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By F. G. Stone

A strain anneal process has been developed for the production of iron tensile test specimens, the gauge length consisting substantially of a single crystal. Since the method has been quite successful and the results of general interest, the process will be described in detail. The essential feature of the method is the continuous, slow increase of furnace temperature during the grain growth annealing treatment. Briefly, the procedure is as follows: I. Heat machined bars to 950°C in vacuum, hold I hr, furnace cool. 2. Strain to 3.5-3.8 pct elongation (axial loading). 3. Anneal, continuously raising furnace temperature from 450 to goo°C at a rate of so0 per day. 4. Hold at 900°C for 100 hr, furnace cool. Tensile test bars with a 1/4- X I-in. gauge section have been machined from 35 in. Armco iron plate and from 3/8 in. rounds of Puron, a high purity laboratory iron. The axes of the test bars were parallel to the rolling direction. During the machining operation the bars were polished in the lathe with No. 600 emery paper, and this polished surface proved satisfactory for subsequent macrographic examination. A micrographic examination of the materials showed that both were high in FeO inclusions, those of the Puron being smaller but much more numerous. An initial vacuum anneal of I hr at 950°C followed by furnace cooling resulted in a ferritic grain size of ASTM No. 3 for Armco and No. I for Puron. Special heat treatments which reversed these initial grain sizes produced no marked improvement in single crystal production after subsequent treatments. The strain for subsequent grain growth was determined by measuring the decrease in diameter of the tensile bar during elongation. The change in diameter could be measured with a micrometer to +0.0001 in., corresponding to an accuracy of 0.08 pct for the elongation. The accuracy of the diameter measurement is also dependent on grain size because of surface roughening during elongation, and for this reason, a No. 3 grain size is preferable. Optimum grain growth was obtained for strains between 3.5 and 3.8 pct elongation. Once this critical range had been cstablished, all tests were held within it, and thus only meager data were obtained on grain growth following strains outside this range. In general, grain size decreased with increasing strain to about 5.5 pct elongation. Grain growth was occasionally ohserved with less than 3.5 pct elongation although this may have been the result of error in measurement. The program control device for the grain growth anneal consisted of a I rpm motor and worm gear drive, operating the dial shaft of a pyrometer controller through a pulley. Dial speeds of 33 and 50°C per day were tried, but the results at the slower speed were not sufficiently better to warrant the increased furnace time. The furnace tube was evacuated at intervals during the run and kept sealed the remainder of the time. When the controller reached 900°C, it was stopped and the temperature held for 100 hr. This eliminated most of the numerous minute crystallites of about 0.5 mm dimension usually visible on the etched surface of the single crystal. Since recrystallization occurs at the A3 point, the top temperature of 900°C provided a 10"

Jan 1, 1949

By C. W. Hazelett

This paper is a resume of some of the accomplishments in direct rolling of strip from molten metal, and a description of some experimental developments in recent years. In all the early developmental work, we used a pair of rolls with a bath of metal between them, maintained by flanges or plates at the ends of the rolls. These flanges produced an excess cooling of the metal and built up enormous pressures at this point as the metal went through the bight of the rolls. Many means were tried for compensating for this excess cooling, such as thickening the strip at the edges, heating the end dams directly or by flowing more of the molten metal against them, leaving an open crotch below the end dam and above the bight of the roll, where the excessive pressures built up could be relieved by some of the metal squeezing out at this point, and so forth. All of these helped somewhat to solve the problem, so that very large heats of many metals melting up to 200°F., having commercially uniform gauges, could be rolled up to 24 in. in width. The rolls were made by mounting heavy rings on heavy shafts, and pressures up to 75,000 lb. per inch in width were used. Cooling of the rolls was generally done by spraying water on the outside surface of the rolls that came in contact with the molten metal. Roll life was commercial with brass, barely satisfactory with copper, and totally impractical with steels. The greatest difficulty encountered in all this work was caused by lack of uniformity in the product, owing to a folding action in the mill. Those who are familiar with the operation of a rolling mill know that a bar entering a mill moves at a lower speed than the peripheral speed of the roll. However, the metal solidifying from a bath in a direct rolling mill is cast at exactly the peripheral speed of the roll. This results in irregular folding of the metal, some irregular remelting of the previously solidified sections, and it is difficult, if not impossible, in some cases to exert enough pressure to weld these folded sections sufficiently into a sound product. In addition to this melange of solid, semisolid and liquid metal in the bath, we know that pressure near the freezing point of any alloy in which the constituents have different melting points—and I believe all of them have—causes the lower-melling-point constituent to be squeezed back until it becomes cold enough to solidify and go through the mill. This segregates all alloys, the segregation increasing with the pressures and the freezing ranges of the metals. Add to these problems the excessive roll-maintenance costs with high-melting-point metals and then, the greatest difficulty of all, the vanity of homo sapiens where a matter of possibly large importance is being considered, and the problems seemed almost insuperable. It was long ago obvious to me that something much more than the size of a corporation's money and self-assuradce was necessary if this process was to be made commercial. I should like to show you first the performance of the only mill we ever really designed and built, to see what might be done with a well constructed mill. We accomplished something new in history with this prccess, first, by producing at Scovill Manufacturing Co. coils of brass

