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By F. H. Willcox

In Bessemer-steel practice, air is blown through a bath of iron, or projected strongly upon its surface to burn out silicon, manganese, and cafbon. Toward the end of the blow, when the iron is not protected from oxidation by these elements and the excess of air becomes great, there is oxidation of the iron. In open-hearth practice, the same difficulty is experienced with dissolved gas and oxides in the product, though not to as great or severe a degree as in the Bessemer process because the oxidizing conditions grow less severe as the end of the heat is approached, and if the bath is allowed to boil for a time it undoubtedly frees itself from a large part of the gas and oxides which have been absorbed in the earlier part of the process. Basic open-hearth steel is usually assumed to contain a larger proportion of oxides than acid open-hearth steel, but it may be said that all steel, Besserner and open-hearth, contains more or less oxide of iron dissolved in the fluid metal at the end of the "blow" or "heat." That certain metals are solvents for their respective oxides has been shown, in the case of copper, by Heyn, and, in the case of iron, by Law. It is indicated that the solubility of iron oxide in iron increases with the purity and temperature of the metal. This confirms what is observed and known by operating men, and these observations may be summarized as follows: 1. Cast iron. is rarely subject to oxidation, as is logical from its composition. 2. Normal steel, unless deoxidizers are added, contains blow holes. 3. Steel known to be oxidized is full of blow holes. 4. The addition of deoxidizers prevents, to a greater or less degree, the formation of blow holes in normal steel. With these observations in mind, it is logical to deduce that the cause of blow holes lies in part in the presence of dissolved oxide of iron in the molten steel and its consequent reaction with the carbon of recarburizers, when these are added, to form gases. (Another factor in the origin of blow holes is, of course, the solubility of gases themselves in the steel and

Jan 1, 1917

By Arthur Knapp

The practical application of mud-laden fluids in wells has been the subject of many papers.' However, there seems to have been little investigation of what actually happens when mud-laden fluids are applied to a loose porous sand. The assumption is that the fluids penetrate the sands and that there is some plastering action. The degree of penetration and the relation of plastering action to wall stability is not generally known. This paper describes a series of experiments made in an attempt to observe, in laboratory apparatus, the action of mud-laden fluids under conditions simulating those to be found in a well. For the purposes of this discussion all fluids containing solid matter in suspension are mud-laden fluids. Series I: Penetration of the Pores of Uncemented Sands The subject of the penetration of porous formations by water is discussed in detail in Water-Supply Paper No. 67 of the U. S. Geological Survey. No attempt was made to repeat the experiments described therein. The results of the first experiment of this series are given simply to show the capacity of the apparatus used. The conditions in this first experiment were maintained throughout the remainder of this and the second series, except where noted. The experiments of Mills, McCoy, and others on subsurface flows, adjustments, migrations, etc., deal with the oil, water or gas within the porous beds.V he experiments described herein deal with the conditions immediately surrounding the bore hole.

Jan 1, 1923

By Arthur Knapp

The practical application of mud-laden fluids in wells has been the subject of many papers.' However, there seems to have been little investigation of what actually happens when mud-laden fluids are applied to a loose porous sand. The assumption is that the fluids penetrate the sands and that there is some plastering action. The degree of penetration and the relation of plastering action to wall stability is not generally known. This paper describes a series of experiments made in an attempt to observe, in laboratory apparatus, the action of mud-laden fluids under conditions simulating those to be found in a well. For the purposes of this discussion all fluids containing solid matter in suspension are mud-laden fluids. Series I: Penetration of the Pores of Uncemented Sands The subject of the penetration of porous formations by water is discussed in detail in Water-Supply Paper No. 67 of the U. S. Geological Survey. No attempt was made to repeat the experiments described therein. The results of the first experiment of this series are given simply to show the capacity of the apparatus used. The conditions in this first experiment were maintained throughout the remainder of this and the second series, except where noted. The experiments of Mills, McCoy, and others on subsurface flows, adjustments, migrations, etc., deal with the oil, water or gas within the porous beds.V he experiments described herein deal with the conditions immediately surrounding the bore hole.

