surface and the tendency of the lead to form pinholes during solidification. Since lead is commonly accepted as cathodic to iron, these exposed areas are ones of accelerated corrosion.

Jan 1, 1937

By Stephen Taber

Introduction.............................. 62 Asbestiform Minerals.......................... 63 Chemical and Mineralogical Relations............... 63 Physical Properties........................ 64 Types of Asbestos............................ 65 Origin of the Fibrous Structure...................... 66 Views of Previous Investigators.................... 66 Discussion of the Evidence.................... 67 Conclusions........................... 69 Origin of Cross-fiber Veins....................... 71 Chrysotile Veins......................... 72 Structural Features of Cross-fiber Veins............... 78 Veins of Crocidolite and Other Fibrous Amphiboles........... 83 Origin of Slip-fiber........................... 84 Origin of Mass-fiber........................... 86 Discussion............................... 87 IntRoduCtion The term asbestos, as commonly used, includes half a dozen minerals all having a well-developed fibrous structure, but differing in chemical composition and in some of their physical properties. In its strict application the name is limited to the fibrous varieties of the monoclinic amphiboles. Commercially, however, the most important of the asbestiform minerals is chrysotile, a fibrous variety of serpentine. About 95 per cent. of the asbestos used in manufacturing is chrysotile, and it commands a much higher price than any of the other fibrous minerals now on the market. Although the production of asbestos has increased rapidly in recent years, comparatively little has been published concerning its origin. The present paper is preliminary in its nature, and therefore does not pretend to exhaust the subject. The ideas herein developed are the result of field investigation, laboratory experiments in the growth of fibrous

Jan 1, 1918

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By Harry H. Angst, Reuel A. Cochrane

The successful exploitation by opencut methods of the low-grade porphyry copper deposits is due to the economical handling of large tonnages. Large tonnages are possible only if the rock material is broken so that the large power shovels can operate with minimum delays. This is particularly true at the New Cornelia mine, where the dense, hard, tough rock material creates problems not encountered in most of the porphyry copper mines. The introduction of churn drills at the New Cornelia for primary drilling, in 1936, necessitated a complete change in the methods of breaking ground as formerly air drills had been used. The blasting operations are of particular interest because of the handling of great quantities of high explosives in safely and efficiently fragmenting the hard rock material. Rock Formations At the New Cornelia mine the rocks are quartz monzonite with a diorite border facies intruding a rhyolitic series. Overlying these formations is a fanglomerate formation composed of boulders of monzonite, diorite, rhyolite, and other types of rock of unknown derivation. (The word "fanglomerate" is used in this paper in referring to the local conglomerate type of rock formations.) The ore body is approximately 4800 ft. long and 2800 ft. wide, and is of the disseminated type. Mineralization occurs principally in the quartz monzonite and to some extent in the adjacent diorite and rhyolite. The principal ore minerals are chalcopyrite, bornite, and a small amount of chalcocite. Over a considerable area the quartz monzonite is extremely hard and siliceous in character, owing to pegmatitic zones of alteration. The hardness of the ground depends on the intensity of the silicification. In a small area in the pit, the monzonite contains an abundance of pyrite accompanied by sericitization and is soft and easily fragmented. This is true also in the remaining oxidized portion of the ore body. The diorite and rhyolite formations, like the monzonite, vary from extremely hard to very soft material, but on the whole are easier to fragment than the monzonite. Jointing is prevalent in all the rock formations and plays an important role in the blasting efficiencies. In the fanglomerate formation, numerous well-defined joints, widely spaced, tend to make the ground blocky when blasted. This is a deterrent to good fragmentation. In the other rocks the joints are more numerous and are closely spaced, except in localized areas where the formations are extremely hard. These descriptions indicate that the lowest blasting efficiency will be obtained in the harder formations, from which the major portion of the mine production is obtained; namely, the monzonite and rhyolite. All rock formations mined at the New Cornelia pit are so hard that excavation

Jan 1, 1943

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,' and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-' Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967