Jan 1, 1945

By Howland Bancroft, Louis S. Cates

WE have come a long way since the order of the day was the chance discovery of mineral deposits, breaking rock with fire and water, melting metals in open fires in holes in the ground or in primitive furnaces, digging pits to collect. oil seepages, burning eroded coal outcrops to develop heat, and so on. During the past 5500 years, gradual improvements in methods and equipment have come about, explosives have been developed and used, steel has been used in increasing quantities and effectiveness as its physical and chemical characteristics, and composition have been altered and made to serve specific ends, hand equipment has given way to almost completely mechanized operation Thus, by the aid of mechanical equipment, one person is now able to move several thousand times as much material as one person was able to move a relatively few years ago. When this Institute was formed 75 years ago, the Suez Canal had been open to traffic but three years. It had taken ten years to complete and was built under the direction of French engineers by workers of whom many were girls. During the first four years of construction, these workers dug up the sand with their fingers, threw it into rush baskets, carried the load a hundred feet or so and dumped it 2 (With the termination of forced labor, dredgers completed the digging of the channel.) At the present time there is in use in the United

Jan 1, 1947

By Edward Martinez

The reactions occurring in the copper segregation process were studied by heating mixtures of chryso-colla, salt, and a reducing agent. The techniques used in this investigation were differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). The initial chloridizing of the oxide copper occurs below 500°C and cupric chloride may be the compound formed. Volatilization and reduction of the copper chloride take place above 550°C, although these reactions do occur to some extent below 550°C. A difference in the distribution of the metallic copper in the reducing agent was found when sodium chloride was used compared to magnesium or calcium chloride. Segregation was obtained with mixtures of cupric oxide, salt, and charcoal with no quartz or silicate present. Preliminary tests indicate that segregation may occur even in the absence of water vapor. The DTA and TGA techniques were found to be of great value in studying these reactions. The copper segregation process is a method for treating oxide copper ores. The ore is heated, most commonly in a kiln, with a reducing agent and a halide salt, generally sodium chloride, to approximately 700°-750°C and held for 30 to 60 min. The addition of the salt results in the migration and reduction of the oxide copper to metallic copper on the surface of the reducing agent rather than in the original mineral structure. The metallic copper can then be recovered by a subsequent leaching or flotation step.1-4 Experimental work in 1923 on oxide copper ores from the Sagasca mines in Chile led to the discovery of the reduction process. It was found that during the reduction of the copper mineral with coal, at about 700°C, the copper migrated to the surface of the coal instead of remaining disseminated in the ore. The unusual behavior of the copper, which caused it to migrate from the ore particles to the coal, was traced to the presence of a small quantity of sodium chloride occurring in the ore. Further experiments with oxide copper ores proved that the presence of a halide, either occurring naturally or admixed with the ore, caused the copper to migrate from the ore particles and to segregate in the charge. The ratio of salt to reducing agent may vary somewhat, but in general 0.5% to 1.5% sodium chloride and 0.5% to 1.0% coal or coke have been mixed with the ore. Less than stoichiometric amounts of salt are required to convert all the oxide copper to a chloride, so that a cycle of reactions appears to be occurring. Several investigations reported in the literature have proposed reactions to explain the mechanism of the process.5-10 There appears to be general agreement that water is necessary for the reactions to occur; that once the sodium chloride reacts with silica or silicates in the ore, the hydrochloric acid formed will convert the cupric oxide in the mineral structure to cuprous chloride. However, there appears to be a conflict of opinion on the reactions involved in the reduction of the cuprous chloride to metallic copper on the surface of the carbon. Rey has indicated that salt, water vapor, and

