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By C. S. Sivaramakrishnan, Manjit Singh, Rajendra Kumar

Regarding liquid nzetals structurally as a suspm-sion of clusters , having derivated solid-state coordination, in truly liquid atoms, the recently developed Kuvlar-Samarin technique of centrifuging- in liquid state enabled the determination of the cluster sizes inAl-Cu mid Pb-Sn systems. It is shown that the colutne fraction of the clusters does not exceed 9 pct and the energy of their formation in Al-Cu is about 5.5 kcal per g-atom and in Pb-Sn eutectic alloys about 25 kcal per y-atoni. STRUCTURAL investigations of liquid state have principally followed the following three courses: i) studies with X-ray, electron, or neutron diffraction; these investigations have shown that there is a certain amount of regularity in the structure of liquid metals which can be defined by a coordination number and that the structure is a derived function of that in the solid state; ii) thermodynamical investigations which are based on the concept of ideal behavior; these describe the liquid state in terms of free-energy values and other thermodynamic functions; although these investigations are of help in the study of the general effects of alloying, they do not provide any structural insight into the precise atomic distribution in liquid state; iii) measurements of surface tension and viscosity; although it is natural to expect that the viscosity is related to the structure in liquid state, these investigations have so far only provided information which can be used by the foundry technologists and has been little utilized in formulating models of the structure of liquid state. As it happens, investigators in the three groups have worked almost independently of each other and there is practically no structural correlation between the results of one group with those of another. The purpose of the present paper is to indicate that the experimentally measured parameters of these three groups of research are closely related to the structure in the liquid state. STRUCTURE OF LIQUID METALS Although atomic distribution in solid and gaseous states is rigorously known, that of the liquid state is only appreciated on the fringes. There is no universal model of atomic distribution in liquid state, but two diverse models are at present hotly contested. The first, largely expounded by ~ildebrand,' regards the liquids as condensed gas since many of their properties and much of their behavior can be adequately described by regarding them as fluids. The second mode12j3 considers that some form of near-solid as- sociation of large number of atoms exists in the liquid state. On the other hand, ~ernal' was able to predict rather precisely the radial distribution functions in liquids on the basis of statistical geometric approach which considered that liquids are "homogeneous, coherent, and essentially irregular assemblage of molecules containing no crystalline regions or holes large enough to admit another molecule". He introduced the concept of pseudonuclei in the otherwise random structure as aggregates of closely packed tetrahedra which gradually merge into irregularity and continually replace each other. To what extent the pseudonuclei can be regarded as regions of near-solid association is indefinite but Bernal suggested that the concept of pseudonuclei can be compromised with the latter model if the near-solid associations are regarded as extremely dense and not necessarily crystalline. The difficulty in projecting the structure of liquid metals arises because they exhibit duplicity of character as some of their properties are closer to those of crystalline solids and others to fluids. There is an increasing tendency to discuss the structure of liquid metals in terms of the second concept according to which the structure of liquid metals may be conceived as consisting of i) clusters of atoms where the aggregation is a close derivative of that in the crystalline state, ii) individual atoms which behave like true liquids in respect to degrees of freedom and iii) excess number of vacancies. It is noteworthy that the introduction of only 5 pct vacancies is sufficient to transform crystalline matter into the liquid state. At any instant of time thermodynamic equilibrium exists between i, ii, and iii, but the relative proportion of the clusters and random atoms is not known. That this is so can be appreciated by the fact that, when liquid metal is rapidly cooled, liquid state vacancies may condense in the form of dislocation loops and vacancies in excess of their equilibrium number in solid state. These dislocation loops have been observed in thin foils of aluminum prepared from rapid cooled aluminum. As temperature increases above melting point the number and volume fraction of clusters decrease but those of vacancies and random atoms increase. Clusters are transient in nature. In pure metals the cluster is an aggregation of the metal itself. In alloys, however, the nature of the cluster largely depends on the interaction between solvent and solute atoms. If the interaction between unlike atoms is greater than between like atoms: the clusters are then aggregates of unlike atoms. Examples of this kind of system are A1-Cu, Mg-Pb, and so forth, i.e., systems which exhibit negative departures from the Raoult's law. In systems where the interaction between unlike atoms is smaller than be-

Jan 1, 1968

By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO,, oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO, can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1M4 per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past y6ar that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ton of high-grade pyrite and results in 1/2 ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15d per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1953

By William P. Jones

THE consumption of sulphuric acid, one of the most important commodities in our modern industrial world, is often used as a barometer for industrial activity. The economics of acid manufacture are largely dependent upon the location of the place of consumption and the availability of raw materials in that locality. Sulphuric acid is made from SO,, oxygen from the air and water. Therefore the sulphur dioxide is the only raw material to be considered in an economic study. SO, can be obtained from almost any material containing inorganic sulphur, such as elemental sulphur, pyrites, coal, sour gas and oil, metallurgical gases, waste gases, or gypsum and anhydrite. Many tons of acid can also be reclaimed by the recovery and concentration of spent acids. The aim of this paper is to present a guide to the economic aspects to be considered when the installation of an acid plant is contemplated. It must be remembered that 1 ton of elemental sulphur produces 3 tons of sulphuric acid and that the shipping of sulphuric acid by tank car is very costly. The size of the plant must also be given careful consideration. For instance, operation of a plant producing 5 tons of acid per day might be warranted in Brazil or Pakistan, whereas economics usually favor buying quantities up to 50 tons per day for use within the United States. Elemental sulphur, when available at the low price of 1M4 per lb delivered at an acid plant, has always been the raw material most frequently used for sulphuric acid. All conditions favor its use at this price. The so-called sulphur shortage has been the subject of so many technical papers, magazine articles, and newspaper items during the past y6ar that it hardly seems necessary to mention it again, but a very brief review of the matter will serve as a foundation for the discussion that follows. There is no shortage of sulphur. Only a shortage of low-cost Frasch-mined brimstone exists today. Other more expensive sulphur-bearing materials are plentiful, both in the United States and abroad. The low cost of Frasch-mined brimstone has discouraged the development of higher cost sources. However, the approaching depletion of Gulf Coast dome deposits and the greatly increased demand for sulphur here and abroad have made it necessary for industry to prepare for conversion to utilize sulphur in other forms. For future planning this situation must be considered permanent and not temporary. This conclusion is based on the fact that although sulphur demand will continue to rise, the production of Frasch-mined sulphur probably will not increase greatly beyond its present level of about 5,000,000 long tons per year. The International Materials Conference in Washington estimates 1952 requirements of the free world at nearly 7 million long tons; and the Defense Production Administration has recently set a new goal for 8,400,000 long tons annual domestic production by 1955. The total sulphur equivalent produced in this country in 1950 was 6 million tons. What, then, are the alternatives for the manufacture of the vital chemical, sulphuric acid? Today about 85 pct of this country's sulphur, and nearly 50 pct of the world supply, comes from our Gulf Coast salt domes and is extracted from the earth by Frasch's hot water process. The Gulf Coast salt dome deposits have been the most important known natural deposits in the world, producing 90 million tons of sulphur during the past 50 years. However, at the present rate of extraction these deposits cannot be expected to last indefinitely. Pyrites Pyrites are, and have been for many years, the source of more than 50 pct of the world's sulphur requirements. The principal use, of course, is in the manufacture of sulphuric acid. The use of pyrites in the United States has diminished greatly because of the availability of low cost native sulphur, but pyrites have continued a major source of sulphur in many other countries. The most available pyrites for use in this country are in the form of lump pyritic ore and in mill tailings from flotation of other minerals such as lead, zinc, copper, gold, and silver. An important factor, when the use of pyrites for acid manufacture is being considered, is the disposal of calcine. A ton of sulphuric acid requires approximately ton of high-grade pyrite and results in 1/2 ton of calcine. If the calcine is a fairly pure oxide, free of harmful impurities, it can be used, after sintering, in an iron blast furnace burden. Its value might be as high as 15d per unit of Fe at the blast furnace; or possibly $10.00 per ton of sinter, if it assays 65 pct Fe. This might result in a credit of $4.00 per ton of acid if the sintering plant and blast furnace are both located adjacent to the acid plant. On the other hand, several factors must be considered before this credit can be realized, i.e., freight to blast furnace, availability of sintering facilities, methods of eliminating impurities, and the removal of valuable metal values. In some locations it would be most economical to dump the calcines.

