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By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By William A. Johnson

The mathematical analysis of diffusion curves in solid metals is carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. Experimental Procedure If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By R. F. Stilwell

There are three things that all coal consumers look for when they burn coal: (1) suitability for their particular requirements and burning equipment, (2) uniformity of shipments, and (3) quality as expressed by heating value and other chemical and physical tests. Suitability, or proper application, is determined generally from previous buying experience. It is a function of (1) the reliability and integrity of the shipper and distributor, (2) of a certain coal field or seam and of (3) uniformity and quality. Quality is limited by the location and geology of the seam and mine, the mining and preparation methods and equipment and the knowledge and ability of the personnel. Uniformity of shipments is in many ways the most important factor in coal selection. Lack of uniformity in chemical quality, size consist and treatment cause most of the customer complaints that arise from faults of the coal shipper. Lack of uniformity destroys suitability and quality standards, causing a large customer turnover, and greatly increases sales expense and reduces the net return to the operator. Oil and gas fuels are more uniform in quality than solid fuels, and there will be more gas and oil competition for coal markets after this war than before, because the size of their market is a direct function of the dimensions of their pipe lines, which have been greatly increased during the war. Present mechanical coal-cleaning equipment based upon gravity concentration has gone a long way toward giving us a coal of uniform ash content. The chart in Fig. I, by Hebley,1 shows the greater uniformity of the ash content of washed coal as compared with that of raw coal. Wide variation in the nature and amount of ash in the coal feed to the washer leads to a coal of non-uniform ash content. Mechanica1 cleaning equipment does not understand such terms as ash-softening temperature, coking properties, size consist and sulphur content. Unless the feed to the washer is uniform, the washed coal probably will not be uniform. Table I shows the ash, sulphur and ash-softening temperature of two mines in the Pittsburgh bed, both raw and washed, loaded over the same tipple; also No. 3 and No. 4 Pocahontas seams, both raw and washed, loaded from the same preparation plant. It is obvious that they must be blended or loaded separately if a uniform product is to be obtained. Why Is Blending Necessary? It was natural for the operators of captive mines producing by-product coals to recognize the necessity for blending raw coals of different quality and coking characteristics. They have had many years of experience with blending high, low and medium volatile coals at their oven plants. They have found that careful blending gives a coke of more uniform quality and better structure. Coals that could not be

Jan 1, 1947

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By C. S. Finney, John Mitchell

There is no field of human thought or endeavor which does not owe much to the past. Yet, surrounded by the prodigious scientific and technological achievements of our day, it is all too easy to forget the extent to which we have stood on the shoulders of giants. The coking industry of the United States is now a little more than one hundred years old. As with the American nation itself, the earliest beginnings of the industry owe a great deal to British influences, and its development owes much to those influences of continental Europe. No serious contribution to the history of coking in the United States can be written, therefore, which does not mention the work of the pioneers of the Old World. It is believed that the use of metallurgical coke dates back to antiquity. The fact that certain coals would soften under the influence of heat to yield a porous solid was known to the ancients of China and India, where a very crude coking operation was carried out by simply setting fire to piles of coal. After active combustion had started, turf or wet straw was used to seal off the pile. The coke obtained was used to forge iron and steel implements and weapons. Perhaps the earliest reference to the coking phenomenon is to be found in the writings of Theophrastus, pupil of Aristotle. In his History of Stones, which was written in or about the year 371 B.C., there appears the following observation. "But the Lipara stone empties itself, as it were, in burning and becomes like the pumice, changing at once both its colour and density; for before burning it is black, smooth and compact.... Certain stones there are about Tetras, in Sicily, which is over against Lipara, which empty themselves in the same manner in the fire." The first comparatively modern reference to coke is to be found in a recommendation for carbonization made in 1584 by Julius, Duke of Braunschweig-Luneberg, owner of the Hohenbuchen mine in the Harz district of Germany. In 1587, Sir Francis Willoughby of. Wollaton, England wrote: "There are twenty rooks broughte into charcoal and laid up in store." A rook of coal was equivalent to some 25 tons, and the coking would probably have been carried out in a manner similar, to that used for the production of charcoal. In 1589, Thomas Proctor attempted to carbonize coal, and in the year 1590 an English patent was granted to John Thornborough, Dean of York, in order that he might "purify pit coal and free it of its offensive smell". Sir Robert Cecil (1595), Robert Chantrell (1607), Simon Sturtevant (1611) and John Rovenzon (1613) were all granted patents for the use of coal or coke