Jan 1, 1923

By N. A. Richard, A. E. Austin, R. E. Maringer

AS part of a detailed study of the structure of metallic meteorites, the concentration and distribution of iron and nickel in the various phases of meteor -itic iron have been measured using an electron-probe microanalyzer. The specimen used was cut from a position about 3 in. below the surface of the Grant meteorite, a one-half-ton iron specimen (containing 9.35 pct Ni) found in New Mexico some years ago. A photomicrograph showing the general Widmanstztten structure, somewhat typical of iron meteorites, is shown in Fig. 1. The line across which the analyses were made is indicated by arrows. This area was chosen so as to evaluate the iron-nickel concentration in the three principal phases visible in Fig. 1. These phases, in the language of meteoritics, are kamacite, taenite, and plessite. Kamacite is the a-

Jan 1, 1960

By A. D. Marriott, J. V. N. Dorr

This paper reviews recent developments in the application of classification practice to the origination of fine-grinding flow sheets and traces the history of the mechanical classifier from its initial application for separating cyanide process sands and slimes down to its present six or more distinctly different applications at copper concentrators; it undertakes to show also, by reference to diagrammatic fine-grinding flow sheets and accompanying operating data from nine copper concentrators in western North America, the advantages gained from improved classi-ficiation flow sheets at these properties in terms of reduced grinding costs, improved flexibility of operation or increased recovery. Comparison is only made between different fine-grinding flow sheets at a given plant and no attempt is made to compare different concentrators, on account of ore variations and differences in metallurgical objectives sought,. The adoption of the flotation process in recent years, and especially the development of selective flotation, has brought a demand for much finer grinding than formerly. This has caused much thought to be given to grinding efficiency, and today there is hardly a mill where the grinding flow sheet is not under close study and subject to frequent changes. When closed-circuit grinding was introduced into metallurgy some years ago, its value was recognized at once, and since then the combination of mills and classifiers has been regarded and operated as a grinding unit. Apart from variations in both the grinding and classifying elements of this unit, there have been many variations in grouping tried by different mills to suit varying conditions of ore and plant limitations. Although operators feel that in most cases their present flow sheets are on trial, and the data on present work are often incomplete, we have felt that a discussion of the progress that has been made and an endeavor to show present trends and their results should be of use to the profession. We have therefore prepared flow sheets of some of the larger mills with which we have been in contact and present them with available data as to their results, in the hope that they may be of service now rather than later when practice may have become more standardized and more complete records and analyses have been made. We believe that the data given,

Jan 1, 1930

By J. S. Pascover, S. V. Radcliffe

The structures and transformation temperatures of high-purity Fe-Cr alloys have been investigated as functions of composition (0 to 10 wt pct Cr) and rate of quenching from the high-temperature Y phase field (up to 40,000°C sec-1). The structures were chmacterized by transmission electron microscopy. The transformation temperatures for each alloy exhibited the progressive decrease to a constant value with increasing cooling rate which has been shown to be characteristic of several iron binary systems. The corresponding structures were found to become increasingly finer in scale with increasing cooling rate and solute content, but to remain essentially equiaxed in character. In all the materials except the high-purity iron and one of the alloys, an additional and lower transformation temperature than the constant value for the equiaxed structures was observed. The structures of specimens which transformed at these lower temperatures (only single thermal wrests were observed in any given run) were martensitic and consisted of arrays of fine ferrite laths which varied in size and morphology with changing solute content. The factors controlling the nature of these transformations are discussed. The composition dependence of the martensitic transformation temperature, ME, in Fe-Cr alloys together with those reported for other iron binary systems indicate that MB for pure iron is some 700°c, rather than the values of 550° and 760°C reported previously. This conclusion is further supported by the results of a compmison of the thermodynamics of mmtensite formation in several systems. ThE extensive investigations of the structures formed on athermal transformation in iron and its alloys have led to the characterization of several forms of martensitic or "military"1,2 transformations and, in addition, a "civilian7' transformation to ferrite or "equiaxed a"* which occurs athermally and at a very high rate.374

Jan 1, 1969

By Hans Lundberg

In order to comprehend the help and information that may be expected from electrical prospecting, it is necessary to have at least a general knowledge of the methods and principles involved in preparing and interpreting results obtained in the field. Electrical prospecting is rather complicated, both in theory and practice, and in order to make a brief description clear to the practical mining man it has been necessary to idealize and generalize the problems, at the risk of having such simplification criticized by the theoretical man. This simplification must not be misinterpreted as showing a lack of theoretical knowledge. For its operation, electrical prospecting mainly depends on the fact that most metallic ores conduct an electric current much more readily than barren rocks. If an electric current flows through a block of ground within which a body of chalcopyrite is enclosed in country rock of schist, the current will find less resistance to its passage through the chalcopyrite than through the schist, even though the passage through the latter be much shorter. This is because the longer path through the chalcopyrite offers less resistance, owing to the superior electrical conductivity of the chalcopyrite (Fig. 1). The good conductor, chalcopyrite, in the poor conductor, schist, thus attracts the current and deflects the normal flow far outside the conduct-

