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By ELTCENE A. WHITE

WE are all interested in our ou7n lines of endeavor and consider ourselves the center of the universe. The farmer thinks he is the most important man because he feeds us. The doctor knows he is the real center because he keeps us well. The lawyer says that he is indispensable because he keeps the peace. The banker furnishes us a place to keep our money and tells us how to make proper use of it. The miner sags that without metals there would be no civilization. I think that my branch has sufficient interest and exhilaration. of accomplishment to fully occupy any man's mind and attention. Mining and metallurgy are as old as the human race. It did not have much, if any, importance in the stone age as there are not found remains of iron and copper, but in the bronze age, which was co-existent with the stone age, it came to the front. Iron and copper were the most important metals. Copper, as bronze, was known in ancient Egypt, I\~:IS important in Rome and other parts of Europe and in Asia; in South America among the Aztecs and farther North were the Mound Builders and the early inhabitants of Lake Superior. At a very early date the Egyptians conquered the Sinai peninsula for the sake of the copper produced there. The history of copper metallurgy can be compared to that of a flower. The seed is sown in darkness and in the Dark Ages the crude metallurgy of copper began. As the shoot comes up from the seed it may be compared to the age of alchemy; the branches of the plant can be compared to the Middle Ages; the flowering shoots to the 17th century, the budding to the 19th and the blossom to our own time from 1870 on.

Jan 1, 1930

President MRS. HARRISON SOUDER south Paramus Road Ridgewood, N. J. First Vice-president MRS. ROBERT HURSH New York N. Y. Second Vice-president MRS. RICHARD LLEWELLYN LLOYD Great Neck, L. I'. N. Y. Third Vice-president MRS. PERCY E. BARBOUR New York N. Y. Fourth Vice-president MRS. E. P. MATHEWSON Tucson Ariz.

Jan 1, 1937

By R. W. Borio, T. S. Spicer

Inflammability and crossing point apparatus were used to study the influence of increasing amounts oi such inerts as ash, fly-ash, pyrite, limestone and Portland cement with several pulverized bituminous coals. The results indicate that it requires large proportions of inerts to substantially suppress the ease of ignition. The ignition phase of the combustion of solid fuels has been under study periodically since 1900. With the advent of pulverized coal firing some 60 years ago, a technique now dominating the coal utilization field, the ignitibility characteristics have become increasingly important. Much of the early work was directed toward the prevention of coal dust explosions and improved mine safety rather than combustion. Many factors affecting ignitibility have been studied and numerous methods devised in an effort to measure the ignition temperature and these have been reviewed by other authors. A recent survey was made by Finney and Spicerl in 1959, so a discussion of previous work will be omitted. Despite these efforts, the initial stage of combustion, termed ignitibility, is still a little understood phenomenon. In fact, no ASTM method has been adopted for the calibration of this illusive property. However, a D-5 Subcommittee XVI on Ignitibility of Coal and Coke of ASTM (now inactive) defined ignitibility:' "The ignitibility of a fuel is that char-

Jan 1, 1963

By A. W. Cochardt

THERE are a number of effects that can cause material damping or internal friction. Some of these are frequency dependent, such as the thermo-elastic effect' and the stress-induced ordering.' Others depend on the amplitude of vibration, i.e., the damping related to the motion of dislocations3 and that due to magneto-mechanical hysteresis.' While many of these effects have been studied, only the magneto-mechanical effect has found extensive practical application. It is the principal source of damping in the current blade material in steam turbines.A magneto-mechanical hysteresis loop is seen in Fig. 1. If an unmagnetized, polycrystalline wire of a material exhibiting magneto-mechanical hysteresis, such as an Fe-14 pct A1 alloy, is twisted in torsion, a relation between shear stress and shear strain y is observed as indicated. The stress-strain curve does not follow Hooke's law -dashed line. Instead, the strain y increases nonlinearly and partly irreversibly, due to the motion of ferromagnetic domain walls,* until a critical stress is reached, which in this case is about 3,500 psi. If the applied stress is raised further, the strain appears to increase linearly and reversibly in accordance with Hooke's law, since all domains are now aligned in easy directions of magnetization nearest to the direction of the applied stress, and plastic flow has not yet started noticeably. On removing the applied stress, a remanent shear strain y, is observed, which is related to the irreversible magnetostriction of the material.' The energy dissipated in the material during a stress-strain cycle is proportional to the critical stress t, and the remanent magnetostrictive shear strain 7,. The purpose of this investigation was to make a survey of the magneto-mechanical damping of ferro-

