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By John Wulff, H. H. Uhlig

Since its first mention in the literature in the eighteenth century12 the phenomenon of passivity in metals has stimulated much speculation and attendant controversy as to its nature and cause. No one of the numerous theories so far proposed has been generally accepted. ‡ Faraday,' in 1836, associated the passivity of iron with a protective film over the surface of the metal, which materially prevents or slows down reaction with corrosive environments. His theory was that oxidizing acids like nitric acid form an unstable oxygen or oxide layer over the iron surface, which protects the underlying metal from further attack. This concept was simple yet plausible, and without alteration has frequently been assigned in present-day discussions as explanation of the passivity of many metals. With the advent in recent times of stainless steels, it is not surprising that this oxide film theory of passivity proposed by Faraday has been used to explain the phenomenal corrosion resistance of stainless steels and other passive alloys. The passive alloys, such as the chrome-iron alloys, are supposedly covered with a protective oxide film, which forms on exposure of the alloy to air, is extremely stable and self-healing, and accounts for the remarkable resistance of these alloys to corrosion. Within the past few years, several investigators, following the theory of film protection, have attempted to gauge the resistance of the supposed film on steels. Brennert8 and Donker and Dengg9 determined the potential at which a negative ion (e.g., C1-) moving in an electric field reacted with the metal anode, as detected by increased current flow or change in potential of the steel electrode in an electrolytic cell. The potential corresponding to reaction Brennert called the film break-through potential.

Jan 1, 1939

By C. K. Stoddard, R. G. Knickerbocker, E. T. Leidigh, R. R. Lloyd, K. L. Mattingly

DURING July 1941, a study was initiated at the Boulder City Experiment Station of the Bureau of Mines on proposed methods for the production of magnesium metal. The major emphasis was placed upon development of a process that required minimum reliance upon the sale or utilization of by-products to meet economic competition from processes already in operation. It was felt that only through the development of such a process could the nation's vast resources of dolomite and low-grade magnesite that are contiguous to large blocks of firm power be properly utilized. During the course of exploratory tests on electrolytic and electrothermic processes, it was noted that fused magnesium chloride would dissolve appreciable quantities of magnesium oxide in the presence of small amounts of boric oxide. The use of such a solution in an electrolytic cell employing a graphite anode and a steel cathode caused the deposition of magnesium at the cathode and the evolution of carbon oxides at the anode with minimal amounts of chlorine The original results were sufficiently encouraging to justify further investigation on an enlarged scale, since the process seemed to present advantages over other proposed processes 1.2 for the direct use of magnesium oxide in a fused chloride electrolyte. When work on a larger scale was initiated it was found that the addition of boric oxide to the electrolyte resulted in dispersion of metal and constantly decreasing current efficiency. However, by this time solubility studies had shown that magnesium oxide was sufficiently soluble in magnesium chloride melts containing no boric oxide to effect the same anode reactions, and development work was continued. Over two years of development work have been carried out, and considerable work remains to be done. It is desired to emphasize the fact that many of the difficulties met require a long period of continuous operation before they become serious enough to affect operation of the cell. ACKNOWLEDGMENTS This paper is one of many reporting on various aspects of the Bureau of Mines' program initiated in August 1939 by passage of the Strategic Minerals Act the scope of which was greatly expanded by subsequent legislation. Some of these papers are published as war minerals reports. others as bulletins, technical papers, reports of investigations

Jan 1, 1945

By J. Cervik, P. C. Thakur, S. D. Lauer

Methane drainage by cross-measure boreholes on retreat longwall faces can be a viable alternative to the vertical gob degas boreholes under favorable circumstances. The research was done in a mine working Pittsburgh coal seam in northern West Virginia under USBM Cooperative Agreement No. 14-09-0050-3252. The study was the first application of this technique to Pittsburgh coal seam. A total of 14 small diameter, inclined boreholes were drilled over a retreat longwall panel from gate roads, to intersect the overlying coal seams. All boreholes were manifolded to a pipeline and the gob gas was extracted by a surface exhaust fan. The methane capture ratio was poor at 7% to 18% at various stages of the longwall panel. A vertical gob degas borehole captured an additional 20% gas. Poor results were due to premature failures of the cross-measure boreholes leading to air leakage. For better performance, the boreholes should be drilled from a point 30 to 45 m (98 to 148 ft) from longwall pillar over the largest chain pillar. The standpipe should be grouted for at least 6 m (20 ft), and the entry containing boreholes and the pipeline must be supported to ensure access for maintenance and optimization of methane capture. Coursing the ventilation air around longwall such that it forces methane migration toward cross-measure boreholes can further improve methane capture. The optimum vertical inclination is 45º ± 10º.