Jan 1, 1953

By Sven Fornander

L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author's reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952

By J. H. Swisher

The rate of internal sulfidation of austenitic Fe-Ti alloys in H2S-H2 gas mixtures is controlled primarily by sulfur diffusion, with counterdiffusion of titanium playing a minor role. At temperatures below 1100°C, enhanced diffusion along grain boundaries becomes important. The rate of internal sulfidation at 1300°C is approximately equal to the rate computed from the sulfur diffusion coefficient. The diffusion coefficient of titanium in y iron has been determined from electron microprobe traces in the base alloy near the subscale interface. The solubility of sulfur in Fe-Ti alloys has been measured in the temperature range from 1150° to 1300°C. The equilibrium sulfur content is found to increase with titanium content, due to the large effect of titanium on the activity coefficient of sulfur. The Ti-S interaction becomes stronger as the temperature decreases. TITANIUM as an alloying element in stainless steels is an effective scavenger for interstitial impurities, carbon in particular. Titanium is known to form stable sulfides; however extensive thermodynamic data on the Ti-S system are not available. Schindlerova and Buzek1 have shown that the Ti-S interaction in liquid iron is moderately strong. There have been no previous studies of the Ti-S interaction in solid iron. Internal sulfidation of Fe-Mn alloys was the subject of a recent investigation by Herrnstein.2 He found the rate of internal sulfidation to be an order of magnitude greater than predicted from available solubility and diffusivity data. A satisfactory explanation for the discrepancy could not be given. In the present study, the solubility of sulfur in austenitic Fe-Ti alloys was measured using a standard gas equilibration technique. Fe-Ti alloy specimens were also internally sulfidized. The rate of internal sulfidation was measured as a function of temperature and alloy composition. Supplementary electron micro-probe measurements were made to provide additional information on the nature of the internal sulfidation process. EXPERIMENTAL The starting materials were alloys containing 0.12, 0.24, 0.38, and 0.54 wt pct Ti. The alloys were made in an induction furnace by adding titanium to electrolytic iron that previously had been vacuum-carbon-deoxidized. The major impurity in the alloys as determined by chemical analysis was carbon. The carbon content of the alloys averaged about 100 ppm; metallic impurities were presented in concentrations of 50 ppm or less. Specimens were made in the form of flat plates, 0.03 by 2 by 4 cm for the equilibrium measurements and 0.5 by 1.5 by 3 cm for the rate measurements. The experiments were performed in a vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction tube. In the gas train, flow rates of the reacting gases were measured using capillary flow meters. The source of H2S was a mixture of approximately 2 pct H2S in H2, which was obtained in cylinders from the Matheson Co. A chemical analysis was provided with each cylinder. The H2-H2S mixture was diluted with additional hydrogen to obtain the desired ratio of H2S to H2, and the resulting mixture was diluted with 30 pct Ar to minimize thermal segregation of H2S in the furnace. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over Pas. The samples used in the solubility measurements were analyzed for sulfur by combustion and iodometric titration. The subscale thickness in the internally sulfidized samples was measured on a polished cross section, using a microscope with a micrometer stage. Electron microprobe traces for titanium in solution were made on several samples that had been internally sulfidized. A Cambridge microanalyzer was used, and the known titanium content at the center of the specimen was used as a calibration standard. The procedure for the microprobe measurements will be described further when the results are presented. RESULTS AND DISCUSSION Equilibrium Data. Fig. 1 shows the sulfur concentration as a function of gas composition for three alloys equilibrated at 1300°C. The dashed line is based on data published by Turkdogan, Ignatowicz, and pearson3 for pure iron. The breaks in the curves are the saturation points for the alloys. The fact that the initial slope decreases with increasing titanium content indicates that titanium interacts strongly with sulfur in solution. To obtain information on the composition of the precipitating sulfide phase, the measurements described in Fig. 1 were extended to higher sulfur partial pressures. These results are shown in Fig. 2. (The initial portions of the curves are reproduced from Fig. 1.) The highest PH2s /pH2 ratio used is believed to be below the ratio required for the formation of a liquid sulfide phase. Time series experiments were used to study the approach to equilibrium in the samples. It was found that equilibrium with the gas phase was reached in less than 4 hr at 1300°C.

Jan 1, 1969

By Ottar Dragge, C. Danielsson, Bo Kalling

DISCUSSION, T. L. Joseph presiding L. F. Reinartz (Armco Steel Corp., Middletown, Ohio) —I would like to know, in the practical application of the Kalling process, what kind of a lining was used, how thick was the lining, and how much metal was treated at one time? S. Fornander (author's reply)—The rotary furnace is lined with a course of fireclay bricks 6 in. thick. This course is backed by 5 in. of insulation. The furnace has a capacity of about 15 tons. Mr. Reinartz—How was the ladle preheated? Mr. Fornander—As pointed out in the paper, the furnace was heated by a gas flame in the beginning of the experiments. During these first tests, however, the desulphurization was inconsistent. We think that this was due to the fact that iron droplets sticking to the furnace walls were oxidized by the gas flame. Now, the furnace is operated without preheating of any kind, and the results are much better. T. L. Joseph (University of Minnesota, Minneapolis, Minn.)—I might add one comment. This furnace was heated with a flame and for a time they had a little difficulty due to some residual metal in the rotating drum that would oxidize in between treatments and they found therefore, that it was very essential to drain the drum completely of metal so that they would not build up any ferrous oxide between treatments and they eliminated some of their erratic heats by maintaining those more reducing conditions. It was interesting to watch this operation. As soon as the drum started to rotate there was considerable flame, at least, at the time I saw it, that came out around the flanges, indicating there was quite a little pressure on the inside of the drum. W. 0. Philbrook (Carnegie Institute of Technology, Pittsburgh)—Is the reaction slag in the Kalling process liquid or solid, and how is it separated from the metal? Mr. Fornander—In the process there is no slag in the usual sense of the word. The lime powder does not melt during the treatment. After the treatment the lime is still in the form of a fine powder. It is separated from the metal by means of a piece of wood of suitable size placed within the furnace before it is emptied. D. C. Hilty (Union Carbide & Carbon Research Laboratories, Niagara Falls, N. Y.)—Dr. Chipman has given us some of his ideas in connection with a specific effect of silicon and silica on sulphur elimination and how silicon might interfere with desulphuriz- ing in the blast furnace. I wonder if he would like to elaborate on the possibility of a similar effect of silicon in the Kalling process? J. Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—Silicon does not interfere with the Kalling process. Anything that has strong reducing action is good for desulphurization. In these tests where the temperature was low compared to blast furnace temperatures, the silicon that is in the metal is a better reducing agent than the carbon. At high temperatures, carbon is the better. It is not the silicon in the metal that interferes with desulphurization, it is the silica in the slag. Mr. Joseph—I might add that the metal that was tapped from the drum after desulphurization was really at quite a low temperature. It was not measured, but I think it was well under 1300 °C, probably 1200" or a little above that. That was one of the difficulties, and I think there is no question about the fact that the Kalling process—in that it affects desulphurization between powdered lime, solid and liquid iron— is a reaction definitely between the solid lime and the liquid iron. E. Spire (Canadian Liquid Air, Montreal, Canada) — This Kalling process seems very interesting to us and after all it is only a mixing action that is taking place between the iron and the slag. We have attempted to do the same thing in another way. We have placed at the bottom of the ladle a porous plug through which we injected an inert gas. It can be nitrogen or argon. This plug is placed at the bottom of the conventional ladle and gas injected through the plug. That has appeared in our patent. To define this new type of treatment, I use the word gasometallurgy. I do not know if you like it, but it is a way of defining methods of treating metal using gases. What we do is exactly what is done in the exchange process in another way. We have a porous plug at the bottom with a high lime slag on top of the metal. Using this method, we have very good agitation of metal and slag, and with a small flow of gas, we can achieve a very strong agitation. For instance, in the 500 lb ladle, we use only 5 liters of gas a minute. We have an agitation compared to very rapidly boiling water in a pail. Moreover, the agitation can be controlled to create any amount of mixing desired. In a few minutes, with this method, the sulphur dropped from 0.58 to 0.11. These results have been improved since, and we have obtained results like 0.08

