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By B. M. Larsen, L. S. Darken

Some years ago we collated all laboratory data then available to us on the distribution at equilibrium of manganese and of sulphur between metal and simple slags, and used the results in setting up an equation, which proved to be in accord with determinations of the distribution ratio of manganese and of sulphur between liquid steel and open-hearth slag, over a wide range of operating conditions. We now present an outline of our calculations and inferences on these two closely related questions, which are of especial importance because of the advisability of conserving manganese wherever possible. In general, our results show that in the open-hearth furnace equilibrium between metal and slag, with respect to both manganese and sulphur, is substantially attained during the finishing period of the heat, or in about a half hour to an hour after any additions were made. This implies that the end result will be identical whether manganese is added as alloy or metal to the liquid steel or as oxide to the slag. The proportion of total manganese retained by the steel is favored: (I) by use of the minimum amount of lime, consistent with other operating limitations, required to give a lime-silica ratio of about 2.4, which usually corresponds to a minimum practical slag volume; (2) by a high concentration in the slag of MnO relative to FeO; (3) by high operating temperature. Absorption of sulphur by the slag from the liquid metal is favored: (I) by large slag volume; (2) by a high concentration of active (or "free") lime and of manganese oxide dissolved in the slag; (3) by low concentration of silica, iron oxide, and phosphate dissolved in the slag. Distribution 02 Manganese between Slag and Metal at Equilibrium On the basis that the distribution of manganese between liquid steel and slag is controlled by the reaction FeO + Mn -& MnO + Fe [A] slag metal slag metal the distribution at equilibrium, at a given temperature, is expressed by the equilibrium constant for this reaction, which is defined as K,, _ aMnO' afe aFeO ' aMn where a is the activity of the molecular species denoted by the subscript. The activity of each of the several components, although it is not known precisely, is approximately equal to the concentration of each component expressed as its mol fraction; that is, as the ratio of the number of mols of the given component to the total number of mols of all the molecular species present in the metal or slag, as the case may be. Moreover, since the activity, or concentration, of iron in the liquid metal is in fact substantially constant, the term afe may be combined with K" to give a new constant K'. Making these changes, 7

Jan 1, 1942

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By R. W. Gurry

Thermodynamic calculations indicate that boron is a better deoxidizer than silicon but probably is not quite as effective as aluminum. Boron should, therefore, be readily oxidized out of the open-hearth bath, which implies that it is not recovered in significant concentration from any scrap charged; also that, if added in the ladle, it tends to oxidize out during teeming unless protected by the presence of a better deoxidizing agent. These conclusions do not apply to liquid cast iron, in which the oxygen content is much lower than in liquid steel. The possibility of conserving certain strategic alloying elements widely used in steelmaking, notably manganese, chromium and molybdenum, by the use of boron, which in small concentration appears to be extraordinarily effective in promoting hardenability, raises a question as to what extent any boron present in the scrap charged into the open hearth is oxidized out during melting and subsequent refining. This question is significant because the optimum concentration of boron in the finished steel, which is fairly critical, would be very difficult to attain if the boron in the charge were largely retained in the metal. Moreover, unless boron is substantially eliminated in the open-hearth process its use on a large scale would eventually make it impossible to produce boron-free steel except by restricting the charge to virgin material. There is at present, unfortunately, virtually no satisfactory direct evidence to provide an answer to this question; but there are indications from practice that boron is oxidized out in the open hearth in the production of medium or low-carbon steel, although it may be retained if the carbon content remains fairly high; that is, if the oxygen is kept fairly low. In the absence of direct data, it is necessary to rely upon the indications of indirect evidence, the best approach now available being a thermodynamic calculation of the deoxidizing power of boron in liquid steel by the general method used so successfully by Chipman1 in his study of the reactions in the open-hearth process. The thermal data for boron, upon which such a calculation must be based, are reasonably satisfactory; the only quantities not directly determined are the entropy of melting of boron, the activity coefficient of boron in liquid steel, and the activity coefficient of B2O3in an open-hearth slag; but these values may be estimated with ample accuracy. The results of this calculation, which is presented later, are given in Table I, together with corresponding data for other deoxidizing elements. This table shows the calculated residual content of oxygen in equilibrium with different residual concentrations of the deoxidizer in the metal;