Jan 1, 1968

By Robert Lowrie

Nine intermetallic compounds were tested in tension at various temperatures. Seven exhibited extensive plastic deformation at elevated temperatures. Correlations of tensile strength and elongation are attempted with melting (decomposition) temperature, valence electron configurations of the component elements, heat of formation, crystal structure, density, and volume decrease accompanying compound formation. A LTHOUGH intermetallic compounds have been -tX known for many years, the study of their mechanical properties, particularly in tension, is just beginning. The problem has been unattractive because of the well-known, erratic behavior of brittle materials tested in tension. The strong influence of surface or internal flaws as stress raisers in non-ductile materials and the effect of eccentricity of loading in superimposing bending stresses on the state of tension in the specimen are extremely difficult to mitigate and impossible to completely eliminate. Thus, tensile properties determined for brittle materials, such as intermetallic compounds at temperatures low in comparison to their melting points, are at best only general guides to the values to be expected in an ideal test of a perfect specimen of the material. It is, nevertheless, surprising that apparently no attempt was made to follow up the pioneer work of Tammann and Dahl1 in this field. Working with crude apparatus, these investigators succeeded in showing unequivocally that at temperatures sufficiently close to their melting points (from 75" to 400°C for the compounds tested) intermetallic compounds did exhibit plasticity. This was indicated by the appearance of slip lines on the surface of the specimen. No observations of strength were made in these tests, which were of a compressive or indentation type. Rossi2 in 1932 attempted to study the physical and mechanical properties of single crystals of a group of intermetallic compounds. However, he was able to prepare only one material, Cu2Z8,, in the form of large, defect-free, single crystals. Thus, he was able to report only the relative fragility of the compounds at room temperature. He reported one compound, Ag,Zn,, to be somewhat plastic at room temperature and Cu,Si to be friable, the latter in agreement with results reported herein. Although test results are available only in classified literature, it has also been announced that MoSi, possesses some ductility at elevated temperatures." In 1948 and 1949 Savitskii and Savitskii and Baron -ublished their work on the hot extrusion of Mg-Zn, Al-Mg, and Cu-Zn compounds. Under the favorable state of stress existing for this process MgZn, MgZn,, MgZn,, ß (Al-Mg), ? (Al-Mg) and 0 (Cu-Zn) could be reduced by amounts up to 90 pct at elevated temperatures. These authors also report that hardnesses of Mg-Zn compounds decrease from room temperature values of about 300 kg per sq mm to 30 to 50 kg per sq mm at 325°C. They found that alloys consisting solely of one Mg-Zn compound were most resistant to softening on heating, mixtures of a compound and eutectic less resistant, and mixtures of two compounds least resistant. The more rapid softening of mixtures of

Jan 1, 1953

By H. K. Work

The Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of stccl-making are partly economic and partly metallurgical.1 In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect—it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Ressemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (1) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. The Control Problem In this day of scientific control of technical processes, where the operating

Jan 1, 1941

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By D. Turnbull, J. H. Hollomon

