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By John V. Beall

With some difficulty we framed the picture of the village on the mountain getting in the railroad bridge and tunnel at the base. It was a charming scene of red-tile roofs on a green mountain in the golden autumn sunshine with the black hole of the railroad tunnel looking like something out of the movie, "The Train." We clicked the shutter, advanced the film and started back to our rented Audi. At which point there was a hail from the other side of the railroad bridge. A man in uniform was brandishing an object in the air which looked suspiciously like a rifle. We peered around. We were the only other persons in view. He must be yelling at us. He was now closing the distance at a brisk, determined gait but was still 100 yards away. The car was handy but the road was straight, paralleling the railroad tracks for some distance. We dismissed the idea of running for it. Who knows, he might shoot. When he came up we didn't have much of a conversation because it had taken us a week to learn three words of Yugoslavian-zhiveli, long life, huhvalla, thank you, and schlivavitza, the national drink (plum brandy). None of these seemed appropriate. We got the Idea that photographs of railroad tunnels and bridges were prohibited. The guard, for such he seemed to be, took the Audi plate number, administered a last scowling reprimand and stalked off. This incident was the only one in a 15-day visit to Yugoslavia which we would have associated with "Iron Curtain restrictions."

Jan 1, 1970

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957

By Lo-Ching Chang, J. Chipman

C. B. POST*—Just what are you showing that has not been shown by fixing the attention on molecular species and choosing the molecular species to give you a perfect solution? J. CHIPMAN (authors' reply)—In general a fairly satisfactory thermody-uamic treatment of slag-metal equilibria can be worked out on the basis of assumed molecular species in the slag. This has been the method used by Shenck and more recently by White. Winkler and I also used it in studying dephosphoriza-tion. Darken and Gurry found that it did not fit satisfactorily in the case of their data on iron oxides. The ionic formulas used here conform to the data much better and probably correspond somewhat more closely with the actual structure of the slags. C. B. POST—It does seem to be similar to you? J. CHIPMAN—It is alternative, and may lead to a more complete understanding. C. B. POST—Have you had a chance to talk to glass technologists on this? Have they been using this type of set-up for glass solutions? J. CHIPMAN—Yes, and the ionic formulas have given them a little better understanding of what liquid glass is like. C. B. POST—Nelson Taylor always said we were going- about slag reactions from the wrong viewpoint when using molecular species. Evidently the glass technologists use ionic species exclusively when dealing with liquid glass reactions. J. CHIPMAN—I agree that it seems more rational and more accurate to use ionic rather than molecular formulas. We should be cautious, however, and not suppose that we really understand the structure of a slag just because we are able to fit its reactions by ionic equations.

Jan 1, 1950

By Charles L. Hosler

My function here today is not to illuminate any particular subject but simply to welcome you to Penn State and to the College of Earth and Mineral Sciences. Our college is, of course, dedicated to the same thing to which most of you have dedicated your lives--the exploration of the earth, the extraction of materials from it, and the production of useful things from those materials. We have about 2,000 students engaged in studying in preparation for service in these activities at the present time. Like other colleges of our type, we've undergone a great expansion just at a time when university budgets are contracting. This creates an interesting situation as to how we can best use our resources. This, of course, is the thing a lot of you are going to be talking about here--how we can best use the world's resources. As you well know, the expectations of the people of the world are rising, and, with the numbers of people increasing and with finite resources, there never was a time in history when it was more important that we become "quantitative" in our discovery, estimation, extraction, and utilization of those resources. I think it is admirable and very timely that you are gathered together to discuss your various approaches to this particu¬lar problem of quantifying and making most efficient use of the resources of the world. Yours is sort of a hidden profession, not just because you actually go underground, but because the public in general is not aware of where the materials they use come from. If you are successful in your professions the public will continue to be unaware. Only if you fail will your essential function become patently obvious. I wish you success both in your professional pursuits and in this particular meeting.