Jan 1, 1961

By Grover J. Holt

In order to provide a clear picture of the development of the sink-and-float process of concentration as applied to the iron ores of Minnesota, a few pertinent facts should be brought out concerning the ores and the products of concentration. Iron ore is primarily a cheap commodity handled in immense quantities. The price of iron ore at present, based on a natural iron content of 51.5 per cent, varies from $2.55 to $2.70 per gross ton f.0.b. cars at the mine or washing plant in Minnesota. Last year 92,000,000 gross tons were shipped from the Lake Superior district (Minnesota, Michigan, and Wisconsin) to the furnaces. Concentrated iron ores have no greater value per unit of iron content than ores that can be mined and shipped direct from the shafts or open pits. For years only the higher grades of concentrating ores could be treated and sold in competition with the immense reserves of direct shipping ore available. These higher-grade "straight wash" ores required only the simplest treatment; namely, the washing out of fine sand from coarse ore particles. As the exhaustion of the " straight wash " ore is reached, rock is found replacing part of this sand, and the ore no longer responds to the former sizing treatment. Substantial tonnages of this marginal (jig ore) remained to be treated. Because of the limitations placed on concentrates by the furnaces—namely, low price of product and minimum amount of fines—iron-ore concentration oil has been and must continue to be a one-pass process. Only an increase in price or a change in structure of concentrates allowed by the ore consumer will encourage departure from this practice. Faced with the necessity of handling large tonnages, with the limitations mentioned, iron-ore research men have found their search for new and more efficient methods of treatment seriously handicapped and removed from the field of fine crushing. Sink-and-float treatment appeared to offer the best field in coarse concentration and has been proved by several plants to be well adapted to our problem. The use of ferrosilicon as a medium solid was decided upon. In our present practice, the ferrosilicon metal, carrying about 83 per cent iron, 15 per cent silicon and 2 per cent carbon and nonmagnetics, is crushed to pass 65 mesh and used without further sizing. When mixed with water the specific gravity of the medium may be controlled to within 0.02 per cent above or below the required gravity. Table I shows examples of a change in solid content of the medium for varying gravities. the I is based on clean ferrosilicon, whereas some contamination is always present in the mill circuit, tending to

Jan 1, 1947

By Henry J. Welge

Laboortory apparatus has been devised which permits study of the displacement of oil from cores by water and by gas. The cores used contained interstitial brine as well as oil. Experiments were run to determine the comparative effect of varying the properties of the fluids used. No great effect was noted on the maximum displacement achieved. This observation made it unnecessary in initial work to use fluids in their exact reservoir conditions. Consequently, the displacements were run at near-atmospheric pressure in Pyrex glass equipment, using stripped crude oils. Introduction and Theory The chief object of this work has been to determine the efficiency of gas and water as primary agents for displacing oil from reservoir rock under laboratory conditions in which capillary phenomena were predominant. To this end the maximum displacement of oil from cores has been ascertained. This maximum displacement may not be equal to the maximum displacement from a reservoir; but it will be a close approxirnation to it sometimes, and other times the laboratory information will be useful in reservoir engineering predictions. It is] believed that the laboratory experimental maximum represents the upper limit for the reservoir recovery. The experiments were carried out by obtaining cores of interest from the reservoir, and filling the pores with interstitial brine and oil with the restored state tech- nique.1 Then the oil was displaced from the core as described later, either by brine from below, or by gas from above. The former type of displacement suggests analogy to production by water drive, but not to water flooding, for reasons discussed below. The latter type of displacement is believed to simulate production by gas cap displacement. The displacements were performed by what may be termed the capillary-pressure method. The cores are placed in capillary contact with an oil-wetted membrane which has very small pores (about I micron in diameter). Pores of this size will transmit oil but Prevent the Passage of gas or water, unless the Pressures used are higher than the capillary Pressures employed in this work. Accordingly, use of the membrane makes it possible to apply a capillary pressure differential between the displacing phase and the oil in the core. AS in the displacement of brine toward that condition of oil and water distribution existing originally in the reservoir,' it may not always be desirable to reduce the oil saturation in this experiment to an absolute minimum. With reservoirs having small productive closure, it is preferable to evaluate and use a displacing pressure no higher than the capillary pressure, Ap, which will ultimately become available for displacement in the reservoir. This pressure may be calculated from a knowledge of the density of the oil-in-place, do, the density of the displacing phase, dl, and Ah, the vertical distance between the section of the