IN the most general sense, solidification refers to the formation of crystalline material from either a gas or a liquid. However, in this symposium, only the formation of crystals from liquids will be considered. Thus, in our present study the problem of solidification becomes that of determining the mechanism of the transition from a liquid to a crystalline solid, and our particular interest is in the transformation of metals from the liquid to the crystalline state. Metal liquids are seldom composed of only one kind of atom. Often solute atoms are added intentionally to make an alloy, or they may be present accidently because of incomplete purification. Furthermore, there may be small solid particles of various other crystals present in the liquid. Such small crystals may persist if their melting points are higher than any temperature to which the liquid is heated. Prior to solidification, the liquid metal usually is poured from one container to another. The second container, called the mold, usually is at a lower temperature than the container, or the crucible, in which the metal is liquified. The first solid that forms upon contact with the mold generally is of a different composition than the liquid, usually containing fewer foreign atoms or dissolved impurities. Heat is evolved upon solidification and is dissipated through the surroundings. Tree-like crystals, or dendrites, grow from the container walls and branch into the melt, enriching the remaining liquid in impurity atoms. In some alloys the remaining, relatively impure liquid continues to solidify until no liquid remains and the branches of the original crystal are cemented together. In other alloys, particles with a second type of crystal structure appear before solidification is complete. First the nature of the liquid and the solid states will be considered and then the mechanism of the initial formation of crystals from pure and alloy liquids. Later the problem of the growth of these crystals and the complexities of solidification in a mold, where the temperatures are not uniform and the composition of the melt changes continuously, will be discussed. LIQUID AND CRYSTALLINE STATES A liquid is an aggregate of atoms arranged with no apparent regularity (over distances of more than a few atom diameters). Nevertheless, any given atom generally has a definite number of nearest neighbors at definite distances, and thus order may be said to exist over a short range. In a crystal, on the other hand, a regular array of atoms continues for many hundreds or thousands of atom diameters, and a long-range order is apparent. Thus, a crystal having long-range order can be reproduced by linear translations for 10-5 cm or more of some fundamental unit possessing short-range order. A crude illustration of the difference between liquid and crystalline structures can be obtained by comparing the possible arrangements of oranges in a crate. If the oranges are simply dumped into the crate haphazardly until it is filled, the oranges will represent a static model of a liquid.

Jan 1, 1951

By L. S. Darken

The manufacture and treatment of metals comprises operations whose effectiveness depends in large measure upon diffusion phenomena. The significance of such phenomena has, for a few simple cases, long been understood, but in more complex cases it has not been adequately recognized. This paper presents a mathematical analysis of some of the cases in which diffusion leads to the formation of a new phase within the metal, and this analysis provides a basis for interpreting quantitatively many apparently diverse experimental observations recorded in the literature, some of which are outlined in the following pages. OBservt1ons Recorded in Literature An outstanding instance is the general type of phenomenon in which diffusion of an element into an alloy is followed by a phase change, which most frequently is a reaction (precipitation) of the diffusing element with one or more components of the alloy to form a compound. Thus in certain alloys heated in contact with oxygen not only the usual oxide scale appears but, in addition, beneath the surface, a well-defined zone in which free oxide particles are dispersed with notabIe uniformity. This zone, commonly referred to as the subscale or zone of internal oxidation, is remarkable in that the visible boundary between it and the unaltered metal is usually sharp. Such a subscale, which appears to have been recognized first in oxidized copper alloys, has been described and studied by C. S. Smith,l by Rhines,2 and by Rhines, Johnson and Anderson;3 but it appears also in other alloys when they are exposed to conditions that bring about the precipitation of some compound, not necessarily an oxide. Another clear case of this same kind is the diffusion of carbon into a steel containing an element such as molybdenum, chromium, vanadium or tungsten, whose carbide is less soluble in iron than iron carbide, the result being that some part of that element is precipitated as a dispersed carbide. A similar phenomenon may occur on the welding of two alloys each of which contains one of a pair of elements that react to form a compound or a new phase of any sort. But in addition to the precipitation of a compound formed from the diffusing element, other effects may result merely from the presence of the diffusing element. For instance, if homogeneous austenite, nearly saturated with respect to carbon, is heated in contact with silicon in the absence of oxygen, one would expect to find, behind the several iron-silicon phases analogous to a scale, a zone of austenite containing dispersed carbide, because of the fact that silicon decreases the solubility of carbon in iron. As still another example, oxidation of an alloy may result in diffusion toward the surface of one or more of the constituents; for instance, during oxidation of a steel containing an element such as "copper, which is less prone to oxidation than iron, there is a notable enrichment of copper just beneath the scale-metal interface. AS an example of a yet more

Jan 1, 1942

By H. K. Work

THE Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of steelmaking are partly economic and partly metallurgical.' In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect-it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Bessemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (I) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. THE CONTROL PROBLEM In this day of scientific control of technical processes, where the operating