Jan 1, 1952

By P. A. Laxen, H. R. Spedden, A. M. Gaudin

WHEN a mineral particle is fractured, bonds between the atoms are broken. The unsatisfied forces that appear at the newly formed surface1 are considered to be responsible for the adsorption of ions at the mineral surface. A knowledge of the mechanism and extent of ion sorption from solution onto a mineral surface is of interest in the development of the theory of flotation.2,3 Study of the adsorption of sodium from an aqueous solution on quartz offers a simple approach to this complicated problem. The availability of a radioisotope as a tracer element meant that accurate data could be obtained.4,5 Three main factors which appeared likely to affect the adsorption of sodium are: 1-concentration of sodium in the solution, 2-concentration of other cations in the solution, and 3-anions present in the solution. Hydrogen and hydroxyl ions are always present in an aqueous solution. By controlling the pH, the concentration of these two ions was kept constant. The variation in the amount of sodium adsorbed with variation in sodium concentration was then determined under conditions standardized in regard to hydrogen ion. The effect of concentration of hydrogen ions and of other cations was also measured. A few experiments were made to get a preliminary idea on the effect of anions. The active isotope of sodium was available as sodium nitrate. Standard sodium nitrate solutions were used throughout these experiments except when the effects of other anions were studied. It was found that sodium adsorption increased with sodium-ion concentration, but less rapidly than in proportion to it. Increasing hydrogen-ion concentration, or conversely decreasing hydroxylion, brings about a comparatively slight decrease in sodium-ion adsorption. Increasing the concentration of cations other than hydrogen or sodium decreases somewhat the adsorption of sodium ion. It would appear as if the kind of anion is a secondary factor in guiding the amount of sodium ion that is adsorbed. Materials and Methods Quartz The quartz was prepared as in previous work in the Robert H. Richards Mineral Engineering Laboratory4 except for the refinement of using de-ionized distilled water for the final washing of the sized quartz, prior to drying5 To minimize the laborious preparation of quartz, experiments were made to determine whether the sodium-covered quartz could be washed free of sodium and re-used. The experiments were successful as indicated by lack of Na' activity on the repurified material and by its characteristic sodium adsorption. Table I gives the spectrographic analyses of the quartz used. The quartz ranged from 16 to 40 microns in size, averaging about 23 microns (microscope measurement), and had a surface of 1850 sq cm per g (lot I), 2210 (lot II) and 2000 (lot III) as determined by the Bloecher method.6 Radioactive Sodium Method of Beta Counting for Adsorbed Sodium: Na22, the radioisotope of sodium, possesses convenient properties.7 It has a half-life of 3 years, thus requiring no allowance for decay during an experiment. On decay it emits a 0.575 mev ß radiation and a 1.30 mev ? radiation. The decay scheme is illustrated in the following equation: [Y Nam S. - 'Net 3 years] The ß radiation is sufficiently strong to penetrate an end-window type of Geiger-Mueller counting tube. This, in turn, makes it possible to use external counting, a great advantage in technique. Furthermore, it permits the assaying of solids arranged in infinite thickness, while assaying evaporated liquors on standardized planchets. The equipment used was standard and similar to that employed by Chang8 The original active material was 1 ml of solution containing 1 millicurie of Na22 as nitrate. This active solution was diluted to 1000 ml. Five milliliters of this diluted active solution was found to give a quartz sample a sufficiently high activity for accurate evaluation of the sodium partition in the adsorption measurements. Also, 1 ml of final solution gave a sufficiently high count for precision on the liquor analyses. The sodium concentration of the diluted active solution was 1.2 mg per liter, so that 6 mg of sodium for 60 ml of test solution and 12 g of quartz was the minimum amount used. The active solution was stored in a Saftepak bottle. Procedure for Adsorption Tests: The method consisted of agitating 12 g of quartz with 60 ml of solution of known sodium concentration for enough time to establish equilibrium between the solution and the quartz surface. The quartz was separated as completely as possible from the solution by filtering and centrifuging. The activity on the quartz and in the equilibrium solution was measured and the partition of the sodium was calculated from the resulting data. The detailed procedure for the adsorption test is set forth in a thesis by Laxen5 In brief, it included the following steps: 1-Ascertainment of linearity between concentration of Na22 and activity measured. 2-Evaluation of factor to translate activity on solid of infinite thickness in terms of activity on an evaporated active film of minute thickness, on the various shelves of the counter shield. 3-Taking precautions to avoid evaporation of water during centrifuging.