Jan 1, 1949

By C. D. King

THE key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the coal washer at Clairton made it possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of IOO per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. I and No. 2 blast furnaces at Rankin, Pa., Carnegie- Illinois Steel Corporation. Clairton By-Product Coke Plant And Coal Washer The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width. These ovens also differ in height and length. The present coal washer has a daily capacity of approximately 14,000 tons, leaving 16,800 tons to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used on all the remaining ovens. The customary arrangement is

Jan 1, 1944

By M. R. Goldick

The Roan Antelope concentrator was originally designed with a nominal milling capacity of 6000 tons of copper ore per day but this was subsequently considerably exceeded. In broad outline the plant consisted of two No. 30 McCully gyratory crushers for coarse crushing, five 5½-ft Standard Symons crushers in open circuit for secondary crushing, ten No. 98 Marcy ball mills arranged in five sections, each two-mill section with primary and secondary Dorr classifiers for two-stage grinding. One stage of flotation roughing was followed by two stages of cleaning, all in airlift type pneumatic flotation machines, with the final concentrates filtered on Oliver drum filters. Tailing was thickened in a 250-ft Dorr traction type thickener before pumping to the tailing dam. Concentrating operations commenced in June 1931, on the completion of the first two ball-milling sections and output was increased during the next few months as the remaining sections were finished. From the start, very few technical difficulties were experienced but a number of evolutionary changes have been made as a result of operating experience and the availability of improved equipment. These have resulted in plant and ore-flow alterations although the general scheme of ore treatment remains substantially as before. The main changes to date were the installation of a new crushing plant at Storke shaft, some 7000 ft west of the original Beatty shaft; the completion of a two-stage secondary crushing plant; an increase of 20 pct in ball-milling capacity; a change-over from pneumatic to a mcchanical type of flotation machine for flotation roughing; the reduction of flotation cleaning from two stages to one stage. Ore Treated Typically the ore treated consists of metamorphosed shales and sandstones with shales as the principal mineral-bearing rock carrying chalcocite, bornite and chalcopy-rite as the main copper minerals. Chalcocite predominated in the original eastern end of the ore body but there is a pronounced trend to an increased proportion of the copper-iron sulphides as mining proceeds westward. Although the ore can be described as soft, this advantage is offset by the extremely fine dissemination of the copper minerals which calls for a high degree of comminution of the ore (go pct minus-zoo mesh Tyler standard) to give a reasonably satisfactory separation of mineral from gangue. Latterly, there has been a tendency for the ore to become harder as shown by a reduction in the ball-milling rate from a previous figure of over goo tons per ball-mill day to the present output of some 800 tons. Chalcopyrite is not so finely disseminated and has also proved more amenable to flotation than chalcocite. Nonsulphide minerals are mainly the so-called oxides such as malachite, cuprite and melaconite with some chrysocolla and

Jan 1, 1949

By Charles H. Sawyer, Walter Knox

All of the coals commonly used in domestic bituminous stokers form coke, and satisfactory operation depends upon the fact that the coke formed is so weakly bound together that it breaks readily in the normal operation of the stoker and automatically maintains a good fuel bed. Some coals, because of their tendency to form solid, blocky coke, are practically excluded from use in small domestic stokers as now built. Other coals, some among the best stoker coals available, can form this troublesome coke under certain conditions. Many contradictory methods have been offered as cures for coke formation. Generally the procedure has been to try various adjustments until a combination was found that seemed to give better results. Such random methods of treatment have not provided any reliable information as to causes. The present paper covers a comprehensive test program undertaken by the Koppers Company's Stoker Coal Research Laboratory at Kearny, N. J. The program had two main objectives; first, to discover what factors affected coke formation, and second; to define corrective steps that could be applied in stoker service work. Conclusions and Results i. The design of the stoker outweighs in importance all other factors capable of improving coke formation. 2. Insufficient air supply aggravates the formation of large blocky coke, although raising the air above 30 to 40 per cent excess (as determined during steady running) does not further improve the character of the coke formed and only reduces its accumulation at the expense of efficiency, increased fly ash, poorer clinker-ing, and other disadvantages. 3. Increasing the coal feed results in a somewhat more friable coke structure and is recommended for persistently troublesome jobs. 4. Increasing over-fire draft improves the character of the coke formed and reduces troublesome accumulations by accelerating off-period burning, although at some expense in efficiency and some increase in fly-ash accumulation. 5. Coke structure was not substantially improved by blocking some of 'the retort tuyeres, although the blocking of tuyeres at the feed-screw end of a rectangular retort did lead to somewhat improved performance, possibly because of considerably better distribution of coke in the fuel bed. 6. With the equipment tested no difference was shown between installation of the same stoker in a steam boiler and a warm-air furnace, or between a sand-filled and a ventilated type of hearth. 7. The following design features had no noticeable effect on coke formation: a. Presence or absence of coal-tube air as provided by many manufacturers to eliminate smoke-back. B. Presence or absence of a flap damper ill the air duct to minimize off-period burning. c. Continuous or intermittent (ratchet and pawl driven) movement of fuel feed screw.