Jan 1, 1929

By Floyd Kelley

THE literature of the last decade is rich with information relating to the cause and means of control of grain growth in pure metals, but is deficient concerning the role diffusion plays in grain growth, although during this period many new products that depend on diffusion for their properties and success have been developed. Among these are cementation products, produced by calorizing, chromizing, and carbonizing, or by mixing, pressing, and sintering powdered metals such as Syke's iron-molybdenum die material, Genelite, and Elcon Metal (copper, tungsten) etc. This is a fertile field for new developments, but before it can be util-ized to the fullest extent there must be a thorough investigation of the processes by which diffusion and grain growth take place. Grain growth plays no small part in the process and certainly the physical properties of these products depend largely on the grain size and state of equilibrium produced. The field of investigation does not end here, but may be extended to the effect of diffusion on impurities, segregations and dendrites in the broad field of ferrous and non-ferrous metallurgy. A number of years ago the author investigated several of these cases and noted, with striking regularity, the pronounced effect of diffusion in promoting recrystallization and grain growth. An example of this phenomenon is given in his paper on chromizing1 which contained photomicrographs of large radial or columnar crystals produced by diffusion of chromium in the solid state. Another manifestation of this effect was discussed by Austen,2 who showed the part hydrogen plays in the decarburization of steel and the effect of diffusion upon the grain structure.

Jan 1, 1928

By B. B. Rath, Hsun Hu

Rates of migration of large-angle boundaries have been studied in zone-refined aluminum crystals, defonned 80 pct by rolling in the (110)[112] orientation at -78°C followed by a recovery anneal at 80°C. Artificially nucleated grains show a marked variation. by an order of magnitude, in their growth rates in different directions. The average activation energy for the migration of all boundaries was found to be about 16,000 cal per mole. The anisotropy of the boundary migration is rationalized on the basis of the boundary structure. It has been observed by Beck and HU,1 Kohara el al,2,3 and Czjzek and Haessner4 that recrystallized grains formed upon annealing Of deformed sing1e crystals of aluminum show anisotropic growth characteristics. Kohara et al. found that single crystals rolled in the (110)[112] orientation, when random nuclei were provided on one side of the crystal by rubbing with emery paper and annealing, developed a sharp recrys-tallization texture on the other side of the crystal upon further annealing. This sharp recrystallization texture consisted of four components, which were related to the deformation texture of the crystal, i.e. (110)[112], by rotations of ±40 deg around each of the two common [ 111] axes' They also noted that recrystallized grains were elongated in directions perpendicular to either of these two common [1111 axes. They attributed this anisotropic growth to the difference in the rate of self-diffusion or diffusion of impurity atoms along the tilt and the twist boundaries. A somewhat similar investigation was conducted by Czjzek and Haessner4 On strained single-crystal sheets Of alum- inum. These authors claimed that the matrix structure of the deformed crystal had a greater effect on the growth anisotropy of the recrystallized grains than did the boundary orientation itself. In the present investigation quantitative measurements of the rate of grain boundary migration in anisotropic growth have been made in zone-refined aluminum (99.9999+pct pure) crystals deformed 80 pct by rolling in the (110) 112] orientation. Crystals of this particular orientation were chosen because of the following desirable features: 1) the crystal does not change its orientation during rolling; 2) the rolling plane contains all the significant crystallographic directions; and 3) when annealed, following deformation, the crystal does not re-crystallize spontaneously but polygonizes to a stable and homogeneous structure. Hence, the initial orientation of the crystal and a constant strain energy in the matrix can be maintained during subsequent grain boundary migration studies. It is essential to keep the driving force constant for the study of boundary mobility.5 EXPERIMENTAL PROCEDURE A cylindrical single crystal of 1 in. diam was grown by the Bridgman method in a high-purity graphite mold. The resistance ratio, R(4.2°K) /R(298°K) , of the grown crystal was approximately 2.0 x 10-4. A number of slices, 1/4 in. thick, were cut from the crystal along the (110) plane and were mechanically and electrolyti-cally polished to remove the strained surface layer. The crystals were then rolled along the [112] direction to 80 pct reduction in thickness at -78°C. To minimize surface friction, the crystals were rolled between two layers of 0.005-in. teflon sheet. Rolling was interrupted, prior to completion, to remove the surface layers and the edges by electropolishing. These and similar precautions in handling the rolled crystals

