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By M. T. Simnad, C. E. Birchenall, M. H. Davies

THE marker movements observed by Davies, Simnad, and Birchenall during the growth of magnetite on wustite have been misinterpreted. It is the purpose of this note to correct the original interpretation. In that investigation wustite specimens were prepared by oxidizing pure iron disks in water vapor until the iron was consumed. Argon was used as a carrier gas for the water vapor and on the complete conversion of the metal to its oxides ('FeO' plus a small amount (10 pct) of surface Fe3O) the water supply was bypassed and the specimens were annealed in argon alone in order to equilibrate the wustite with the overlying magnetite. After cooling, the magnetite was ground off, a crude magnetic test being employed to determine its complete removal. Radioactive silver streaks were then applied to the surface and the specimen was oxidized completely in water vapor to prevent hematite formation. After complete oxidation the markers were found to enclose about 80 pct of the magnetite with the other 20 pct lying outside the markers. This observation was interpreted to mean that oxygen transport was four times as great as iron transport during the growth of the magnetite. The conclusion would have been correct if, as in the case of wustite growing on iron, all the iron had started from one side of the marker and all the oxygen from the other side initially. Actually a material balance is required. For simplicity, take wustite to be exactly FeO, and magnetite to be Fe3O,. Then at the start of the reaction 3 FeO + O -> Fe,O., All of the iron and three-fourths of the oxygen of the final product will be within the marker inter- faces. The other fourth of the oxygen is in the gas phase outside the marker. From the experimentally determined final position of the markers simple calculation shows that one-fifth of the total iron has crossed the marker interface, while one-twentieth of the total oxygen has crossed in the reverse direction. The simplified result favors iron transport in the ratio four to one. However wiistite is not stoichiometric FeO. At 900°C, the temperature of the measurement, the composition is about FeO When the material balance for the same experimental result is repeated, assuming the product will be 1 mol of Fe3O4, it is found that 0.6 gram atoms of iron and 0.19 gram atoms of oxygen must have passed the marker in the same direction. (This is readily apparent from the reaction to form 1 mol of Fe3O4 SFeO The total oxygen supplied from the atmosphere is 0.61 gram atoms, but the iron which passes the marker interface, i.e., 0.6 gram atoms, requires 0.8 gram atoms of oxygen to convert it to Fe,O,.) If all the transport during magnetite growth is due to iron ion diffusion, then the marker would enclose about 85 pct of the final magnetite and the original measurement is in error by about 5 pct. This error is probably less than the uncertainty in locating the markers by autoradiography. The possibility also exists that the starting wustite was not quite saturated with oxygen and underwent further enrichment with consequent envelopment of the marker before magnetite caught up with the marker interface. In any case it appears that these measurements actually favor iron ion diffusion in magnetite overwhelmingly as the factor controlling its growth, although further experimental measurements are needed to eliminate the error in material balance described. Such studies are planned.

Jan 1, 1954

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By E. I. Salkovitz, F. W. von Batchelder