Jan 1, 1977

By Reich G. Gaertner

Almost every mining engineer who has had charge of extensive underground workings will have observed how often directions as to course and levels, deduced from careful theodolite measurements, have been slighted or disregarded by mine-foremen and shift-bosses, and how often these tedious measurements had to be repeated, even for minor works, such as ventilation-drifts or winzes, in order to carry them on with the required or desirable regularity. Besides the time and care absorbed by theodolite surveys, there is still another inconvenience, namely, the interruption of transportation during the time of observation, and, in heavily producing mines, the loss consequent upon such interruption. In proposing a subsidiary instrument to the theodolite, it is my purpose not to present a new one, but simply to recommend to the consideration of American mining engineers one which has been in use in nearly all the prominent mines of Europe for many decades, and has there fulfilled its purpose admirably. I refer to the mining or hanging compass (Fig. 1). At my urgent request, the firm of Keuffel & Esser, of New York, have lately constructed this instrument in a form which adapts it better to use in this country. By the addition of the trigonometer, the banging compass becomes at once an instrument which will prove of value even in the hands of foremen and practical miners, who have little or no knowledge of trigonometrical calculations. Probably many will say that me have no use for needle-instruments ; that our modern theodolites are of such perfect description, and leave so little to be desired, that the introduction of a compass would look like a step backwards compared to the fine results obtained by angle-instruments. I concede all that, and do not pre-

Jan 1, 1886

By AIME AIME

MINING geology was granted two sessions, Wednesday morning and afternoon, Feb. 17. The morning session, at which H. Foster Bain presided. first considered Paul M. Tyler's paper, "Economic Notes on Steel-making Alloys." The elements used in these important alloys are chromium, manganese, molybdenum, nickel, phosphorus, silicon, titanium, tungsten and vanadium. Edward Sarnpson and C. K. Leith asked whether chromite concentrates could be used, Mr. Tyler replying that they could if not too high in iron. G. W. Pawel said that they were used at Niagara Falls, nlixecl with coarse ore. In reply to a question asked by A. O. Hayes, Mr. Tyler said that molybdenum had not affected the price of tungsten. After this discussion, E. S. Moore's paper on nickel was considered. H. Foster Bain thought that nickel is well controlled and in good hands, technically and politically. The popular stainless steel in America is the 18:8 Cr-Ni metal. In Germany a Cr-Mn steel has possibilities. It is easy to make, cheaper. has better workability, will stand 85 per cent reduction between heats.

