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By R. W. Kraft, L. D. Graham

The process of' spheroidization, or more properly coarsening, of Al-CuAl,eutectic alloy specimens with various initial microstructures was studied by quantitative metallographic and X-ray diffraction techniques. By measuring the rale at which specimens with a very fine dispersion of phases (produced by quenching molten droplets of the alloy in water) coarsened it uias determined that the rate-controlling mechanism for coarsening was diffusion, probably of aluminum in the aluminum-rich phase. The lamellae in specimens with a high degree of microstructural and cr-ystallog/uphic anisotropy (produced hy unidirectional solidification of ingots) thickened during heat treatment by recession of the CuAl, platelets from jaulted regzons, yet the specinlens retained a very high degree of. anisotropy after prolonged heat treatments at a temperature within 8°C of the eutectic temperature. In such specimens the crystallographic orientation relationship between the phases remained constant and no change in the crystallographic substructure occurred. Based on these observations a model was developed for the coarsening—or rate of' thicken-ing—oj- the lamellar structures which predicts that the rate of decrease of interface area is proportional to the square of lamellar interface area. Experiments with degenerate and very coarse lamellar microstruc -tures preduced by extremely slow unidirectional solidification) indicate that initial microstructure is a most important factor governing the final micro-structure after heat treatment. The particle size and shape of dispersed phases are important parameters affecting the properties of a wide variety of two-phase materials. As is well-known, varietythe dispersed-phase particles tend to coarsen at appropriately high temperatures because the interface energy of the system is reduced by the concomitant reduction in interface area. The phenomenon of

Jan 1, 1967

By J. F. Peters

The term solution loss is discussed and defined. Examples are given showing that solution loss may either have a favorable or unfavorable effect on blast furnace performance. A theory is advanced explaining the contradictions encountered during earlier studies of the problem. MANY papers have been written and numerous theories advanced concerning the chemical reactions in the iron blast furnace. Richards, discussing the utilization of fuel in the blast furnace, said: "All the carbon burnt in the furnace should be first oxidized at the tuyeres to CO and all the reduction of oxides above the tuyeres should be caused by CO, which thus becomes CO,. This dictum is not Gruner's own words, but expresses their sense, and from the point of view of the present discussion, it is the correct principle upon which to obtain the maximum generation of heat in the furnace from a given weight of fuel." Richards also said the cubic feet of wind per pound of coke does not express how efficiently a furnace is running, but it will be shown later where Howland paid much attention to this figure. Richards pointed out a shortcoming of Grun-er's discussion in that Richards claimed there is not enough CO generated in a good working blast furnace to possibly combine with the oxygen of the ore, so some of it must be reduced by solid carbon. Mathesius2 made two important contributions. First, he wrote the direct and indirect reduction equations showing the heats of formation in each case and stressed that the indirect reduction reaction produces heat while direct reduction absorbs heat. Secondly, he substantiated Richards' conclusion that there may be a deficiency of CO gas and that some direct reduction is required, but he pointed out that "direct reduction in the hearth has often been confused with direct reduction in the stack, which more correctly should be termed 'premature combustion'." Then he said that "as this carbon is consumed partly by economical (direct reduction in the hearth) and partly by wasteful reactions in ever varying proportions, it is evident that the relation of this total carbon gasified above the tuyeres to the fuel consumption of a furnace cannot possibly have a direct bearing on the economy of furnace operation. The premature combustion of carbon (CO2+C?2CO) must therefore in all cases be considered a detrimental reaction." Johnson3 discussed this whole problem. Through experience Johnson found that when departure from Gruner's ideal working is considerable, the fuel economy is poor, and when the quantity of blast goes up, the fuel economy goes up in the same proportion. Johnson said that the wind per pound of coke is a measure of fuel economy, which will be shown to be wrong. Howland4 established the fact from operating data that there was no relationship between the coke consumption of a furnace and the percentage of coke burned at the tuyeres. But some of his calculations have led to questionable conclusions, such as "it is practically impossible to obtain low coke consumption unless we keep our wind low." Howland made an important contribution when, in his concluding paragraphs, he reached certain negative decisions as to why one coke works better than another. He said the reason one coke works better than another in a blast furnace is not because: 1—there is any difference in the percentage gasified at the tuyeres, or 2—there is any difference of wind required per pound of coke. Korevaar5 propounded a new theory on combustion which disagrees with Gruner because "as far as we can see, this is sufficient proof for the invalidity of Gruner's ideal, for if it was valid, the Low coke consumption should always be accompanied by a higher percentage of carbon burned at the tuyeres. This not being the case, we must deliberately give up our belief in Gruner's ideal." The part in italics will be proved to be wrong. Martin" contended that there was not enough reducing capacity in the blast furnace unless solution loss occurs. He came to a series of conclusions, such as: 1—The greatest efficiency of the blast furnace may not be attained when the reduction is performed entirely by carbon monoxide as demanded by Gruner's definition of the ideally perfect working of the blast furnace. 2—The so-called solution loss reactions, which should more properly be termed direct reduction reactions, promote furnace efficiency. 3—In modern blast furnace practice, the carbon consumption of the process is determined primarily by the carbon needed for reduction purposes, any thermal deficiency created by the reduction process being balanced in practice by the use of blast heat. From a practical standpoint further discussion of the theory of chemical reactions is of little moment. There is however one phase of the general theory of chemical reactions which is very important and that is the combustion of coke in the blast furnace. The purpose of this paper is to show that the reaction