DURING the last few years several papers1-' have been published in which internal friction measurements have been used to determine the quantity of carbon or nitrogen dissolved in a iron. This method is based on the fact that, in pure Fe-N and Fe-C alloys, nitrogen and carbon cause peaks in the internal friction vs. temperature curve; at a frequency of 1 cycle per sec (cps) these peaks appear at $-200 and +360C, respectively, and if internal friction is expressed as Q-1, which is equal to times the logarithmic decrement, this figure will, by coincidence, give the weight percentage of nitrogen or carbon in solid solution.' In most of the studies published, very pure iron (Puron) was used. In one case the influence of manganese on the behavior of nitrogen in a iron was mentioned.4 It would be of great value, especially for the study of aging and related phenomena, if this method could be applied to commercial mild steel with norrnal percentages of manganese, phosphorus, sulphur, etc. As a rule, in such steels carbon and nitrogen are present together, and the amounts of these elements in solid solution should preferably be determined separately. The fact that their internal friction peaks appear at different temperatures (+36° and + 20°C in pure iron) seems promising for such a selective determination. It is necessary, however, that the peaks are narrow enough not to interfere with one another, and further, that there is no effect from carbon on the behavior of nitrogen in stress induced diffusion, and vice versa. According to Fast,' however, in the presence of manganese the nitrogen peak gets wider and appears at a higher temperature nearer the carbon peak, and thus the prospects for selective determination are reduced. (The carbon peak was not affected by the presence of manganese.) But even if fully quantitative de- terminations of the two elements are not attained, some relative figures on the sum of them and an indication of which one is the predominant one, would be of value. Some results from experiments along these lines will be reported here. An internal friction measuring device was assembled mainly following a description by KG." The measurements were also carried out as reported in that paper. Table I gives the chemical compositions of the four different materials used in this investigation. All materials were drawn to wires with diameter about 0.8 mm, and the analyses refer to these final shapes. Determination of Nitrogen Peak Wires from steels A, B, and C were decarburized in wet hydrogen (about 30 pct H2O) at 700°C until no carbon or nitrogen could be found by chemical analysis. No peak was then found in the internal friction. The wires were further annealed at 580°C for 16 hr in hydrogen bubbled through a solution of 6.8 pct NH3 in distilled water. Chemical analyses gave 0.04 pct N in A and C, and 0.06 pct in B. After annealing at 580°C for 15 min in a lead bath and water quenching, the internal friction was immediately measured. The resulting curves are shown in Fig. 1. At these high values of the internal friction the accuracy is comparatively poor; at Q-1 - 0.030 it is estimated to be 0.002. In order to make possible a calculation of the activation energy for diffusion of nitrogen, measurements were made at two different frequencies. Steel A shows rather broad peaks, and their temperatures can hardly be expected to be very accurate. Steels B and especially C are better in this respect. The finding of Fast' that manganese broadens the nitrogen peak is con-

Jan 1, 1953

By Robert L. Grayson, Y. J. Wang, R. Mike Mishra

Prediction of ventilation needs in long range mining projections requires serious consideration when formulating those projections. Predicting the behavior of the ventilation system of an old, complex mine poses an especially provocative problem. Air-flow around and through mined-out areas via bleeder systems, leakage flows through stoppings or other air control devices, and the use of multiple fans all add to the basic complexity of a ventilation system and make predictions of ventilation changes very difficult. Fortunately, the task of making ventilation decisions can be greatly assisted by ventilation surveying and computer simulation. The Nemacolin Mine of Jones and Laughlin Steel Corporation, located in Southwestern Pennsylvania, is one such old mine which used the computerized approach successfully. A mine-wide pressure-quantity survey was used to obtain realistic values for airway resistance factors. These values, together with network topology, formed the basic input for computer simulation. Results from this simulation indicated that air quantities generated at critical airways by the model were generally within a couple of percent of those measured in the actual survey. It was then concluded that the model was acceptable for practical application, and it was used immediately for studying the effects on the ventilation system of changing the blade settings of fans. Additionally, the model was modified to incorporate projected mine development and used to predict future ventilation.

Jan 1, 1982

By Jan M. Mutmansky, Gordon H. Walrod, Y. J. Wang

The selection of a shaft size for ventilation purposes is a classic problem of concern to mining engineers. This presentation is concerned with the sizing of conventionally-sunk circular shafts with concrete or shotcrete linings. Costs of sinking shafts of three different depths, from 150 m to 300 m (500 ft to l000ft), and six different diameters, from 4.27 m to 7.32 m (14 ft to 24 ft), were obtained through questionnaires to shaft contractors. The primary objective of the economic model presented is the balancing of detailed annual capital and operating costs to achieve the minimum overall cost of the shaft installation over its life. The economic model is similar to previous analyses but treats several of the individual cost categories in an updated fashion. Included in the paper is a detailed analysis of the effects of varying power costs on optimal shaft size. Also included are a statistical analysis of current shaft costs and comments on the choice between shotcrete and concrete linings.

Jan 1, 1980

By E. Dow Whitney, Ravrinda M. Chhatre, George Y. Onoda

Phosphate deposits in Florida are a possible source of byproduct uranium. In this paper, the distribution of uranium in several recently mined areas is described. Flowsheets are established for several mines describing how the uranium becomes distributed during the beneficiation of the phosphate matrix.