Jan 1, 1967

By G. P. Airey, R. F. Mehl, T. A. Hughes

The coarsening of cementite particles in a ferrite matrix has been studied in a series of steels with 0.15 pct C only and 0.15 pct C plus 1 pct Ni, Mn, and Cr, respectively. Two initial states were employed: quenched nartensite, and quenched and cold-rolled martensite. A series of tempering temperatures between 500' and 700" and tempering times of up to 190 hr were used. The structures were studied by replica and transmission electron microscopy. Particle size distribution curves were determined. From the average size value coarsening curves were obtained. These were plotted in accordance with the Wagner analysis assuming diffusion control. A discussion of the significance of the results is given. L HE reactions occuring upon the tempering of martensite have long engaged the attention of metallurgists. The latter stages, when cementite particles coarsen in a ferrite matrix, have been studied both qualitatively and quantitatively. Studies of such coarsening processes have recently been spurred by the publication of the Lifshitz-Wagner theory1, and the extension of this to the a Fe-Fe3C system by Oriani3 and by Li, Blakely, and einold. Following Wagner the coarsening process is often designated as "Ostwald Ripening". The only quantitative data on the rate of coarsening, except for the work of Hyam and uttin,' in the a Fe-Fe3C system are those of Bannyh, Modin, and odin' for a commercial eutectoid steel and those of Heckel and ereorio" using a pure eutectoid steel. The data of Bannyh, Modin, and Modin have been employed by 0riani3 to derive the a Fe-FeE interface energy. The reaction is one of the most important ones in steel and is worthy of detailed study. This is the purpose of the present study. Laboratory heats were prepared; these were steels with approximately 0.15 pct C, selected so that the num ber of carbide particles would be relatively small and thus so that the overlapping diffusion fluxes would be minimized, presumably a desirable circumstance.'-3 In addition to Fe-C alloys, comparable heats containing 1 pct of Ni, Mn, and Cr, respectively, were included with a view of appraising the effect of alloying elements. This report includes an account of the micro-structures observed, primarily with the electron microscope, and of kinetic data and their interpretation. MATERIALS AND TREATMENT The alloys were prepared from electrolytic iron ("Plastiron") and high-purity graphite; these were melted in a zirconia crucible using a vacuum furnace. The alloy steels were made by adding electrolytic nickel, electrolytic manganese, and "vacuum grade" chromium, respectively, under a partial pressure of argon. Each melt was poured into a mold within the vacuum furnace and cooled in the mold. The ingots were 2 in. in diam. and 8 to 10 in. long. The analysis of the alloys is given in Table I. These ingots were hot-rolled to strip 0.1 in. thick, then cold-rolled to 0.05 in. and each alloy split into two batches. One batch was austenitized at 1200 for 1 min, quenched in cold brine, then cold-rolled to 0.02 in.; samples given this treatment are hereinafter designated as "worked". The other batch was cold-rolled to 0.025 in., austenitized at 1200" for 1 min, and quenched in cold brine; such samples are hereinafter designated as "quenched". These two batches were then tempered, as below. The purpose of the treatment given the first batch was to provide an initial structure of cold-worked martensite, with the expectation that the additional defect structure created by cold work would encourage a higher rate of nucleation of cementite on tempering and hence a more uniform distribution of cementite particles. Individual specimens were sealed in evacuated quartz or Pyrex tubes, then tempered in a muffle furnace. The temperature control was better than 3'C at 700. Tempering treatments wer: performed at 400°, 500°, 550°, 600°, 65o°, and 700C for time periods between 15 min and 190 hr. PREPARATION OF SPECIMENS Specimens for optical and replicalelectron microscopy were mounted, polished conventionally, and etched with 2 pct nital. For electron microscopy, single-stage "formvar" replicas were made, dry-stripped and rotary-shadowed with chromium at an angle of 30 deg. Carbide extraction replicas were prepared from electropolished specimens usirig the method described by Smith and uttin.' Thin foils for electron transmission microscopy were prepared by chemical thinning in an H202-HF bath prior to electropolishing in a chromium trioxide-acetic acid solution. The most