Jan 1, 1932

By J. Gurland

The effect of four different second-phase additions on the strength of composite alloys with a common matrix was investigated. The four compositions each consisted of 85 pct by volume of silver with additions of 15 pct of either tungsten, molybdenum, tungsten carbide, or nickel. These particular additives were chosen because of their low mutual solid solubilities with silver at room temperature, the alloys consisting essentially of a dispersion strengthened silver matrix in which the second phase is distributed randomly. Test specimens were prepared by a powder metallurgy procedure consisting of ball milling the mixed powders, compacting, and sintering at 920°C for 1 hr in hydrogen. The constituent powders were of CP quality and of particle size between 2 and 10 ?. The compacts were subsequently hot pressed at 1000 psi and 1400° in an Inconel die, coined at room temperature at 60,000 psi and finally annealed and outgassed in vacuum at 800°F. The microstructures of the alloys are shown in Fig. 1, and the microscopically observed porosity grade was A-2 or better as evaluated by ASTM Recommended Practice B 276-54. The properties of the sintered compacts are listed in Table I, and the load-deformation curves in bending are shown in Fig. 2. The samples, of rectangular cross section, were loaded at the center of 58 in. span, and the reported stress was calculated on the basis of linearly elastic behavior in order to allow the comparison of specimens of slightly different dimensions. It is apparent that the tungsten, molybdenum, and tungsten carbide alloys exhibit very similar deformation curves. The moduli of elasticity were determined from the slopes of the stress-deflection curves at small loads. The measured values agree quite well with those calculated by the strength of materials approximation proposed by Paul1 for the elastic constants of mixtures, the calculated values being 15.0, 15.0, 17.4, and 13.4 million psi, respectively, for the tungsten, molybdenum, tungsten carbide, and nickel combinations with silver. The strength of the Ag-Ni composition is appreciably lower than that of the other three alloys. The discrepancy between the two groups is accounted for by the following characteristics of deformation and failure which were observed microscopically during the tests: A) The deformation of the W, Mo, and WC alloys did not involve the second phase particles to any appreciable extent. Slip and fracture took place in the silver-rich matrix alone, although the fracture path generally skirted the particles by favoring the phase boundaries. The deformation proceeded according to the following sequence: 1) formation of small, discontinuous microcracks in areas of the matrix adjacent to a particle, 2) general slip in the matrix and extension of cracks, 3) failure of specimens by propagation of cracks through matrix. The near coincidence of the 3 load-deflection curves suggests that the nature of the second phase particles does not decisively influence the plastic behavior of composite alloys of this composition as long as the particles do not undergo any considerable deformation themselves. B) A markedly different behavior was exhibited by the Ag-Ni composition where the relatively low flow strength is associated with the low yield strength of the nickel grains. Slip in the nickel grains was first observed at a stress of approximately 10,000 psi, although failure, at a later stage, took place by the propagation of cracks through the matrix. The ductility of this aggregate, in which both components deform plastically, is appreciably greater than that of the elastic-plastic composites. In summary: 1) The measured values of the moduli of elasticity of the composite alloys under discussion are in good agreement with the "strength of materials" approximation proposed by Paul.' 2) The overall plastic behavior of these particle-strengthened alloys is unaffected by the nature of the second phase particles, if the latter remain elastic. This work was supported by the Office of Naval Research. The experimental results are presented

Jan 1, 1962

THE LIFE and works of Alexander Agassiz, first president of the Calumet & Hecla Mining Co., were recalled to memory when a monument bearing his statue was unveiled in Agassiz Park, at Calumet, Mich., on Sept. 26, The statue is the work of Paul W. Bartlett, of New York, and was erected by George R. Agassiz, eldest son of Alexander Agassiz. We are indebted to Rodolphe L. Agassiz, now president of the Calumet & Hecla Consolidated, for the accompanying photograph of the statue. The principal address at the unveiling ceremony was delivered by Allen F. Rees, of Houghton, who said, in part: To the world at large Alexander Agassiz was preeminently the man of science. With all his devotion to the industrial life of this district, he found the time to devote to the con-tinuation of his work of scientific research which had been the life work of his fa-ther, Louis Agassiz. Not only did he acquire eminence for his scientific at-tainments and learn-ing, but he was recognized and hon-ored throughout the civilized world for his achievements and accomplishments in the realm of original research. His work in the fields of nat-ural science, in oceanography, in marine zoology, and in other similar lines of research, has added much to our knowledge of the world's mysteries. His life was one of accomplishment also in the industrial world. The union in one life of acknowledged achievement as a scientist and the accomplishment of great results in the prac-tical industrial world is a rare thing, and its possibility has never been exemplified in greater measure than in his life and its results.