Jan 1, 1957

By P. Rama Rao, D. H. Sastry, T. R. Anantharaman

Deformation (a) and twin (a') stacking-fault densities in cold - wor ked filings of fcc silver alloys containing 2, 4, and 6 wt pct Sb have been estimated from Debye-Scherrer peak shifts and asymmetries, respectively. Evidence has been obtained for a possible strain-induced transformation in a two-phase alloy containing 9.0 zut pct Sb. Using Fourier analysis of X-ray line profiles, the effective particle sizes and root mean square strains have been determined for the three fcc alloys in the cold-worked condition. The values of the compound fault probability 0.5a + a') evaluated from peak shifts and asymmetries are in reasonable apeement with those derived from peak broadening. COLD work of fcc metals may produce both deformation and twin (also called growth) stacking faults, which can be detected and quantitatively estimated by X-ray diffraction techniques.' In addition to peak broadening, deformation faults produce a shift in peak positions and twin faults an asymmetry of the Debye-Scherrer reflections. Besides stacking faults, a reduction in the size of coherently diffracting domains and distortion within these also broaden the powder reflections of deformed fcc metals and alloys. Fourier analysis' of peak shapes provides quantitative infor- mation about the effective domain sizes, lattice strains, and also the compound fault probability (1.5a + a'), where a and a' represent deformation-and growth-fault density, respectively. The Paterson method2 for determination of a from peak shifts, the warren3 or wagner4 method for evaluation of a' from peak asymmetries, and the Fourier analysis for quantitative estimates of all the contributory causes of peak broadening have, in the course of the last decade, been extensively applied to obtain data for a number of deformed fcc metals and alloys. One of the useful results of earlier measurements of a in several solid solutions is a correlation between a and the solute valence as well as electron concentration per atom (p) in alloy systems based on a particular solvent. The work of Smallman and westmacott5 on Cu-Zn, Cu-A1, and Cu-Sn, of Foley, Cahn, and ~aynor' on Cu-Si and Cu-Ge, and of Rama Rao and Anantharaman7 on Cu-Si and Cu-Sb has revealed a common trend in the increase of a with p and also a with valency of the solute. Cahn and Davies' and Ad-ler and wagnerg have observed similar trends for silver alloys containing cadmium, indium, and tin. Data on a for silver alloys with a pentavalent solute element are not, however, available. It is primarily to fill this need that the present investigation on Ag-Sb alloys was undertaken. Utilizing the Patersonand Warren methods, values of a and a', respectively, have been determined in three silver alloys containing 2, 4, and 6 wt pct Sb. By Fourier analysis of the broadening of Debye-Scherrer peaks, effective particle sizes, lattice strains, and the compound fault probability (1.5a +a') have also been evaluated.

Jan 1, 1967

By Phillip B. Bucky, R. S. Taborelli

The term "longwall mining" is best known to coal men, although modifications of the method are continually being used in other fields. Longwall mining is of interest today because it makes for greater inechanization and better supervision at the working face, and therefore lower production costs and increased safety. It is an approach to the factory system of production, the high efficiency of which as compared to that in mines is well known. There is available an accumulation of experience regarding this work but coordination of experience is lacking and this series of experiments was undertaken to help serve this purpose. Model experiments were used for reasons of safety, cost and time, and because it has been previously shown1,2,3 that a scalar inodel built of the same material as the prototype will behave in a manner similar to that of the prototype, with time effects the same, if the effective weight of the model is increased in the same proportion as its linear dimenbions are decreased. This is accomplished by substituting a centrifugal for the gravitational field; i.e., placing the model in a centrifuge and controlling the strength of the centrifugal field by varying the rate of rotation. Many factors affect the behavior of the geologic material overlying a bed, therefore results and conclusions contained in this paper apply only to the conditions presented herein. Longwall Mining What Is Longwall Mining?—Agreement should be reached as to what constitutes longwall mining and therefore what constitutes a longwall face. Let longwall mining be defined as the mining procedure in which the roof and overlying bed breaks tend to parallel the working face. In the ordinary stope or room-and-pillar mining the roof breaks tend to