Jan 1, 1955

By W. B. Boggs, J. N. Anderson

An account of the operation of the Noranda smelter covering the period from December, 1927, when the smelter started, until December, 1929, was given in a paper published by the Canadian Institute of Mining and Metallurgy early in 1930.' The object of the present paper is to review matters of interest in the original paper and to describe the present construction and operation of the smelter, with particular reference to the reverberatory-furnace practice. The Noranda smelter was built by Noranda Mines, Ltd., from the designs of A. E. Wheeler, consulting metallurgist of New York, for the reduction of ores and concentrates from the Horne mine and to treat, on a custom basis, ores and concentrates from other mines in the Rouyn district. The smelter is at Noranda, about 330 miles directly north of Toronto. Construction work was started in June, 1926, and copper was first produced in December, 1927. The smelter was built throughout as two duplicate units, each with a rated capacity of 500 tons of ore per day. Operations were started with one unit and after several months it was found that one unit alone could smelt 1000 tons of ore a day. At that time there was only one hoisting shaft, No. 3, and its hoisting capacity and the capacity of the original crushing plant were insufficient to supply ore for the two units at the increased tonnage. Accordingly No. 4 shaft was sunk and a new crushing plant provided to handle the ore hoisted there. Operating two units at capacity also required the installation of two more converters to treat the additional quantity of matte produced. This work was completed in the latter part of November, 1929, and since then both smelter units have been operating continuously. In 1928, a mill to treat 500 tons a day of concentrating ore was completed. Since then the concentrator capacity has been increased twice, and at present 2000 tons a day of ore are being concentrated. The layout of the surface plant of the mine, concentrator and smelter is shown in Fig. 1 and the general plan in Fig. 2. The smelter is shown in more detail in Fig. 3. The original hoisting shaft, No. 3, is now used only for handling men, supplies and waste rock, and the original crushing

Jan 1, 1934

By Erland Johnson

BRINE was discovered at Avery Island, La., in 1790, but it was not until 1862 that rock salt was found about 13 ft below surface-the first discovery of rock salt on the continent. Maximum elevation of the island is 152 ft and elevation at the shaft 31 ft. The mining level is 530 ft below elevation at the shaft and the shallowest salt about 12 ft below surface. A shaft was sunk in 1869 when the mining operation started. In 1898 the present shaft was sunk, and the mine has been operated by International Salt Co. ever since.