Jan 1, 1981

By Henry S. Drinker

(Canal Zone Meeting, November, 1910.) FEW men reach middle life without having had the experience of failure in one or more undertakings; and most of us can look back with gratitude to help or advice given us by friends at critical periods of our lives. If, as men, we ask and take the benefit of such aid, why should we expect our sons to be stronger? A parent can make no greater mistake than to send a boy, however steady and intelligent he may be, off' to school or college, and expect the boy always to cope successfully with all the new conditions and new difficulties that may confront him. This is undoubtedly more the case with a freshman, in his first year at college, than in later years, or than it is with a boy at day- or boarding-school, where the boy receives a greater degree of care and oversight than can be given to the young man entering college; of all periods in life, the youth in his freshman year-fresh from the overshadowing care of home and school-may need judicious advice and timely aid. The change from the restraint of home and school to the freedom of college life is sudden and marked, and it is in this the first year of the boy or young man of 17, 18, or 19 years of age, that some tactful, judicious aid should be near him in his work and course. Some boys go to college so well prepared that they become careless and finally fall behind in their work from over-confidence. Others meet trouble from ambitiously trying to do more than their previous preparation, or physical or mental strength, can sustain. Others fall behind from illness-from injuries-from natural inability to grasp at first, without more aid than comes to them in the regular course of instruction, the higher mathematics-or mayhap the modern languages, or other subjects presented by the advanced curriculum of the present day. When a boy or youth begins to

Jan 1, 1911

By WALTER B. JONES

PIG iron was first produced in Alabama in 1818 from limonite or brown ore and since then much of this ore has come from the so-called mineral district of northern Alabama, especially along the Cretaceous-Paleozoic contact. For many years the Russellville district in Franklin County, where the first blast furnace was erected, produced more than 100,000 tons of brown ore annually. Limonite has been reported at many places in the Coastal Plain region, where the formations are of Mesozoic and Cenozoic age, but these scattered deposits were never considered to be of much commercial importance. However, in the last three years a considerable quantity of this ore has been scraped up and shipped, particularly from the city of Greenville in Butler County.

Jan 1, 1938

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1' and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,'' by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.'= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By Axel Hultgren

In ingots of silicon-killed carbon steel-made without addition of aluminum, transparent spherical or nearly spherical inclusions, up to about 0.15-mm diameter, are generally present. They may be glassy or crystallized, wholly or partially In steels of high carbon contents they consist of silica,4,12 in steels of lower carbon contents and, in consequence, higher oxygen contents, of iron-manganese-silicate with higher iron and manganese contents the lower the carbon content. Small silicate inclusions, about 0.01 mm or smaller, may occur, just as sulphide inclusions do, in portions that have been the last or nearly the last to freeze,l0,12,17 this location being verified by primary etching.10 Hence, it may be concluded that they have separated from liquid steel that has become enriched in oxygen through segregation during freezing. Silicate inclusions with a diameter larger than about 0.02 mm appear, at least in ingots of moderate size, to be distributed at random in relation to the primary structure and therefore may be assumed to have existed as droplets in the liquid steel before freezing started at the point in question. The average size of such large inclusions has been found to increase toward the axis1' and their amount to increase from the top downward in the axial region.2,10 It has been assumed that this accumulation is a result of the droplets being brought down by the slowly settling metal crystals.2 It has been suggested that large silicate inclusions generally form,6 or may form,'' by coagulation of smaller ones, or by small drops being caught by larger ones during the rising of the latter.9 The occasional occurrence of a large inclusion surrounded by a swarm of small ones has been taken as a proof of this mechanism but, as suggested later, may be explained in another way. It has been pointed out that an inclusion droplet in the liquid steel may grow at the expense of an adjacent one, which implies diffusion of soluble inclusion-forming elements in the liquid steel.'= Further, it has been pointed out that, on cooling in ladle or mold, the metal-silicate equilibrium is displaced in the direction of separation of silicate. Thus inclusions may grow in size and amount.2,3,8,12,13,17,19,20 The exposure of the liquid steel to the oxygen of the air during tapping and pouring, and the consequent reaction, has been mentioned as a source of the formation of inclusions19.20 but this possibility has not received particular attention. Further, the admixture of furnace slag during tapping1 or of refractory material from various sourcesl,20 has been considered. The inclusions due to the latter may be recognized, however, through their resistamce to hydrofluoric acid, imparted by the alumina content. Silicate inclusions are often referred to as the natural and inevitable product of reaction on adding silicon or silicon