Jan 1, 1938

By Phillip B. Bucky, R. S. Taborelli

The term "longwall mining" is best known to coal men, although modifications of the method are continually being used in other fields. Longwall mining is of interest today because it makes for greater inechanization and better supervision at the working face, and therefore lower production costs and increased safety. It is an approach to the factory system of production, the high efficiency of which as compared to that in mines is well known. There is available an accumulation of experience regarding this work but coordination of experience is lacking and this series of experiments was undertaken to help serve this purpose. Model experiments were used for reasons of safety, cost and time, and because it has been previously shown1,2,3 that a scalar inodel built of the same material as the prototype will behave in a manner similar to that of the prototype, with time effects the same, if the effective weight of the model is increased in the same proportion as its linear dimenbions are decreased. This is accomplished by substituting a centrifugal for the gravitational field; i.e., placing the model in a centrifuge and controlling the strength of the centrifugal field by varying the rate of rotation. Many factors affect the behavior of the geologic material overlying a bed, therefore results and conclusions contained in this paper apply only to the conditions presented herein. Longwall Mining What Is Longwall Mining?—Agreement should be reached as to what constitutes longwall mining and therefore what constitutes a longwall face. Let longwall mining be defined as the mining procedure in which the roof and overlying bed breaks tend to parallel the working face. In the ordinary stope or room-and-pillar mining the roof breaks tend to

Jan 1, 1938

By J. W. Bolton

THIS paper discusses some fundamental metallurgical principles involved in production of sound cast bronze. In a previous paper the writers advanced the theory that "oxidation" in bronze castings is due to incipient shrinkage, and showed the effect of reducing melting atmospheres. In the present paper the effects of certain impurities and of actual oxidizing conditions are shown. The appendix deals with the appearance of various inclusions. For many years the prevailing opinion has been that unsoundness, dark colored fractures and other phenomena accompanying porosity and weakness in bronzes are due to oxidation. The actual troubles are caused by fissures of intercrystalline type, which are often mistaken for intercrystalline films. These weaken the metal and make it porous. Grave doubt regarding the accuracy of the oxidation theory appears when several research papers presented within the last 10 years are reviewed critically. In 1919, Comstock conducted metallographic researches, attempting to identify "oxides" in synthetically prepared metals. He found that oxides of tin, aluminum, zinc, etc. are different from the intercrystalline films (or cavities) to which porosity is due. Apparently he believed that these "oxide films" may be caused by volatile oxides of zinc or of phosphorus or by dissolved gases thrown out of solution during solidi-fication of the metal. In 1923, Woyski and Boeck3 definitely questioned the accuracy of the oxidation theory and indicated the danger from reducing atmospheres. They say that "oxidation, gassing and shrinkage may produce effects very similar."

Jan 1, 1930

By E. P. Polushkin, Henry L. Shuldener

This paper describes the results of microscopic examination of a series of brass pipes removed from apartment and office buildings in New York City, adjacent localities on Long Island, and Philadelphia. They were selected as typical of approximately four hundred pipe specimens obtained over a period of five years during an investigation of corrosion in hot-water installations. A part of the investigation is reported in this paper and includes a brief history of the pipes, a description of their inside surface and microstructure, and a study of the effects of corrosion, with particular reference to the structural aspects of local and selective dezincification. Although the bibliography on the corrosion of brass pipes is quite extensive, it refers almost entirely to corrosion in sea water. The authors believe that their examination of this series of pipes, which had been subjected to the corrosive action of fresh water for various lengths of time, may throw some additional light on the problem of corrosion. Pipes Examined The pipes were made by different manufacturers and their sizes range from 3/4 in. to 4 in. nominal inside diameter, the majority being within I to 2 in. They can be divided into two groups according to chemical composition: (I) with a copper content of 60 to 62 per cent and (2) with a copper content of 65 to 68 per cent. The first group (pipes made of Muntz metal) comprises 22 pipes and the second (pipes made of high brass) comprises 18 pipes. The pipes had been in service in various locations in the hot-water systems of the buildings involved. Some were taken from horizontal lines in the basement, some from overhead distributors and some from vertical risers. The distance, in terms of feet of pipe, of the specimens from the hot-water generator was no less than 75 ft. and often IOO to 300 ft. In the majority of cases the water-heating equipment was provided with a regulator to limit the temperature of the hot water supply. The normal range of temperature in pipe systems of this kind is Ioo° to 160°F. Water Supples The average chemical composition of the water supplies carried by the pipes is shown in Table I. In evaluating the corrosiveness of a natural water, four factors are considered of prime importance: namely, hardness, alkalinity, pH and silica content. The waters listed in Table 1 are characterized by relatively low hardness, 10, alkalinity, low pH and low silica content. The waters of lower pH and higher CO2 content are more corrosive. A characteristic of all of these waters is that they do not deposit a protective mineral coating as do waters with high bicarbonate of lime content, which would be reflected