Jan 1, 1944

By J. W. Spretnak, G. Sachs

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By G. Sachs, J. W. Spretnak

The: iron-rich iron-nickel alloys have attracted considerable academic interest in recent years. The carbon-free alloys are of minor practical importance, but they are the base of many alloys with various outstanding properties. The iron-nickel alloys, therefore, have been investigated extensively regarding both their structures and their properties. The researches on these alloys up to 1938 have been collected and critically reviewed by J. S. Marsh,l and will be discussed in some detail in the sections of this paper dealing with specific subjects. These numerous investigations have not succeeded in establishing the equilibrium conditions in this system. Alloys containing more than a certain amount of nickel (8 to 10 per cent Ni) undergo the allotropic transformation extremely sluggishly, both on heating and cooling, showing a large hysteresis," which is not dependent upon the rate of cooling and persists even with very slow rates of cooling.3 Honda4 and Merica4 have therefore resigned themselves to proposing a diagram (Fig. I) for practical use, illustrating the structural relations under commercial conditions instead of attempting to establish the true equilibrium diagram. Marsh is less pessimistic and suggests an equilibrium diagram (Fig. 2) which conforms approximately to the facts known about this system. Recent X-ray investigations by Owen-Sully5 and Bradley-Gold-schmidt6 on powdered alloys indicate that the previous work on the iron-nickel system yielded very incomplete results. These investigators agree (Figs. 3 and ,+) that alloys in the powdered form containing more than 8 per cent and up to about 35 per cent Ni decompose into a stable heterogeneous mix-

Jan 1, 1941

By J. H. Nead, T. S. Washburn

The grades of commercial steel produced in large quantities can be divided into two general types from the standpoint of ingot structure— killed and rimmed. Killed steel covers a wide variety with carbon contents throughout the range of the steel portion of the iron-carbon diagram, and is the kind usually used in the production of alloy steels. Rimmed steel is normally associated with carbon ranges under 0.30 per cent, and is not yet used to a large extent in alloy practice, except for copper-bearing steels. The fundamental differences in the ingots made from these two types of steel can be seen most easily in Figs. 1 to 7. In the rimmed ingot shown in Figs. 5 to 7 there are two lines of blowholes approximately parallel to the sides and coming together at the top and at the bottom of the ingot. In the killed ingots shown in Figs. 1 to 4 these blowholes arc not present. Also, the rimmed ingot has no well defined pipe, as compared to the deep pipe on the killed ingots, and there are numerous primary blowholes in the lower portion of the rimmed ingot perpendicular to the surface and close to it, while on the killed ingot there are no blowholes of this type in the ingot shown in Fig. 1 and very small ones close to the surface in the lower part of the ingot shown in Figs. 2 to 4. With respect to the presence of pipe and the primary blowholes, the structure may vary considerably in both rimmed and killed ingots, therefore these cannot be considered as fundamental structural characteristics differentiating the two types of steel. The primary blowholes in rimmed ingots may be much less pronounced than those in the ingot shown in Figs. 5 to 7—as, for example, in "ingot iron," which is entirely free from them. An example of a cross section of an ingot-iron ingot is shown on page 16 of "Research and Methods of Analysis of Iron and Steel," published by the American Rolling Mill Co. (1920). A certain amount of pipe may also occur in rimmed ingots, though it is normally porous and not as well defined [or deep as in the killed ingot of Fig. 1. In killed ingots, primary blowholes may occur near the surface, as in Figs. 2 to 4, and