Jan 1, 1986

By T. Sterry Hunt

THIS remarkable mine, to which attention has lately been drawn, is situated not far from the New River, in Ashe County, North Carolina, on a spur of the Blue Ridge which lies between the main crest of this name and the so-called Iron Mountain, a part of the Unaka or Smoky Mountain range. It is on a true fissure-lode, which cuts the strata of gneiss and mica-schist of the region. These, which have the lithological characters of what I have called the Montalban or White Mountain series, have here a dip of about forty-five degrees to the southeast, while the lode is vertical, with a course north 60° east. Both the country-rock and the lode, as is usual in this region, are decomposed to considerable depths ; and the latter exhibits a cap of hydrous peroxide of iron or gossan, blocks of which, left by the denudation of the softer inclosing rock, are scattered over the surface, and first called attention to the locality as a source of iron ore. In sinking upon this lode, it was found that the porous gossan at a certain depth became charged with carbonate and red oxide of copper, and lower down was replaced by sulphuretted ores of this metal of remarkable richness. This deposit was worked for copper, in an irregular manner, before the late civil war, but was afterwards abandoned, and only reopened during the present year, by Messrs. S. S. & J. E. Clayton, of Baltimore. The outcrop has been traced for 1900 feet, and the sulphuretted copper ores have been met with in five shafts in a distance of 661 feet, a drift having moreover been carried for the above distance through the solid ore. The breadth of the lode, so far as opened, varies from six to eight feet to fourteen feet in places, and that of the outcrop of gossan is, in some parts, twenty feet. After comparing this deposit with the copper mines of Ducktown, Polk County, Tennessee, and those of Carroll County, Virginia, it is evident that we have, at Ore Knob, to do with the same kind of black ores as were met with in these mines, and will be noticed further on. Beneath the gossan, at Ore Knob, is found, in some parts, an iron-black, friable, drusy, crystalline, sulphuretted ore, inclosing grains of quartz, garnet, and magnetite, besides a black non-magnetic mineral, not attacked by nitric acid. This ore contains about 36 per cent. of copper, and portions have the mineralogical charac-

Jan 1, 1874

By Stephen Burke

THE oxidation of pyritic sulphur associated with coal is important for the following reasons: 1. It is the predominant cause for the formation of acid mine drainage issuing from bituminous coal seams. This drainage pollutes the streams in coal regions, making the water unfit for industrial purposes and causing the disappearance of fish and wild life. As a consequence the movement of industry and especially recreational industry, so important to the population of these areas as an alternative means of livelihood, is impeded. 2. It is instrumental in effecting a series of reactions, which bring about the degradation and ultimately result in the spontaneous combus-tion of bituminous coal in storage. 3. It contributes to the breaking and shattering of the coal structure and is one of the causes of roof falls and floor lifts in mines. 4. It is the primary cause of the many nuisances associated with gob piles and the refuse of cleaning plants. 5. Its proper control and application might possibly be employed in the preparation of coal to reduce the inorganic sulphur content. The research that has been conducted on the oxidation of the various forms of iron sulphides is extensive and the literature voluminous. Nevertheless, few efforts have been made to determine experimentally and with some precision the mechanism of the reaction under the condi-tions of its occurrence in bituminous coal mines. It has generally been accepted that the oxidation of pyritic sulphur proceeds according to the reaction 2FeS2 + 21120 + 702 --> 2FeSO4 + 2H2S04 [1] The ferrous sulphate in the drainage streams is further oxidized by air to produce ferric hydroxide and more acid. Yet the literature fails to dis-close any pertinent investigation on the mechanism of this reaction. The present contribution is concerned primarily with this aspect of the problem and while the work to be reported is not yet complete, it has yielded results from which interesting and significant conclusions may be drawn.