Jan 1, 1952

By K. R. Carson, J. Weertman

An attempt is made to ascertain the mechanism of tangle and cell formation and its dependence upon dislocation-interstitial carbon interactions. The strain-hardening behavior of single crystals of 3.25 pct Si-Fe was determined at 300° and 425°K and under conditions of both continuous and interrupted tensile strain. Significantly enhanced hardening was observed in crystals deformed at the elevated temperature, and it was further accentuated by interrupted straining. Transmission electron microscopy was used to study the resultant dislocation structures. Strain aging was found to aid tangle and cell formation at 425°K, but at both temperatures embryo tangles formed solely from primary glide dislocations, presumably by a process involving cross slip and "mushrooming". IN the course of plastic deformation all bcc metals and alloys develop a dislocation structure characterized by loose-knit groups of tangled dislocations. With increasing strain the tangles become more tightly knit and grow larger; finally a three-dimensional cellular substructure is formed:1 This process has been observed with the transmission electron microscope.'-l7 However, most investigations were confined to the study of nearly pure polycrystalline metals at relatively low temperatures. At intermediate temperatures, 0.17 to 0.14 Tm where T, is the melting temperature in degrees absolute, the mobility of interstitial impurities such as carbon is high enough to permit migration to nearby glide dislocations but is still low enough so that a significant drag force is exerted.18,19 it is also in this temperature range that a hump occurs in the curve of work-hardening rate vs temperature for iron. Analogous plots for tantalum" and columbiumzo show a definite upward trend in the work-hardening rate. Keh and Weissman1 have pointed out that this behavior may be explained solely on the basis of changes in the dislocation configuration: at low temperatures the dislocations tend to be relatively straight and uniformly distributed, but at intermediate temperatures tightly knit tangles and cellular substructure appear. The interference of these tangles with glide dislocations causes the observed increase in the work-hardening rate. This explanation appears reasonable, yet one might ask what factors cause tangle formation to be so favorable at intermediate temperatures. It seens likely that the strong dislocation-interstitial interactions which are known to occur in this temperature range are at least partly responsible," with the magnitude of the effect being proportional to the interstitial concentration. The purpose of the present work is to study the relationship between tangle formation and strain hardening in a bcc metal in the temperature range 0.17 to 0.4 Tm. Particular emphasis was placed upon a study of the effects of interstitial-dislocation interactions. Single crystals of 3.25 pct Si-Fe containing about 200 ppm of C in solid solution were used in the investigation for the following reasons: 1) The mobility of interstitial carbon in 3.25 pct Si-Fe is negligible at 300°K but increases rapidly at slightly elevated temperature22. Hence, differences between the flow curves and dislocation structures of crystals deformed at 300°K, 0.17 T,, and crystals deformed, say, at 425°K, 0.24 Tm, should be appreciable because of the enhanced dislocation-carbon interactions at the elevated temperature. This effect was accentuated in some samples by interrupted straining, thereby introducing a certain amount of aging. 2) Near room temperature, slip in suitably oriented 3.25 pct Si-Fe single crystals is largely confined to the (110) planes.23'24 Dislocation structures formed under conditions of single glide are the least complicated and their method of formation is the most easily discernable. 3) Dislocations in Si-Fe can be tightly locked with carbon atmospheres by a low-temperature aging treatment. The subsequent thinning of samples to foil thicbess causes little or no rearrangement in the dislocation structure.25 EXPERIMENTAL PROCEDURE Large single-crystal sheets of 3.25 pct Si-Fe were donated by Dr. C. G. Dunn of the General Electric Research Laboratory, Schenectady, N. Y. The orientations of the sheets were determined and slabs 1.0 by 0.25 by 0.05 in. were cut such that the desired tensile axis corresponded to the long dimension. The slabs were mechanically polished and subsequently decar-burized by heating at 1000°C for 3 days in a flowing wet-hydrogen atmosphere. A carbon content of about 200 ppm was introduced by heating at 805°C for 25 min in a flowing atmosphere of dry hydrogen containing heptane vapor. Shaped copper tools were then used to spark-machine at 0.125 by 0.50 in. gage length onto each slab. Vacuum annealing at 1225°C for 2 days followed by a quench into the cold end of the furnace to retain carbon in solid solution concluded the soecimen preparation. Continuous tensile flow curves for crystals of severa1 orientations Were obtained both at 300' and 425°K. A strain rate of 6.67 x 10-4 Per set was used in these and all other tests. Crystals oriented for single glide, B and D in Fig. 1, were subjected to a 3.5 pct plastic elongation to insure uniform slip along the gage length; they were then immediately subjected to interrupted strain cycling as indicated in Fig. 2(a). Each cycle consisted of unloading to 1.5 kg per sq mm, holding

Jan 1, 1969

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5'7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

By M. C. Udy, F. W. Boulger

AN incomplete phase diagram for the U-Ti systern was determined earlier 1 and more recently, a tentative diagram was presented for the uranium-rich end of the system.' In the present re-examination of the whole system of U-Ti alloys, high purity materials were used. Melting stock for the alloys was high purity uranium, containing about 0.09 pct C as the only appreciable impurity, and high purity iodide-process titanium purchased from New Jersey Zinc Co. Both metals were cold rolled to about 1/6 in. thickness, sheared to about I/' in. squares, and cleaned by pickling. The alloys were arc melted under a helium atmosphere in a water-cooled copper crucible. A thoriated-tungsten electrode was used. The furnace chamber was evacuated, then flushed with helium, prior to each melting. It was finally filled with stagnant helium at one atmosphere pressure. Each alloy was remelted three times after the original melting, to insure homogeneity. The alloy button was turned bottom side up before each re-melting operation. Some 22 alloys were examined. Their compositions were spaced at appropriate intervals between 100 pct Ti and 100 pct U. Analyses were made on chips taken after fabrication. The major contaminant was carbon, which varied from 0.03 to 0.08 pct. It appeared in the microstructure as titanium carbide. Alloy compositions were calculated to a carbon-free basis for consideration on the diagram. Tungsten and copper, possible contaminants from the melting operation, were generally less than 100 parts per million each. Fabrication All alloys were forged and rolled to bars approximately V8 in. square. They were clad either in SAE 1020 steel or in a 5 pct Cr-3 pct Al-Ti-base alloy, depending on the fabrication temperature. A temperature of 1800°F (980°C) was used for alloys near the compound composition. This necessitated using the titanium-base alloy, since iron reacts with titanium at this temperature, producing a low melting alloy. Other alloys were fabricated at 1450°F (790°C), using steel jackets. No iron-titanium reaction occurred at this temperature. The jackets were welded in place in an argon atmosphere. Those alloys sheathed in steel were declad and then reclad between rolling and forging operations. On the other hand, those clad with the titanium alloy were cut to a roughly rectangular shape prior to clading and were then carried through both the forging and rolling operations without opening. Those alloys near the compound composition were found to be cracked when the clading was removed. The cracked materials had been plastically deformed, however, and at least some of the cracking had OCcurred during cooling. Heat Treatment The rolled bars, after being declad and shaped to remove surface contamination, were all given an homogenizing treatment of 160 hr at 2000°F. (Samples were taken for analysis following the declading and shaping operations.) All were heat treated at the same time in one furnace, but each was sealed in a purified argon atmosphere in an individual Vycor glass tube. Argon pressure was such that it was approximately atmospheric at temperature. One end of each tube contained titanium chips and this end was heated to 1200°F (650°C) for 10 min prior to the heat treatment. This purged the atmosphere of residual reactive gases. The balance of the tube was warmed during the purge to liberate adsorbed moisture and gases, which also reacted with the hot chips. The bars were furnace cooled from the homogenization treatment. Specimens of each alloy were water quenched after 2 hr heating at 1000°, 1200°, 1400°, 1600°, 1800°, and 2000°F (540°, 650°, 760°, 870°, 980°, and 1095°C). In addition, some were treated at intermediate temperatures of 1300°, 1500°, and 1700°F (705", 815", and 925°C) and at 2150°F (1175°C). Specimens, about '/s in. cubes, were cut from the bars, sealed in individual Vycor tubes, and heat treated as described. All specimens heat treated at the same temperature were processed together. Samples were quenched by breaking the Vycor tube rapidly under water. Metallographic Examination Specimens were mounted in bakelite and ground wet on 180 grit paper held on a 1750 rpm disk. They were then ground wet by hand, using 240, 400, and 600 grit papers. The rough grinding was continued long enough to get well below the surface. Specimens were mounted separately because of the variation in the rate of etching between alloys. The specimens were polished with rouge on a 4 in., 1725 rpm wheel covered with Miracloth. Alloys on the titanium side of the compound composition were etched with a solution of 2 pct hydrofluoric acid in water saturated with oxalic acid. A few crystals of ferric nitrate were added as a bright -ener. Specimens were immersed 5 sec, polished to remove the etch, then re-etched. With the higher titanium alloys, it was often necessary to start the etch on the polishing wheel, because of the formation of a passive film. In some instances, a plain 2 pct hydrofluoric etch was satisfactory. For the alloys on the uranium side of the compound, a distinction between the compound and the uranium phase developed after standing a short time in air. This could be hastened by the application of heat, such as obtained by placing the specimen on a radiator. A deep etch was necessary to develop details in the uranium-rich phase, such as the Widmanstaetten pattern sometimes obtained by quenching y uranium. A 2 pct hydrofluoric acid solution was used for this deep etching.