Jan 1, 1937

By John Howe Hall

One's first thought, upon being chosen to deliver the Henry Mario Howe lecture, is of pride at being selected for this post of honor, but ther succeeds immediately a deep sense of the Obligation thereby incurre to give of one's very best in order to make a contribution worthy of hir in whose memory these lectures are given. One who had the goo fortune to be associated with Henry ill. Howe, upon sitting down t prepare such a paper as this, irnrnediately falls to musing upon thc day when his face and his footfall were familiar from constant association, an recalls with singular vividness his active figure, his mobile, alert face, an his keenness in penetrating to thc corc of the subject under discussior Like Dr. Mathews, I was a young man when I first worked under hi direction, now nearly a quarter of a century ago, and in those early day he oft,en seemed a hard taskmaster—a man whose standards it woul never be possible for me to meet. I well recall his insisting upon m proving for the third time the truth of a conclusion which I had brc unwilling to submit to him until it had been confirmed by two carefull planned experiments. To my impatient protest that thc third .demor stration he asked for was but a repetition of the second, with differer samples, he replied, "Yes, that is true, but the inherent improbability ( your conclusions is so evident that I can not accept them until you prov your case again." "Shall I ever do a thing well enough to suit him? I thought. Looking back today upon many similar incidents, 1 suspect that h never expected me to attain the excellence he preached, and held up t me and to himself as a model, but knew out of the fullness of his experienc. that in no other way could he so impress upon me the necessity in researc of the patient, never-failing attention to detail and to accuracy tha distinguished his own work. How painstaking he was in the preparation of his many books an professional papers, as well as in his experimcntal work, was ncvcr s

Jan 1, 1929

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By N. P. Goss

Asterism appearing in X-ray Laue diagrams is an extremely sensitive index of changes in the internal structures of individual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.l-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not conclusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made between mosaic and distorted grain structures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example: has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-l4 to 10-l5 c.c., or 10-15 cm. in size. These crystallites, or blocks, appear to survive the most drastic cold-working, for it has been shown, and more elaborately by Wood's recent work," that cold-working cannot reduce the size of these crystallites smaller than of the order 10-5 cm. The interesting correlation brought out by the experiments of Goetz and Wood is that the block size after severe cold-working is of the same order of magnitude as the groups that formed in the metal just before crystallizing from the molten state. The work of Ewald and Rennenger17 and the now classical experiments of Darwin and James12,13 all strongly suggest the existence of a periodic structure of crystal. lites smaller than the grain itself. Related to this effect is the appearance of veinlike markings in the microstructures. Ammer-man and Kornfeld,16 in their experiments, did not observe any evidence of veining in specimens of alpha iron annealed below A3 and believed that veining was not due to impurities in the iron, as Northcott16 suggested; veining was observed by them only in specimens annealed above A3. Hanemann,16 Schrader and Tangerding found that annealing in hydrogen did not diminish veining and so it could not be caused by oxides. They concluded that veining was due to a slight difference in the orientation of ferrite lattice blocks. This viewpoint is well supported by the evidence presented here.

Jan 1, 1941

By H. S. Martin

Although it was known some years ago at the Utah Copper Co. mills that fine grinding improved flotation recoveries, no accurate data were available until recently as to just how far the grinding could be carried economically. In 1923 the ultimate degree of fineness for flotation feed was supposed to be about 10 per cent. on 65 mesh, with approximately 55 per cent. through 200 mesh, which meant that most of the mineral would pass 100 mesh. At this time Garfield and Wilfley tables were used ahead of flotation and a good deal of the coarse mineral removed prior to the ball mill regrind. Shortly afterwards, mill-scale tests developed the fact that on a feed containing not over 10 per cent. +65-mesh material flotation alone would give a copper recovery equal to that obtained by the combination of tables and flotation, but that on much coarser feed the recovery with flotation alone was lowered. This was at a time when all the sulfide minerals were floated if possible, so that the only requisite was to grind fine enough to free the mineral from gangue. Earliest Use of Microscopic Examination of Tailings As early as 1921, the writer had attempted to determine by chemical analysis the relative proportions of copper minerals in tailings from an ore that made extremely poor flotation results. Chemical analysis was not satisfactory or conclusive, and samples of these tailings were sent to the U. S. Bureau of Mines Station at the University of Utah for microscopic examination. The question at that time was to determine, if possible, which copper minerals had been lost and why, but R. E. Head, in his report, revealed other interesting data. He said in part: Briefly stated, the mineral partieles or grains may be classified into scparate groups as follows: 1. Free grains of pyrite, chalcopyrite, chalcocite and bornite, respectively, which contain 110 other included sulfides; 2. Grains in which all three of the copper sulfides are representel (the core may be of chalcopyrite, partially altered to boruite, these two minerals being cntirely surrounded by a shell of chalcocite); 3. Grains composed of equal amounts of bornite and chalcocite or chalcopyrite and chalcocite. The grains of free mineral particles are perhaps the most numerous, taking the ore as a whole, but it is noticeable that of the grains of combined or associated sulfides