Jan 1, 1944

By C. D. King

THE key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades' of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the coal washer at Clairton made it possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of 100 per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. I and No. 2 blast furnaces at Rankin, Pa., Carnegie-Illinois Steel Corporation. CLAIRTON BY-PRODUCT COKE PLANT AND COAL WASHER The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width. These ovens also differ in height and length. The present coal washer has a daily capacity of- approximately 14,000 tons, leaving 16,800 tons to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used on all the remaining ovens. The customary arrangement is

Jan 1, 1943

By R. F. Stilwell

There are three things that all coal consumers look for when they burn coal: (1) suitability for their particular requirements and burning equipment, (2) uniformity of shipments, and (3) quality as expressed by heating value and other chemical and physical tests. Suitability, or proper application, is determined generally from previous buying experience. It is a function of (1) the reliability and integrity of the shipper and distributor, (2) of a certain coal field or seam and of (3) uniformity and quality. Quality is limited by the location and geology of the seam and mine, the mining and preparation methods and equipment and the knowledge and ability of the personnel. Uniformity of shipments is in many ways the most important factor in coal selection. Lack of uniformity in chemical quality, size consist and treatment cause most of the customer complaints that arise from faults of the coal shipper. Lack of uniformity destroys suitability and quality standards, causing a large customer turnover, and greatly increases sales expense and reduces the net return to the operator. Oil and gas fuels are more uniform in quality than solid fuels, and there will be more gas and oil competition for coal markets after this war than before, because the size of their market is a direct function of the dimensions of their pipe lines, which have been greatly increased during the war. Present mechanical coal-cleaning equipment based upon gravity concentration has gone a long way toward giving us a coal of uniform ash content. The chart in Fig. I, by Hebley,1 shows the greater uniformity of the ash content of washed coal as compared with that of raw coal. Wide variation in the nature and amount of ash in the coal feed to the washer leads to a coal of non-uniform ash content. Mechanica1 cleaning equipment does not understand such terms as ash-softening temperature, coking properties, size consist and sulphur content. Unless the feed to the washer is uniform, the washed coal probably will not be uniform. Table I shows the ash, sulphur and ash-softening temperature of two mines in the Pittsburgh bed, both raw and washed, loaded over the same tipple; also No. 3 and No. 4 Pocahontas seams, both raw and washed, loaded from the same preparation plant. It is obvious that they must be blended or loaded separately if a uniform product is to be obtained. Why Is Blending Necessary? It was natural for the operators of captive mines producing by-product coals to recognize the necessity for blending raw coals of different quality and coking characteristics. They have had many years of experience with blending high, low and medium volatile coals at their oven plants. They have found that careful blending gives a coke of more uniform quality and better structure. Coals that could not be