Jan 1, 1945

By H. G. Papacharalambous, S. C. Sun

Experimental results indicate that wet cyclones could be effectively used for the preliminary classification of the tested synthetic abrasive materials, thus supplementing the currently used sedimentation method. An empirical formula is also proposed on the basis of the test data to calculate the particle size of separation. One of the basic operations in the abrasive industry is the classification of the crushed and ground materials into different sized products. The relatively coarse grains, plus 325 mesh, are commonly sized by dry screening with satisfactory results. On the other hand, however, the currently used grading tank, for classifying grains finer than 325 mesh, is intermittent. Consequently, it is difficult to operate efficiently and keep pace with erratic market requirements. Little success was made in an attempt to substitute air settling and continuous hydraulic settling for the grading tank, because size specifications1 for abrasive powders are very stringent and difficult to meet. Finally, a wet cyclone was chosen for experimentation. Even though wet cyclones have not been extensively used in the classification of abrasives; however, their performance as a classifier has been verified by Driessen2,4 on coal, McCarrel5 with manganese, and Herkenhoff6,7 on iron ore. Experimental work on silicon carbide, boron carbide, and fused alumina has shown that the cyclone

Jan 1, 1963

By E. Hein, R. A. Dodd

The fatigue softening of prior strain-hardened poly crystalline copper has been determined by measuring changes inflow stress resulting from fatigue treatments. Tensile fatigue does not soften the metal, while the softening due to reversed stress fatigue depends on the extent to which fully reversed stressing is approached. True tensile fatigue is shown to be possible only in the case of long wire specimens. Annealing following fatiguing of strain-hardened metal shows that tensile fatigue is very effective in modifying normal recovery and recrys-tallization. OBSERVATIONS by Ludwik and Scheu,' Kenyon,' Polakowski and Palchoudhuri, Kemsley, and Broom and Ham,596 have shown beyond doubt that strain-hardened metals are softened by reversed-stress fatigue. To some extent the softening might be associated with a rearrangement of dislocations, but the results of Broom and Ham5 on the temperature dependency of the fatigue hardening of annealed copper, and those of McCammon and Rosenberg7 on the partial recovery at 100'C of fatigue-hardened copper suggest that point defects may be involved. Since lattice vacancies are the only species of point defect present in appreciable quantities in thermody-namic equilibrium, most attention has been accorded them in the various theories advanced to explain hardening and softening effects resulting from fatigue. Precise mechanisms remain uncertain, and while some effects may be due to single vacancies, defects arising from vacancy clusters may also contribute to the changes in properties. All types of plastic deformation result in point-defect formation, one frequently invoked formation mechanism involving the nonconservative motion of jogs formed by the intersection of, for example, mixed dislocations. But since fatigue deformation is thought to be a particularly effective way of forming point defects, additional mechanisms peculiar to fatigue must be sought. One possibility is that jogged loops contract during the unloading cycle to give rows of vacancies. A local high-vacancy concentration could conceivably promote polygonization and recovery by climb, and, therefore, could explain the fatigue softening of strain-hardened metals under appropriate conditions of temperature. Conversely, the experiments by Broom and Ham6 on the fatigue hardening of copper single crystals involving subsequent tensile testing of previously fatigued specimens, resulted in the observation of distinctly lowered yield points. This could be due to vacancy atmospheres associated with dislocations, possibly augmented by jogs on dislocations. In addition to the yield-point phenomenon, a post-yield hardening was observed, with a temperature-dependence resembling the friction-hardening of irradiated metals,9 this again suggesting a point-defect mechanism. An important development in this field has been the observation,10 by transmission electron microscopy, of high concentrations of prismatic loops in fatigued aluminum. By analogy with quenched aluminum filmso11 it seems certain that these loops originate in the collapse of vacancy clusters formed during deformation. Metals, such as copper, having a relatively low-stacking fault energy would tend to produce Frank sessile loops (in practice tetrahedral defects with stacking faults on all (111) planes) rather than the glissile prismatic loops observed in aluminum. The manner in which these various defects affect the different aspects of fatigue behavior has not yet been fully investigated. The present work was designed principally to indicate whether tensile fatigue gives rise to hardening and softening effects similar to those associated with reversed stress fatigue, and with the hope of providing additional information on the contribution of point defects to fatigue deformation. Despite the uncertain ty often associated with the interpretation of resistivity data, i.e., the relative contribution of stacking faults and other defects, such measurements are conveniently employed to study point defect pheno-