Jan 1, 1930

By Arthur S. Coffinberry, Ralph Hultgren

We have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, combined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atoms, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electron-to-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such information is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938

By Arthur S. Coffinberry, Ralph Hultgren

We have studied the gold-aluminum system by X-ray diffraction and by the microscope over the entire range of composition for temperatures between 300° and 500° C. Results obtained are shown in Fig. 1, combined with the work of Heycock and Neville1 at higher temperatures. The diagram differs in important details from that given by Hansen2 in his critical compilation of the literature of binary alloy systems. This work was undertaken both because of the intrinsic value of a knowledge of the phase diagram of this system and because of the need of theoretical metallurgy for precise and accurate data, particularly X-ray diffraction data. Systematic studies of equilibrium diagrams, particularly by Hume-Rothery,3 have shown regularities that yield a certain insight into the nature of alloying forces. It has been shown, for example, that solid solubility depends on the concentration of free electrons in the alloy, on the relative radii of solvent and solute atoms, on the forces of attraction between atoms, and on the relative stability of intermediate phases. The well-known Hume-Rothery rule states that the crystal structures and compositions of many intermediate phases depend on the electron-to-atom ratio. This has been confirmed and extended by wave mechanical calculations.4 A knowledge of the forces between atoms in alloys, even an imperfectly developed empirical one, should be a valuable guide in the preparation of technological alloys of desirable properties. Furthermore, such information is basic in such problems as rate of diffusion, age-hardening, phase transformations, and others. The most valuable data for this purpose are furnished by X-ray diffraction studies. Unfortunately, work has been

Jan 1, 1938

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By R. C. Ku, A. J. McEvily, T. L. Johnston

The microplastic response of a series ofas-quenched Fe-Ni-C martensites has been measured at 77°K. At strains less than JO'3 the flow stress is governed primarily by the transformation-induced dislocation structure of the martensite. Only at strains in excess of 10-3 is the influence of carbon manifested in the flow stress. At these macroscopic strains, typically 10-2, the solid-solution hardening is proportional to (wt pct C)1/3, and, in an alloy containing 0.39 wt pct C, amounts to 50 pct of the flow stress. THE technological significance of high-strength ferrous martensite has stimulated many investigations of its structure and properties. Although our knowledge of the characteristics of martensite has increased immensely, especially with the advent of high-resolution techniques, an understanding of the basic strengthening mechanism still remains elusive. The purpose of the present paper is to consider certain aspects of micro-plastic behavior of Fe-Ni-C martensite which we feel can help to resolve this important problem. Such alloys are particularly suitable for experimental investigation because their compositions can be adjusted to reduce the M, to a temperature low enough essentially to eliminate the diffusion of carbon in the freshly formed martensite.1 The mechanical properties in this condition are of interest inasmuch as they reflect a state that is free of the important but complicating influence of precipitation processes. In this virgin martensite the carbon is distributed as it was inherited from the parent austenite; i.e., it is present interstitially, and gives rise to tetragonality through strain-induced ordering.' In order to determine the source of strength of such alloys, Winchell and Cohen1 investigated the low-temperature macroscopic stress-strain behavior of a series of virgin martensites of increasing carbon content but of common M, temperature (-35°C). They found that the flow stress increased rapidly with carbon content up to 0.4 wt pct; beyond this point the flow stress increased at a much slower rate. It was concluded that martensite is inherently strong. To account quantitatively for the strength of virgin or as- quenched martensite in terms of the role of carbon, Winchell and cohen3 suggested that the carbon atoms, trapped in their original positions by the diffusionless martensite transformation, interfere with dislocation motion according to a model akin to that of Mott and Nabarro. 4 In this treatment, individual carbon atoms are considered to constitute centers of elastic strain and thereby generate an average stress resisting the motion of dislocations throughout the lattice. The additional stress necessary to move dislocations, over and above that necessary for motion in a carbon-free martensite, is given by where L is an effective length of dislocation capable of motion. L was assumed to be limited to the spacing between the twins that are an essential structural element of Fe-Ni-C martensites. They assumtd the spacing to be invariant and of the order of 100A. However, recent work5 has shown that L is variable and can be in excess of 1000Å, so that the assignment of an appropriate value of L is not straightforward. In contrast to the above conclusion that there is an intrinsically high resistance to plastic flow, it has been suggested by Polakowski6 that freshly quenched martensite is in fact "soft" in the sense that dislocations are initially free to move upon application of stress. The high indentation hardness and macroscopic yield stress of ferrous martensites are then a consequence of rapid strain hardening that depends upon carbon in solution. Consistent with this point of view are the results of Beau lieu and Dubé who measured the rate of recovery of internal friction as a function of aging (tempering) temperature in a freshly quenched steel containing 0.90 wt pct C, 0.37 wt pct Mn, 0.1 wt pct Cr, and 0.07 wt pct Ni. The kinetics were clearly consistent with the idea that many dislocations are unpinned in the as-quenched state and that during aging they become progressively pinned by carbon at a rate controlled by carbon diffusion in the body-centered martensite lattice. In order to provide a basis upon which to distinguish between the "hard" and "soft" interpretations indicated above, we have made studies of the initial stages of plastic deformation in Fe-Ni-C martensites similar to those'used by Winchell and Cohen. It will be shown that the results support the contention that dislocation segments in as-quenched material are indeed