Jan 1, 1947

By Daniel R. Hull

IN 1026 Genders' reviewed the existing theories of this subject and stated his views in support of the gas-pressure theory. Again, in 1937, the subject was thoroughly reviewed by N. B. Vaughan,3 and by Phillips and Brick,2 so that no resume is called for here. The purpose of this paper is to describe certain observations made in the course of mill work, and to point out that they mostly tend to confirm the gas theory of Genders. VAPOR SEGREGATION There is, however, one type of inverse segregation that can be accounted for by considering the volatility of one of the constituents of an alloy. The most familiar case is ordinary brass, which is subject to a zinc enrichment of a few tenths of a per cent at the surface of a chill casting. This has been noted in 70-30 brass by Genders, and a typical example of it is given in Table I, which represents a [ ] cylindrical billet 7 in. in diameter by 5; in. long. After lathe-turning 1/32 in. from the surface, the remaining distance to the center was sampled at six equally spaced intervals. The lead, which is essentially the same throughout, will be mentioned later. Consider a brass-mill mold, either round or rectangular in cross section, standing several feet high. It may require a minute or two for pouring. Before it is full, the metal in the lower end has partly solidified and contracted somewhat away from the mold. The initial shell of solidification follows not far behind the top of the column, even if the central portion is liquid for a long way down. There is, then, a space between metal and mold that is filled with zinc vapor. The vapor has no exit, because the liquid at the top of the rising column is not only in contact with the mold but keeps up a fresh supply of zinc vapor, which has, perhaps, already begun to condense in the lower portion. The cycle is short. Within a minute or two after the mold is full the bar has cooled enough to condense all the zinc. Some of it may condense on the mold; it might be expected that most of it would condense there, but the mold at that time is well coated with a velvety carbon residue from the oil dressing, overlain by fluffy zinc oxide that commenced covering the inside of the mold as soon as pouring began. The clean skin of the freshly cast brass offers a preferred surface for condensation. Reabsorption is quick and inevitable. A simple experiment indicates that a surprisingly large quantity of zinc vapor is trapped in the space between mold and

Jan 1, 1941

By James K. Stanley

Preferred orientation, particularly in irons and low-carbon steel, is a phenomenon that is both of considerable importance and theoretical interest. At times it is a liability and at other times an asset. In deep-drawing operations, preferred orientation is extremely undesirable because it necessitates trimming operations and increases scrap loss. Furthermore, oriented metals are likely to crack more easily than randomly oriented material because the forming of symmetrical and unsymmetrical shapes out of preferentially oriented metals and alloys increases the probability of rupture in regions of high stress, owing to differential ductility.' In the electrical industry, on the other hand, preferentially oriented silicon irons are in demand for transformer application because of the improved magnetic permeabilities in the rolling direction.2 This phenomenon of preferred orientation in soft magnetic materials has been responsible for the tremendous improvement in transformer design and construction in recent years. Directional properties in metals have received a great deal of attention in the metallurnical -literature,3-9 in which much of the information reported about orientation has been obtained by conventional methods, mechanicai properties and X-rays. A wealth of data has been obtained and often at a great expenditure of time. The recent introduction of the magnetic torque measurements on ferromagnetic materials provides a very simple and rapid method of evaluating orientation. The judicious use of the method can supply important information, but it should be borne in mind that such studies must be supplemented by X-rays, optical methods,10 and etch and pressure figures" to get a rational understanding of the orientation phenomena. No claims are made that the magnetic torque of evaluating orientation will reveal the behavior of the metal in deep drawing. For this purpose the accepted tests for deep-drawing quality must be used. For a good drawing stock, which must have low impurities, desirable grain size, ductility, strength, hardness, good surface, random orientation, and good recrystallization behavior, it cannot be expected that any simple test will be satisfactory for appraising all the factors. The only factor on which the magnetic method can be used is orientation, which is, of course, of considerable importance. When directionality can cause a 10 to 15 per cent change in tensile strength and a IOO to 300 per cent change in tear length,12 it goes without saying that a reliable as well as rapid method for detecting these changes would be desirable. There are certain inherent advantages in testing orientation by the torque method: The method is rapid with the proper type of equipment; no elaborate preparation of specimens is required—it is only necessary to punch or machine a I-in. disk of the sheet material and insert it into the testing device.

