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By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

THE problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce light-weight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough so that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, particularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating." The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. Commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the purpose of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By Frank S. McKenna, Myron A. Pugacz, Clarence E. Jackson

The notched-bar impact test has proved worth while in certain applications as a test for control of the quality or the heat-treatment of steel. In view of the serious thought that even so simple a test as the tensile test has evoked during the past years, it is not surprising that the notched-bar impact test should have inspired much experimental work. The correlation of the great number of data has not been successful, although steady progress has been made toward a better understanding of this test. Progress has been made, especially, in the isolation of the effects of the many variables that control the results. The stress system imposed on a specimen with a notch is so complicated and unpredictable that no simple evaluation of the test has been possible. Because of this uncertainty, many engineers hesitate to use the notched-bar impact test, and this attitude may well continue until a better understanding of the effects of the variables in the test are available. Without doubt, any additional data that may be presented should be accompanied by as complete a description of the - details of test as possible, so that it may be added to the general fund of information that is to serve as the basis for the theory of the notched-bar impact test. The many factors that may control the test results have been pointed out repeatedly. The importance of the effect of the type and dimensions of the specimen has been recognized. Most of the work reported by American investigators has been limited to small-size (Charpy) specimens tested as a simple beam; two types of notches (Fig. I) have been commonly used. Considerable data have also been presented by many investigators using a small specimen tested as a cantilever beam; this commonly being called the Izod test. Here, however, a shear component of stress makes the stress system even more complex than that present in the simple beam type of test, hence a critical analysis is difficult. Much work has also been reported by investigators using the tension type of specimen. A second variable that must be controlled is the testing temperature. An indication that the tests were performed at room temperature is not sufficient, since in many steels a variation of a few degrees in the actual testing temperature may be sufficient to give an entirely different range of results. Other factors, such as the composition and condition of the material being tested and the speed of test, should also be considered. Many investigators have contributed data and theoretical discussions on the problems encountered in notched-bar test-

Jan 1, 1944

By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By Per Anders Eidem, Merete Tangstad, Jens Davidsen

"During excavations of submerged arc furnaces producing silicomanganese, silicon carbide (SiC) has been found. Contributing to the size of the inactive area of the furnace, the active area of the furnace where reactions occur will decrease, thus reducing the potential for pre-reduction in the furnace.This work studied the formation of SiC from the liquid-solid reaction between slag, metal, and metallurgical coke. Slags and metals with different levels of silica (S1O2) and silicon (Si) have been studied. The slag and metal has been heated together with coke, and the samples investigated by microprobe. The results show that SiC was formed on the coke particle through reactions with both slag and metal. For the metal, the carbon most likely diffused through the SiC to react with Si in the alloy. SiC formation with slag is likely to go through the reduction of Si02 to Si.IntroductionToday, Silicomanganese (SiMn) is produced in submerged arc furnaces (SAF) by reduction of S1O2 and manganese oxides, mainly with metallurgical cokes. Typically, the tapped metal has a silicon content of 17 - 20 wt.%. To achieve higher levels of Si, the metal can be refined by adding off-grade silicon metal, yielding low carbon SiMn. [1]. What is believed to be SiC that has been found during dig-outs of SiMn furnaces producing high silicon alloy. It is possible that excess amounts of SiC in the furnace cause operational problems, since SiC will occupy furnace volume. As SiC accumulates, the active volume of the furnace will decrease, increasing the flow of material and gas in the active areas of the furnace. Formation of SiC is inevitable, so it is desired to keep the formation as low as possible. To be able to control the formation of SiC, one has to understand the basic mechanisms."

Jan 1, 2012

By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Gust Bitsianes, Joseph H. M. Beaty

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By A. V. Deforest, C. W. Macgregor, A. R. Anderson

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By Thomas A. Read

THE internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of l00 when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose-that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals will be presented. EXPERIMENTAL PROCEDURE The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrement A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were .made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders ¼ in. in diameter and 1 ½ to 2 ½ in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is ¼ in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Marie L. V. Gayler

WITHOUT diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange-e.g., of diffusion-is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult-if possible to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, ßFeSi is formed in the solid as the result of the reaction aFeSi + Al?ß FeSi. The particles of aFeSi become sur¬rounded with a reaction ring of ßßFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of ßFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By A. V. Deforest, A. R. Anderson, C. W. MacGregor