Jan 1, 1969

By Thomas Egleston

The ores of mercury of North California are composed of metallic mercury and cinnabar. They are found in serpentine, and are very often associated with chalcedony, in masses more or less irregular, often concentrated enough, however, to furnish ores yielding from three to ten per cent., and sometimes richer. This deposit makes its appearance in Vallejo where it has been worked. North of here the mines are more developed. Most of the quicksilver mines, however, are situated in Sonoma and Napa Counties. On its outcrop the serpentine rocks have become decomposed, and have often been washed away to a considerable depth, so that in many cases in their neighborhood, what is apparently nothing but ordinary dirt, will frequently contain from two to three per cent. of metallic mercury, with but a trace of cinnabar, in which case, as at the Sonoma mine, it is made up into adobes and distilled. Such material does not require to be mixed with dirt to be made into adobes. Very often, also, the outcrop of the rock, where it is not decomposed, is filled with metallic mercury, so that by striking a pick into it, as at the Rattlesnake mine, a pound or more of mercury at a time will sometimes spurt out. Such rock as this is found in several localities in every stage of impregnation, and usually makes very rich ore. There is generally, however, very little of it, and it is found only in the first workings; the ore in depth is always cinnabar. At the Rattlesnake mine near Pine Flat, where large quantities of metallic mercury are found, the rock contains so much petroleum that it has been necessary to make special arrangements to burn the carbides of hydrogen, since the distillation of the petroleum causes an extra quantity of poor soot to be formed in the condensation-chambers. At the Geysers the ore is associated with large quantities of sulphur and gypsum, so that in a hand specimen there is often more sulphur than cinnabar, which is a serious impediment to working, especially for the modern style of furnace with iron condensers, and causes so much soot to be formed that it has been known to penetrate as far as the blower, and to so completely clog it as to prevent its revolution. The ore coming from the mine is more or less hand-picked. In one or two cases attempts have been made to treat the poorest, and especially the very fine ores, mechanically as at the California works.

By T. V. Philip, R. E. Lenhart

When commercial silicon iron sheets of varying magnetic quality are isothermally annealed at high temperatures, extremely large grains develop in the material having good magnetic properties. These grains are of the (110) [001] orientation and are formed by secondary recrystallization. The primary driving force for this secondary recrystallization is grain boundary free energy. For the secondary grains, activation energies of 103 kcal per mole for nucleation, and of 75.5 kcal per mole for growth, were obtained. The activation energy for nucleation of the secondary grains is consistent with a model involving redistribution of a precipitate acting as the primary grain growth inhibitor. SINGLY oriented silicon iron sheet was first produced in 1935.1 The material as commercially produced today has a very highly developed preferred orientation or texture; up to 95 pct of the grains are crystallographically oriented with their (110) planes in the plane of the sheet and their [loo] directions parallel to the rolling direction. This texture, usually written as (110) [00l], is referred to as the "GOSS" or the "cube-on-edge" texture. Because the magnetic properties of this material are superior to those of the nonoriented sheets in the direction of rolling, the oriented silicon iron has acquired tremendous industrial importance especially in the manufacture of transformer cores and other electrical equipment. The commercially produced material is essentially an iron-silicon alloy containing about 3 1/4 pct Si with minor impurities totaling less than 0.15 pct. The silicon steel heat is melted in the open hearth or electric furnace. The ingots are hot rolled, with or without being slabbed, to strips of 0.100 to 0.080 in. thickness. They are then cold reduced to an intermediate thickness, recrystallized, cold reduced to final thickness, decarburized, and finally annealed at a high temperature. During this high-temperature anneal, extremely large grains with the cube-on-edge texture are produced in the sheet. Several papers have appeared in the literature2-10 relating to the production of the Goss-textured material. Most of these describe the textures produced on cold rolling and on subsequent annealing of single crystal or polycrystalline silicon iron. May and Turnbull11,12 have recently shown the necessity of a second-phase dispersed impurity in the material for the production of the Goss texture. However, none of these papers describes in detail the nucleation and growth kinetics of the (110) [001] grains during the final high-temperature anneal.* The present work, therefore, is an attempt to understand the nucleation and growth kinetics of the cube-on-edge grains in the silicon iron sheet during the final high-temperature anneal.