Jan 1, 1944

By William A. Johnson

THE mathematical analysis of diffusion curves in solid metals is Carried out ordinarily by analogy with the flow of heat in a continuous medium and no account is taken of the fact that the materials involved are composed of discrete particles that move discrete distances at irregular intervals. It is possible to treat the problem on the basis of simple assumed atomic mechanisms, in which case, because of the small scale of the elementary process compared to the gross effects observed experimentally, the two procedures lead to the same expression for the variation of concentration with distance. Thus, for engineering purposes, the usual methods are quite satisfactory. If, on the other hand, our purpose is to go beyond the mere collection of data, however desirable this may be, it is necessary to recognize and understand the factors that are of fundamental importance. One factor that has not hitherto been considered when dealing with solid metals is the difference in atomic weights of the isotopes of a single metal. While all the atoms of a given element are alike chemically, their weights may vary by a small but significant amount, and atoms of different weights may have different diffusion rates. With gases this variation in isotopic weight produces a change in the rate of diffusion by a factor inversely proportional to the square root of mass. While, except for the lightest gases, this is not a large effect, it is, for example, sufficient to permit a considerable concentration of one isotope at the expense of others. If metals exhibit a similar phenomenon, some modification of the analysis of the diffusion process will be required, since the different isotopes of a given metal will have different probabilities of moving and the heat-flow analogy will contain a fundamental error. This situation cannot be rectified by using a diffusion coefficient based on the average probability of moving, and it can be shown that even when the diffusion coefficient is independent of composition, the diffusion curve will not agree with the simple theory except in the rare cases where only one isotope exists; e.g., gold. If, however, the mass effect in the solid state were no larger than in the gaseous, the errors arising therefrom in the analysis of ordinary diffusion curves would be quite negligible. Nevertheless, our desire to obtain all possible information concerning the details of the diffusion process, and the possibility of diffusion in the solid state as a means for separating isotopes are cogent reasons for undertaking an experimental study to determine whether isotopes of different masses diffuse at different rates. EXPERIMENTAL PROCEDURE If isotopes of different masses diffuse at different rates, the ratio of the concentration of one relative to another will vary with the distance from the diffusion inter-

Jan 1, 1946

By A. L. Marshall, F. J. Norton

The object of this investigation was to make a comprehensive study of the degassing of molybdenum in order to determine how rigorous a treatment was necessary to completely remove sorbed gases from molybdenum electrodes in vacuum tubes. Some work has also been done with tungsten, nickel, iron and carbon. As a logical development of this work it has been shown that the gas is present throughout the body of the metal and a study has been made of the solubility of nitrogen in molybdenum and tungsten and the rate, of diffusion of nitrogen through molybdenum has been calculated. Tests were made on molybdenum from all the commercial sources and no difference was discovered in the nature of the gases present, the amounts or the ease of removal. The reason for this was apparent when a study was made of the manner in which gases are absorbed by gas-free molybdenum. It is necessary to heat molybdenum to 1760°C. in a vacuum of the order of 0.001 micron for a time which varies lineally with the thickness, in order to obtain a condition in which no further gas is evolved by the sample. A sample so degassed can be handled and subsequently assembled in a tube and then degassed readily. The gases obtained from molybdenum are carbon monoxide and nitrogen, the nitrogen being the more difficult to remove. Apparatus and Technique The apparatus is shown in Figs. I and 2. It consisted of two units, a degassing system and an analytical system. Each had a bake-out oven, as shown surrounding the systems in the sketches. The system , will be traced, starting from the sample in the degassing system. A water-cooled quartz chamber surrounded the sample. The high-frequency coil, which heated the sample, extended only around this chamber and was cooled by an air blast. High-frequency power of 1800-meter wave length was obtained from a self-rectifying oscillator circuit with a maximum power input of 20 kw. A graded seal connected the quartz to the rest of the apparatus, which was of hard glass. The temperature of the molybdenum sample was observed by an optical pyrometer through an optical window about 40 cm. distant from the sample. Since the object viewed under these conditions was not a black body, true temperature was not observed, but the so-called "brightness temperature." The correction of this to true temperature is discussed in a later section. The apparatus was taken apart just above the graded seal; the quartz chamber was slipped off, washed with nitric acid, water and alcohol, and dried by an air stream. The old sample was removed by unscrewing the lower nut, and the new