One of the important problems in the design of structures and machine parts subjected to rapidly applied loads is the determination of the strength and ductility of the material itself under such conditions. Realizing the need for such information, many investigations have been carried out in the past. Most of these experiments have been made using notched bars in bending either with the Charpy or Izod impact machine. While yielding valuable data on the effect of notches in the energy absorption of the material and on the condition of heat-treatment, this form of test does not lend itself readily to a determination of fundamental stress-strain relations. For this and other reasons, more attention has been paid recently to the tension impact test. An extensive literature already exists on the subject and only those investigations somewhat closely related to the present paper will be mentioned. For a more comprehensive list, the reader is referred to the Symposium on Impact Testing or the A.S.T.M., 1938. The work of Mann.' Clark and Dätwyler,2 Nádai and Manjoine,3 Winlock and Leiter,4 Deutler,5 and Brinkmann,6 however, deserves especial mention. In most of the previous investigations on the subject, when stress-strain relations were obtained under high rates of loading, it was the common procedure to determine stresses based on the original area and strains based on the original length. Stress-strain curves were then constructed by P ALo plotting So = 1/A0 as a function of eo = ALr,o where A0 and Lo refer to the original area and gauge length, respectively. At present there exists a paucity of true stress-strain data in the impact problem. The advantages of constructing so-called true stress-strain curves in order to reveal the fundamental physical properties of the material for the tension test were discussed recently by one of the authors.7'8 It was shown that the true physical behavior of the material in the tension test could best be represented P by plotting the average true stress, S = 2P as a function of 6 = q' = log —r = log ~9L where P, A, L, S, E, and q' refer to the load, the cross-sectioned area while the load P is applied, the actual gauge length, the average true stress, the true strain and true reduction in area, respectively. Besides giving a better physical representation, the method has certain additional advantages in that the stress-strain curve so plotted becomes a straight line from the maximin load point to fracture. The construction of such curves, however, while comparatively simple for the slow rates of loading customarily used in the tension test, presents certain dificulties for tensile impact in that both loads and diameters are required throughout the test. The continuous measurement of test-piece diameters to fracture under impact conditions offers considerable experimental difficulty. In order to make it feasible to

Jan 1, 1942

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Huey-Lin Luo, T. R. Anantharaman, William Klement

Two new metastable phases have been obtained in Au-Ge alloys by rapid cooling from the melt. One is of the hep structure with near-ideal axial ratio and may be considered a Hume-Rothery phase. The other has a complex tetragonal structure (a = 11.627Å and c = 22.191Å for the Au60Ge40 alloy) and may be looked upon as a superlattice made up of forty-four fee unit cells. Alloys with the tetragonal phase are charactevized by marked preferred orientation. The metastable constitution of the Au-Ge alloys is discussed with reference to the rate of cooling from the melt. THE Au-Ge equilibrium diagram features a rather deep eutectic near 27 at. pet Ge with a maximum solid solubility of 3.2 at. pet Ge in gold and is similar to the Ag-Ge, Ag-Si, and Au-Si diagrams.' The present study of the effects of rapid cooling from the melt on the structure of Au-Ge alloys constitutes an extension of similar investigations2-8 in this laboratory on alloys of noble metals with germanium and silicon. Nonequilibrium hep structures have so far been obtained by quenching Ag-Ge2, 3 and Ag-Si4, 5 alloys from the melt; an Au-Si alloy of approximately eutectic composition has been found6 to solidify in a noncrystalline state. EXPERIMENTAL PROCEDURES Twenty-nine alloys prepared from gold of 99.9+ pet and germaium of 99.999 + pet purity were investigated. The method of alloy preparation, the technique of rapid quenching from the melt, and the X-ray diffraction procedures were similar to those described previously.3, 4 Essentially, small sections (-20 mg) of thin alloy rods (-1 mm diam) were rapidly heated up to 1200°C in a graphite crucible under argon and the liquid alloy ejected by a helium blast onto a polished copper strip held on the inner periphery of a rotating wheel. The resulting thin foils were examined with or without the copper substrate in a G.E. X-ray Diffractometer or in a 114.6-cm-diam Debye-Scherrer camera. RESULTS Table I gives the constitution of liquid-quenched Au-Ge alloys, as estimated from intensities of X-ray reflections from the corresponding phases, viz., a (fee solid solution), ß (hep phase), ? (tetragonal phase), and diamond-cubic (dc) germanium. Despite unavoidable variations in the quenching rates, the proportions of the phases in different alloys were generally reproducible and stable at room temperature. There was no evidence of quenching strain, since the a doublets were well-resolved in high-angle Debye-Scherrer reflections in all cases except where stacking faults in the a fee and ß hep structures contributed to X-ray line broadening. The ß and ? metastable phases showed signs of decomposition to the equilibrium a phase and germanium only after a few hours annealing above 100°C. A few alloys around the eutectic composi-

Jan 1, 1965

By David W. Mitchell

WHILE pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superheating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is miscible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetallic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck' states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones6 who studied the physical properties of low iron magnesium alloys observed a