Jan 1, 1962

By Robert S. Archer, Zay Jeffries

It is about fifteen years since the development in Germany, largely by Alfred Wilm, of the aluminum alloy called duralumin. In this alloy, combining as it does the tensile strength of mild steel with the lightness and corrosion resistance of aluminum, a distinctly new material was presented to the engineering world. Despite the evident usefulness of this material, however, its commercial development has been slow, due in part to the difficulties involved in its fabrication. In view of the potentially great utility of strong aluminum alloys, it seemed desirable to find means of producing such alloys with better fabricating properties, and work was undertaken with this object in the laboratories of the Aluminum Company of America several years ago. This work has resulted in the production of two new types of aluminum alloy of the "strong alloy" class, having distinctly improved fabricating qualities. The knowledge gained has also made it possible to produce alloys of the duralumin type with greater strength and hardness than previously obtained. There have thus been made available some new engineering materials which it is the object of this paper to describe. These alloys, induding duralumin, are fundamentally wrought alloys. Castings of the same compositions heat treated in the same manner give inferior physical properties, particularly as to ductility. The statements made subsequently concerning properties and heat treatment apply to material that has received sufficient working to thoroughly break down the cast structure. The material referred to has, in general, undergone a reduction in section of at least 80 per cent, by mechanical working. It may be mentioned in passing that other compositions have been found that are suitable for the production of the maximum physical properties in heat-treated castings.

Jan 1, 1925

By D. W. Smith

THE beta solid solution phases of the systems copper-zinc, copper-aluminum, copper-tin and silver-zinc are structurally analogous.1 R. F. Mehl and 0. T. Marzke2 have shown that the a phase upon segregating from the 0 phase in the system copper-zinc takes the form of needles lying parallel to a [111.] direction or some similar direction, such as [556], of the parent solid solution, and that the a phase upon segregating from the ß phase in the system copper-aluminum also takes the form of needles. By analogy they assume that in this case also the segregate needles lie parallel to the [111] or [556] direction in the ß lattice. The purpose of this investigation is to determine whether the structures resulting from segregation of the a phases from the respective 0 phases of the systems copper-tin and silver-zinc are analogous to those obtained by Mehl and Marzke in the systems copper-zinc and copper-aluminum.

Jan 1, 1932

By A. I. Blank, S. E. Maddigan

Many experimental and theoretical investigations have been made on the processes involved in annealing and recrystallization of metals. Most of these, however, have treated the time element as constant and heat-treatments used have been for relatively short times. Aside from the early work by Carpenter and Elam,' the few that have investigated the effect of time on the processes have usually done so for fairly short time periods. During recent years the growing interest in long-time creep properties of metals and alloys under stress has made increasingly important a better knowledge of the recrystallization during prolonged heating. The recrystallization temperature of 70-30 brass given by Clark and White" in 1932 was somewhat above 400°F. (204°C.) but under 500" (260°C.), whereas in our laboratory recrystallization has been observed in creep specimens at 204°C., the lowest temperature of Clark and White's range. Since the creep properties are quite different above and below the recrystallization temperature, erroneous conclusions can readily be drawn by the application of short-time recrystallization data to creep problems. It was thus considered of both practical and theoretical value to make long-time annealing studies near the minimum recrystallization temperature. In this way useful additions could be made to data on recrystallization temperatures and, since the reactions in this range are relatively slow, additional insight could be obtained into the factors involved in annealing. Several comprehensive reviews of recrystallization processes have been written,3-6 therefore only a brief review of the generally accepted facts will be given here. Though the effects of heat-treatment usually are expressed as related to observations with varying temperatures, it is logical to assume that the same order of occurrence will exist with time as a variable. Thus, we may postulate that with increasing time we mill observe the following

Jan 1, 1940

By S. E. Maddigan, A. I. Blank

Many experimental and theoretical investigations have been made on the processes involved in annealing and recrystallization of metals. Most of these, however, have treated the time element as constant and heat-treatments used have been for relatively short times. Aside from the early work by Carpenter and Elam,' the few that have investigated the effect of time on the processes have usually done so for fairly short time periods. During recent years the growing interest in long-time creep properties of metals and alloys under stress has made increasingly important a better knowledge of the recrystallization during prolonged heating. The recrystallization temperature of 70-30 brass given by Clark and White" in 1932 was somewhat above 400°F. (204°C.) but under 500" (260°C.), whereas in our laboratory recrystallization has been observed in creep specimens at 204°C., the lowest temperature of Clark and White's range. Since the creep properties are quite different above and below the recrystallization temperature, erroneous conclusions can readily be drawn by the application of short-time recrystallization data to creep problems. It was thus considered of both practical and theoretical value to make long-time annealing studies near the minimum recrystallization temperature. In this way useful additions could be made to data on recrystallization temperatures and, since the reactions in this range are relatively slow, additional insight could be obtained into the factors involved in annealing. Several comprehensive reviews of recrystallization processes have been written,3-6 therefore only a brief review of the generally accepted facts will be given here. Though the effects of heat-treatment usually are expressed as related to observations with varying temperatures, it is logical to assume that the same order of occurrence will exist with time as a variable. Thus, we may postulate that with increasing time we mill observe the following