Jan 1, 1941

By H. K. Work

The Bessemer process is one of the most interesting methods of making steel. At one time it was by far the most important. In recent years, however, it has steadily lost ground to the open-hearth process. The forces working against this method of stccl-making are partly economic and partly metallurgical.1 In this paper, dealing as it does with the control of the process, the metallurgical factors alone will be considered, although it is obvious that economic factors must play a part in determining the ultimate status of the Bessemer process. This discussion has been limited in another respect—it deals primarily with the acid Bessemer process in bottom-blown converters, although much of the information is applicable to basic and side-blown converters. The fact that open-hearth steel has superseded Ressemer steel to a large extent has tended to create an impression that Bessemer steel is inferior. As a matter of fact, Bessemer steel is actually superior to open-hearth for many applications.2 There are, however, definite metallurgical limitations to the use of Bessemer steel, resulting largely from two factors: (1) the physical properties conferred by nitrogen and phosphorus, and (2) the variability from blow to blow. These, of course, are not entirely independent, since some of the variability covered in the second item is undoubtedly due to nitrogen. But the variability is also caused by other factors. One of these is the relatively small size of the Bessemer heats. Because of this, a given shipment of Bessemer steel is more likely than a shipment of open-hearth steel to contain the product of several heats, each with its own distinctive and slightly different characteristics. Added to this is the fact that the refining of Bessemer steel proceeds so rapidly that the timing of the end point is limited to a matter of seconds, whereas the finishing period in the open hearth extends over a period of one or two hours and the timing of the end point may vary by several minutes without seriously affecting the product. There is no doubt that this has contributed to the variability of Bessemer steel and has led to the use of open-hearth steel in many optional applications. That Bessemer steel may vary is not necessarily objectionable, and it may even prove an advantage, providing a precise control is available to secure the desired qualities for any specific application. With this in mind, a comprehensive research program was undertaken, one phase of which was directed toward securing more accurate control of the blow. The results have been encouraging, and it is the purpose of this paper to describe a method in which modern scientific instruments, based on photocells, are currently being employed to assist the blower. The Control Problem In this day of scientific control of technical processes, where the operating

Jan 1, 1941

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By Leslie F. Tedsen, Alan E. Flanigan, John E. Dorn

IT is necessary occasionally to use aluminum-alloy sheet where moderately elevated temperatures are encountered. Considerable attention has been directed toward determining the influence of "artificial aging" on the room-temperature properties of the precipitation-hardenable alloys, as testified by numerous company reports and by references 1 to 4. Investigations on the properties at elevated temperatures are few, however,5-7 and have not always covered the range of times and temperatures of greatest interest. The present investigation was instituted to overcome this deficiency. The work was done for the Office of Production Research and Development of the War Production Board, under the supervision of the War Metallurgy Committee, as a part of the "restricted" Project NRC-548. It has been released for publication by the Office of Production Research and Development. As is well known, the high-strength aluminum alloys achieve their remarkable properties as a result of precipitation-hardening. In production they are subjected to a solution heat-treatment followed by quenching, to retain the supersaturated solid solution. The solution treatment is followed by "aging" (precipitation-hardening) either at room temperature or at a suitable elevated temperature. A considerable increase in tensile and compressive yield stresses results from precipitation at room temperature ("natural aging"). Through the elevated-temperature process ("artificial aging") it is possible to obtain values of yield stress considerably higher than those attainable by natural aging. The increase in yield stress is accompanied by a smaller gain in ultimate tensile stress and by a decrease in elongation. During [TABLE I.-Sources of Materials Used in the Testing Program MATERIAL ORIGIN AND TREATMENT 24S-T Alclad.... From Lockheed stock. 24S-RT Alclad... Direct from mill. 24S-T80 Alclad.. 24S-O Alclad from Lockheed stock, solution-heat-treated (925°F., water quench) and aged at 375°F. for t0 t % hour. 24S-T8I Alclad.. 24S-T Alclad from Lockheed stock, plant stretched up t0 I per cent and aged t0 ± % hr. at 375°F. 24S-T86 Alclad.. 24S-RT Alclad from Lockheed stock aged 534 ± 34 hr. at 375°F. 6IS-W (bare).... From Lockheed stock. 6IS-T (bare) 6IS-W (bare) from Lockheed stock aged 8 hr. at 350°F. XB7SS-T Alclad. From Lockheed stock.] the first stages of artificial aging the yield stress increases steadily until it reaches a maximum value. In this condition the material is said to be "fully aged." Further exposure results in "overaging," attended by a steady decrease in yield stress. In the production of the artificially aged materials, temperatures and times are selected to achieve full aging. The following important characteristics are associated with the process: I. The higher the temperature, the more rapidly is the fully aged condition attained.