Jan 1, 1948

By Thomas A. Read

The internal friction of single crystals of metals is affected markedly by a variety of factors, which, according to the literature, are without influence on the internal friction of polycrystalline metals at strain amplitudes less than 10-5. For example, the internal friction of a suitably oriented zinc single crystal is multiplied by a factor of ioo when the vibration amplitude is slightly increased, and the internal friction of a copper crystal is markedly increased by the application of a stress of 30 lb. per sq. in. for one minute. In this paper it will be shown that these, together with the other phenomena associated with the damping of mechanical vibrations in metal single crystals, can be satisfactorily explained, at least qualitatively, in terms of an atomic mechanism that has been proposed for quite another purpose—that of accounting for slip in metals. The extraordinary agreement between the observed behavior of the metal single crystals and the behavior that could be predicted on the basis of this atomic mechanism leads to the belief that the latter is probably essentially correct. If this is so, it follows that valuable information about the slip process in metals may be gained from measurements of internal friction on single crystals. In this paper the results of the only study to date on the damping of mechanical vibrations in single crystals of metals mill be presented. Experimental Procedure The internal friction of a material is a measure of the rate at which the energy of mechanical vibrations is converted into heat. The measure of internal friction used in the present paper is the decrcment A, which is defined as the fraction of the energy of vibration lost per half cycle. The measurements described here were made for longitudinal oscillations at a frequency of 33.5 kc. for the copper crystals, and at a frequency of 39 kc. for the zinc crystals. The method used is that of the composite piezoelectric oscillator. The single-crystal specimens are in the form of circular cylinders M in. in diameter and I 1/2 to 21/2 in. long. The crystal rods are waxed in a V-block and sawed to the proper length with a fine jeweler's saw. The ends of the specimen are ground flat, and one end is cemented with a very thin film of beeswax and rosin to the end of an x-cut quartz rod which is 1/4 in. in diameter and 3 in. long. The length of the specimen rod is determined by the condition that its natural frequency for longitudinal vibration be the same as that of the quartz rod, within 0.5 per cent. The lengths of the specimens are thus different for different orientations of the cylinder axis with respect to the crystallographic axes. When the specimen and quartz rods are thus matched in frequency the adhesive is at a node of stress, and it has been shown experimentally that under these circumstances

Jan 1, 1941

By Joseph H. M. Beaty, Gust Bitsianes

Successful blast-furnace operation depends upon securing an optimum balance between a number of important variables. This balance will vary somewhat from furnace to furnace in the same plant and with raw materials available in different plants. It is difficult to isolate the effect of any one variable unless it has a rather pronounced effect upon the efficiency of operation. The physical properties of iron ore and coke are known to affect the process, yet it is difficult to set up any definite yardstick by which these differences can be appraised. In recent years, whenever practicable, operators have taken steps to obtain better control over the absolute size and uniformity of size of the ore and coke. The size and physical character of the stone, however, have received comparatively little attention, emphasis being placed upon chemical composition, fluxing efficiency, and action as a desulphurizing agent. Since the stone occupies only about 10 per cent of the volume of the stock column, its influence upon permeability is less than that of the ore and the coke. The large pieces now used have a tendency to roll to the center and thus increase the permeability of this part of the stock column. Smaller pieces would be more effective in promoting the permeability of denser portions of the stock. The size and physical properties of blastfurnace stone are important also for reasons best understood by considering the results obtained by the crushing and the sizing of iron ore. Crushing ore to about 2 in. at Provo, Utah, and to about I in. in Alabama produced material somewhat less permeable to gases, even though sized. In spite of some sacrifice in permeability, the efficiency of the process was improved by crushing and sizing the ore, as indicated by a substantial saving in fuel and increased output. This saving in fuel is due in large measure to more thorough reduction of ore in the upper part of the furnace and to a corresponding decrease in the amount of carbon consumed prematurely above the tuyeres by the reaction CO2 + C = 2CO - 70,080 B.t.u. [I] The physical properties of stone, its size and rate of calcination are important because they influence the rate at which CO2 is released and the completeness of calcination before reaching a level in the furnace where the temperature does not exceed 1050°C. (1920°F.). Briefly, carbon dioxide from the limestone or from the reduction of ore may cause premature corn bustion of carbon above the tuyeres. Assuming that 1000 Ib. of limestone is used per ton of pig iron, about 435 Ib. of CO2 will be liberated during calcination of a good grade of stone. If all this CO2 from the stone were to oxidize carbon prematurely, about 120 lb, would be consumed above the tuyeres in a heat-absorbing reaction. The amount of carbon thus consumed when a