By J. R. Long, A. H. Roberson, T. R. Graham, R. S. Dean

Experimental work on the properties of high-purity alloys of the copper-man-ganese-zinc system has necessarily required extensive metallographic work to determine the equilibrium conditions in this system. Previous work on these alloys is fragmentary and, unfortunately, based on alloys made with impure grades of manganese, thus introducing significant amounts of iron, silicon, aluminum and carbon. Since these elements are known to affect equilibrium conditions, it became desirable to re-examine these alloys made from the pure metals. The alpha solid solution field was of particular interest and, therefore, was chosen for the initial work, which was outlined to determine the composition limits of this field. Previous Work Heuslerl conducted an extensive survey of the liquid-solid regions of this system and also made an estimate of the solid-phase boundaries at 340°C. The pertinent part of his diagram is given in Fig. I, but it is of limited usefulness, since it applied to a single temperature only and is based on impure alloys under admittedly nonequilib- rium conditions. Bauer and Hansen,2 likewise working with impure alloys, have determined the phase boundaries for alpha-beta brasses containing small amounts of manganese and indicate an increase in the extent of the alpha field with increasing manganese. This is not in accordance with Heusler or with data obtained on pure alloys.3 They also described a third constituent precipitating in the alpha plus beta field below 350' to 400°C. but did not identify this constituent. Guillet4 and Heike and Ledibur6 have also noted this precipitate. Each of these investigators recognized that impurities present in the manganese could and did have an effect on the structure and properties of their alloys. Corson6 in particular pointed out the hardening effects of silicon, aluminum, and carbon in copper-manganese alloys and Heusler reported that his alloys containing more than 25 per cent manganese were extremely brittle. In all probability this brittleness was due to the impurities present. This early work, therefore, should be taken as a general guide for preliminary studies only, and high-purity alloys may be expected to produce different results. The work of the Bureau of Mines laboratories with electrolytic manganese has been briefly summarized by Dean7 but includes only a short section on this system. Later work3 outlined a limited portion of the alpha field in the neighborhood of 65 per cent copper, 10 per cent manganese, and 25 per cent zinc. The present work was under-

Jan 1, 1945

By Lawrence K. Jetter, Robert F. Mehl

SOME advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory.? Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selected for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatometric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system-a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation ;2,3,4 there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type-the ideal case which Becker5 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1942

By Charles Barrett

THE copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possi-bility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previ-ously the structures in this system are unique in their; origin, for one terminal solid solution will precipitate the other, and ice versa. In most of the other systems for which crystallographic data on the precipi-tation (or transformation) process are available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system1 is 779°C. At this temperature copper -dissolves 4.3 atomic per cent (7.0 weight per

Jan 1, 1935

By J. Rourke, F. S. Minshall, E. G. Zukas, C. M. Fowler, O&apos

The Hugoniot curves were determined for Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si. The pressure of the transition increased as the silicon content of the alloy increased. Single crystals of 2.9 wt pct Si-Fe were also studied. The pressure of the transition was not dependent on crystallo-graphic orientation. All of the Neumann bands (mechanical twins) were attributable to (112) planes but not all of the {112} planes showed twin markings. A thorough study of the iron Hugoniot (the relationship between specific volume and pressure) under plane wave shock loading revealed a pressure transition at about 130 kbar shock pressure. The results of this investigation were reported by Bancroft, Peterson, and inshall1 in 1956. At the time of this discovery, it was felt that this was probably the a, to y transition normally found in iron and many of its alloys. Subsequently a number of iron alloy systems were surveyed in which the alloying element has a considerable effect on the normal a, to y transformation. The influence of carbon and nickel and/or chromium have already been reported.2,3 At the present time, there appears to be some doubt that this pressure transition is the usual a, to y transition In this study, Fe-Si alloys containing up to 7 wt pct (13 at. pct) Si were chosen for several reasons. To the present, the transition has been found only in iron-base alloys which were originally in the a, phase (bcc). Secondly, the y loop at atmospheric pressure extends to only about 2.5 wt pct Si. If the transition were a, to y, then one might expect a rather drastic pressure effect for alloys containing more than 2.5 wt pct Si. Finally, single crystals of Fe-Si alloys large enough for shock loading studies are readily available thereby making it quite easy to determine the effect of crystal orientation on the transition pressure and on the twinning behavior of the alloy. EXPERIMENTAL PROCEDURE Fe-Si alloys containing up to 7 wt pct Si were produced by normal vacuum casting procedures. Single crystals of Fe-2.9 wt pct Si were purchased from Monocrystals Co., Cleveland, Ohio. The orientations of these crystals were determined and samples cut so that the shock wave would be parallel (to within 1.5 deg) to either the (loo), (Ill), or (112) principal orientations. Three distinct experimental testing techniques were used. First, the pin technique, described elsewhere,4 was used to determine the transition pressure for the polycrystalline alloys as well as for the (111) and (112) orientations of the 2.9 wt pct Si single crystals. Secondly, the recovery studies, described in detail in an earlier paper,2 were used for determining the effect of alloy composition and crystal orientation on the plastic II compression-plastic I rarefaction interaction zone for several specific shock pressures. Finally, measurements of pressures above the two-wave threshold were made on the polycrystalline alloys so that more complete Hugoniot curves could be constructed for this alloy system. The optical techniques described by Rice et al.5 were used to measure the shock and free surface velocities of the samples from which the Hugoniot data were obtained. This method is applicable only in the single wave region, since velocities are obtained from the measured total transit times of the disturbances through measured sample thicknesses.