Jan 1, 1940

By M. Schwartz, S. K. Nash, R. Zeman

Knoop hardness in the rolling plane and in the longitudinal plane of hot-rolled and cold-rolled sheets of sublimed magnesiu?w was measured as a function of the angle between the long axis of the indenter and the rolling direction. These measurements were correlated with similar data taken on the (0001) and (1010) planes of a single crystal of magnesium where the hardness was measured as a function of the angle between the long axis of the indenter and the [1120] direction. The results were analyzed for compliance with the hypothesis of Daniels and Dunm to account for slip, and with a similar hypothesis to account for twinning. Some hardness anisotropy data are also presented for magnesium-indium and magnesium-lithium solid solution alloys. It is well known that the hardness of a crystalline specimen is different for its different surfaces, and also that the hardness is a function of direction within a single surface. Variations in hardness for single crystals have been found to be much larger than those for polycrystalline materials. Also, materials having low crystal symmetry were found to have a greater anisotropy of hardness than those of high symmetry. 0'Neill1 and Pfeil,2 using a 1-mm Brine11 ball, studied single crystals of aluminum and iron, respectively; and they found a variation of hardness of about 10 pct between readings taken along the principal crystallographic faces. Daniels and Dunn3 found that the Knoop hardness number varied about 25 pct as the long axis of the indenter rotated on the basal plane of a zinc single crystal. The variation on the (1450) plane was about 100 pct, and the average hardness on this plane was about twice that of the basal plane. They also studied the variation of hardness within the (loo), (110), and (111) faces of a single crystal of silicon ferrite and found variations of about 25 pct although the average values for these planes were almost identical. Single crystals of zinc were also studied by Meincke.4 He found that the Vickers hardness numbers varied about 30 pct depending on whether the axis of the indenter was parallel or perpendicular to the (1010) and (1110) planes. Mott and Ford,5 using a Knoop indenter, found a 25 pct variation in hardness on the basal plane of zinc. Crow and Hinsley6 studied heavily cold-rolled bronze, steel, brass, copper, and other metals. They found that the difference in hardness numbers based on the difference in the length of the diagonals of the Vickers indenter was from 5 to 12 pct. Some minerals and synthetic stones show a very large anisotropy of hardness. Robertson and Van Meter7 found the Vickers hardness of arsenopyrite to vary from 633 to 1148 kg per mm2. stern8 using the double-cone method on synthetic corundum found the hardness number to vary from 950 to 2070. And winchell9 reported a variation of hardness number from 184 to 1205 in kyanite. The variation of hardness as a function of direction in a given crystallographic plane in single crystals possesses a periodicity which is related to the symmetry of the lattice. Daniels and Dunn3 found a six-fold periodicity of hardness in the (0001) plane of zinc. They found that the hardness curves of silicon ferrite had a four-fold symmetry in the (100) plane, a two-fold symmetry in the (110) plane, and a six-fold symmetry in the (111) plane. Mott and Ford5 also reported a six-fold symmetry of hardness in the basal plane of zinc. And vacher10 found two-, four-, and six-fold periodicities of hardness in copper on the (110), (100), and (111) planes, respectively. The purpose of this paper is to report the results of an investigation on the anisotropy of hardness as a function of orientation in single crystals of mannes-ium, and samples of rolled magnesium, magnesium-indium, and magnesium-lithium solid solution alloys. The anisotropy of hardness of pure magnesium which had been hot rolled, and then cold rolled various amounts to fracture, was studied by means of Knoop indentation hardness numbers; and the results were correlated with the preferred orientation as determined by quantitative X-ray pole-figure data. A comparison was made of the hardness data obtained from the rolled sheets and those of single crystals of magnesium. In order to obtain a more fundamental understanding of the variation of hardness and of Knoop hardness testing, the data were analyzed by

Jan 1, 1962

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By G. S. Cole, G. F. Bolling