Jan 1, 1943

By Nelson Severinghaus

Mineral fillers have been defined as inert materials that are included in a composition for some useful purpose. Because this definition and the scope of this review are not specific-indeed, exceptions abound-accurate total statistics are unavailable. One source estimates the total production in the United States in 1979 at 11.3 Mt (12.5 million st) valued at $534 million, averaging $49.19 per ton. Included are a broad group of minerals-asbestos, barite, bentonite, ground limestone and dolomite, clays, diatomite, feldspar, micas, silica, talc. Additional references will be made to synthetic mineral-derived fillers such as aluminum hydrate, precipitated calcium carbonate, and pyrogenic and precipitated silicas and silicates. A section on related uses at the end of this chapter covers absorbents and filters. Mineral fillers can be included in compounds to accomplish a variety of final results. Hardness, brittleness, impact strength, compressive strength, softening point, fire resistance, surface texture, electrical conductivity, and a host of other physical characteristics may be modified by the inclusion of fillers. These effects are the result of properties of the fillers, including chemical activity, hardness, particle size, shape and distribution, surface structure, color, density, and refractive index. To facilitate an overview of the mineral filler industry, this chapter will review the general usage of fillers, the inherent characteristics that intensify their utilization, and similarly their manufactured characteristics. Major using industries will then be examined in detail. Specific information on deposits and processing for industrial minerals will be found in the appropriate commodity chapter. All of these same minerals have additional significant uses based on their chemical composition or other characteristics. References will be found in other use chapters and summarized in commodity chapters. The chart in Table 1, updated from the 4th edition of Industrial Minerals and Rocks, illustrates the major mineral fillers (both natural and manufactured) and their more important end uses. Use of Mineral Fillers Archaeologists have found that more than 5000 years ago, bitumen used for mortar and waterproofing contained mineral contaminants that acted as fillers. Since that time man has added mineral products to compounds to improve certain characteristics. Perhaps the most common objective of filler usage is reduction of cost of the end product. Certainly the inclusion of a filler that costs 2¢ per 0.45 kg (lb) will reduce the cost of a plastic product whose resin costs 50¢ per 0.45 kg (lb). But the decision to use a specific filler is not that simple. It may "soak up" binder, making a compound more viscous and perhaps preventing its flow into a mold as an injection molding compound, but similarly will give good anti-sag characteristics to putty, caulking compound, or undercoating. Fillers may be incorporated to modify: 1) Cost 2) Physical characteristics 3) Flow characteristics 4) Fire resistance 5) Density 6) Heat conductivity 7) Color or brightness and opacity 8) Hardness, brittleness, impact strength 9) Deformity, viscosity, softening point 10) Processing problems 11) Electrical conductivity 12) Surface texture 13) Thermal expansion characteristics 14) Abrasion resistance

Jan 1, 1983

By A. J. Phillips, C. G. Grant, Wm. B. Price

Admiralty nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Wm. B. Price' described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.~ A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm. Gallimorr & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four binary copper-nickel alloys of the compositions shown in Table 1. Various a~ilounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by iiielting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of thcsc castings was polished and etched for examination. The castings were not homogenrous solid solutions, but showed the usual cored structure associated with cast alloys. Howcvrr, frorn an exarrlination of these sections we roughly determined

By W. R. Shimer, F. O. Kichline

The investigation herein described was carried out for the purpose of studying, both by chemical and metallographical means, the extent of over-oxidation of steel that can be accomplished by excessive overblowing in a Bessemer converter. 111 addition there are appended some results of basic open-hearth and crucible steels. Remarks on Chemical Methods. The test block used was hemispherical in shape, 4.5 in. in diameter and 2 in. thick. Drillings for analysis were obtained by drilling through the entire solid part of the block, carefully avoiding all cracks and blow-holes and mixing these drillings thoroughly. Drillinga were carefully examined for scale and the finest were gone over with a microscope to be sure all scale from whatever source had been removed. Oxygen was determined by the well-known method of Ledebur, modified according to Cushman,1 with, however, the removal of the preheating tube, which was found unnecessary. This method has been found to give concordant results. Blanks run from 0.0003 to 0.0006 g. Duplicate determinations varied not more than 0.001 to 0.003 per cent. It seems to be generally supposed that the hydrogen method gives only that oxygen which is combined with iron. Whether this be true or not, the content of oxygen existing as iron oxide no doubt predominates sufficiently, so that the result obtained is sufficient to indicate whether the steel is over-oxidized or not. We are well aware that the oxides of manganese and chromium, when existing alone, are not reduced by hydrogen at a red heat. To learn of their action in steel the following work was carried out: A sample of ferro-manganese and of ferro-chrome were each exposed

Jan 1, 1914