Jan 1, 1955

By C. T. Liu, J. Gurland

The deformation behavior in tension of spheroidized carbon steels was studied at room temperature as a function of carbon content, 0.065 to 1.46 wt Pct, and carbide particle size, 0.88 to 2.77 p. It was found that the Hall-Petch strength-grain size relation is directly applicable to the yield and flow stresses of the two lower-carbon steels , 0.065 and 0.30 pct C. The strength data for the medium- and high-carbon steels, 0.55 to 1.46 pct C, also satisfied the Hall-Petch relation, provided that these data are based upon the particle spacing. Beyond 4 pct strain, the flow stress data of all the steels studied could be represented by the same Hall-Petch relation with dinerent spacings for grain boundary and particle strengthening. The behavior of the higher-carbon steels was consistent with the postulated formation of a dislocation cell network during processing and initial deformation (up to 4 pct strain). The cell size was assumed to be equal to the planar particle spacing. The true stress at the ultimate tensile strength was also found to be a function of the particle spacing. At a given temperature and strain rate, the yield and flow stresses of carbon steels depend on the type and dimensions of the microstructure. Starting with the work of Gensamer et al. in 1942,' experimental studies on pearlitic and spheroidized carbon steels revealed that the strength of steels is a function of two main parameters: the ferrite grain size2'3 and the carbide particle spacing;1'4'5 on this basis, two different strengthening mechanisms have been developed to apply to steels of low and high carbon contents, respectively. In polycrystalline iron and mild steels the grain boundaries are regarded as the major structural barriers to slip. The relation between strength and grain size is generally represented by the Hall-Petch equation which is based on a linear proportionality between strength and the inverse square root of the average grain size.2'3y677 However, Gensamer et al.' and Roberts et related the yield strength of medium -and high-carbon steels to the carbide particle spacing alone, and they found a linear relation between the logarithm of the mean free path in the ferrite and the yield strength in both spheroidized and pearlitic steels. By means of the electron microscope, Turkalo and LOW' extended the study to finer structures; they concluded that the logarithmic relation is not valid for the entire range of microstructures unless grain boundaries are also included in the measurement of the mean free path. For the specific case of spheroidized steels, Ansell and aenel' found that the yield strength data,4'5 when plotted as a function of mean free path, fit the Hall-Petch equation; however, T'ysong found that the same data fit the 0rowanl0 relation if a planar inter-particle spacing is used. Recently Kossowsky and ~rown" studied the strength of prestrained spheroidized steels, 0.48 and 0.95 pct C, and concluded that the strength due to the carbide dispersions varies linearly with the reciprocal of the square root of the mean free path between carbide particles and dislocation networks. Such networks were first observed by Turkalo." The conclusion common to all these studies is that the available slip distance in the ferrite is the most important variable in determining strendh. Previous work on carbon steels is restricted to limited composition and strain ranges. The mechanism which governs the flow properties is not clearly understood, and, in particular, little is known about the composition dependence of the transition between grain boundary strengthening and particle hardening. The purpose of the present work is to investigate the strengthening mechanism in spheroidized steels over a wide range of carbon content, 0.065 to 1.46 wt pct, and plastic strain, yielding to necking. The spheroidized structure was chosen because of its relative simplicity and the relative ease of control and measurement of the structural parameters. The experimental work is limited to tensile testing at room temperature at constant extension rate. The effects of the carbide particles on the fracture behavior of spheroidized steels are discussed elsewhere.13 EXPERIMENTAL PROCEDURE Eight different grades of vacuum-cast carbon steels were supplied in the form of forged and rolled plate by the Applied Research Laboratory of the U.S. Steel Corp. The compositions furnished with these steels are given in Table I; the carbon content ranges from 0.065 to 1.46 wt pct, or from 1.0 to 22.3 vol pct of carbide. The steel plates were cut transversely into rods a little larger than the test specimens, 1 in. gage length, i in. diam. The rods were austenitized in air (enriched with CO by a consumable carbon-rich muffle) at 50° C above theA, orA., temperature for 2 hr and then quenched in oil with vigorous stirring. The as-quenched rods were tempered in two stages in order to obtain the desired distributions and sizes of carbide particles. The rods were first tempered at 460° C for 10 hr and then at 700" C for periods ranging from 4 hr to 3 days, in vacuum. After final machining, all specimens were vacuum-annealed again at 650°C for 1 hr in order to relieve residual stresses. The tension tests were carried out in two steps. The initial part of the load-strain curve, up to about 2 pct strain, was determined on a Riehle testing machine with an extensometer of small strain range, 4 pct strain, in order to obtain the yield and initial flow piopertiesi As soon as the first part of the test was finished, the specimen was placed in an Instron testing machine equipped with a strain gage extensometer with a maximum strain range of 50 pct. The load-strain curve to fracture was

Jan 1, 1969

By K. P. Gupta, P. C. Panigrahy

The stabilization of the R, a-Mn, and 0-Mn phases have been studied in the Mn-Ti-Fe and Mn-Ti-Co systems. Iron and cobalt both appear to stabilize the (Mn-Ti) R phase to almost the sarne extent. The R-phase region was found to extend from the lowest e/a to slightly beyond the maximunz e/a limit known for this phase. But, while iron appears to stabilize the a-Mn phase, cobalt tends to stabilize the p-Mn phase. In the two systems manganese appears to get replaced by iron and cobalt in each of the mentioned phases. The instability of the a-Mn phase in the Mn-Ti-Co system and the /3 -Mn phase in the Mn-Ti-Fe system cannot be explained on the basis of adverse size effects because atomic diameters for both iron and cobalt (C.N. 12 at. diam) are ziery similnr and not much different from manganese which they replace. Qualitatively, the reason for the stability of the a-Mn and the p-Mn phases can be traced to the more favorable e/a ratio prevailing in the respective systems and to a competing tendency between the two phases. In transition metal alloy systems the o, p,P, R, a- Mn,' and p-Mn2 phases have been claimed as electron compounds. A large volume of work has been done to establish the criterion for the formation of the o phase but until very recently practically no systematic work was done on the a-Mn and the /3-Mn phases. A recent investigation on the P-Mn phase3 indicates the e/a criterion for p-Mn phase stabilization. Since the R phase was first known to appear only in certain ternary systems1 no detailed work was then possible for this phase. The R phase has been recently discovered as a binary intermetallic compound in the Mn-Ti~ and Mn-si~-' binary systems. The existence of binary R phases opens up the possibilities of studying the effect of alloying elements on the stabilization of the R phase. Of the two binary systems possessing an R phase, the Mn-Ti system appears to be more interesting because at a suitable high temperature it is possible to find the three electron compounds, the a-Mn, p-Mn, and R phases, side by side and it is possible to study the effect of a third transition element on these three electron compounds. For the present investigation iron and cobalt, so called B elements for the formation of electron compounds, have been used as the third element to study the stabilization of the a-Mn, P-Mn, and R phases. EXPERIMENTAL PROCEDURE The alloys were prepared by using 99.9 pct pure electrolytic Fe and Mn, 99.5 pct Co, and crystal bar titanium, supplied by Semi Elements Inc., New York and Gallard Schelsinger Mfg. Co., New York. Weighed amounts of the components were melted in recrystal-lized alumina crucibles in an inert atmosphere (argon) high-frequency induction melting unit. Titanium was made into fine chips for easy dissolution and a special charging procedure was adopted to avoid contacts of titanium chips with the alumina crucibles. Up to 20 at. pct Ti, the maximum titanium content in the investigated alloys, there was no visible sign of reaction of titanium with the alumina crucibles. With a careful control of melting time and temperature the losses were minimized and were always found to be below 0.1 pct. Because of such small and almost constant weight losses, the alloys were not finally analyzed. The alloys were wrapped in molybdenum foil and annealed in evacuated and sealed silica capsules at 1000" * 2°C for 72 hr and subsequently quenched in cold tap water. Annealed samples were examined metallographically and by X-ray diffraction. For all high manganese alloys oxalic acid solutions of various concentrations and 1.0 pct HN03 solution were found suitable as etching reagents. Best contrast between the a-Mn and the R phases could be obtained by using freshly prepared 60 pct glycerine + 20 pct HN03 + 20 pct HF solution. For high iron and cobalt containing alloys, especially for alloys containing the a-Fe, y-Fe, and P-Co phases, 15 cc HNOJ + 60 cc HC1 + 15 cc acetic acid + 15 cc water solution was found to be the best etching reagent. All X-ray diffraction work was carried out (using specimens prepared from annealed powders) with a 114.6 mm diam Debye-Scherrer camera using unfiltered FeK radiation at 25 kv and 10 ma. All calculations for X-ray diffraction work were carried out using an IBM 7044 digital computer RESULTS AND DISCUSSION The two ternary systems, MnTiFe and MnTiCo, were investigated near the manganese rich end, Figs. 1 and 2, and show some common features. In both alloy systems large extensions of narrow R phase regions occur at almost constant titanium contents. At titanium contents higher than that of the single phase R-phase alloys, the same unidentified X phase was found in both ternary systems. The extensions of the X phase close to the Mn-Ti binary indicate that this phase could be the TiMns phase. Too few X phase diffraction lines were present in the diffraction patterns to make positive identification of the X phase. In contrast to this similarity the two systems show opposite behavior in the extensions of the a-Mn and 8-Mn phase regions; while iron tends to stabilize the a-Mn phase, cobalt