Jan 1, 1944

By S. Isserow

RECENTLY, a description of the wartime work in this laboratory on the U-Si phase diagram was published. This diagram was available earlier in the open literature; as were Zachariasen's crystal structure identifications for the compounds in the system. The uranium end of the phase diagram is shown in Fig. 1. The most recent work on this system has emphasized the peritectoid E phase, of particular interest for a number of reasons. The early work provided evidence of this phase's resistance to corrosion in water and of its slight ductility. Further information on these properties has been obtained here. Work elsewhere4 has provided evidence of stability under irradiation. This body-centered-tetragonal phase is relatively isotropic compared to the more usually applied a or ? uranium phases. Unlike the other compounds in this system, it contains no Si-Si covalent bonds.3 In addition, consideration on the basis of Pauling's concepts leads to the conclusion that in the E phase, uranium has a higher valence than in any of the other phases. Definition of the composition of the ? phase has been of prime concern in the study of this alloy. Evidence is presented below that its silicon content is slightly higher than that of stoichiometric U8Si, the composition frequently assigned this phase on the basis of Zachariasen's identification. This work on the composition required careful attention to the method of dissolving the alloy for analysis, since apparently low silicon contents could be found under certain conditions, see Appendix. Preparation: Melting, Casting, and Heat Treatment—Almost all the samples were from castings with a diameter of 13/4 or 2 in. and about 1 ft long, weighing 10 to 15 lb. The U-Si charge was melted by heating to about 1650°C in an induction heated vacuum furnace. Beryllia crucibles were used at first, but were replaced by zirconia-washed graphite as the technique of keeping the carbon content low enough (about 500 ppm) was mastered. The alloy was bottom-poured at about 1650°C into graphite molds. A few small buttons, weighing no more than 50 g, were prepared in a small arc melting unit.' Since cast material has a preponderance of uranium and U8Si2, heat treatment is necessary to ob-tain the ? phase by the solid-solid peritectoid reaetion. Once obtained, the ? phase is stable to room temperature, obviating the need for speeial attention to the method of cooling after epsilonization, see Fig. 1. It was found desirable to epsilonize at 800°C for a week. For some purposes, in which residual uranium and/or U8Si2 are tolerable, shorter periods may be adequate. The temperature of 800°C is not critical, since essentially the same results were obtained from 785° to 825°C. Further departure from this epsilonization range is inadvisable.

Jan 1, 1958

By C. D. King

The key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future, by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the cog! washer at Clairton made ii possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of IOO per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. I and No. 2 blast furnaces at Rankin, Pa., Carnegie-Illinois Steel Corporation. Clairton By-product Coke Plant and Coai, Washer The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width. These ovens also differ in height and length. The present coal washer has a daily capacity of approximately 14,000 tons, leaving I6,800 tons to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used pn all the remaining ovens. The customary arrangement is 7

Jan 1, 1944

By C. D. King

The key to maximum production of ingots for the war effort is maximum production of pig iron. For any given furnace and ore, the most important single influence on blast-furnace production is the quality of the furnace coke. It is generally recognized that undoubtedly deterioration of Pittsburgh coking coals will be accelerated by the depletion of some of the better grades of coal; the extension of mine mechanization, with attendant degradation of coal quality; and the opening of new coal fields, some of which are known to be fairly high in sulphur. All of these factors, contributing as they do to higher ash and sulphur, and not infrequently to inferior quality of coke, made it desirable that an extensive study be undertaken to determine the effect of washing some coals that closely approximate the average chemical composition of coking coals to be expected in the future by the subsidiaries of the United States Steel Corporation in the Pittsburgh district. It was deemed advisable to study the improvement obtained by washing such coals and to determine the need for supplementing the existing coal washery at Clairton to assure continued maximum production of pig iron from presently available furnace stacks. The existence of the coal washer at Clairton made it possible to conduct tests on coals used in raw form and on similar coals after washing. This study covers an investigation of the quality of furnace coke as affected by washing coking coals, and is confined to the use of 100 per cent high-volatile Pittsburgh seam coals from Fayette and Greene Counties in the manufacture of furnace coke. It covers the improvement in chemical and physical properties as well as the degree of uniformity in coke obtained by washing these coals, and includes the effect on blast-furnace production and practice. The test period involved is four months; the plants, Clairton by-product coke plant, and the Carrie No. 1 and No. 2 blast furnaces at Rankin, Pa., Carnegie-Illinois Steel Corporation. Clairton By-product Coke Plant and Coal Washer The Clairton by-product coke plant carbonizes 30,800 net tons of coal daily in 22 batteries containing 1482 ovens. Three oven sizes are used, commonly known as wide, medium, and narrow types, recognizing the difference in oven width, These ovens also differ in height and length. The present coal washer has a daily capacity of approximately 14,000 tons, leaving 16,800 tans to be carbonized in raw form. Washed coal is used on all the narrow ovens and on three of the six batteries with ovens of medium width, raw coals being used on all the remaining ovens. The customary arrangement is

Jan 1, 1944

By C. H. Mahoney, P. E. LeGrand, A. L. Tarr

MAGNESIUM, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, on the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.1 Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point. It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-bearing group by raising the temperature of the melt after the refining treatment to some 25e C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730° C. (1350 F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (1600°F.) and 930°C. (I700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.2 It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying constituent-the binary alloy containing r.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery. During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack formation, as well as grain size, and a discussion without any definite conclusions on the theoretical aspects of superheating. A short article by Murphy, Wells and

Jan 1, 1945