Jan 6, 1957

By Theodore W. Robinson

WHEREVER the amount of work renders it practicable the plan of using permanent standard solutions, in connection with the colorimetric carbon test, affords such manifold advantages that it is to be strongly recommended. That it has not attained a wider and more general application, is mainly due to the fact that, as the method is generally employed, the difficulty attending the production of the colors, and their doubtful stability when produced, have been only too evident to those who have undertaken their composition. The old method of using standard solutions made from sugar, coffee, etc., has always been hampered by the tendency of the colors to change upon exposure to the light, and the consequent liability to serious error, unless they are closely watched. Appreciating these difficulties, while recognizing the desirability of permanent colors, Mr. Magnus Troilius, at the suggestion of Prof. F. L. Erkmann, investigated the properties of cobalt, copper and ferric chlorides, with the view of determining their efficacy in the production of standard solutions. His results, as obtained, seem to have been satisfactory, but his treatment failed to eliminate many of the objections that have rendered the use of organic colors undesirable. The

Jan 1, 1888

By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962

By Martial P. Corriveau

Almost everyone agrees that coal and oil shale are the only fossil fuel resources in which the United States is self-sufficient. Of the two, only coal has a technology sufficiently developed to be of intermediate term benefit. Since it takes at least 20 years to bring advanced technology into practice, it seems logical that the major focus on energy developments should be aimed at coal. Meanwhile, we need to trade-off between actions to meet our immediate needs and the various political regulations and social demands that are disrupting the coal industry and the industries dependent upon it. The largest single user of coal is the electric power generation industry. Over 300 million tons of coal are presently being consumed each year. In view of the 5-to 7-years lead time to bring in a base-load fossil-fuel fired generating station, our requirements for double this tonnage in 1980 are already well forecast; that is, if the coal companies are allowed to mine and the utilities are allowed to burn the coal.

Jan 2, 1974

By R. H. Brown, F. Keller

Because of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1, 2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. Not only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of A17s-T, 17s-T and 24s-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in 24s alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential difference between the core and coating may be less than 0.16 volt, depending uponIthe thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24s-T, two are generally used; namely, the metallo-graphic and the solution potential methods.3 Metallographic Methods Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24s-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. Consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By F. Keller, R. H. Brown

Because of the extensive use of Alclad 24s alloy sheet in aircraft construction, there is much interest in the metallurgical changes caused by heat-treatment of this product.1, 2 One of these changes is the result of the diffusion of soluble elements from the core into the coating during treatment. This paper deals with the thermal treatments that may influence diffusion and with the practical effects of diffusion on the serviceability of the product. As is well known, Alclad 24s-T sheet has a core of high-strength alloy combined with surface layers of relatively pure aluminum. The microstructure of a cross section of this product is shown by Fig. I. Not only does the relatively high-purity coating have a high resistance to corrosion, and hence serves as a mechanical barrier between the core metal and the corroding environment, but in addition this coating exerts electrochemical protection over areas where the core may be exposed, such as cut edges. In addition, the coating affords electrochemical protection to projecting heads of A17s-T, 17s-T and 24s-T rivets, or attached members made from these alloys. Under some conditions of heat-treatment, however, diffusion of copper into the coating will alter the electrochemical relationship between the coating and the core to the extent that only partial protection will be obtained under some corrosive conditions. The reason for the electrochemical protection lies in the fact that the coating layers of pure aluminum are anodic to the alloy core. The addition of copper to aluminum produces alloys in which the potential is lower than that of the pure metal. Moreover, as the amount of copper in solid solution in 24s alloy is increased, the potential of the alloy becomes more cathodic. When heat-treated at 920°F. and quenched in cold water, 24s-T is about 0.16 volt cathodic to pure aluminum. However, copper will diffuse from the core into the coating, and if it reaches the surface the potential will be altered in a cathodic direction. Thus the potential difference between the core and coating may be less than 0.16 volt, depending uponIthe thickness of the coating, and the time and temperature of heat-treatment. Of the methods available for determining the extent of diffusion of copper from the core into the coating of Alclad 24s-T, two are generally used; namely, the metallo-graphic and the solution potential methods.3 Metallographic Methods Metallographic methods will reveal the progress of diffusion of copper into the coating. For instance, the diffusion zone in the coating intermediate between the coating surface and the core is shown in Fig. I. This photomicrograph is of a polished and etched cross section of 0.040-in. Alclad 24s-T sheet. Diffusion proceeds into the coating more rapidly along the grain boundaries than through the body of the grains. Consequently, the diffusion zone is not of uniform width