Jan 1, 1970

By Don L. Kendall, Martin G. Buehler

A simple physical model has been developed to fit carrier-removal data in silicon irradiated near room temperature with reactor spectrum neutrons. Commonly observed donor and acceptor defect energy levels are assumed to be introduced linearly with neutron fluence. The donor levels (in ev) are Ev + 0.16, Ev + 0.27, and Ev + 0.31 and the acceptor levels are Ec - 0.55, Ec - 0.40, and Ec - 0.1 7, where Ev and Ec are the valence and conduction band energies, respectively. The introduction rates of each level are adjusted to fit literature initial carrier-removal rate data. When normalized with respect to the Ev +0.27 level, the relative values of introduction rates are 5.3, 1.0, 3.1, 1.0, 2.0, and 20.0, respectively for the six levels indicated above. To fit p-f (hole concentration vs neutron fluence) and n-f (electron concentration us neutron fluence) data, the introduction rates are multiplied by a factor which preserves the relative values given above. This factor depends upon irradiation temperature, reactor energy spectrum, neutron fluence calibration, and oxygen content of silicon. An extensive study of the effect of neutrons on carrier-removal in silicon irradiated with reactor spectrum neutrons (E > 10 kev) has been given by Stein and Gereth1 (SG) and Curtis, Bass, and Germano' (CBG). They measured initial carrier-removal rates for both p- and n-type silicon over an impurity range typical of silicon devices. In this work, we attempt to fit a simple theory to this data to establish a usable relationship between hole and electron concentration, p and n, respectively, and neutron fluence f. The p-f and n-f relations are needed to assist in the design of neutron tolerant silicon devices and are needed to clarify presently used empirical resistivity-fluence relationships.3 Neutron damage in silicon produces a variety of defects ranging from simple point defects to defect clusters. For the purpose of this treatment, we assume that simple point defects dominate carrier-removal effects. In contrast to this view, stein4 has proposed that defect clusters are responsible for a significant portion of carrier-removal effects. In the following section, it is shown that the carrier-removal effect in n-type silicon with an electron concentration less than 1015 cm-3 can be explained adequately by assuming that the divacancy is the dominant defect and that its introduction rate is independent of the electron concentration. For electron concentrations greater than 1015 cm-= an additional acceptor defect center is needed, and for simplicity the A-center (vacancy-oxygen pair) has been chosen. Although the E-center (vacancy-phosphorus pair) can account for some of the results, the A-center was chosen because the E-center requires a more involved treatment which the presently available data do not justify. In p-type silicon three radiation-induced donor levels are assumed, namely the divacancy and two other centers of unspecified nature located at Ev + 0.16 ev and Ev to 0.31 ev. The donor divacancy at Ev + 0.27 ev is assumed to be introduced at the same rate in p-type as in n-type. However, this rate is too low to fit p-type initial carrier-removal data. The dominant centers in p-type silicon are assumed to be the Ev + 0.16 ev and Ev + 0.31 ev levels where the latter is not the divacancy. The introduction rates are chosen to fit initial carrier-removal rate data. Assuming that the introduction rates are independent of Fermi level, the ratio between them is fixed for subsequent p-f and n-f calculations. Using the same ratios, the initial carrier-removal rate data1,2 as well as p-f and n-f data1,5 can be fit provided the absolute value of the introduction rates are adjusted to account for irradiation temperature, reactor energy spectrum, neutron fluence calculation, and the oxygen content of silicon. THEORETICAL ANALYSIS This analysis is basically the same as that used by Hi116 to analyze electron damage in silicon except we express the degree to which an impurity level is ionized not in terms of the Fermi level, but in terms of carrier concentration. Landis and pearson7 have used the latter approach to analyze y-damage in silicon. Neutron-induced defects responsible for carrier-removal at room temperature are assumed to be simple point defects with no interaction between defects so that they may be represented by discrete energy levels. It is also assumed that no constituent of a defect complex is used up and defects stabilize shortly after irradiation. Defects are assumed to be introduced linearly with fluence according to the product Rtf where Rt is the defect introduction rate and f the neutron fluence. Taking into account the ionization of defects according to Fermi statistics, and considering charge neutrality where minority carriers are neglected, the n-f relation is where no is the preirradiation electron concentration. The parameter Nt is the electron concentration at which the ionized defect concentration is one-half the total defect concentration (Rtf) or where Et is the defect energy level. For silicon at 300°K, ni = 1.45 X 1010 cm-3 and Ei = Ev+ 0.542 ev which was determined using Ec — Ev = 1.11 ev and me* = 1.07 mo and mh* = 0.558m0. The spin degeneracy factor, which usually appears as a number multiplying the Nt/n term of Eq. [1], is taken as unity. In effect, this factor has been incorporated into the defect en-