Jan 1, 1962

By F. Lynwood Garrison

The study of the microscopic structure of the iron of car-wheels, which it is the aim of this paper to describe, was made at the suggestion of Dr. Dudley, whose paper upon the constitution of cast-irons (page 795 of the present volume) should be read in connection with this one. Although the two wheels referred to in that paper possess nearly an identical ultimate chemical composition, they possess, as Messrs. Dudley and Pease have shown, physical properties so widely different, as to make one of them nearly worthless for the purpose for which it was cast. Considering the chemical similarity, such a marked difference in strength cannot but be very striking, and goes to show how little reliance can be placed upon chemical analysis alone, if not properly interpreted. I say " not properly interpreted," because I believe that very few analyses of iron or steel are thus fairly dealt' with. That an analysis may read so much of one thing and so much of another, tells us very little as to the properties of the metal; for these are determined to a large extent by the conditions and relations in which the elements are present. To the unaided eye the difference between the two wheels under consideration is not striking. The inferior one would be described as light gray, and the other as somewhat darker. Upon careful examination of an etched fragment, however, the difference in structure will be found to be very marked, as may be seen in Figs. 1 and 2 (produced from photographs by the Ives process). It is exceedingly difficult to produce a photograph giving a fair notion of the appearance of the metal under the microscope, so as to give to persons not familiar with microscopical study, a proper appreciation of what a microscopist would consider a decided difference in structure. I would, therefore, urge any one especially interested in this subject, not to depend upon the photographs of others, but to prepare and etch the specimens himself, and then examine them with a good microscope. As is well known, iron possesses the property of uniting with a number of elements, forming products which are either highly intimate mixtures of several substances, or else compounds of an indefinite character. Indeed such mixtures may be regarded as alloys, or as Matthiessen puts it, " solidified solutions of one sub