Jan 1, 1944

By W. C. Phalen

INTRODUCTION NOBODY will dispute the fact that the conservation in every legitimate manner of our valuable high-grade phosphate-rock deposits is a present-day problem of importance. The table and curve, given herewith, show. that during the past 10 years the exportation of high-grade rock has averaged very close to half the total output of the entire country. The bulk of this exportation is from Florida, for obvious reasons. It is plain that the deposits in this State, more particularly, are being wastefully depleted under a system of selecting the cream of the product for exportation to Europe, leaving the comparatively low-grade rock, running from 65 to 70 per cent., and under, in bone phosphate of lime, for our own n fertilizer manufacturers to work up when all the best rock is gone. In this paper the writer has endeavored to make a point of describing in some detail the important methods of production and conservation in Tennessee. These ought to prove of educational value to our American agriculturists and fertilizer manufacturers, and should result in a demand for the highest-grade rock, both for direct application to the soil and for use in making acid phosphate. It is certainly evident that the European

Jan 10, 1916

By R. Wachtell

IN order to study better the phenomena at work in various phases of diffusion of the Fe/Si system when compounded and alloyed by powder metallurgy methods, several attacks have been planned. Electrical, hardness and other measurements have been discussed e1sewhere.l,2 The metallographic phenomena will be considered here. Concerning the metallography of the ferrosilicon alloys, some initial discussion is in order. As this laboratory discovered to its chagrin, there are many traps that lie in wait for even the experienced metal-lographer when he deals with alloys of high silicon content. Chief of these is probably the anomalous behavior of these materials under conventional etching techniques. We have before us, for instance, Corson's paper" of 1928, wherein is mentioned and illustrated (probably for the first time) the peculiar "barley shell" structure sometimes found in these alloys. Again in 19412 he same author reports the structure in 5-14 pct silicon irons. Houghton and Becker mention its presence' but make only tentative effort to explain it. In 1943, Hurst and Riley6 discussed the "barley shell" and declared it to be a false structure, resulting from the peculiar and characteristic film-forming propensities of the alloy. At about the same time, Wrazej7 proved correct the contentions of Hurst and Riley, establishing pretty well the mechanisms of formation and identifying the constituents involved. Hurst and Riley6 a1so describe in their paper (1943) a "cracked film" structure, also a pseudo-morph, the precise nature of which they do not suggest. Careful examination of such a film reveals that it not only cracks but begins to curl away from the surface of the metal and peel, much in the manner of flaking paint. The careful microscopist will be able to focus on the topmost edge of the flake, and, by optical sectioning, follow it down to the metal surface. We have been able, by oblique illumination of such specimens, to observe the raised segment of the film, the shadow that it casts, and the mating segment on the metal into which it fits. As late as 1946, Hurst and Riley8 found occasion to correct misinterpretation of this "cracked film" structure in a work by others on a 12 pct Si/Fe alloy. The "barley shell" and "cracked film" pseudo-morphs are not the only ones encountered in studies of these materials. A third pseudomorph, which may, however, have some structural significance is a fine striation of the surface. Closely spaced and parallel striae extend entirely across single grains. Each grain shows a different direction for the striae, and different closeness of the spacing. The regularity of this structure, and the fact that the striae do not cross from one grain to another, suggest that the structure is a film cracking controlled in some way by the crystal plane orientation of the surface being etched. In general it is wise for the metallographer dealing with these alloys to cultivate a feeling of uncertainty not only of the more complex questions of interpretation, but also of the basic question of whether that which he sees is indeed a true representation of the structure. We have taken, as a first test of the validity of a structure, its reproducibility "in situ" after repolishing and re-etching of the samples. Thus we knew the "barley shell" to be false (fig. 1) even before encountering the definitive works on the subject. The Metallography of Silicon Diffusion in Laminate Bars: As a first step in the study of the metallography of the diffusion process, we have pressed a series of laminate bars. These bars, or "sandwiches" as we have termed them, were pressed with covering layers of iron powder, and a "filler" of the Fe/Si master alloy under study. Bar dimensions were approximately %, x 3 x 1/4 in. The total