Jan 11, 1923

By D. R. Bomberger, M. Deul

An automatic microscope has been developed to measure the size and populations of macerals and minerals in fine coal particles. Differentiations are made on the basis of reflectance. This study is concerned with the size distribution of pyrite inclusions. Most fine coal cleaning processes do not remove pyrite as completely as a straight density separation. Consideration of the pyrite size distribution is suggested as a more accurate method of predicting sulfur reduction by a cleaning process. Analyses of float-sink results and Deister Table operation in terms of pyrite particle sizes are made. Other potential applications of automatic microscopy are also discussed. In the study of coal cleaning by pseudo-gravity methods (tables, cyclones, hydrotators, etc.), it is customary to express the deficiency of the process relative to float-sink measurements in some form of "percent efficiency". These have been calculated in many different ways in order to provide a means of extrapolation of test data to untested coal feeds. This works quite well with coarse coal (here defined as larger than one-eighth in.). Large, heavy pieces of refuse are rejected rather thoroughly by many cleaning processes, and the efficiencies relative to float-sink results approach 100%. In coarse coals, the difference in the sizes of fine pyrite is masked by the averaging effect of the large coal envelopes. The existence and fate of fine pyrite is often hidden in the larger numbers representing coarse (and easily removed) pyrite. There are cases where it is desirable to subject fine coal (here defined as smaller than one-eighth in.) to cleaning processes. This is true of naturally occurring fie coal streams and in cases where comminution followed by cleaning is necessary to provide the quality desired. It is in this area that the use of process efficiency relative to float sink fails. Percent efficiencies decline to very low figures, and equivalent separation densities become a matter for conjecture. The net result is that an attempt to estimate product quality from float-sink data and a process efficiency figure often results in large errors. This work represents a new approach to the problem by observing the fate of pyrite particles, grouped by sizes, in a cleaning process. Examples are given which relate pyrite size measurements to float-sink washability and to a Deister Table operation. EXPERIMENTAL WORK The automatic microscope used here has been previously described.' Briefly, it is an instrument which measures the diam of particles (as defined by a range of reflectance) exposed on a polished specimen. The instrument scans a sample briquet, measures diam of exposed pyrite inclusions and records the data by size intervals. Preparation of the briquet is critical, due to the automatic nature of the process. The principal requirement is for an optically flat surface, so that focus will be maintained as the motorized stage moves the specimen under the lens. The various substances present must be polished to the same level in spite of the wide difference in hardness between coal substance and minerals. The polishing method must not pluck out small grains, which might be rather loosely held by surrounding coal. The procedure below was successful in producing all of these results. The coal sample (8 mesh or finer) was riffled (a micro vibrating riffle is essential) to obtain 15 g. One volume of Lucite powder (thermosetting plastic mounting medium) was mixed with three volumes of coal and mixed thoroughly. A briquet was formed using a cylindrical die (1 1/4 in. diam) at 3000 lb per in.* pressure and 150°C. Preparation of the optical surface was accomplished on automatic polishing equipment, according to the following schedule: 1) Grinding: 3 stages, using successively fine Carborundum grits of 180, 320 and 600 mesh. 2) Rough polishing: 2 stages, using 3µ alumina on cast iron, followed by 1µ alumina on lead. 3) Fine polishing: 2 stages, using 0.5µ alumina on napless broadcloth over bronze, followed by 0.1µ alumina on silk filament cloth over bronze. Raw data were corrected for the fact that the chords

Jan 1, 1964

By Adolf Gurlt

It has long been known that minute quantities of foreign substances, when alloyed with steel, are capable of materially altering its physical properties. Thus, half a century ago, Faraday and Stodart, in England, discovered in the famous Indian steel, known as " wootz," small quantities of aluminum, from 0.0728 to 0.693 per cent., and attributed its extraordinarily good quality to the presence of such minute quantities of that metal. Since aluminum is now produced by electrolytic means on a large scale and at low cost, its addition to cast-steel has been frequently recommended of late. Chromium was alloyed with steel fifty years ago by the celebrated French metallurgist, Berthier, of Paris, and has recently been successfully applied to the same purpose by Holtzer, of Terre-Noire. In 1860 titanium was alloyed with crucible steel by Robert Mushet, of Coleford, the alloy containing up to 0.50 per cent. of titanium, which was extracted from Norwegian ilmenite. The titanium-steel was much vaunted by him for its excellent qualities. Rhodium, a very rare metal of the platinum series, was maintained by Berthier to improve steel materially in strength and hardness. Manganese has always been held by Sheffield steel-melters to provide steel with excellent qualities, and this influence was quite recently investigated by H. M. Howe and L. Campredon. Nickel was tried as an addition by Berthier, not to speak of gold, silver and platinum ; and nickel-steel has recently been brought into prominence by J. Riley and others, who recommend it for its great strength and toughness, particularly as material for armor-plates.