Jan 1, 1963

By C. F. Cockrell, H. E. Shafer, J. W. Leonard

A significant technological development is discussed for the processing of certain power plant flyashes that are a problem because they contain a high water-soluble mineral content and yield inferior flyash-based brick. This development is based on the addition of hydrochloric acid to the flyash-bottom ash-sodium silicate blends used for the production of flyash-based structures. Favorable changes are evi-dent in sodium silicate consumption, where about half the amount used for making brick from normal flyash is required, processing costs, and strength and appearance of the resulting freshly formed green and fired structural products. In some high cost in-stances (above the $30 or less per thousand brick estimated for normal flyash), hydrochloric acid additions can replace or reduce other costly additives normally required for problem flyashes. This results in savings of as much as $9 per thousand brick. These developments offer promising possibilities for utilizing problem flyashes as well as flyashes which may come into contact with water soluble sulfur as a result of the eventual application of certain experimental air pollution control processes. Much of the research datal-6 accrued through work by the Coal Research Bureau of West Virginia University for the Department of Interior's Office of Coal Research on converting waste power coal ash to valuable brick and other structural products, can be categorized as follows: (1) general ash-to-brick tech- nology; (2) specific ash-to-brick optimization; (3) pilot plant progress; (4) production cost estimates. A summary of the progress on bench-scale experiments indicates that coal ash can yield two types of brick. An acceptable brick is obtained by mixing 73.6% fly-ash, 23.5% bottom ash and 2.9% sodium silicate solution (dry basis). Depending on the flyash and bottom ash used, optimum brick can be manufactured by mixing 72-77% flyash, 20-25% bottom ash and 2.3-3.0% sodium silicate (dry basis) with Na2O : SiO2 ratio varied according to the composition of the flyash used. These blends are thoroughly mixed and mechanically formed into green brick shapes at pressures ranging from 1000 to the more usual 3000 lb per sq in. The green shapes then are dried and fired at temperatures ranging from 1975-2150°F using clay brick cycles that are shorter than standard. Other findings reported to date indicate that when making optimum brick, it is necessary to carefully control the top size of the moisture-releasing bottom ash so that it falls between 8 and 30 mesh, depending on the flyash used. Moreover, the chemical composition of bottom ash and flyash have been found to be of little significance with the exception of a few problem flyashes which are the subject of this paper. Finally, the pilot plant, which was previously reported under construction, is now in operation. This will indicate, among other things, the cost of brick production, which was earlier estimated for non-problem flyashes at $30 or less per thousand brick. The foregoing bench-scale technology is applicable to all the initially tested ashes as well as to the majority of ashes examined during the course of research. However, a few of the ashes yield green and fired products that may be structurally inferior or unacceptable, necessitating excessive and diverse reagent addition, and/or may be coated with unsightly surface deposits. These problem ashes generally originate in certain areas of Illinois, western Ken-

Jan 1, 1969

By B. W. Howlett, M. B. Bever, Somnath Misra

The heats oj- formation at 0°C of the compounds AuSn,, AuSn2, AuSn, and the £ phase were measured in a metal -solution calorimeter with liquid tin or a liquid Sn-Bi alloy as solvent. The melting point, heat of fusion, and heat capacities near the melting point of- the compound AuSn in the solid and liquid state were measured in a constant temperature gradient calorimeter. The free energy and entropy of formation of the compound AuSn at its melting point and at 298 °K were calculated from the experimental results and published data. The heats of formation are discussed in relation to the nature of the compounds. The heat capacity below the melting point, heat of fusion, and entropy of fusion of AuSn are interpreted in terms of processes oc-curring before melting. The atomic arrangement in liquid Au-Sn alloys and the bonding in the intermediate phases of. the Au-Sn system are discussed in the light of the measured thermodynamic properties. THE available thermodynamic information on the intermediate phases in the Au-Sn system consists of the heats of formation of the compounds AuSn4, AuSn2, and AuSnly2 and of one composition of the < phase2 besides values of the heat content of the compound AuSn from 0" to 635".&apos; However, the heats of formation refer to different temperatures ringing from 90" to 450°C. Also, the reported error limits of some of the values are large and several inconsistencies are apparent. In the investigation reported here the heats of formation of the compounds AuS-, AuSnz, and AuSn and of three compositions of the < phase were determined for a single reference temperature of 0°C by liquid metal-solution calorimetry. The compound AuSn, which is the only congruently melting intermediate phase in this system, was further investigated in a constant temperature gradient calorimeter by measuring its heat of fusion, melting point, and heat capacity in the solid and liquid states near the melting point. From these data and published free energies of the liquid of composition Au~n,&apos; the free energies of formation of the compound AuSn at the melting point and at 298°K were calculated. The results shed light on the solid-liquid transition of AuSn and on the atomic bonding and state of association of gold and tin in the solid and liquid phases. 1) EXPERIMENTAL PROCEDURES 1.1) Preparation of Samples. Stoichiometric amounts of gold and tin, each 99.99+ pct pure, were melted in evacuated Vycor capsules (12 mm ID). The melts were maintained approximately 150°C above the liquidus for about 12 hr and shaken repeatedly. Samples of the compound AuSn were cooled slowly to room temperature. Melts of the other phases, all of which solidify by peritectic reactions, were transferred to the narrow end (5 mm ID) of the capsule, which was then quenched into iced brine. The solidified samples were annealed in the unopened capsules for 10 days at 30" to 50° C below the respective solidus temperatures. The absence of microsegregation and second phases was confirmed by metallographic examination. At least two batches of each composition were prepared. 1.2) Solution Calorimetry. The heats of formation were determined by liquid metal-solution calorimetry. In this technique, the difference between the heat effects on dissolution in a liquid metal, or alloy bath, of the compound and a mechanical mixture of its annealed components, adjusted for changes in composition of the bath, is the heat of formation of the compound at the temperature from which the samples are added. Details of the equipment and technique have been described."&apos; A tin bath at 300" or 350°C was used with the compounds AuSn,, AuSnz, and AuSn. The high gold content of the £ phase would have caused it to dissolve with an appreciable exothermic heat effect. In order to achieve thermal compensation, the samples were added from 0°C to a bath at 350°C consisting of 66.2 wt pct Bi (99.999+ pct pure), balance Sn (99.99+ pct pure). This solvent gives thermal compensation because gold dissolves exothermically in tin and endothermically in bismuth. The calorimeter was calibrated by adding from 0°C approximately 0.015 g-atom of the solvent.