Jan 1, 1970

By R. S. Busk

Niels Engel (University of Alabama, University, Ala.)— In this paper it was pointed out that the electron-gas and energy-band theory accounts for the fact that the lattice parameters exhibit a sudden change when the electron concentration (number of bonding electrons per atom) exceeds a certain number around two. This statement is said to support and prove the electron-gas theory. But this theory is not able to account for a series of experimental data. Also several expectations, deduced from this theory, are not found to exist. In Figs. 6 and 7 the energy bands of the second and third periods are given as they must be assumed in order to account for the electrical properties of the elements in these periods. In Figs. 6 and 7 the electron-gas and energy-band theory is compared with the electron-oscillator hypothesis in accounting for the properties of the elements in the second and third periods. Fig. 6 shows the second period, The energy-bands are overlapping and separated to be in agreement with the electrical conductivity of the elements. The oscillator hypothesis explains conductivity due to electron vacancies. In graphite there is a closed s-shell in every other atom and two vacancies in the others. Conductivity is therefore only maintained by migration of s-electrons in graphite. In boron there are no s-electrons. The diatomic molecules of nitrogen and oxygen and the paramagnetism of oxygen can be accounted for by a similar behavior as the s-electrons of the bonding electrons. But this explanation will deviate too much for the purpose of this discussion. Fig. 7 shows the third period. In the energy-band picture about two s-electrons are assumed in magnesium and aluminum, but only one s-electron is assumed in silicon. The diamond lattice is assumed to be controlled by a sp3 hybrid. However the electron distribution develops ideally according to the oscillator hypothesis. Only sodium, magnesium, and aluminum exhibit electron vacancies and conductivity. To account for the insulator properties in Si, P, and S in the third period it must be assumed that the four last added p-electrons must be taken up in bands containing only one electron per band.' (Compare the electron band picture in Hume-Rothery.' Hume-Rothery does not consider the insulator properties of the nonmetals.) In the second period already the first p-electron must have entered a single electron band. Based on the energy-band picture in Figs. 6 and 7, the following questions must be asked: 1—Is it consistent with the energy-band idea that electrons of the same kind (p-electrons) can be divided into separated bands? 2—Is it consistent with the energy band idea that single electron bands can exist? 3—Why are the first two p-electrons (in boron and diamond) separated into two single electron bands in the second period, but overlapping in the third period (aluminum)? 4—Why are s-electrons and d-electrons taken up in continuous overlapping bands, while p-electrons are divided into single electron bands? 5—Why do the peaks and valleys (y and w and further x and z) of the energy band below four electrons per atom not show up in the electrical conductivity of alloys? For example consider the Li-Mg system or the alloys between Mg and three electron metals where the mentioned discontinuity in the lattice parameter is found. 6—Why does the beginning of the p-electron band (x) not show up in the lattice constants similar to the filling up of the s-electron band (z) ? In magnesium alloys the electron-gas theory postulates the first Brillouin zone to be filled at about two electrons per atom. This is claimed to explain the sudden change in lattice spacing and c/a values of several magnesium alloys when the electron concentration exceeds a few percentage points over two electrans per atom. This was emphasized in the paper by Busk. If the electron-gas energy-band theory is correct a sudden change in electrical conductivity and possibly other properties .should be expected when the same electron-concentration or temperature is exceeded. A sudden change in lattice spacing or other properties should also be expected when the filling degree is such that p-electrons are introduced into the p-band, for example at x in Figs. 6 and 7. Such phenomena are at found by experiment. and If the number of electrons should vary with the energy level depending on the average number of bonding electrons per atom, the electrical conductivity should be expected to vary in accordance with the energy band layout (Figs. 6 and 7) caused by different numbers of conducting electrons at different filling up degrees. Nothing indicating such a behavior is observed. In addition to these discrepancies between the electron-gas and energy-band theory and measured data, the theory violates the principles developed along with the Bohr theory of atomic structure. According to these principles a filled shell is saturated and therefore unable to form bonds. Therefore two S-electrons per atom should form a closed or saturated shell, which has been pointed out as accounting for the inability of helium to form bonds. Beryllium, magnesium, or calcium atoms with two s-electrons should be expected to form inert atoms with properties almost like the helium atoms. Several other inconsistencies and disagreements with measured data of the energy-band theory can be mentioned. Some of these are discussed with reference to other papers. 8 Because the electron-gas and energy-band theory seems to fail on several points, I have developed another theory which can account for all the phenomena the electron-gas theory is able to account for. This new theory is further able to account for things which are impossible to explain by the electron-gas theory at the present state.

Jan 1, 1953

By E. F. Reed

CONSIDERABLE deep hole prospect drilling has been done in the last few years in the Globe-Miami mining district about 70 miles east of Phoenix, Arizona, and in the San Manuel-Tiger area about 50 miles south of the Globe-Miami region. More than 205,000 ft of churn drilling have been completed by the San Manuel Copper Corp. at their property in the Old Hat Mining District in southern Pinal County. The deepest hole on this property is 2850 ft; there are 49 holes deeper than 2000 ft. At the adjoining Houghton property of the Anaconda Copper Mining Co., where only one hole reached 2000-ft depth, there were 27,472 ft of churn drilling and 3436 ft of diamond drilling. Three churn drill holes were deepened by diamond drilling methods. Near Miami in the Globe-Miami district the Amico Mining Corp. drilled four holes by combined churn and rotary drilling methods, the total amounting to 13,879 ft, of which 2256 ft were drilled with a portable rotary rig. In the same district, besides doing a large amount of shallow prospect drilling, the Miami Copper Co. drilled two holes of 2560 and 3787 ft, respectively, which were completed by churn drilling methods. The rocks encountered in drilling at San Manuel and Tiger are described by Steele and Rubly in their paper on the San Manuel Prospect' and by Chapman in a report on the San Manuel Copper Deposit.' The rocks are well-consolidated Gila conglomerate, quartz monzonite, and monzonite porphyry. In some places these formations stand very well while being drilled, and three holes were drilled without casing, the deepest of which was 2200 ft. In other holes faulted and fractured ground made drilling difficult. In the Globe-Miami district the deep drilling was done in the down-faulted block of Gila conglomerate east of the Miami fault and in the underlying Pinal schist. The geology of this area is described by Ranaome. In the Amico holes the conglomerate varied from material consisting entirely of granite boulders and fragments to a rock made up of schist fragments in a sandy matrix; in the Miami Copper Co. holes there were more granite boulders and the material was poorly consolidated. Drilling was much more difficult and expensive in the Miami area than in the San Manuel district, mainly because of the depth of the holes and the formations drilled. All the deep hole prospecting described in this paper was done with portable rigs. The churn drill rigs were of several types, of which the Bucyrus-Erie were the most popular. Bucyrus-Erie 28L, 29W, and 36L rigs were used on some of the deeper holes on the San Manuel property. A few Fort Worth spudder types were tried, and the deepest hole at San Manuel was drilled with a Fort Worth Jumbo H. The spudder type is considerably larger than most other rigs used on this work and required a larger location site. The spudders were belt-driven machines with separate power units, and time required for setting up and moving was much longer than with the more portable drills. All the churn drilling was done by contractors or with machinery leased from them. A few of the contractors had complete equipment, including most of the necessary fishing tools. Unusual and special fishing tools were obtainable from the supply companies in the oil fields of New Mexico or in the Los Angeles area. Most of the contractors used equipment with standard API tool joints, so that much of it was interchangeable. Failure of tool joints is one of the principal causes of fishing jobs. It can be minimized if the joints are kept to the API specifications and the proper sized joints are used in the various holes. The minimum sizes that should be used with various bits are as follows: 12-in. and larger bits, 4x5-in. tool joints; 10-in. bits, 3Y4x41/4-in. tool joints; 8-in. bits, 23/4x 3 3/4-in. tool joints; 6-in. bits, 21/4x31/4-in. tool joints; 4-in. bits, 15/ix25/s-in. tool joints. Two rotary drill rigs were tried at San Manuel on the same hole, and a portable rotary drill rig was used on the Amico drilling for test coring the formation and for drilling in holes 3 and 4. Rotary drilling differs from churn drilling or cable tool drilling in that the bit is revolved by a string of drill pipe and the cuttings are removed from the hole by a thin solution of mud pumped through the drill pipe. The principal parts of a rotary rig are the power unit, a rotating table to revolve the drill pipe, hoists to raise and lower the pipe and to handle casing, and a pumping system to circulate the drilling liquid. The rig used on the Amico property at Miami was mounted on a truck. The larger rig used on the San Manuel property was hauled by several trucks and had separate turntable and pumping units. Diamond drill coring equipment was used successfully with the rotary rig in the holes on the Amico property. To allow for 2-in. drill pipe with tool joints, 31/2-in. core barrels and bits were used. With the standard 31h-in. core barrel there was considerable difficulty in maintaining circulation with mud, so a barrel was designed with a smaller inner tube and a broad-faced bit. This allowed coarser material to circulate between the barrels. Rock bits of 5 to 37/8 in. were used with the rotary rig for drilling between core runs. Diamond drill equipment is much lighter than churn drill tools, so that fishing tools can usually be obtained from supply houses by air express when needed. Three churn drill holes on the Houghton property at Tiger were deepened by diamond drilling with Longyear UG Straitline gasoline-driven machines. The open churn drill hole was cased with 21h-in. black pipe. In deep hole churn drilling, casing is one of the most important items, especially in drilling in un-consolidated material like the formations drilled by