Jan 1, 1937

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By H. W. McQuaid, E. W. Ehn

It is usually assumed that chemical specifications are sufficient for steel to be used for case carburizing, and if the steel analyzes within the ordinary limits specified for steel for this purpose, no difficulty traceable to the steel used should be encountered in obtaining satisfactory results in the case carburizing and hardening. Much work has been done to determine the effect of various alloying elements on the rate of carbon penetration, etc. but, to our knowledge, little if anything has been published in regard to the effeet of the quality of the steel on the final results in the hardening of case-carburized steel parts. The writers believe that the structure of the case both before and after quenching is greatly affected by the actual condition of the steel itself as made, and that for good results in the case-carburizing and hardening departments, the steel should be of the best possible quality as regards non-metallic impurities. It is the purpose of this paper to prove that the presence of excess dissolved oxides in the steel, as made in the melting furnace, affects permanently the results obtained in carburizing and hardening and that it is possible that the presence of dissolved oxide call result in total unfit-ness of low-carbon steel for case hardening purposes. When races and rolls for roller bearings are made from a low-carbon steel, case carburized and hardened, it is of primary importance that the results of this treatment be of the highest quality. It is necessary, therefore, that in the case-carburizing work each detail be rigorously checked to avoid any defects which would cause the loss of much time and material. The case carburizing with which this paper deals was done in under-fired oil furnaces. The temperature of each furnace is controlled by means of a platinum platinum-rhodium thermocouple, in connection with a potentiometer indicator and potentiometer recorder. The temperature of each furnace is registered every 15 min. by an operator, who is continually checked by the automatic recorders.

Jan 1, 1922

By Sarat C. Rubra

Geographically, British India includes India or Hindustan proper, Burma, and a part of Beluchistan. In ancient times India occupied a very important position anlong the producers of minerals and metals; in fact, as late as the middle of the seventeenth century, it contributed a very considerable quota of the mineral and metal supplies of the world. The branches of the industry worthy of special note are gold, silver, lead, antimony, copper, iron, diamonds and other precious stones. The famous " Damascus steel" was originally manufactured in India, Damascus being only a mart; and it is interesting to note that even at the present time this product is still made in India. Prior to the discovery of diamonds in Brazil in 1728, India was the sole producer of this important mineral; and while no diamond-mines are now systematically worked, fine specimens are occasionally reported to be found in river-beds and in alluvial diggings. For ages, nearly all of the minerals of present commercial value have been produced and worked in India, and many of the deposits may still play an important part in the world's mining and mineral history. Despite the patient work of the ancient Indians, the limited knowledge they possessed of pumping and ventilation precluded the possibility of attaining any great depth in mining. Under special conditions, shafts have been sunk to 600 ft., but the average depth was much less. As a result of this limitation, the ancient miners confinecl their work to the available ores in sight, leaving large bodies of ore intact, which can be profitably worked with modern methods of mining. As an evidence of this statement may be mentioned the mines of the Kolar gold-fields in Mysore, which have reached in some shafts a. depth exceeding 2,400 ft. Traces of ancient work in these

Jan 1, 1904

By H. J. Hand

STATISTICAL methods are becoming increasingly important for interpreting routine reports, or for analyzing special test data in industrial plants, such as steel plants. They have already become practically a necessity to the plant metallurgist. A paper by Chancellor,' written in 1933, gives many examples of the benefits the plant metallurgist can derive from the use of these methods. The present paper discusses applications of importance to many others who must analyze reports in the steel plant, as well as other examples of interest to metallurgists. Statistical Methods Logically Suited to Plant Problems.-Statistical methods are not new as a branch of mathematics. Until comparatively recently, however, practical applications were confined mainly to actuarial science,, biology, and economics; fields in which an observed result is obviously influenced (and often determined) by a complicated set of variables more or less constantly tending to affect it. As pointed out by Daeves,2 a decade or more ago, problems in industry are basically similar to those in these other fields in that a given result is at least partly due to that chance combination of causes happening to be present at the time. When trying to do the same thing repeatedly, constant results are never attained; they vary about the desired result with more or less well defined mathematical regularity. Such a condition arises out of the great number of factors tending to affect the final result. If statistical methods are so valuable to the biologist or economist, why then should .they not also be of great value to plant managers and engineers, and to all who must interpret reports from various sources in the industrial plant? Within the last few years, industry has become conscious of this situation, and the use of these methods has been rapidly expanding in such plants. † Many Useful Statistical Devices Available.-Many statistical methods of attack are available for the analysis of plant data. It is the object of this paper to discuss applications of some of these methods to the solution