Jan 1, 1949

By E. S. Davenport, R. J. Hafsten, R. A. Grange

The influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,' and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely relarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths. Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745ºF. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245ºF. (675°C), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarsegrained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite—that is, at temperature levels above about 1000°F. (540°C.)—but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to he presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000ºF. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. Material and Experimental Procedure The material investigated was a cornmercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent Mo. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By R. J. Hafsten, E. S. Davenport, R. A. Grange

The influence of austenite grain size upon the hardenability of steel is now fairly well understood; for a given austenite, increasing the grain size increases the depth of hardening, and, since the latter is related to the fundamental transformation behavior of austenite, it follows that austenite decomposition must, in general, be retarded by increasing grain size. To date, very little quantitative information bearing directly on the effect of austenite grain size upon the progress and result of isothermal transformation has been published. Davenport and Bain,' and Zimmerman, Aborn and Bain2 have shown that the transformation is definitely relarded in hypereutectoid plain carbon steels at temperatures near and above the upper region of rapid transformation (Ar') when the austenite grains are increased in size. More recently, Griffiths. Pfeil and Allen3 investigated the effect of a series of different heating (austenitizing) temperatures upon the progress of isothermal transformation at 1245°F. (675°C.) and 745ºF. (395°C.) in a medium carbon, low-alloy steel; while they reported no measurements of the austenite grain size, their results suggest that increase in grain size retards austenite transformation at 1245ºF. (675°C), but has no appreciable effect at 745°F (395°C.). The present paper deals with the results of a study of the isothermal transformation of austenite in a single commercial alloy steel in which a fine-grained or a coarsegrained state was induced by appropriate selection of austenitizing temperature. The data are presented in the form of isothermal transformation diagrams, which clearly show that coarsening the grains lessens the rate of transformation of austenite to proeutectoid ferrite and pearlite—that is, at temperature levels above about 1000°F. (540°C.)—but is without significant effect at lower temperatures where the transformation product is bainite or martensite. It is to he presumed that the foregoing statement would be valid, at least in principle, for many other grades of steel; it confirms again that the mechanism of transformation to a pearlitic structure is fundamentally different from that to an acicular structure. A number of related observations were made, which seem to throw some light on the transformation process as it takes place in alloy steels, particularly at temperature levels in the vicinity of 1000ºF. (540°C.), where the transition from lamellar to acicular structures occurs. These data are discussed briefly in the belief that they may lead to a clearer understanding of this aspect of the subject. Material and Experimental Procedure The material investigated was a cornmercial grade of S.A.E. 4140 steel, the composition of which was as follows: 0.37 per cent C, 0.77 per cent Mn, 0.98 per cent Cr and 0.21 per cent Mo. It was hot-rolled to a 1 1/8-in. round bar and normalized by air-cooling from 1800°F. (980°C.).

Jan 1, 1941

By E. H. Burdick

THE difficulties inherent in table concentration operations as applied to gold, silver, lead and zinc ores, are accentuated in the scheelite mill, which has a flowsheet that is similar in general principles. The narrow "spread" in the specific gravity between scheelite and the usual gangue in which it occurs often makes its clean separation extremely difficult and in some cases impracticable. The problem is further complicated by the extreme friability of the mineral and its inordinate tendency to "slime," particularly where fine grinding is necessary and wet grinding methods are employed. The physical aspect of the occurrence of scheelite in the ores, the kind and character of the rock in which the mineral is present, its hardness, friability and the specific gravity of its constituents, as well as like characteristics of the associated mineral-spyrite, pyrrhotite, sphalerite, and others, all have a bearing on the successful milling of crude ores and the production of a concentrate that is marketable with minimum price penalty or none at all. Most tungsten deposits are considered low grade when the limiting factor of low percentage recovery by gravity methods is borne in mind. The great majority of deposits developed or in process of development carry from 0.4 to 1.0 per cent tungstic oxide. Ore carrying 1 per cent is considered good grade; 0.7 to o.8 per cent, fair, and below that figure, low grade. Steady mill feed averaging upward of 1.0 per cent WO3 is exceptional. Inasmuch as buying specifications demand a 60 per cent WO3 content, the mineral content of the ores as mined must be concentrated to at least that degree. A few companies have constructed chemical plants for the treatment of their complex concentrates and low-grade flotation product, but the smaller operator must rely on table concentration, borrowing the tools and to a large extent the methods of his predecessors in the gold, silver, lead and zinc mills. Whether these are the best tools and methods that can be devised is an open question. Except in rare instances, table concentration, however carefully conducted, does not yield a satisfactory final recovery of the mineral content in headings as indicated by chemical determinations of tungstic oxide content. A saving of 6o to 65 per cent is considered fair, and an average 80 per cent recovery, exceptional. Each scheelite ore body is a separate problem. Details of handling that give best results in one case may not be successfully operative at a property on the same contact zone and but a short distance removed. Supplementary treatment of tailings by flotation may be successful in producing a low-grade concentrate of around 15 per cent W03, which is adapted to further treatment chemically at a given property and entirely unsuccessful at another. This problem constitutes another of the unanswered questions. The following paragraphs relate solely to the beneficiation of scheelite ores by table concentration and supplementary methods.