Jan 1, 1953

By E. F. Reed

CONSIDERABLE deep hole prospect drilling has been done in the last few years in the Globe-Miami mining district about 70 miles east of Phoenix, Arizona, and in the San Manuel-Tiger area about 50 miles south of the Globe-Miami region. More than 205,000 ft of churn drilling have been completed by the San Manuel Copper Corp. at their property in the Old Hat Mining District in southern Pinal County. The deepest hole on this property is 2850 ft; there are 49 holes deeper than 2000 ft. At the adjoining Houghton property of the Anaconda Copper Mining Co., where only one hole reached 2000-ft depth, there were 27,472 ft of churn drilling and 3436 ft of diamond drilling. Three churn drill holes were deepened by diamond drilling methods. Near Miami in the Globe-Miami district the Amico Mining Corp. drilled four holes by combined churn and rotary drilling methods, the total amounting to 13,879 ft, of which 2256 ft were drilled with a portable rotary rig. In the same district, besides doing a large amount of shallow prospect drilling, the Miami Copper Co. drilled two holes of 2560 and 3787 ft, respectively, which were completed by churn drilling methods. The rocks encountered in drilling at San Manuel and Tiger are described by Steele and Rubly in their paper on the San Manuel Prospect' and by Chapman in a report on the San Manuel Copper Deposit.' The rocks are well-consolidated Gila conglomerate, quartz monzonite, and monzonite porphyry. In some places these formations stand very well while being drilled, and three holes were drilled without casing, the deepest of which was 2200 ft. In other holes faulted and fractured ground made drilling difficult. In the Globe-Miami district the deep drilling was done in the down-faulted block of Gila conglomerate east of the Miami fault and in the underlying Pinal schist. The geology of this area is described by Ranaome. In the Amico holes the conglomerate varied from material consisting entirely of granite boulders and fragments to a rock made up of schist fragments in a sandy matrix; in the Miami Copper Co. holes there were more granite boulders and the material was poorly consolidated. Drilling was much more difficult and expensive in the Miami area than in the San Manuel district, mainly because of the depth of the holes and the formations drilled. All the deep hole prospecting described in this paper was done with portable rigs. The churn drill rigs were of several types, of which the Bucyrus-Erie were the most popular. Bucyrus-Erie 28L, 29W, and 36L rigs were used on some of the deeper holes on the San Manuel property. A few Fort Worth spudder types were tried, and the deepest hole at San Manuel was drilled with a Fort Worth Jumbo H. The spudder type is considerably larger than most other rigs used on this work and required a larger location site. The spudders were belt-driven machines with separate power units, and time required for setting up and moving was much longer than with the more portable drills. All the churn drilling was done by contractors or with machinery leased from them. A few of the contractors had complete equipment, including most of the necessary fishing tools. Unusual and special fishing tools were obtainable from the supply companies in the oil fields of New Mexico or in the Los Angeles area. Most of the contractors used equipment with standard API tool joints, so that much of it was interchangeable. Failure of tool joints is one of the principal causes of fishing jobs. It can be minimized if the joints are kept to the API specifications and the proper sized joints are used in the various holes. The minimum sizes that should be used with various bits are as follows: 12-in. and larger bits, 4x5-in. tool joints; 10-in. bits, 3Y4x41/4-in. tool joints; 8-in. bits, 23/4x 3 3/4-in. tool joints; 6-in. bits, 21/4x31/4-in. tool joints; 4-in. bits, 15/ix25/s-in. tool joints. Two rotary drill rigs were tried at San Manuel on the same hole, and a portable rotary drill rig was used on the Amico drilling for test coring the formation and for drilling in holes 3 and 4. Rotary drilling differs from churn drilling or cable tool drilling in that the bit is revolved by a string of drill pipe and the cuttings are removed from the hole by a thin solution of mud pumped through the drill pipe. The principal parts of a rotary rig are the power unit, a rotating table to revolve the drill pipe, hoists to raise and lower the pipe and to handle casing, and a pumping system to circulate the drilling liquid. The rig used on the Amico property at Miami was mounted on a truck. The larger rig used on the San Manuel property was hauled by several trucks and had separate turntable and pumping units. Diamond drill coring equipment was used successfully with the rotary rig in the holes on the Amico property. To allow for 2-in. drill pipe with tool joints, 31/2-in. core barrels and bits were used. With the standard 31h-in. core barrel there was considerable difficulty in maintaining circulation with mud, so a barrel was designed with a smaller inner tube and a broad-faced bit. This allowed coarser material to circulate between the barrels. Rock bits of 5 to 37/8 in. were used with the rotary rig for drilling between core runs. Diamond drill equipment is much lighter than churn drill tools, so that fishing tools can usually be obtained from supply houses by air express when needed. Three churn drill holes on the Houghton property at Tiger were deepened by diamond drilling with Longyear UG Straitline gasoline-driven machines. The open churn drill hole was cased with 21h-in. black pipe. In deep hole churn drilling, casing is one of the most important items, especially in drilling in un-consolidated material like the formations drilled by

Jan 1, 1953

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

MINING ENGINEERING presents the annual membership report of the Society of Mining Engineers; see page 109.

Jan 7, 1963

The University of North Dakota, State Geological Survey, Grand Forks, N. D A G. Leonard, State Geologist. Two publications of the State Geological Survey are of interest Fourth Biennial Report, The clays and clay industries of North Dakota, and Bulletin 4, Lignite deposits and lignite industries of North Dakota. Bulletin 11 of the University is of interest: Geology and natural resources of North Dakota For further information, address the above

Jan 1, 1933

By C. H. Mathewson

THIS paper was prepared upon request as a contribution to a symposium covering the manufacture, properties, and uses of the important non-ferrous metals. In approaching a subject as broad as this, there is a natural desire to build up a comprehensive and finished production which shall constitute a dependable source of information on all questions properly belonging to this branch of metal technology. There are, however, a number of circumstances, apart from the mere routine of labor and thought involved, which operate rather effectively against the possibility of completing such an ambitious program at the present time. First of all, as far as any public record of results is concerned, the commercial rolling, drawing, and forming of zinc with relation to changes of structure and properties-and this we consider to constitute the elements of metal technology-might as well be an unpractised art. We have never seen a published photomicrograph showing the structural characteristics of either hard or soft sheet or strip, although the structure of castings has been frequently described, and other coarse-grained structures resulting from hard-hammering and annealing have been reproduced. Thus, an author in this field must proceed to his task without much assistance from the literature, and the outcome can represent only a personal estimate of principles, facts, or findings, and not a summary

Jan 9, 1919