Jan 1, 1938

By R. T. O’Brien, J. M. W. Mackenzie

A microelectrophoresis technique has been used to measure the zeta potential of quartz over a range of pH and Ni (11) and Co (Ilj concentrations. Results have been discussed in terms of adsorption of Ni (11) and Co (11) cations and hydroxide precipitates. Possible relationships between the experimental results and the formation of lateritic nickel deposits have been discussed. The adsorption of metallic cations to the surface of silicate minerals is of significance in many industrial and natural processes. In an earlier publication,' the adsorption of Fe (111) to the quartz surface, a phenomenon of importance in flotation, was studied qualitatively using microelectrophoresis techniques. This paper reports the extension of this work to an investigation of the adsorption from aqueous solution of Co (11) and Ni (11) to the quartz surface. The adsorption of these metals was of interest for two reasons; firstly, the importance of such an adsorption process in the formation of nickel deposits by the lateritization of nickeliferous rocks, and secondly, the comparison of electrophoresis data for these metals, whose hydroxides precipitate in the pH range 7-8, with similar data for Fe (111) where the hydroxide first precipitates at pH 2.8. The development of laterites is essentially a near-surface geological process involving vertical and, in part, horizontal redistribution of elements derived from rock-forming minerals. This redistribution of elements leads to the formation of layers within the lateritic profile which are enriched in one or more of these elements and, depending on the nature of the original rocks, continued lateritization may give rise to iron ores, bauxites or nickeliferous laterites. The mechanisms discussed in this paper deal with the last mentioned type of deposit although the considered factors are applicable to laterites in general. Nickeliferous laterites are derived from basic and ultrabasic rocks containing ferro-magnesian silicates. These rocks may be partly or wholly converted to serpentinites. Besides their high Mg, Si and Fe contents, they also contain small amounts of Mn, Al, Cr, Ni, Co, Cu and Zn. The nickel content is usually near to 0.2-0.3%, but for economic use this must be increased during lateritization to over 1% and preferably over 2%. The zone of nickel enrichment is usually at some depth within the lateritic profile. Unpublished work by Mr. O'Brien on nickel-bearing laterites in eastern Australia indicated four visually different types of material which were separated from crushed samples under a stereo-microscope. Although chemical analyses indicated that all four types of fragments contained 2-4% nickel and smaller amounts of cobalt, X-ray diffraction and optical studies revealed only quartz, hematite and chromite as well as, in one of the types, a serpentine mineral. No distinct, nickeliferous minerals were detected. Furthermore, it was possible to extract some 60% of the nickel content of the laterites with cold 0.5N hydrochloric acid. It was therefore postulated that much of the contained nickel was present as amorphous, adsorbed material. In considering this fact, as well as the problem of the actual method of transfer and fixation of elements within the lateritic profile, it was further postulated that the transfer of these elements probably took place partly as solutions and partly as colloids and that the fixation of these was caused by adsorption and flocculation. The existence of nickel in solution in water draining from serpentinites has been confirmed by Smurov.2 Although we have no evidence for the transportation of nickel in the colloidal state, it is well accepted that colloids are important in the formation of laterites. Previous work by Mr. Mackenzie' has already indicated that iron may be adsorbed on quartz under conditions which could be expected in a lateritic profile, but no information was available for nickel or cobalt. Although adsorption possibly also takes place on minerals other than quartz, the latter is significant because silica is an important constituent of the silicate parent rocks. During lateritization, it is released to form free quartz and it is likely that it is initially extremely fine-grained. This would provide abundant opportunities for adsorption and it was de-