Jan 1, 1942

By M. E. Nicholson

IT has been suggested by a number of investigators, I including Hume-Rothery and Raynor,' that certain intermediate phases in metal systems take on interstitial crystal structures because of an appropriate ratio of radii of the two atoms. If the size factor is an important parameter in determining whether or not an intermediate phase will have an interstitial structure, then it would appear reasonable that the relative sizes of interstitial atoms should have a direct relation to their solubilities in interstitial compounds. It was on such a basis that Petch,' in his discussion of the cementite structure, concluded that nitrogen is the only possible element which could replace carbon. Recent X-ray studies by Jacka indicate that the solid solubility of nitrogen in cementite is negligible. If this is the case, then on the basis of size factor it would not be expected that any element can replace carbon in FeaC, since according to Schwarzkopf and Kieffer4 the covalent atomic radii of nitrogen, carbon, and boron are 0.71, 0.76, and 0.87A, respectively. Nevertheless, Vogel and Tammann in 1922 indicated that a quasi-binary relation exists between the interstitial compounds FeaC and Fe2B and that the solid solubility of boron in FeaC at approximately 1150°C is 1.4 pct B by weight. Because of the apparent disagreement between theory and experiment, the solid solubility of boron in FeaC has been reinvestigated. In addition, the influence of boron on the saturation magnetic moment (per gram) and Curie temperature of cementite was determined. Experimental Procedure A series of Fe-B-C alloys which varied in boron content from 0 to 5.4 wt pct B were prepared by arc melting a 50-g ingot using carbonyl iron, Ache-son AUC graphite, and Cooper grade A boron for starting materials. The composition of these alloys is listed in Table I and shown graphically in Fig. 1. The samples represented by the solid circles were used for X-ray analysis and Curie temperature measurements; by the squares, samples used for quantitative metallography; and by the triangles, samples used for saturation magnetic moment measurements and Curie temperature measurements. After arc melting and subsequent quenching from 1000°C, so that all phases in the resulting microstructure were brittle, one half of the 50-g ingots were pulverized until a powder was obtained which was less than 100 mesh. These powders were then homogenized in evacuated Vycor capsules at 1000°C for 24 hr and water quenched. Although the homogenized powder had sintered somewhat, it was suitable for saturation magnetic moment and Curie temperature determinations, for which the 60 to 100-mesh fraction of the powder was used. For X-ray analysis the homogenized powder was crushed again until a 300-mesh powder was obtained. After crushing, the powder was mixed with Alundum of approximately the same grit size to prevent sinter-