Jan 1, 1886

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963

By J. Szekely, G. P. Martins

A formulation is given for describing the rate of expansion of spherical bubbles rising in liquids the freeboard of which is evacuated. The computer solution of the resultant differential equations has shown that, for low freeboard pressures (less than about 5 mm Hg), on approaching the free surface the bubbles expand much less rapidly than predictable from equilibrium considerations. In other words, in this region the pressure inside the bubbles will be significantly larger than the static pressure in the liquid corresponding to the position of the bubble. These theoretical predictions were confirmed by experimental work, using two-dimensional air bubbles rising in mercury. The important consequence of these findings is that the expansion of gas bubbles in vacuum degassing operations will be a great deal less than expected from hydrostatic considerations. This would lead to a significant reduction in the available interfacial area and may explain the apparent poor efficiency of many vacuum degassing units. VACUUM degassing as a treatment for liquid steel has gained widespread popularity in recent years; the number of known installations exceeds several hundred at the present time.' Although much information is available on both the thermodynamics of the system and the overall performance of various industrial units, much less is known about the fundamental aspects of the process kinetics.2-4 The basic physical situation common to virtually all vacuum degassing operations is the interaction between gas bubbles (swarms of bubbles) and the surrounding molten metal, held in a container, the freeborad of which is at a low absolute pressure. Once formed (or introduced from an external source) the bubbles will ascend, due to the buoyancy forces, and, during this ascent, a significant increase in their volume will occur. This progressive increase in the bubble volume is due to two factors: a) the continuous reduction in the static pressure acting on the bubble during its rise; and b) mass transfer into the bubble from the surrounding molten steel. In a recent paper Richardson and Bradshaw developed equations5 for describing mass transfer into gas bubbles from molten metals at reduced pressures. However, in deriving these expressions it was assumed that the pressure inside the bubble was identical to the static pressure in the adjacent liquid. In other words, the volume of the bubble was considered to be in equilibrium with the pressure of the fluid adjacent to it. This assumption, thus their analysis presented, was thought to be reasonably accurate for most of the bubble's ascent; however, it was unlikely to be valid in the immediate vicinity of the free surface, held at a low pressure. It was pointed out in the discussion6 that the region close to the surface may be of considerable importance as both the driving force and the interfacial area available for mass transfer are at their highest value here. The ' 'anomalous" behavior of gas bubbles when approaching a free surface at low pressures was recently confirmed in a preliminary investigation by Szekely and Martins. ?1 Here high-speed motion photography was used to study air bubbles rising in a column of n-tetradecane with a freeboard pressure of 0.1 mm Hg. It was found that significant distortion of the bubbles occurred on approaching the free surface; furthermore, the expansion observed was much less than what one could expect from hydrostatic considerations, i.e., factor a previously discussed. It follows from the foregoing that a detailed study of these phenomena would be justified both from fundamental considerations and because of their potential relevance to technology. The purpose of the paper is to present a more realistic formulation for the expansion of a gas bubble approaching a low-pressure region, together with a comparison of the theoretical prediction with experimental measurement. An inert bubble will be considered in the first instance; it is thought that the understanding of the fluid mechanics is an essential first step toward the realistic formulation of the mass transfer process. This latter problem will be the subject of a subsequent publication. FORMULATION The Physical Model. Consider a spherical bubble, of initial radius Ro, rising in a fluid, having a density pL. Initially let the bubble be at a distance H from the free surface, and at a pressure Pgo, as illustrated in Fig. 1. Pgo, the initial pressure in the bubble, is given by the following equation: pgo = Po = Ptp +pLgH [ la] where Po is the pressure in the liquid corresponding to the initial position of the bubble and Ptp is the pressure at the free surface. The fluid pressure at

Jan 1, 1970

By Cyril Smith

A STUDY of the mechanical properties of the alloys of copper and silver led to the discovery that the solubility of silver in copper was greatly different from that generally supposed, therefore some work was done to determine the solubility with greater accuracy than had previously been achieved. After the work had been completed, two papers were published1 giving solubility figures which agreed closely with one another and with the work described herein. A detailed comparison of that work with the present will be given later. PREPARATION OF ALLOYS The copper used in making the alloys was electrolytic ingot of high purity. The silver was prepared by precipitation as chloride from nitric acid solution, followed by fusion of the washed precipitate with sodium carbonate and potassium nitrate. This method gives metal containing at least 99.99 per cent silver. The copper was first melted under charcoal in a small electric resistance furnace and the silver added as pure silver, it being unnecessary to make any intermediate alloys. After thorough stirring the metal was poured into a mold of suitable form. The alloys contained between 0.008 and 0.015 percent of oxygen. Small amounts of oxide were visible under the microscope, but it is not believed this would have much effect on the results. Copper-silver alloys are notorious for segregation, consequently a few experiments were carried out to find a form of casting with as little segregation as possible. A mold 6 in. long and 1/2-in. dia. was first used, and an alloy nominally containing 5 per cent silver was cast in it, while some of the same alloy was poured directly into water to obtain the maximum rate of cooling possible. Analyses were made both on this sample and on turnings from the top and bottom of the 1/2-in. dia. casting, the turnings being separated into three parts according to the position