Jan 1, 1970

By Lawrence Addicks

Some three years ago the smelter connected with the Chrome, N. J., refinery of the United States Metals Refining Co. found itself embarrassed by constantly increasing piles of unsmelted blast-furnace flue dust. The charge was fine and 10 to 15 per cent. of it was blown over into the flue. Sulphur was at that time too scarce to make the sintering of the finer part of the charge attractive, and raw-ore smelting in a reverberatory with a partly oxidized charge was not to be thought of. A great many schemes were considered, including leaching, blowing into the converters, and briquetting, the problem finally narrowing down to blast roasting and nodulizing. It was found by experiment that blast roasting would not yield a satisfactory sinter without the addition of coke dust or sulphide fines to augment the fuel value of the flue dust, and on this account, together with the low first cost of a kiln, the latter was decided upon. A couple of tons of flue dust were tried out in the experimental kiln in the laboratory at Yorktown, Va., of J. H. Payne, who acted as consulting engineer in this connection. This kiln was approximately 2 ft. in diameter and 20 ft. long and was fired with fuel oil. A run of several hours yielded excellent nodules. The ki1n showed no tendency to build in and form "nose rings" and gave a fuel consumption of 50 gal, of oil per ton of flue dust. There was no indication of any stack loss. The roasting was strongly oxidizing. A study of what full-size kilns were doing on cement clinker and on nodulizing pyrites cinder indicated that a 60 by 6 ft. kiln would certainly not consume over half of the oil per ton of flue dust shown on the test and as fuel oil at that time was selling around 2 1/2 c. per gallon it was decided to let it go at that. A 60 by 6 ft. kiln was decided on, as that size is standard in cement practice, although fast being replaced by much larger ones with their greater fuel economy, and as it fitted in the building space available. A 6-in. brick lining brought the net diameter down to 5 ft. The inclination

Jan 1, 1915

By C. A. Bruch, W. E. McHugh, R. W. Hockenbury

Commercially pure molybdenum specimens were irradiated in the Materials Testing Reactor for an estimated exposure of 1.9 to 5.9x10 20 thermal nvt. Prior to irradiation, the material was ductile in the tension test; whereas after irradiation, it was brittle. The results of tension tests conducted at various temperatures revealed that the transition temperature for this material had been increased from —30' to +70°C as a result of the radiation exposure. From metallographic studies, it is concluded that the embrittlement is due to submicroscopic changes which raise the flow stress-temperature curve of the material. PRIOR to ten years ago, the bombardment of metals with high speed heavy particles such as protons, deuterons, a particles, and neutrons was primarily of academic interest. These particles existed in extremely small numbers in a few laboratories and only under very special conditions. With the introduction of the nuclear power reactors, these particles are now available in enormous quantities and it has become important from a practical standpoint to learn how well metals withstand severe reactor radiations. The principal radiations of concern in reactors are neutrons and y rays, since the heavier charged particles exist only in limited regions of reactors. Seitz,' in a theoretical approach, has shown that all of these high energy particles, except y rays, have enough energy to knock atoms from lattice sites and that these knocked-on atoms have enough energy to cause additional displacements of neighboring atoms. The result of this process would be a lattice containing many imperfections in the form of interstitial atoms and vacancies. Hence, it would be expected that the properties of metals can be changed by reactor radiations, and such has been found to be the case. Only a limited amount of data have been published in the open literature,2,3 and these data have been for relatively low integrated-neutron-flux exposures. In general, one effect of reactor radiations on the mechanical properties of metals has been to increase strength and decrease ductility. It is now possible to irradiate specimens in the Materials Testing reactor at much higher fluxes and to higher integrated exposures than previously possible.' The data which are being presented here describe the effects of a relatively high exposure on some mechanical properties of molybdenum. Experimental Procedures Material: The molybdenum used in this investigation was obtained from the Climax Molybdenum Co. The two heats from which the material originated were melted under a vacuum of 5 to 30 microns and cast in 7 in. diam water-cooled copper molds. One ingot contained 0.061 pct C and the other 0.066 pct. Both ingots were hot worked by extrusion and rolling into % in. diam rods, after which they were annealed and straightened. The rods were subsequently heated to 1100°C in a hydrogen atmosphere and swaged to ½ in. diam rods at the Research Laboratory of the General Electric Co. The resulting material had an average hardness of 264 VPN, or 99.2 Rb, and had an average of 5000 grains per sq ml in the transverse section, Test Specimens: Substandard-size tensile specimens were prepared according to the specifications shown in Fig. 1. These specimens were used also for hardness measurements. The metallographic specimens were small disks which were polished, etched, and photographed at X1000 prior to irradiation. The field studied was