Jan 1, 1945

By M. C. Udy, P. C. Rosenthal

The use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace. The present study presents the results of a systematic survey of the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels. Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. Experimental Work Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. Table i.—Nominal Composition of the Two Base Alloy Steels composition. Per Cent. steel Mn Si Ni Cr Xi-Cr-Mo Wrought 0.28-0.70-0.15-o.45—o.45-0.32 0.90 0.25 0.55 0.55 Cast 0.28-0.70-0.35-0.45-o.45- 0.32 0.90 0.45 0.55 0.55 hln-&lo Wrought 0.28-I .go-o.0.15-0.32 1.70 0.15 Cast o. 28- I.40- 0.35- 0.31 1.70 0.45 a Sulphur was 0.040 per cent maximum and phosphorus 0.030 per cent maximum. Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions was prepared with boron additions in amounts of o.oo15, 0.003, and 0.006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two commercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120. Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel. scrap were used for melting stock. Deoxidation was carried out in the furnace with 0.10 per cent aluminum. The aluminum addition was

Jan 1, 1948

By C. E. Sims

The carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner writhout reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the Product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature For the carbon-oxygen reaction C + O ^ CO this is expressed simply as % C X % O -%co where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1948

By M. C. Udy, P. C. Rosenthal

The use of minute boron additions to steel has been given considerable attention in recent years. Comparisons made between boron-free and boron-containing heats of otherwise identical analysis have indicated, beyond a doubt, the potent effect of boron for increasing hardenability. The actual hardenability increase has been expressed as a multiplying factor, or in terms of the percentage of other alloying elements boron might replace. The present study presents the results of a systematic survey of the use of boron as an addition to two types of alloyed steels and as a replacement for various percentages of molybdenum in these steels. Both cast and wrought steels of the two basic compositions were prepared. Molybdenum, because of its scarcity at the time the investigation was started, was selected as the element to be replaced by boron. Attention was also given to the effects of boron on other properties of the steels, particularly their notched-bar toughness, to investigate other advantages or limitations of this element as an alloy addition. Experimental Work Steels Investigated The two basic compositions used in this survey of boron as a replacement for molybdenum are given in Table I. The cast steels were higher than the wrought steels in silicon content to improve the casting quality. Table i.—Nominal Composition of the Two Base Alloy Steels composition. Per Cent. steel Mn Si Ni Cr Xi-Cr-Mo Wrought 0.28-0.70-0.15-o.45—o.45-0.32 0.90 0.25 0.55 0.55 Cast 0.28-0.70-0.35-0.45-o.45- 0.32 0.90 0.45 0.55 0.55 hln-&lo Wrought 0.28-I .go-o.0.15-0.32 1.70 0.15 Cast o. 28- I.40- 0.35- 0.31 1.70 0.45 a Sulphur was 0.040 per cent maximum and phosphorus 0.030 per cent maximum. Each of these base steels, both cast and wrought, was made with molybdenum contents of o, 0.10, 0.20, 0.30, or 0.40 per cent, the total comprising 20 steels. In addition, each of these 20 compositions was prepared with boron additions in amounts of o.oo15, 0.003, and 0.006 per cent as ferroboron; and in amounts of 0.002 and 0.005 per cent as two commercial intensifier alloys, designated alloys A and B. The boron-treated steels totaled 100, and the entire series 120. Test Procedure Each steel was melted as an individual heat in a 50-lb., magnesia-lined induction furnace. Ingot iron scrap or mixtures of ingot iron and steel. scrap were used for melting stock. Deoxidation was carried out in the furnace with 0.10 per cent aluminum. The aluminum addition was