Jan 1, 1951

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan' investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0'~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther' investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By H. H. Hausner, H. S. Kalish

IN recent years zirconium and beryllium have become of great interest because of their special properties. Zirconium is known for its remarkable ability to absorb the gases oxygen, nitrogen and hydrogen, has extensive use as a getter in electron tubes and has indeed become the primary metal in the manufacture of photoflash bulbs. Beryllium is of interest because it is light metal and as such could supplement aluminum and magnesium in light metal applications. The late development of zirconium ductile at room temperature produced by both the iodide and calcium reduction methods has stimulated frequent articles on this metal in the recent literature. Beryllium is so closely akin to zirconium crystall-ographically that some investigators are of the opinion that beryllium should be ductile at room temperature if it were pure enough. The crystallographic relationship of beryllium and zirconium, the interest created in Be-Zr alloys where the zirconium is believed to function as a remover of solid solution gas in beryllium and thus increase the ductility of the beryllium rich alloy, and the amenability of these metals to powder metallurgy methods stimulated this approach to an investigation of the system Be-Zr. Preliminary work showed that a zirconium compact melted when pressed in contact with a beryllium compact and sintered at 1250°C, without any apparent final bond between the two. A search of the literature revealed nothing pertinent about the Zr-Be system or about any zirconium - beryllium alloys. In 1936 Misch³ vaguely identified the compound ZrBe2 and reported that it has a deformed cubic structure. Two patents," , were issued to Mach-lett Laboratories in 1943 and in 1946 regarding the addition of small amounts of zirconium to beryllium in order to improve the ductility of beryllium so that it may better be used for X ray windows. In considering the alloy formation of beryllium with other metals Raynor thought it unlikely that zirconium would have any solid solubility in beryllium. From this indefinite information nothing could be ascertained about the possible use of Zr-Be alloys or the use of these metals intimately. A brief preliminary study of the system Zr-Be by powder metallurgy methods was undertaken to provide regions for more intense studies of Zr-Be alloys and as a guide to a formal phase diagram determination. The investigation described in the following pages was completed in less than three weeks. The usefulness of this rapid method to facilitate phase diagram studies and new alloy investigations will be shown. Materials and Procedure Zirconium powder was produced from crystal bar stock of high purity supplied by Foote Mineral Co. The crystal bar was converted to hydride at 730°C, crushed, and the hydride decomposed in purified argon at 850°C. 60 pct of the powder passed through a 325 mesh screen, 40 pct of the powder was —140 mesh, +325 mesh and the average particle size of the total was 8 to 12 microns. The beryllium powder was used as re-