Jan 1, 1956

By W. C. Leslie

W. C. Leslie (Edgar C. Bain Laboratory for Funda mental Research)—This investigation, with its com bination of high-purity metal, calorimetry, and metallography, will serve as a model for annealing studies for a long time to come. The evidence for a competition between recovery and recrystalliza-tion is particularly convincing. The demonstration of edge-nucleated recrystallization was so clear that it may obscure the necessity for other types of "nucleation" sites; otherwise, single crystals of aluminum could not be recrystallized after cold work. At least three types of sites have been found to operate in iron: 1) high-angle boundaries, probably in the same manner as in aluminum, 2) matrix sites, 3) inclusions or second-phase particles. In each instance, the cells developed during cold work and perfected during recovery are the "nucle for recrystallization. Observations by ourselves and others of the dislocation structure of cold-worked metals and of the structural changes that occur during annealing have led us to doubt the validity of the basic assumption of the Lucke-Detert theory, and of the modification developed by Gordon and Vandermeer, that during recrystallization of a metal containing foreign elements in solid solution a high-angle boundary is ad vancing into a cold-worked matrix having a random distribution of solute atoms. We contend that an es sential part of the cold-working and annealing of solid solution alloys is the trapping of solute atoms by the low-energy "wells" afforded by individual dislocations and by dislocation arrays. If cells are formed during cold work, the cell walls are stabilized by this concentration of solute atoms. Thus, solutes inhibit recrystallization not only by decreas-ing the rate of high-angle boundary migration, but also by preventing the formation of high-angle boundaries by subgrain growth or coalescence, i.e., solutes can inhibit both "nucleation" and growth. In addition to stabilizing the dislocation Structure, the solute-dislocation interactions may produce clusters of solute atoms which are not as readily assimilated into the recrystallized grains as are individual solute atoms. There is an additional complication. The dislocation structure formed upon cold working a dilute solid solution may not be the same as that formed during cold working of the pure solvent metal. The solute can either enhance or minimize the formation of cells during cold working. Both effects have been observed in binary alloys of iron. The annealing process is inextricably connected with the mechanisms of strain hardening and solid solution hardening. Although the correlation between experimental boundary migration rates and the predictions made from the theoretical equations are impressive, it should be mentioned that in at least four other instances (Pb-Ag and pb-Au,15, Fe-Mn,16, Fe-Mo)17 the agreement was rather poor. In brief, while it is probable that the migration of high-angle boundaries is held back by solutes in the manner described, this is only a partial explanation of the total effect of solutes upon recrystallization of cold-worked alloys. Paul Gordon and R. A. Vandermeer (author's reply)— The authors first wish to thank Dr. Leslie for his compliments of this work. It is perhaps worth pointing out that some of Dr. Leslie's remarks are directed toward subject matter covered in two earlier papers in our work.18,19 We agree with Dr. Leslie's main contention that the exact nature of the metal structure in the vicinity of a boundary should have an effect on the boundary migration. The theory of Lucke and Detert does not take such detail into account, nor does it account for orientation effects on the migration rates. We assume that since our data checks the theory so well, the effects of detailed structure are statistically averaged out by the polycrystalline techniques used just as are the effects of orientation factors.

Jan 1, 1963

By Fred L. Morritz, Harold M. Manasevit, Richard Nolder, Arnold Miller

Experimental evidence is presented which confirnis the epitaxial relationship between the deposited silicon and the sapphire substrate. Four distinct modes of orientation relationships have been established. These have been shown to be Single-crystal gvowth retention as a function of surfaces oriented off ideal has been qualitatively indicated. Both full-circle goniometer X-ray techniques and replica electron microscopy have indicated varying amounts of microtwinning in the silicon. film, which may he caused by the mode of silicon formation. Parameters have been found where twin density is less than I pct. The early stages of' epitaxy of silicon m sapphire have been examined by electron-microscope techniques... and mechanisms have been proposed. THE first report of the deposition of single-crystal silicon on sapphire (single-crystal aluminum oxide) was made at the American Physical Society Meeting in Canada' by one of us and was subsequently published in the Journal of Applied physics.* This paper summarizes some of the work carried on in this area since that time, in addition to reviewing some of our earlier observations. The initial single-crystal deposits of silicon on sapphire reported were obtained on sapphire planes produced by cutting a sapphire rod perpendicular to its fastest growth direction, which is approximately 60 deg from the C axis. Direct correlations between the microstructure and X-ray data as to the single crystallinity as shown in Fig. 1 are evident. These deposits were identified as (111) silicon on the substrate oriented near the (1123) of sapphire. (Sapphire notations are designated according to the c over a ratio of 2.73.) It became evident that substrate quality and surface play an important part in successful epitaxy. For example, in Fig. 2 we observe an interesting