Jan 1, 1931

By V. Leroy, A. G. Guy

Serious disagreements are often found between experimentally determined intrinsic diffusion coefficients and those calculated employing the usual form of the vacancy theory. In the new theory it is proposed that the total intrinsic flux, Ji, of component i, is the sum of a part, f, due to the usual random exclzanges of component i with the vacancies, and a second part, Ji, due to exchanges with the uacancies composing the net vacancy flux. The present treatment, while less powerful than that of Manning, has the advantage of easy uisualization and of facilitating the application of the vacancy-flux effect to complex systems. IT is becoming increasingly evident that there are serious deficiencies in the version of the vacancy theory of diffusion that has been widely used for the past 20 years. One type of evidence is the frequent lack of agreement between intrinsic diffusion coefficients and tracer diffusion coefficients, even taking account of the thermodynamic factor. A second kind of evidence is the observation of a Kirkendall shift larger than theoretically possible, that is, larger than can be accounted for without assigning a negative value to one of the two intrinsic diffusion coefficient.'- The thermodynamic factor could conceivably make both coefficients negative, but not just one. It is clear that a cause of these anomalies, apart from any inadequacy of the usual vacancy theory, might lie in an oversimplified treatment of the data. Adequate experimental techniques, including the use of moderate pressure during the diffusion anneal, are now available to insure that porosity, lateral expansion, and so forth, can be kept negligibly small in most cases. The effect of differences in atomic volume can be of major importance, and it is essential that one of the available methods4 be used to account for this factor. In the present treatment this is accomplished by the consistent use of moles per cubic centimeter as the unit of concentration. Of the various possible inadequacies of the vacancy theory, attention will be given here only to effects of the net vacancy flux. annin' has previously considered this question, beginning with an analysis of atomic jumping of tracer atoms. When he added the effect of a concentration gradient, new terms arose that could be associated with the flow of vacancies. The present treatment uses quite a different approach. The usual vacancy flux, J,, is introduced explicitly, and a simple analysis predicts major changes in the intrinsic diffusion coefficients from this cause. The usual assumptions are made that only a vacancy mechanism is operative, that the formation of voids can be neglected, and that changes in the partial molal volumes, vl and v2, are negligible. The significant diffusion coefficients for the present topic are Dl and D,, the intrinsic coefficients, which enter in the equations, where the flux Ji, moles per sq cm per sec, is that crossing the Kirkendall interface. The concentration, ci, is in units of moles per cu cm, and the concentration gradient, aci/ax, is evaluated at the Kirkendall interface. It will be recalled' that the calculation of Dl and D2 involves the measurement of areas on the diffusion curve with respect to the positions of the Kirkendall and Matano interfaces. In the case of the anomalies mentioned earlier, the Kirkendall shift is too large to be accounted for by the diiferetzce in fluxes (J2 -J1), given by Eqs. [I] and [2]. The logical inference is that the flux of the solvent atoms, J1, is actually in the same direction as the flux of the solute atoms, Jz. In terms of Eq. [I] this requires that Dl have a negative value. However, it would be somewhat misleading to state that the solvent atoms are diffusing up their own concentration gradient. The explanation that will be advanced here pictures competing processes producing the net flux of solvent atoms: 1) diffusion of the solvent atoms down their own gradient by random exchanges with vacancies; and 2) diffusion of solvent atoms in the opposite direction by exchanges with the net vacancy flux. ACTION OF THE NET VACANCY FLUX Theories of vacancy diffusion can be formulated with varying degrees of refinement, and the present theory has purposely been kept as simple as appeared adequate to explain the phenomenon in question. In particular the following aspects have been neglected: 1) the gradient of vacancy concentration in comparison to the gradient of the atomic species; 2) departure of vacancy concentration from the local equilibrium value; 3) variation of the jump frequency, LO, with the specific surroundings of the atom-vacancy pair being considered; 4) correlation effects. These and other refinements can be considered once the essential mechanism has been established. The essential idea of the present analysis is to calculate the total intrinsic flux, Ji, of component i as the sum, JlJ?±j{ [3] where J; is attributable to the usual random atomic jumping, and J{ is a contribution arising from the net vacancy flux, J,. The latter quantity, of course,