Jan 1, 1951

By Irwin Roman

NUMEROUS results and formulas have been published for analyzing seismic records, but most of them apply only to large-scale phenomena such as are encountered in studying earthquakes. In a few cases,1 formulas have been published for some of the simpler structures. In the present paper, an attempt will be made to analyze several types of struc-tures without using methods more advanced than those of a first course in calculus. In, tracing a disturbance through a medium, it is almost always possible to base the analysis on Fermat's Principle of Extreme Time, which states that waves of displacement travel between points in such a manner as to make the time of travel an extremum with respect to all neighboring paths. In the simpler cases, comprising most of those used in optics or geophysical prospecting, this time is a minimum and the principle is often referred to as the Principle of Least Time. Within a homogeneous medium, having a uniform speed of transmission of the disturbance in all directions and throughout the medium, the paths are straight and are refracted at the interfaces in accordance with the Snell law of refraction, which states that the ratio of the sine of the angle, made by the ray with the normal to the interface, to the speed of trans-mission is the same on both sides of the interface. Thus, in any medium composed of homogeneous sections, this same ratio has a constant value at all points. In particular, if all interfaces are horizontal, it is apparent that the angles of incidence are the angles made by the ray with the vertical direction. Furthermore, the incident ray, the refracted ray and the normal to the interface are all in the same plane at each refraction;

Jan 1, 1933

By A. L. Fentress, P. R. Bucky

The purpose of this paper is to present a scientific method for determining the proper span and shape of roof for safe and economical mining; at present, these two vital factors wherever pillars are left to support the roof are determined by local practice or general experience. To develop the method described here, experimental laboratory work was done. The arch adopted was a segment of a circle, a flat roof being considered an arch with an infinite radius. Hitherto, arches have been used underground without the background of stress analysis that generally precedes arch construction on the surface. In many cases results have not been as expected, because of the lack of knowledge of the factors affecting its strength and behavior. A theoretical and experimental study of arches should furnish information that will make it possible to design safe and economical surface structures as well as underground openings. For example, on the subject of mine drifts and tunnels, the present idea is that arching their backs increases their strength; this paper will indicate that this is not always true, and if it can be shown that under certain conditions arching becomes unnecessary an economic saving will result. In room-and-pillar work a question may arise as to whether arching the roof and gobbing the excavated material will result in timber saving, and a decrease in the dangers from falls of roof. It is to be distinctly understood that each mine must be treated as an individual problem, and that answers to these questions and many others can now be found after experimental laboratory data have been obtained. Mine-Arch Structure Fig. 1 shows the elements that affect the strength or behavior of the experimental arch. They are the span, crown thickness, radius of curvature, rise and restraint. The restraint in all cases was made sufficient to cause the arch to fail without displacing the restraining sides. Fig. 2a is a photograph of a model arch prepared for testing in the centri-

Jan 1, 1934

By Daniel N. Beshers, Ralph H. Condit

An expression for the diffusion coefficient of inlerstitial atoms in the bcc lattice is derived which takes account of jumps between tetrahedral and octahedral interstices. The results are applied to the case of carbon diffusion in iron to find values for jump frequencies of the types, octahedral-tetrahedral, tetra-hedral-tetrahedral, and tetrahedral-octahedral. ThERE has been renewed discussion1-5 concerning the mechanism of diffusion of interstitial atoms in the bcc lattice. This lattice has both octahedral and tetrahedral interstices, and it has been pointed out that the interstitial atoms may make jumps of the octahedral-octahedral type, hereafter called o-o, octahedral-tetrahedral, o-t, and tetrahedral-tetrahedral, t-t. Doubt has been cast on the applicability of snoek's8 model for internal friction to some interstitial migrations in bcc lattices wherein he proposed 0-0 jumps as the principal mechanism of migration. Also, the anomalous excess diffusion of carbon in iron at high temperatures4 has been ascribed to t-t jumps,2,3 even though the sites normally occupied are octahedral. In this paper an expression is derived for the diffusion coefficient, taking account of the three types of jump mentioned. The relationship of the coefficient to the corresponding internal friction relaxation time is found for the limiting case corresponding to Snoek's model. These results are applied to the case of carbon in iron. In Fig. 1, the structure is shown with the locations of the interstices. Each o site has four t site neighbors coplanar with it, and each t site lies halfway between two o sites. There are four t site first neighbors of a t site lying at the vertices of a tetrahedron. Let the average fraction of atoms occupying o sites and t sites be No and Nt, respectively. Since there are six o and twelve t interstices per unit cell having a lattice parameter, a, the concentration of interstitial atoms will It will be assumed that three types of jumps may be distinguished, t — t, t — o, o — t,for which the jump