Jan 1, 1965

By M. E. Wadsworth

The region about the south shore of Lake Superior is to geologists one of the most interesting districts of the United States, embracing as it does, in a limited area, old crystalline rocks, together with forms that are almost in their original condition of a beach sand and mud. In this region was first established the base of the geological column, the Azoic (" without life") System of Foster and Whitney, or the Archæan (" the beginning ") of Dana. Overlying this system are found the sandstones and limestones of the Paleozoic (" ancient life "), and their associated lava-flows (Algonkian ?). These systems possess a strong economic interest, owing to the stores of iron in the Azoic and of copper in the Paleozoic or Eozoic of this district, which forms one of the most important mining regions in America. The geology of this section is so difficult and complicated that, in its general discussion, perhaps no proposition can be stated concerning any portion of it to which exceptions cannot be taken. Indeed, out of the general discussion of different points comes in time the truth, and various geologists, even now, are working over this region in the endeavor to arrive at some consensus, or at least to determine upon what points they can agree, and upon what points difference of opinion will have to exist between them at present, until further evidence can be obtained. The writer will endeavor to give in a brief form that which appears to him at present to be the most correct statement of the geological structure of the region, admitting that from time to time, as more complete evidence shall be obtained, he expects to change his views in the future, as he has done in the past, if that evidence shall cause him to believe that he has been mistaken.

Jan 1, 1898

By H. M. Hobart

THIS paper deals principally with investigations undertaken by the Welding Research Sub-committee of the Welding Committee of the Emergency Fleet Corporation. The general object of the investigations has been to extend the use of welding in the construction of merchant ships and, specifically, to provide a definite basis for obtaining the best economy and efficiency in employing welding in place of riveting in the construction of the hulls of such ships. Composition of Ship-plate Steel The chemical composition of the steel employed in such hull construction varies with the thickness of the plates. Through the courtesy of Mr. H. Jasper Cox of Lloyd's Register of Shipping, the following information may be given concerning the kind of steel plate employed in American Shipyards in 1918 for the hull construction of merchant ships. Lloyd's requirements do not relate to the chemical composition. They require a tensile strength of 58,000 lb. per square inch (40.75 kg. per sq. mm.) for their lower limit and 72,000 lb. per square inch (50.59 kg. per sq. mm.) for their upper limit. For the information of the Committee, Lloyd's obtained from their surveyors at various works data of the carbon content, which is as follows:

Jan 2, 1919

By W. W. Mullins

The development, by the mechanism of volume diffusion, of a grain boundary groove on an interface separating a solid phase and a saturated fluid phase is calculated under the following assumptions: 1) isotropy of the interfacial free energy 's, 2) applicability of the Gibbs-Thompson formula relating curvature and chemical potential, 3) a nearly planar groove surface. The groove profile is found to have a .fixed shape and linear dimensions that are proportional to (time)1/3. The constant of proportionality is evaluated and involves ?s in such a way that the latter my be evaluated from grooving kinetics. A grain boundary that intersects an interphase interface will tend to produce a groove along the line of intersection (Fig. 1). The ultimate motivation for the formation of the groove is the reduction in interfacial free energ that occurs as the grain boundary contracts. Smith has discussed the way in which the free energy of the interfaces determines their dihedral angles at the groove root and has given a detailed analysis of the effect of the dihedral angles upon the nature the microstructures developed in polyphase alloys. Herring2 has extended the considerations to the case in which the free energy of an interface depends on its orientation and has thus added torque terms to the condition for interface equilibrium. Although the grain boundary and the interphase interface may quickly achieve the proper equilibrium angles where they intersect, as determined by the balance of equivalent tensions and torques,"2 the groove will generally continue to grow (though with decreasing speed). Thermodynamically, this continued growth reflects the fact that the lowest free energy cannot be achieved until the entire grain boundary has been eliminated; mechanistically, the growth occurs in response to inhomogeneities of chemical potential that are caused by the constraint of fixed dihedral angles at the groove root. The latter point is illustrated in Fig. 1, which shows that atoms* near the groove are on the convex side of a cylindrically curved surface and therefore have a higher chemical potential than atoms on the flat interface beyond. Thus atoms tend to leave the curved groove shoulders and force the groove to deepen. When both phases are solid additional chemical potential gradient may arise from whatever strain fields are necessary to insure continuity of material across the interface. In the discussion that follows, this complication due to strain will not occur since we always assume one phase to be a fluid and the other a solid. The transport processes that may operate to permit growth of the groove are surface (interface)* diffusion, volume diffusion in the phase on either side of the interface, and evaporation-condensation when one phase is gaseous. (Also a melting-freezing process is responsible for groove enlargement on a solid-melt interface as discussed in Sec. VI). The theory of grain boundary grooving has been discussed in detail for the processes of surface diffusion and of one type of evaporation-condensation.3'4 The theoretical predictions for the mechanism of surface diffusion have been confirmed in an experimental study of grooving kinetics in copper.5 In this paper, the theory of groove development by volume diffusion will be presented. Volume diffusion can occur either by atomic migration in the solid S or by diffusion of S atoms in the fluid phase, or solvent, adjacent to the groove surface. As discussed in Sec. V, volume diffusion in the solid should be less important than surface diffusion in forming a groove. Apart from verifying this statement then, the main interest of the present analysis centers on diffusion in an external solvent. The solvent may be either a liquid (e.g., water, or-