Jan 1, 1967

By C. E. Sims, C. A. Zapffe

MANY hundreds of publications have appeared during the past 78 years that treat the subject of hydrogen in iron and steel,105 but conclusions regarding the functions of hydrogen in causing some important defects in steel are still unsatisfactory to many; and other hydrogen-caused phenomena yet remain to be identified with this gas. The most widely discussed of these defects is hydrogen embrittlement, but the conception, perhaps the popular one, that embrittlement is due to hydride formation does not conform to the known facts.104 The true identity of hydrogen embrittlement seems instead to lie in a mosaic nature of metal crystals, which is a concept not yet accepted by most metallurgists. A study of hydrogen embrittlement therefore provides new viewpoints in regard to the crystalline substructure of steel. A second widely discussed hydrogen-caused defect is the "flake" or "shatter crack." Although it is generally agreed that the presence of hydrogen is a prerequisite for their appearance, it is also realized that internal stress plays a decisive part. The relationship of hydrogen to internal stress has not been explained very clearly; nor is it always clear what the relationship is between a "flake" and a "snowflake," or between a "fish eye" and a "shatter crack." More importantly, the relationships among hydrogen embrittlement, hydrogen-caused fissures such as "flakes" and the ultramicroscopic structure of steel have scarcely been recognized. The present investigation attempts to provide an explanation for the embrittlement of steel by hydrogen by showing cause for accepting the "block" concept of metal crystals, and then to show how the numerous hydrogen-caused defects are interrelated in the light of this concept. EVIDENCE OF SUBSTRUCTURE IN METAL CRYSTALS It appears that the concept of a crystal as an aggregate of smaller multi-atom units must be accepted in some form if the behavior of metals is to be understood. The abundant literature on the evidence of an ultramicroscopic "mosaic" structure in metals and other crystalline substances suggests that the physicist has provided the metallurgist with an invaluable new insight. The exact picturization that any one physicist provides may be open to question, but the fact that there is some such fundamental substructure seems undeniable. The present work makes no pretense of comprehensively treating the imperfection structure theories. Nor will conclusions be drawn here regarding the exact nature of the substructure of crystals. However, the acceptance of some imperfection theory of fundamental attributes seems so necessary to an understanding of the behavior of hydrogen in steel that the following brief

Jan 1, 1941

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By E. H. Jr. Dix

THE success of the Charpy impact test in the steel industry has led those interested in aluminum alloys to investigate the possible applica¬tion of this test to aluminum and its alloys. In this paper are set forth the results of a few preliminary tests made at the Lynite Laboratories of the Aluminum Manufactures, Inc. In order to study more thor-oughly the significance of the Charpy test, slow-bending tests have been made duplicating the arrangement of the impact machine. Tests have been made on both notched and unnotched specimens of a series of copper-aluminum alloys. APPARATUS The standard American-made Charpy impact machine delivering a blow of over 200 ft.-lb. was- much too large to test aluminum-alloy specimens of the same type used for steel, so that it was necessary either to adopt a larger specimen or to have a special light-weight hammer made. Since there is no known relation between specimens of different sizes, even though geometrically similar, it was decided to adhere to the 10 by 10 mm. specimen. Accordingly, Sauveur and Boylston, the American makers of the machine, were asked to construct a special light-weight pendulum adapted to their standard machine, this pendulum to have one-tenth the capacity of the standard. The writer wishes here to acknowledge his indebtedness to Mr. H. M. Boylston for the personal interest and care exercised in constructing this pendulum. The machine with, the light-weight hammer in place is shown in Fig. 1. It is mounted on a concrete foundation with the concrete covering the flange on the base of the machine. Vibration is further prevented by four 5/8 -in. (15.8 mm.) foundation bolts. The large standard hammer shown against the wall was also used for some of the unnotched bars that requited more than 20 ft.-lb. to rupture.

Jan 4, 1920

By C. Richard Tinsley, Norman Miskelly, S. James Hodge

Construction of the Ranger uranium project, located 230 kms east of Darwin in the Northern Territory, Australia, commenced in January 1979. Energy Resources of Australia Ltd (ERA) was incorporated in February 1980 to acquire all the rights in the project. The total cost to ERA of these rights was A$407 million, made up of A$125 million in cash to the Federal Government and the issue of 125 million A$1.00 shares at par, plus a payment of A$16 million in cash to each of Peko-Wallsend Ltd. (Peko) and EZ Industries Ltd. (EZ). ERA's cash requirements to complete the project were estimated in October 1980 to be A$553 million. Project loans, secured by first ranking debenture stock, were arranged for a total of US$390 million, while second-ranking debenture loans totalling A$60 million were [ ] obtained from the vendors, Peko and EZ. Overseas participants (power utilities who had agreed to purchase uranium yellowcake under contract) arranged to take up 25% of the equity capital for A$102.5 million; Peko and EZ were allotted 30.5% each as satisfaction of vendors' consideration; and 14% representing A$57.5 million was issued to Australian residents in an underwritten public flotation in November, 1980. The loan and equity financing arrangements required the successful resolution of many complex and interlocking factors, including technical and economic feasibility, agreement with Aboriginal interests, compliance with Government policies, and securing of sales contracts.

Jan 1, 1985