Jan 1, 1894

By AIME AIME

OPPORTUNITY may not be knocking but it, at least, is waiting for you, your family and your friends in that amazing republic south of the Rio Grande. For the first time we are able to publish the official itinerary for the forth-coming Mexico City meeting of 1936. As shown on Page 351, the deluxe special train leaves St. Louis on Thursday. Nov. 5 at 5:30 p.m., returning to St. Louis on Nov. 18 at 8:15 a. m. The schedule provides seven days and six nights in Mexico City with numerous excursions to nearby towns and resorts. The oldest surviving city in' North America is Mexico City, dating back at least to the twelfth century. It was the Aztec capital when Cortez arrived in 1519. The famous cathedral still standing was built on a foundation of sculptured Indian images and the remains of a great Aztec temple. Today it is a city of romance.

Jan 1, 1936

Single orders 2.5 c. Pamphlets 10. c. each in lots of three or more. Pamphlets 5 c. each in lots of fifty or more. These prices prevail for orders for pamphlet, of the same or different titles. The pamphlets listed on the following sheets are advance copies printed to facilitate discussion at the meetings of the Institute. They are offered for sale at the reduced prices given above as long as the supply, lasts. This list is published in the Bulletin in order that members may have the first opportunity to secure pamphlets, which sometimes are in such great demand that the supply is exhausted before the wants of members can be supplied. The following list includes only a fraction of the pamphlets that have been published by the Institute. Any other paper published by the Institute may be obtained for the price of $1, except those published in Volume XXXI, which are rare.

Jan 5, 1917

By John Freeman

THIS paper relates entirely to the casting of brass under fluid pressure in steel dies. Die castings of metals and alloys of low melting point have been available for many years but the development of brass die castings has been relatively recent, occurring within the past five years. The successful development of brass die castings has resulted from the availability of alloy steels that would give satisfactory life as dies and the development of suitable die-casting machines. The melting point of copper is 1084° C. (1983° F.) and of a high brass about 900° C. (1652° F.), as compared to 327.5° C. (621.5° F.) for lead, 419.4° C. (786.7° F.) for zinc and 658.7° C. (1217.7° F.) for aluminum, temperatures that are indicative of the casting temperatures required for the various types of alloys, of which the melting points are somewhat lower than those of the pure metals.

Jan 1, 1935

By A. Hellawell

Specitlrens of the Al-Ge eutectic alloy have been frozen unidivectionally at rates between 2.5 x 10-6 and 2.5 x 10-4 cm per sec and the structure examined by optical and X-ray methods. There is no epitaxial relationship between phases, the aluminum having random orientation and the germanium a preferred (011) fiber textuve. Lamellar colonies which are BINARY eutectic alloys occur between either silicon or germanium with the metals aluminum or silver. common in this alloy are constructed from axial and nonaxial (111) plates of germanium which are related by a variety of twin configurations. Irregular or globular regions of the microstructure are composed of continuous single crystals of each phase, the germanium being heavily twinned. There is limited solid solubility in these systems, and the eutectic phases all involve diamond cubic with fcc crystal structures. In the microstructures of these eutectic mixtures the silicon and germanium crystals exhibit an almost infinite variety of shapes which are notably sensitive to

Jan 1, 1968

THOSE MARKED THUS * ARE MEMBERS, MARKED THUS ?ARE ASSOCIATES. THESE SIGNS DOUBLED INDICATE LIFE MEMBERS AND ASSOCIATES RESPECTIVELY. THE FIGURES AT THE END OF THE ADDRESS INDICATE THE YEAR OF ELECTION. HEAVY-FACED TYPE SIGNIFIES HONORARY MEMBERSHIP. *AARONS, J. BOYD, Vivian Gold Mining Co., Ltd., Harris, West. Australia. '05 *ABADIE, EMILE R., Cons. and Min. Engr., 214 Union Savings Bank Bldg., Oakland, Cal. '76 *ABBOTT, CHARLES W., Min. Engr. Pioche, Nev. ?08 *ABBOTT, JAMES W., Min. Engr: Ploche, Lincoln Co., Nev. '94 *AOTT, ROBERT R., Met. Engr., Peerless Motor Car Co., Cleveland, Ohio. '12 || ARAHAMS, ALEXANDER I., Student.. .67 E. 93rd St., New York, N. Y. '13