Jan 1, 1967

By J. A. Scott, F. R. Hensel

The paper deals with the investigation of two types of coreless induction furnaces, one of 60 cycles, the other of 5000 cycles. Nickel was used as test material and the absorption of oxygen by molten nickel was chosen for determining the influence of the frequency on the metallurgical characteristics of the furnaces. Dr. Herty's aluminum method, slightly modified, was found suitable for determining the nickel oxide content in nickel. Also an electrolytic method for determining alumina in nickel was worked out. The solubility-temperature relations for nickel oxide in molten nickel were determined approximately. It was found that the solubility of nickel oxide increases with the temperature. Comparative tests on the rate of oxygen absorption made in a 60 and a 5000-cycle furnace showed that the absorption of nickel oxide in nickel is an increasing function of turbulence, time and temperature. The rate of oxygen pickup in the 60-cycle furnace is about three times as great as in the 5000-cycle furnace. In the 60-cycle furnace the maximum oxygen content of the melt comes close to the saturation limit. Melting under an oxygen-free atmosphere prevents oxidation in both types of furnaces. DISCUSSION (Iloward Scott presiding) H. Scott, East Pittsburgh, Pa.—When Professor Desch was in Pittsburgh recently he mentioned that the induction furnace has practically replaced the crucible furnace in Sheffield except for the carbon tool steels. Dr. Hensel is to be congratulated on the development of analytical methods for determining inclusions and for getting two different methods to agree. F. R. Hesnsel—Recently the purification of molten metals with hydrogen or other suitable gases has become an important issue and a number of patents have been taken out covering gaseous treatments of molten metals. In this connection I wish to call