Jan 1, 1968

By C. G. Dunn

It is well known that plastic deformation alters many of the properties of a metal and subsequent heat-treatment partially or completely restores these properties.l In the deformed or strained state, the metal is unstable and tends to change toward a condition called a "strain-free state." The transformation occurs through recovery, recrystallization, and grain growth—processes that may take place singly or in combination. The distortion of the lattice of an individual grain of a metal in a state of strain may be rather complex in nature, because plastic deformation produces: (I) dislocations within mosaic blocks; (2) elastic variations of the lattice spacings; and (3) gross alterations throughout the lattice, especially along slip planes, along composition planes between a grain and its mechanical twins, and along boundaries of deformation bands. These gross alterations are of the nature of bent planes or rotated regions of the crystal lattice and are revealed by a spread in the orientation of the grain. Although we cannot describe these strains and their formation accurately because of insuffcient knowledge, we can, nevertheless, use the information as well as possible to obtain a better understanding of recovery processes. In recovery, the lattice of a grain is not made anew as it is in recrystallization, but is improved or mended in such a way that the basic structure remains unaltered: Until recatly observations were .that recovery produced no marked changes in the shapes of spots in Laue diffraction patterns, whereas recrystallization did, but now it is known for silicon ferrite2 that Laue spots may become quite sharp entirely through recovery. Consequently, the shape of Laue spots alone would not be a suitable test to distinguish between recovery and recrystallization. There is considerable evidence that the micro-structure usually does not change visibly during recovery. Absence of a visible change in the microstructure, therefore, provides a sufficient test of recovery in many cases. However, including this observation in a definition of recovery as a necessary condition (this is usually done) is unfortunate, because recovery may, as will become evident later, produce new grain boundaries that are visible not only in the microstructure but also in the macrostructure. For the present, therefore, let us say that a necessary condition for a process to be one of recovery is that the principal orientation or orientations of a deformed grain be essentially unchanged throughout the transformation toward the strain-free state. Several transformations may occur that fulfill this condition, and the nature of the distortion in a grain indicates what these must be if the lattice is to be mended in part or fully. Consequently, it will be convenient as well as

Jan 1, 1947

By C. G. Dunn

It is well known that plastic deformation alters many of the properties of a metal and subsequent heat-treatment partially or completely restores these properties.l In the deformed or strained state, the metal is unstable and tends to change toward a condition called a "strain-free state." The transformation occurs through recovery, recrystallization, and grain growth—processes that may take place singly or in combination. The distortion of the lattice of an individual grain of a metal in a state of strain may be rather complex in nature, because plastic deformation produces: (I) dislocations within mosaic blocks; (2) elastic variations of the lattice spacings; and (3) gross alterations throughout the lattice, especially along slip planes, along composition planes between a grain and its mechanical twins, and along boundaries of deformation bands. These gross alterations are of the nature of bent planes or rotated regions of the crystal lattice and are revealed by a spread in the orientation of the grain. Although we cannot describe these strains and their formation accurately because of insuffcient knowledge, we can, nevertheless, use the information as well as possible to obtain a better understanding of recovery processes. In recovery, the lattice of a grain is not made anew as it is in recrystallization, but is improved or mended in such a way that the basic structure remains unaltered: Until recatly observations were .that recovery produced no marked changes in the shapes of spots in Laue diffraction patterns, whereas recrystallization did, but now it is known for silicon ferrite2 that Laue spots may become quite sharp entirely through recovery. Consequently, the shape of Laue spots alone would not be a suitable test to distinguish between recovery and recrystallization. There is considerable evidence that the micro-structure usually does not change visibly during recovery. Absence of a visible change in the microstructure, therefore, provides a sufficient test of recovery in many cases. However, including this observation in a definition of recovery as a necessary condition (this is usually done) is unfortunate, because recovery may, as will become evident later, produce new grain boundaries that are visible not only in the microstructure but also in the macrostructure. For the present, therefore, let us say that a necessary condition for a process to be one of recovery is that the principal orientation or orientations of a deformed grain be essentially unchanged throughout the transformation toward the strain-free state. Several transformations may occur that fulfill this condition, and the nature of the distortion in a grain indicates what these must be if the lattice is to be mended in part or fully. Consequently, it will be convenient as well as