Jan 1, 1965

By David W. Brunton

From the old-fashioned " grab-sample " to the modern timing-device, which takes a machine-sample with mathematical precision, there is a wide gap, which was only crossed by many years of toil and unremitting endeavor. Even to-day, notwithstanding the advancement in the art, " grab-sampling " is still practiced—sometimes to afford the unscrupulous mine-promoter a basis for fairy-tales with which to entrap the too-gullible investor, and often by milling and smelting companies to determine the amount of moisture in custom-ores. The latter practice is almost as reprehensible as the former, and it causes more trouble and ill-feeling between seller and buyer than all other factors put together. -NO reputable concern to-day would think of attempting to determine by grab-sampling the amount of gold, silver, lead, or copper contained in an ore, and yet many buyers expect the miner to accept the results of grab-sampling in the determination of the amount of water contained in the ore, forgetting that accurate results are just as necessary here as in the determination of the metals, because the result determines the percentage of weight of the ore which shall be excluded and considered to have no value whatever. Samples for the determination of moisture should be taken with as great care as samples for the determination of metallic content, and in order to avoid the extra expense of a separate operation moisture-samples should be taken from the sample-safe. As the sample reaches the sample-bin in a smaller stream and by a more circuitous route than the " reject" travels in its path to the outgoing car, it loses more moisture en route, and a constant should be added to compensate for this difference. Carefullg ,con ducted experiments have shown that the differ.elice in loss of moisture between the two routes does not exceed 10 per cent. in summer and 7 per cent. in winter. For instance,

Jan 1, 1910

By D. K. Crampton

Internal stress and season cracking in brass have been studied for many years and the technical literature contains many data on various phases of the subject. A resume of the literature shows certain fairly well established points upon which various authors are mostly agreed: 1. Season cracking is primarily caused by the presence of relatively high internal stresses, or possibly in some cases by external stresses, or both. 2. A specific corrosion is also essential to season cracking. Certain agents, particularly mercurous salts, mercuric salts and ammonia salts, have such a specific corrosive effect. 3. The tendency to season crack under given conditions increases with increasing zinc content, brass containing less than 20 per cent. zinc being relatively immune. 4. In alpha brass the season cracks are intercrystalline; in alpha-beta brass they lie between the two constituents; and in beta brass they are transcrystalline. 5. The ordinary impurities or added elements in special brasses have little or no effect on the tendency to season crack. 6. Internal stresses can be eliminated, or at least reduced to a safe limit by annealing treatments at temperatures that do not produce visible microstructural changes or appreciable softening of the worked brasses. There are, however, some points in connection with the phenomenon of season cracking which have not been thoroughly investigated, or wherein different authors and investigators are not entirely in agreement. The investigations described in this paper were undertaken to determine: 1. The correlation between mercurous nitrate tests and actual season cracking on long-time atmospheric exposure. 2. The quantitative effect of type and degree of drawing operations on the intensity of internal stress and on the tendency to season crack in brass tubes. 3. The possibility of drawing high-brass tubes in such a manner as to prevent the occurrence of harmful stresses rather than to find a remedy for such stresses once having obtained them.

Jan 1, 1930