Jan 1, 1933

By P. Beardmore, B. W. Howlett, B. D. Lichter, M. B. Bever

The heats of formation at 273°K of the compounds Mg2Ge, Mg2sn, and Mg2b, the heats of fusion and melting points of Mg2Sn and Mg2Pb, and the heats of solution of magnesium, germanium, and lead in liquid tin have been measured. The excess free energies of the liquid alloys and the free energies of formation of magnesium-Group IVB compounds at their melting points and their standard free energies of formation at 298°K have been calculated. The stability and bonding of the compounds are discussed with reference to these properties. Some thermodynatnic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. THE compounds of magnesium with the Group TVB elements, silicon, germanium, tin, and lead, have often been considered to constitute a nearly ideal homologous series. In particular, their thermodynamic stability has been assumed to decrease with increasing atomic number of the Group IVB element.' The binary-phase diagrams of the magnesium-Group IVB elements given by Hansen and Anderko2 have the same form. Each system has a single con-gruently melting compound of limited homogeneity range. The structures of these compounds, which have the formula Mg2X, are anti-isomorphous with the calcium fluoride structure. A recent investigation has found evidence of a second compound in the system Mg-Pb.3 The solid compounds Mg2Si, Mg2Ge, and Mg,Sn are semiconductors, while the conductivity of Mg2Pb approaches that of a metallic conductor. This difference suggests that other properties may also show a discontinuity. The investigation reported here is concerned with the thermodynamic properties of magnesium-IVB compounds and particularly their variations with the period of the Group IVB element. The heats of formation at 273°K of the compounds MgzGe, Mg2Sn, and Mg2Pb and the heats of fusion and melting points of Mg2Sn and Mg2Pb have been measured. The results, combined with published data, are interpreted in relation to the stability and the bonding characteristics of the compounds. Some thermodynamic aspects of the liquid phases in the systems Mg-Sn and Mg-Pb are also considered. In the course of the investigation the heats of solution of magnesium, germanium, and lead in liquid tin have been determined. 1) EXPERIMENTAL PROCEDURES 1.1) Samples. Samples of the compounds Mg2Ge, Mg2Sn, and Mg2Pb, supplied by Professor P. Aigrain, Compagnie Générale de Télégraphie Sans Fils, were used in measuring heats of formation, heats of fusion, and melting points. Samples of Mg2Sn and Mg2Pb, supplied by Dr. V. B. Kurfman, Dow Metal Products Co., samples of Mg2Sn, prepared at the Air Force Cambridge Research Laboratories, and samples of MgzPb, prepared in this laboratory, were used for additional measurements of the heats of fusion and the melting points. The samples were stored in evacuated Pyrex capsules or under nonreacting liquids. 1.2) Heats of Formation. The heats of formation at 273°Kof the compounds Mg2Ge, Mg2Sn, and Mg,Pb were measured by tin-solution calorimetry. In this method, samples of the compound and of a mixture of the constituent elements are added alternately from 0°C to a tin-rich bath. The difference between the heat effects, corrected for the change in composition of the bath, is the heat of formation of the compound. Details of the method have been given elsewhere. 4 The bath was maintained at 350°C for the dissolution of the compounds MgzSn and Mg2Pb. Since at this temperature the dissolution of Mg2Ge was too slow, a bath temperature of 400" or 450°C was used with this compound. At least three calorimetric runs, each of approximately six additions, were made with each compound. 1.3) Heats of Solution. The determination of the heats of solution of magnesium, germanium, and lead in tin was included in this investigation because they were not well-established at the time this work was started. To obtain the heat of solution, the difference