Jan 1, 1948

By M. L. Holzworth, Joseph C. Kremer, Paul A. Beck, L. J. Demer

FOR alloys which are in practice heat treated to obtain increased strength, such as steels, duralumin, copper-beryllium, and others, the treatment usually involves heating to a relatively high temperature. At such temperatures the grain size of the product is largely determined by grain growth. Even in metals and alloys annealed merely to relieve work hardening, recrystallization is generally followed by a certain amount of grain growth. Thus, effective grain size control, which is often of great practical importance in manufacturing processes, depends on the grain growth behavior of the material used. Despite its importance, grain growth has been the subject of few investigations of a fundamental nature. The term "grain growth" has been used to designate a group of related, but distinctly different, phenomena. The two most important and best known of this group are illustrated by the following example. Curve a in Fig r shows the increase of the average grain size of a copper-beryllium alloy, containing 2 pct Be and 0.15 pct Co, with increasing annealing temperature. The time of annealing was 2 hrs. The grain size was quite uniform in all specimens. The results of a similar experiment with an alloy containing 2 pct Be and 0.31 pct Co are shown by curve b. It is seen that for any annealing temperature below T. the grain size was smaller than in the previous case. Grain growth became slower with the higher Co content. This "inhibiting" effect of the higher Co addition was associated with the appearance in the microstructure of fine, light blue particles of the CoBe phase. Up to temperature T. the structure of the inhibited alloy (curve b) was just as uniform as the structures represented by curve a. However, after annealing at T, or at higher temperatures, the inhibited alloy showed some extremely large grains (much larger than the grain sizes developed by the uninhibited alloy with low Co content) mixed with the small grains according to curve b. The presence of these mixed or "duplex" structures is indicated in Fig 11 by the vertical lines branching off curve b. The type of grain growth occurring in uninhibited Cu-Be alloys (curve a) has has been most frequently and best investigated in brass. This type has been designated as "normal grain growth," while the grain growth phenomena occurring in inhibited materials were, at times, referred to as "abnormal grain growth." However, since the latter term has been applied occasionally to the phenomenon of critical recrystallization, which also results in large grains although by an entirely different mechanism, in the present paper a different nomenclature has been adopted in order to avoid confusion. Typical of the grain growth in uninhibited metals and alloys is the continuous

Jan 1, 1947

By C. H. Mahoney, A. L. Tarr, P. E. Le Grand

Magnesium, it is now generally realized, differs in some important aspects from most other structural metals, not excepting even its close neighbors, the aluminum-base alloys. This is particularly true with respect to the effects of elevated temperatures on the two light metals when in the molten state. Aluminum, 0' the one hand, should not be raised above its melting point any higher than is absolutely necessary if one is to avoid danger of gas absorption and a tendency toward grain growth in the resultant casting.' Magnesium alloys, in sharp contrast, actually benefit by being heated to temperatures considerably above their melting point, It is a commonly accepted practice to establish the desired fine grain in the industrial magnesium alloys of the aluminum-hearing group by raising the temperature of the melt after the refining treatment to some 250°C (482°F.) above the melting range. To recall briefly the typical practice for magnesium alloys, the molten metal is refined by fluxing at about 730°C. (I350°F.), and after the melt has been covered with a suitable flux, the temperature is raised to between 870°C. (I600°F.) and 930°C. (1700°F.). It is then cooled as quickly as possible to the casting temperature. This superheating, as it is called, results in a fine-grained cast metal structure which has superior mechanical properties, enhanced amenability to 'solution heat-treatment, and better machinability than cast metal that has not been superheated. The minimum temperature of superheating varies to some extent with the composition of the alloys to be treated and usually increases with the percentage of magnesium in alloys containing the same constituent metals.' It should be noted that the grain-refining effect of superheating is markedly apparent only in connection with the alloys containing aluminum as an alloying Constituent—the binary alloy containing 1.5 per cent manganese, for example, is not refined in grain to any noticeable extent by a superheating effort. While the phenomenon of superheating is well known in the magnesium industry, the mechanism of the process has remained a mystery During the superheating cycle something occurs that forces a fine grain upon the solidifying metal. The process has been controlled in an empirical manner, and occasionally, especially on large-scale melts, and for no apparent cause, no grain refinement is obtained from a superheating treatment. Only a few papers of importance have been published on the subject. Of these, one of the most helpful is the paper by Achenbach, Nipper and Piwowarski,3 which gives considerable data concerning the effect of superheating on various properties such as fluidity, shrinkage and hot crack