ThE exact type of fluid flow which occurs in a solidifying ingot is important in determining subsequent grain structure. This has been shown in studies of natural Convection" and of forced stirring or other disturbances of the melt."16 We shall explicitly argue that a complement to the existing natural flow in an ingot should be more effective than other types of flow in promoting the columnar-to-equiaxed transition. The ultimate effects of fluid flow upon structure is one of the topics of solidification that we have investigated in the alloy system Pb-Sb, under conditions simulating casting. In Fig. 1, the essential features of a bidirectional growth apparatus are shown; horizontal freezing from water-cooled faces within a low-thermal-conductivity lavite boat is a reasonable simulation of an ingot section. Details such as the furnace and thermocouples are omitted in order to show the location of four permanent. magnets, each with a pole separation of 21 in. providing a central field of about 1000 Gauss. When coupled with a dc current imposed through appropriate connections made at the cooled faces, a flow of fluid is produced as shown schematically. This technique described by Pfann and ~orsi" is ideal for our purpose since the flow indicated is the same as that we observe to occur naturally in this system. Components of 99.999 pct purity were used for study and all due precautions were taken in alloy preparation to avoid contaminants. Sections of the specimens were taken to ensure results representative of the interior as well as the surface of specimens. All proportions of equiaxed and columnar regions were measured by tracing the etched grain structures onto graph paper and simply counting squares. Four alloys were examined at superheats of 40" * 5°C and 100" * 9°C. Preliminary tests had shown that no appreciable enhancement of structure was obtained with magnetic field alone, so that this condition is not reported; it should nevertheless be noted that other configurations of magnetic field will reduce convection and thus enhance columnar growth.'8 For the tests reported the magnetic field was applied to a specimen by bringing the four preassembled magnets to a position 2 mm from an outer tube immediately after the ingot was poured. The dc current of 30 amps passed through the sample throughout the entire solidification cycle, resulting in a power dissipation of 9 w per sq cm of interface. This may be compared to the evolution of latent heat of approximately 18 w per sq cm. Table I contains the results of this experiment in terms of the total area ratio, equiaxed/columnar grains, as a function of the field interactions, solute concentrations, and superheats employed. The total structure of the ingot is seen to be most influenced when both the field and current are applied simultaneously; when current acts separately, little effect may be noted in spite of the heat supplied. In addition, the change in structure from the no field-no current case to the field-current condition is more pronounced at the higher superheat, and the higher the concentration of antimony. An example of the grain refinement, as well as the increased equiaxed zone, is shown in Fig. 2. It is now important to prove that there is indeed an increase in fluid flow due to the presence of the field-current interaction; this is done by temperature measurements in the liquid metal. Let us consider a bidirectional casting in which heat is applied to and removed from the system, in such a way that rate of solidification is zero.* When a sensitive thermocouple

Jan 1, 1967

By J. B. Hess, C. S. Barrett

Single crystal rods of cadmium collapse under uniaxial compression into peculiar kinks if the (0001) glide plane is nearly parallel to the axis of compression. In his report first describing this behavior, Orowan1 proposed that these "kink bands" do not develop entirely by ordinary gliding and twinning but by a special mechanism in which glide lamellae of uniform thickness snap abruptly to a tilted position that permits lattice continuity across the glide planes. He concluded that a portion of each boundary of a kink band consists of a plane (non-crystallo-graphic) which bisects the angle between the glide planes on the two sides of it, and along which the bending and the dislocations are concentrated. The data presented by Orowan seemed to us to be insuffcient to conclude that a wholly new mechanism of deformation was responsible for the kinks. Therefore, we have investigated zinc, which is hexagonal close-packed and has an axial ratio near to cadmium, to see whether similar bands are produced, and whether the ordinary mechanisms of glide, bend-gliding, twinning, and the formation of deformation bands can account for its mode of deformation. We find that kinks form profusely in zinc as shown in Fig 1. The structure of these kinks, reported below, seems to require no new mechanism for their explanation, but indicates that kink bands are a special form of deformation bands and develop gradually, solely from basal glide. A theory covering the formation and structure of the bands is presented in detail because it is seldom possible to study deformation bands under such simple conditions, yet many principles applying to these kinks should also apply to deformation bands in general. Experimental Procedures Single crystal rods of 2-3 mm diam and 10-15 cm length were grown by the Brideman technique from swaged wire of Horsehead Special zinc in un-coated pyrex tubes. Orientations of the rods were determined with an optical goniometer after cleaving the rods at liquid air temperature. Crystals of desired orientations were then selected and used as "seeds" to grow additional crystals approximately 4 ft in length from which all specimens were cut. The wires were compressed in two ways: in a simple hydraulic handpress —a "soft" machine—and in a Riehle hydraulic testing machine modified to produce very "stiff" action by the simple expedient of inserting lengths of steel bars at the sides of the zinc crystals between the compression plates. For metallographic examination, the specimens were mounted in sealing wax. Hand polishing was employed, with no grits coarser than No. 1 paper; following the abrasives about 0.025 in. was removed by an etch-polishing reagent.* Final etching to reveal ori-

Jan 1, 1950