Jan 1, 1967

By J. H. Slater

There is nothing particularly new about the use of sinter in a blast-furnace burden. For many years flue dust has been sintered at the various blast-furnace plants to put it in a form that could be recharged to the furnace with some assurance that it would stay in the second time. This paper is not a compilation of scientific data but only an attempt to give our experience with sinter. There are some unexplained discrepancies in the tests given here, such as the flue dust produced and iron tonnages, but the results given are the results that were obtained. Sinter is not the cure-all for blast-furnace problems. A good coke is still the most important factor in good furnace operation. However, good sinter is a big help. As flue dust is produced under varying operating conditions and fluctuates greatly in carbon content, it is difficult to produce from flue dust alone a uniform sinter, which will give satisfactory blast-furnace results. Sinter made from flue dust alone will change in character with every carbon variation. Almost invariably flue dust contains carbon in excess of the amount necessary to make good sinter, and this excess must be burned out. This, of course, necessitates reduction of the speed of the sintering machine and thus a decrease in tonnage. An alternative is to dilute with a carbon-free material to use up the excess carbon. High-carbon material when sintered results in a very dense, undesirable product, since the excess heat melts the charge into a hard, nonporous mass, and tends to form refractory silicates. At the Republic Steel plant in Cleveland, there had existed since 1924 a continuous-type sintering machine having 224 sq. in. of grate-bar area, capable of producing 9 to 11 tons of sinter per hour from flue dust. Under a former management, it was the practice to sinter only the flue dust from the blast furnaces, no attempt being made to recover the gas-washer sludge. As the dust was limited, the plant operated only part time. In other words, there was a sintering plant representing considerable investment, with good facilities for screening and preparation of raw materials, and flue dust available for only part-time operation. The sinter produced was costly and not a very desirable product. The first step was to install equipment for the recovery of the gas-washer sludge. This was done in the form of two large thickeners and a filter, which have proved very satisfactory. It was then decided to screen out the minus 3/8-in. fines from the Mesabi ores, mix them with flue dust and coke breeze when necessary, and operate the plant at full capacity. The tonnage increased to 18 tons per hour and the product was much improved. Sintering costs fell and the product was a preferred blast-furnace material, which on an iron unit cost compared very favorably with good Mesabi ores. On the average, 40 per cent flue dust and 60 per cent fine ore was being used. The oversize from the ore screening also became a preferred product for the

Jan 1, 1941

By J. H. Slater

There is nothing particularly new about the use of sinter in a blast-furnace burden. For many years flue dust has been sintered at the various blast-furnace plants to put it in a form that could be recharged to the furnace with some assurance that it would stay in the second time. This paper is not a compilation of scientific data but only an attempt to give our experience with sinter. There are some unexplained discrepancies in the tests given here, such as the flue dust produced and iron tonnages, but the results given are the results that were obtained. Sinter is not the cure-all for blast-furnace problems. A good coke is still the most important factor in good furnace operation. However, good sinter is a big help. As flue dust is produced under varying operating conditions and fluctuates greatly in carbon content, it is difficult to produce from flue dust alone a uniform sinter, which will give satisfactory blast-furnace results. Sinter made from flue dust alone will change in character with every carbon variation. Almost invariably flue dust contains carbon in excess of the amount necessary to make good sinter, and this excess must be burned out. This, of course, necessitates reduction of the speed of the sintering machine and thus a decrease in tonnage. An alternative is to dilute with a carbon-free material to use up the excess carbon. High-carbon material when sintered results in a very dense, undesirable product, since the excess heat melts the charge into a hard, nonporous mass, and tends to form refractory silicates. At the Republic Steel plant in Cleveland, there had existed since 1924 a continuous-type sintering machine having 224 sq. in. of grate-bar area, capable of producing 9 to 11 tons of sinter per hour from flue dust. Under a former management, it was the practice to sinter only the flue dust from the blast furnaces, no attempt being made to recover the gas-washer sludge. As the dust was limited, the plant operated only part time. In other words, there was a sintering plant representing considerable investment, with good facilities for screening and preparation of raw materials, and flue dust available for only part-time operation. The sinter produced was costly and not a very desirable product. The first step was to install equipment for the recovery of the gas-washer sludge. This was done in the form of two large thickeners and a filter, which have proved very satisfactory. It was then decided to screen out the minus 3/8-in. fines from the Mesabi ores, mix them with flue dust and coke breeze when necessary, and operate the plant at full capacity. The tonnage increased to 18 tons per hour and the product was much improved. Sintering costs fell and the product was a preferred blast-furnace material, which on an iron unit cost compared very favorably with good Mesabi ores. On the average, 40 per cent flue dust and 60 per cent fine ore was being used. The oversize from the ore screening also became a preferred product for the