Jan 1, 1945

By R. E. Steiner, A. F. Weinberg, R. J. Van Thyne

Uranium solubility in molten bismuth was determined in the temperature range 350" to 600°C, varying from 0.09 wt pct to near 2 wl pct, respectively. Zirconium and magnesium, simulated fission products, and sodium were found to increase or decrease uranium solubility in bismuth in the temperature range 370° to 420°C, depending upon the addition or temperature. Data were obtained by both chemical analysis of samples obtained by filtration from saturated melts and by measurement of the variation of electrical resistance with temperature. IN a study for the United States Atomic Energy Commission, a Liquid Metal Fuel Reactor Experiment (LMFRE) was proposed in which a solution of uranium dissolved in molten bismuth served as both the fuel solution and the primary coolant. It was proven necessary to add other elements to this solution for certain desirable properties: 1) zirconium acts to prevent reaction of the fuel solution with the graphite core (which would result in the formation of uranium carbide) and also to inhibit mass transfer of iron and chromium from the walls of the reactor tubing to cold spots resulting in blockage; and 2) magnesium acts as a deoxidant and prevents loss of uranium. In addition to these intentional additives, other elements entering the solution are: 1) fission products which are a by-productof reactor operation, 2) sodium (the secondary coolant) through possible small leaks in the heat exchange system, and 3) iron and chromium from the container walls. Each of these elements may affect the solubility of uranium in the fuel solution. Since the concept of this reactor is based upon a liquid solution, the relatively low solubility of uranium in bismuth will dictate the minimum temperature at which the reactor heat exchanger can be operated. The solubility of uranium in liquid bismuth and the effect of some additives on this solubility have pre- viously been investigated1-' (more recent results6" became avaliable after initiation of this investigation). However, some discrepancies between the various results have been noted, and also the cumulative effect of the several additions or impurities was not known. This investigation was commenced to obtain definitive results. MATERIALS Analyses of the materials used are presented in Table I. Although ostensibly of extreme purity (99.999 wt pct), the bismuth was found to contain a significant amount of impurities, probably oxides. Except for determination of the binary system, Bi-U, prior to use all bismuth was hydrogen-refined and

Jan 1, 1962

By E. W. Davis

IF the tonnage of merchantable iron ore remaining in the Lake Superior district is divided by the average of the annual shipments for the past 20 years, it will be found that this ore supply will be exhausted in approximately 35 years. This computed exhaustion period would be an indication of the future activities of the iron-mining industry if it were not for the fact that merchantable ore is being manufactured from low-grade ore, of which there is an almost inexhaustible supply in the Lake Superior district. It is true that at present only the simplest of these low-grade ores are being concentrated to any considerable extent, but progress is being made with the treatment of the more complex ores, and now, in addition to 20 washing plants on the Mesabi Range, three plants are equipped with jigs for the treatment of ore that cannot be concentrated simply by washing. The latest addition to the ore-treating plants of the Mesabi Range is a magnetic roasting and concentration plant at Cooley, Minn., in which ore that cannot be concentrated either by washing or by jigging is roasted to the magnetic state and concentrated on magnetic separators. This plant is beginning its third season of operation, and while it is too soon to make definite predictions, there are strong indica-tions that this new process may make commercially possible the manu-facture of high-grade, merchantable iron ore from large quantities of low-grade ore now considered worthless. After the iron oxide contained in an ore has been converted to mag-netite, almost any desired grade of concentrate can be produced, using magnetic-concentration equipment of the types now in general use for the concentration of the natural magnetites of New York, New Jersey and Pennsylvania. The conversion of hematite (Fe2O3) to magnetite (Fe3O4) is easily accomplished by heating the ore to a dull red tempera-ture in a reducing atmosphere. The reaction is slightly endothermic, and while it requires 200 B.t.u. to heat to 900° F. one pound of hematite ore containing 45 per cent Fe, it requires only 100 B.t.u. to convert the oxide into magnetite. In the laboratory, using small quantities of ore, this conversion is very simple, but large furnaces suitable for commercial

Jan 1, 1936