Jan 1, 1961

By Robert F. Mehi

The mechanical behavior of metals and alloys is presumably conditioned by two factors; namely, the crystallinc symmetry and the interatomic forces. Considerable attention has been given to the first of these factors through the recent advances in X-ray technique. It is the purpose of the present paper to call attention to the importance of the second of these factors, to point out promising methods of investigation, and to present some pertinent data. Plastic deformation takes place by slip along atomic planes.' This slip may be inhibited in a number of ways: by the interatomic forces of, cohesion which bind the atoms rigidly in a lattice structure, which in pure metals is usually of high symmetry; by latticc distortion caused by solid solution formation or by mechanical strain; by the intercrystalline boundaries whcrc slip is restrained, probably by the non-registration of the atom planes in adjacent crystal1ites;2 and by the presence of small hard particles which serve to "key" the slip along the atom planes.5 In pure metals, and perhaps also in solid solutions, the atom planes of easiest slip are those exhibhing the greatest density of atomic population and the greatest interplanar distance4 and apparently can now be pre-dict,ed from the analysis of the lattices. Concerning the interatomic forccs, which resist this slip by holding the atoms firmly together, little is known. Most textbooks on physical metallurgy, following the work of Bot-tone,5 correlate the hardness of the pure metals with the atomic volume,

THIS chapter and Chapter 19 deal with the heat quantities involved in open-hearth steelmaking, including the thermal efficiency of the furnace as a generator of high-temperature heat, the heat storage in the steel and slag produced and in the furnace walls, and the heats of the various chemical reactions involved in combustion, in the formation of slag, and the refining of steel. The fundamental laws to be considered are the first two laws of thermodynamics as applied to problems involving sensible and potential (or latent) heat only: 1. Heat input equals heat outflow plus storage. 2. Heat may be transferred only from a hotter body to a colder one. The first of these laws relates to the various heat quantities or the heat balance of the process. No one has as yet made an open-hearth heat balance that came out almost exactly balanced. The cause probably lies in the difficulties of accurate temperature and flow-rate measurements at the high temperatures involved and the inherent complexities in flow distribution and air leakage present in any real open-hearth furnace system. Some idea of the magnitude of the heat quantities involved can be obtained by a brief, crude outline of the heat balance of a 90-ton heat of steel. We will assume a 60 to 70 per cent hot- metal charge in a fairly fast working and only moderately efficient furnace, burning fuel oil, with a fuel consumption of around 4 million Btu per net ton of ingots produced. The time from start of charge to tap is 9 hr. During this period, the oil burned represents 360 million Btu and the sensible heat in the preheated air at the port ends is 117 million Btu, so that the total heat input at the ports is 477 million Btu. Heat stored in the steel and slag at the end of the heat, plus the various amounts absorbed by certain bath reactions, amounts to a total of 195 million Btu, but 120 million of this is supplied by the heat in the hot metal and by various heat-evolving reactions in the bath,

Jan 1, 1951

By Irwin Roman

PART I. INTRODUCTION THE literature of geophysics as applied to the discovery of mineral deposits has been very extensive during the past few years, but there seem to be few references to the use of the method of least squares for obtaining better interpretations of the observed data .2 There seems to be a general reluctance among geologists and. engineers to acquire the technique of least squares, in spite of the fact that a thorough knowledge of the theory is not necessary for the use of the method.

Jan 1, 1931