Jan 1, 1917

An abstract of a paper from the Canadian Mining and Metallurgical Bulletin of August 1978 by E. Stamboliadis, J. McHardy, T. M. Salman, Department of Mining and Metallurgical Engineering, McGill University, Montreal, Quebec, states that: “The recovery of gold, silver and other heavy metal cyanides from mill solutions is technically possible using the ion exchange technique. However, the costs involved are greater than the costs of the zinc precipitation technique used for gold recovery. There are two main reasons for this: one, the fact that in gold ore cyanidation metal cyanides other than gold and silver occupy most of the resin capacity and hence reduce the adsorption efficiency of the resin for the Au and Ag cyanides; secondly, the high cost of the eluting agents.” Resin, therefore, cannot in most cases be efficiently used for recovery of precious metals. With copper in solution, only 1.47% of the resin capacity is used for gold and 0. 8970 for silver; the rest is occupied by unwanted metal cyanides, such as copper occupying 73.7%. On the other hand, although activated carbon will adsorb copper cyanides, they will be preferentially displaced by gold and silver cyanides. Ion exchange is by one or two orders of magnitude more expensive than the conventional method of zinc precipitation. The cost of removing impurities, such as copper from the resin, is greater than the cost of recovering gold. With an oxide ore amenable to cyanidation and with a low content of other metals, such as may occur with some of the Soviet gold deposits, ion exchange would be an efficient as Carbon-In-Pulp.

Jan 1, 1981

By William Marsh Baldwin

THE ROLLING OPERATION proper is applied to metals and alloys not only in the production of flat products but also in the production of shapes, rods, wire and even in specialized forms in the production of tubes. The present discussion of rolling copper and copper alloys will be [ ] limited to a consideration of rolling flat products such as strip, sheet, foil, plate, and others. In this case (as in the others listed above), the rolling operation itself is only part of an integrated sequence of operations. In Fig I such a sequence going to make up a brass strip mill is sketched out. It is seen that the rolling opera-

Jan 1, 1948

By W. W. Wen, S. C. Sun

The objective of this investigation was to study the electrokinetic behavior of oxidized coals to indicate the feasibility of separating oxidized coals from ash materials and pyrite by an amine flotation process. The effects of soluble inorganic electrolyte products from coal oxidation were also examined. The electro-kinetic behavior of coals of different rank and degree of oxidation were studied by an electro-phoreses technique. Generally, increasing the oxidation increases the negative value of the zeta-potential and decreases the isoelectric point (IEP). Flotation results indicate that the flotation recovery increases with decreasing pH values, and that with ferrous sulfate at pH 6.5 the flotation recovery is optimum while the pyrite is depressed. Comparing the flotation results with the electokinetic results verified that in the presence of ferrous sulfate, the maximum hydro-phobicity of oxidized coal with dodecylamine and frother is near its IEP, which is around pH 6.5 to 7.0.

Jan 1, 1978

By T. Yoshioka, Paul A. Beck

SILICON, germanium, and tin occur with both the white tine-type structure and the diamond cubic structure. In the latter form these elements are semiconductors; in the former they are metallic. The metallic form of germanium and silicon is obtained only under high pressure.' For all three elements the transition from the semiconductor to the metallic state is accompanied by a decrease in the atomic volume of somewhat more than 20 pctily2 Table I. At such a large compression the widening of the s and p bands is sufficient to make the energy gap of 1.1 ev, or less, of the semiconductor disappear, giving rise to the metallic state.*

Jan 1, 1965

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962