Jan 1, 1958

By J. C. McDonald

A DDITIONAL experimental data are presented in this note on a phenomenon which has been touched on but lightly in the literature. The common magnesium base rolling alloy (AZ31B) contains about 3 pet A1 and 1 pet Zn. When cold rolled, it hardens until it starts to break up in the rolls at 30 to 50 pet reduction. When it is heated after rolling to full hardness, it softens. However, other magnesium alloys have shown themselves capable of being cold rolled indefinitely, provided the ratio of roll diameter to starting gage is sufficiently high. As measured by the tensile test, these alloys actually soften when the reduction becomes large (60 to 90 pct). A subsequent heating at 300' to 500°F can produce hardening of this metal. Heating at higher temperatures (600' to 800°F) causes recrystalliza-tion and softening. Menzen' has shown that a magnesium base alloy can be cold rolled without intermediate anneals as much as 90 pet. The alloy studied, Mg-1.5 pet Mn, softened considerably between 20 and 90 pet reduction, as measured by tensile properties; a decrease in yield strength of 30 pet, and an increase in elongation from 3.2 to 16.7 pet (longitudinal direction of the sheet). However, Menzen gives no data on the reaction of this metal. to heating. Ansel and Betterton2 and Hurst and Hatch3 report a similar effect in Mg-1.5 pet Mn-0.1 pet Ca. Their data show an initial hardening, followed by softening. The former authors also show that the alloy softened by cold rolling will harden when heated at low temperatures, and that these effects are absent in Mg-3 pet Al-1 pet Zn. In the course of work4, 5 some years ago, the author observed similar effects with alloys containing cerium, thorium, or zirconium; but not with elements like aluminum, silver, or zinc. Table IA contains the results of an experiment which shows these effects rather well. A binary alloy with 0.3 pet total rare earths (Mischmetal* added) was rolled hot to 1/16 in. and then annealed to full softness by heating 30 min at 800°F. Rolling was continued at 1.5 pet per pass to 80 pet total reduction on 8 in. diam rolls. The metal was harder after 20 pet work than initially but, at 80 pet reduction, properties were back to their original values. Heating for 1 hr at 450°F produced about the same hardness whether the reduction was 20 or 80 pet. At intermediate reductions, the metal hardened, but not to as high values. Extensive cold rolling may also be carried out on metal hot rolled at temperatures sufficiently low to produce a semihard temper. Mg-0.6 pet Zr was rolled to 0.1 in. at 700° to 800°F, 30 pet per pass. As shown in Table IB, a further cold reduction of 85 pet, at 1.5 pet per pass, definitely softened the metal.

Jan 1, 1959

By W. E. D. Stokes

WHEN history is written, the year of the blitzkrieg will go down as giving aviation its greatest impetus. No perceptible drop in military business, even with cessation of hostilities abroad, seems likely. The combined air force of the U. S. Army and Navy on July 1 was approximately 5000 planes, as against 50,000 planes currently discussed as necessary. Observers at the fronts are giving designers and metallurgists back home some realistic ideas to shoot at. As conventional runways reveal the location of airports to enemy raiders, operating bases are now masked. Difficult, often muddy and rough landing strips, requiring strong landing gears and exacting take-off and maintenance characteristics, are the specifications of war. This is "old stuff" to numerous mining operators in mountainous jungle areas where gradients up to 8 per cent are in more or less common use in such mountain landing fields. Although airplane building is not readily adaptable to assembly-line methods, a trend towards mass productions is now in evidence. Incidentally, a U.S. Army "Curtiss P-40" requires about 10,000 man hours of work to complete and is tied together with 75,000 rivets. During the past year a number of aircraft factories adopted the "shot-

Jan 1, 1941

By E. Ray Webb

A interest to geologists and to mining and petroleum engineers is a laboratory method for determining the dip and strike of sub- surface structures, as well as the direction of fault planes traversing them. The information is derived by making use of the magnetic properties of borehole cores which must show visible representations of bedding or fault planes. Complete knowledge of these factors aids greatly in the successful exploitation of both ore and petroleum deposits.