Jan 1, 1941

By H. G. Doll

'This paper discusses a method and apparatus for determining the dip of formations traversed by a drill hole, by means of electrical measurements in the hole. The process consists in recording the Spontaneous Potentials present along three oriented generatrices in the hole. By comparison of the three curves thus obtained, after application of a correction factor to compensate for any deviations of the hole, the dip angle and the dip direction are determined. Excellent accuracy is obtained for dip angles over 10°. Because the method is simp1e and the apparatus rugged, the measurements are rapid and reliable; consequently, they can be made at all the levels that are of interest at any time after the well has been drilled. Mechanical cores are not needed to evaluate the dips. A convenient, time-saving procedure is to perform the dipmeter survey at the time the electrical log is taken, using for both operations the same cable and truck. Actual examples of results obtained in wells of the Gulf Coast area are given. Introduction The problem of determining the angle and direction of the dip of the strata traversed by a drill hole has practical interest, and sometimes vital importance, which need not be emphasized to the oil industry. The need for that type of information has existed ever since wells have been drilled. Certainly it has not subsided, in spite of the numerous inventions and improvements made in other fields of the art of drill-hole exploration. The few examples given in this paper are but illustrative of this fact. In the past, methods have been devised, and used, to solve this problem, but generally they have met with limited success, possibly because they failed more or less to answer the requirements of a modern age for fast yet accurate measurements. If accurate, the results were obtained at the cost of very tedious and lengthy operations. The new S. P.* dipmeter service offered to the oil industry is the result of exhaustive and in this particular field. In 1032 a dipmeter and electromagnetic teleclinom-eter service was made available. The apparatus employed then was of a rather delicate and costly construction, and the measurements had to be made with precautions sometimes difficult to secure on the rig. Although the information given by the electromagnetic dipmeter was limited to the direction of the dip, very interesting results were obtained in California, Trinidad, Venezuela, Rumania and, most notably, in the Netherlands East Indies.+ Apparatus The S. P. dipmeter surveys present none of the drawbacks mentioned above. The apparatus is rugged and free from constructional complications, therefore well adapted to field use. This, combined with the new, basically simple approach to the problem, explains the rapidity of execution of the measurements. The results are remarkably accurate and they are complete, giving the

Jan 1, 1946

By H. G. Doll

'This paper discusses a method and apparatus for determining the dip of formations traversed by a drill hole, by means of electrical measurements in the hole. The process consists in recording the Spontaneous Potentials present along three oriented generatrices in the hole. By comparison of the three curves thus obtained, after application of a correction factor to compensate for any deviations of the hole, the dip angle and the dip direction are determined. Excellent accuracy is obtained for dip angles over 10°. Because the method is simp1e and the apparatus rugged, the measurements are rapid and reliable; consequently, they can be made at all the levels that are of interest at any time after the well has been drilled. Mechanical cores are not needed to evaluate the dips. A convenient, time-saving procedure is to perform the dipmeter survey at the time the electrical log is taken, using for both operations the same cable and truck. Actual examples of results obtained in wells of the Gulf Coast area are given. Introduction The problem of determining the angle and direction of the dip of the strata traversed by a drill hole has practical interest, and sometimes vital importance, which need not be emphasized to the oil industry. The need for that type of information has existed ever since wells have been drilled. Certainly it has not subsided, in spite of the numerous inventions and improvements made in other fields of the art of drill-hole exploration. The few examples given in this paper are but illustrative of this fact. In the past, methods have been devised, and used, to solve this problem, but generally they have met with limited success, possibly because they failed more or less to answer the requirements of a modern age for fast yet accurate measurements. If accurate, the results were obtained at the cost of very tedious and lengthy operations. The new S. P.* dipmeter service offered to the oil industry is the result of exhaustive and in this particular field. In 1032 a dipmeter and electromagnetic teleclinom-eter service was made available. The apparatus employed then was of a rather delicate and costly construction, and the measurements had to be made with precautions sometimes difficult to secure on the rig. Although the information given by the electromagnetic dipmeter was limited to the direction of the dip, very interesting results were obtained in California, Trinidad, Venezuela, Rumania and, most notably, in the Netherlands East Indies.+ Apparatus The S. P. dipmeter surveys present none of the drawbacks mentioned above. The apparatus is rugged and free from constructional complications, therefore well adapted to field use. This, combined with the new, basically simple approach to the problem, explains the rapidity of execution of the measurements. The results are remarkably accurate and they are complete, giving the

Jan 1, 1946