Jan 1, 1947

IT may perhaps seem to you that I have deviated from sequence by having entered into the narration of this arrangement of the bellows, but, although they are not furnaces or vessels for containing the melts, they are essential agents for bringing to port the bark of your labors. Returning to our regular pathway, and supposing that, besides making the moulds, you have melted and cast not only statues and bells but also guns, it is true that a certain procedure is required in order to finish them. For this you should have the moulds full, and they should have come out very well, for in truth reason does not allow that they turn out otherwise for one who uses precaution. [II2V] Then you have taken your casting from the pit and have freed it of clay. Since I have told you nothing beyond this, do not be dismayed if you see the castings so rough and in a form that scarcely shows what they really are, for I wish to open up part of the way into the great labor of finishing them so that it may seem to you that you have been somewhat helped by me. Therefore, when it is a gun, first see that the iron spindle that has been placed in the middle of the core is taken out. You can do this easily by striking the heel of the core, especially if the spindle had first been covered with ashes, hemp, or a little rope. Then saw off the feeding head above the mouth, using either a dun steel saw with tiny straight teeth that has been tempered with oil or some other fat, or a hay sickle whose edge is gently hit by a little hammer. Then have the clay that is attached to the curls or other bronze parts lifted away with a chisel. Then with a scouring brush and water uncover the emblems, coats of arms, borders, and cornices that you made as ornaments. Striking it with a hammer, push inwards every superfluous bit of bronze. Finally, having cleaned the bronze by washing, scraping, and cutting away every bit of clay, strike its surfaces gently with a large hammer and thus make it very smooth. Likewise finish the mouth and all its cornices as exactly and completely as possible with files and any other instrument that serves best. Then take a long, powerful tool that has some steel on the point, made like a chisel and somewhat bent, or with three points like the iron blade

Jan 1, 1942

By D. B. Rushmore, K. A. Pauly

Of primary importance in mine-installations is the hoist, which has a very direct bearing on the successful operation of a mine. Conditions vary greatly with different mines, and especially in different localities. Such factors as depth, incline, the number of levels, permissible or desirable speeds, conditions of ore, etc., are always more or less special in each case. Veins of ore are never exactly duplicated, and the nature of the ground through which shafts are sunk may considerably modify permissible values. As mining-laws are made by the different States, they necessarily vary somewhat, and, even when not fully observed, they introduce factors which qualify the conditions of hoisting men and ore. The amount of timbering required is often of importance as relating to hoisting-conditions. Methods of loading ore affect the time required, as also does the question of the use of cars or skips. Safety-precautions must be very carefully considered, and the number of men in each mine, the number of compartments, and often the method of removing water from the mine, must have careful consideration. While a general discussion of the subject of hoisting is possible, most cases are entirely special, and can be considered only in connection with the peculiar conditions pertaining to that particular installation. The cost of installation of the hoisting-plant may be an appreciable amount, while the cost of raising the ore may be but a small part of the total operating-charge. In many cases, however, the output of the mine is limited by the capacity or the hoist, and the latter thus becomes of the first importance.

Jan 1, 1911