Jan 1, 1940

By E. C. Wright

The bessemer process is nearly one hundred years old. William Kelly, the American inventor, was able to demonstrate that he had accomplished the pneumatic purification of molten pig iron as early as 1847; Henry Bessemer's English patent was granted in 1855. The application of this steelmaking process since then and the present position of bessemer steel are concisely discussed on pages 355 and 356 of the fifth edition of "The Making, Shaping and Treating of Steel." The great expansion of the automotive, machine-tool, chemical and oil industries after I9I0 opened up a large market for special steels, whereas the output of steel before that time was mainly for structural purposes. The need for building more blastfurnace capacity complementary to bessemer operations, combined with the availability of the' necessary amounts of steel scrap, both contributed to the extension of open-hearth plants at the -exense of besskmer capacity. The ability of the open-hearth furnaces to consume virtually all types of raw materials as far as phosphorus content is concerned, and the need for selecting low-phosphorus ores of rapidly decreasing sources for the bessemer, also played a part in the reduction of bessemer steelmaking operations and the increase in basic open-hearth plants. As a consequence, the proportion of bessemer steel made, in this country decreased from 65.7 per cent of the total in 1900 to 37.1 per cent in 1910, and only 6.8 per cent of the total in 1937. The metallurgical concepts existent between 1910 and 1920 caused the writing of many specifications of very low phosphorus and sulphur content, which definitely barred bessemer steel from many commodities. Now sulphur is being added to many open-hearth and bessemer steels in amounts far exceeding the maximum sulphur content of good bessemer steel. Re-phosphorizing is also widely practiced for several specific applications. Even today, the chemical-analysis limits of many important steel specifications have an arbitrary and archaic tinge. The old standard "0.30 to 0.60 per cent manganese" might be mentioned in this connection as similar to the rigid requirements for maximum sulphur and phosphorus that were established at least 25 years ago. The literature is full of vague and complee discussions of the effects of nitrogen and oxygen where these elements existed in steel in amounts less than 0.02 per cent. Many failures have been attributed to these elements without reasonable proof on which to base the conclusion. Methods of determining oxygen in steel require such complicated equipment that only a few research laboratories have the required apparatus. Even so, the accuracy of oxygen determinations in steel has been only recently reproducible. Up to the present time, no one has succeeded in obtaining a sample of molten steel that accurately indicates the full oxygen content of the metal in the furnace or ladle because the molten sample

Jan 1, 1944

By E. C. Wright

The bessemer process is nearly one hundred years old. William Kelly, the American inventor, was able to demonstrate that he had accomplished the pneumatic purification of molten pig iron as early as 1847; Henry Bessemer's English patent was granted in 1855. The application of this steelmaking process since then and the present position of bessemer steel are concisely discussed on pages 355 and 356 of the fifth edition of "The Making, Shaping and Treating of Steel." The great expansion of the automotive, machine-tool, chemical and oil industries after I9I0 opened up a large market for special steels, whereas the output of steel before that time was mainly for structural purposes. The need for building more blastfurnace capacity complementary to bessemer operations, combined with the availability of the' necessary amounts of steel scrap, both contributed to the extension of open-hearth plants at the -exense of besskmer capacity. The ability of the open-hearth furnaces to consume virtually all types of raw materials as far as phosphorus content is concerned, and the need for selecting low-phosphorus ores of rapidly decreasing sources for the bessemer, also played a part in the reduction of bessemer steelmaking operations and the increase in basic open-hearth plants. As a consequence, the proportion of bessemer steel made, in this country decreased from 65.7 per cent of the total in 1900 to 37.1 per cent in 1910, and only 6.8 per cent of the total in 1937. The metallurgical concepts existent between 1910 and 1920 caused the writing of many specifications of very low phosphorus and sulphur content, which definitely barred bessemer steel from many commodities. Now sulphur is being added to many open-hearth and bessemer steels in amounts far exceeding the maximum sulphur content of good bessemer steel. Re-phosphorizing is also widely practiced for several specific applications. Even today, the chemical-analysis limits of many important steel specifications have an arbitrary and archaic tinge. The old standard "0.30 to 0.60 per cent manganese" might be mentioned in this connection as similar to the rigid requirements for maximum sulphur and phosphorus that were established at least 25 years ago. The literature is full of vague and complee discussions of the effects of nitrogen and oxygen where these elements existed in steel in amounts less than 0.02 per cent. Many failures have been attributed to these elements without reasonable proof on which to base the conclusion. Methods of determining oxygen in steel require such complicated equipment that only a few research laboratories have the required apparatus. Even so, the accuracy of oxygen determinations in steel has been only recently reproducible. Up to the present time, no one has succeeded in obtaining a sample of molten steel that accurately indicates the full oxygen content of the metal in the furnace or ladle because the molten sample

Jan 1, 1944

By C. E. Birchenall, M. H. Davis

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. 'The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew' suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman's' observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952