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By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at subcritical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.1 Westgren, Phragmén and Negresco2 identified the following carbides in chromium steels: [Cementite Fe3C (containing up to about 15 per cent Cr) Trigonal carbide Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide Cr4C (or Cr23C3) (containing up to about 25 per cent Fe) Orthorhombic carbide . Cr3C2 (containing only a few per cent Fe)] The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus.4 By means of dilatometric and microscopic studies, sections of the diagram were established. This diagram showed the presence of the special carbide Cr7Ca in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in r per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7Ca occurs in chromium steels containing more than about 1 per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. EXPERIMENTAL PROCEDURE The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into 1-in. round bars, and all heat-treatments were conducted on specimens of this section .size. Sections of the bar stock 8 in. long were hardened in air, oil or water depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after auenchine. The quenched bars were cut into

Jan 1, 1942

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick's law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert's law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick's Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By W. E. Brigham, P. W. Reed, J. N. Dew

By Ed Van Eeckhout

As part of a U.S. Bureau of Mines-sponsored project on the utilization of "stiff" backfill to minimize potential rock burst hazards, a finite element study was undertaken to predict stresses and displacements around a stope mined up from the 5400 level of the Sunshine mine, Kellogg, Idaho. This stope was to be backfilled using a high-modulus fill. In preparation for that configuration, certain instrumentation was installed near the 5400 level to monitor stress changes. Due to untenable economics, only 2 cuts of the stope were ever made. This paper presents the results of the instrument readings taken during the first cut and compares them with the numerical predictions, as well as presents the modeling results of closure and fill stresses in the stope if it had been mined.

Jan 1, 1984

By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942

By Cyril Stanley Smith

On the 6th of February 1684, Dr. Martin Lister mentioned at a meeting of the Royal Society1 that "brass is magnetical," and promised to give an account of that assertion at some other time. He repeated his promise but never fulfilled it, and it was left for William Arderon2 to show, in 1758, that brass could be made magnetic by hammering and that it would retain polarity after magnetizing. Twenty-seven years later Caval103,4 examined the matter in great detail. Working with cast calamine brass, he showed that it could be made magnetic by hammering and nonmagnetic by subsequent annealing at a red heat. He found that annealing at a very high temperature caused the samples to lose their magnetic quality permanently, even after subsequent cold-working, but that remelting and cold- working restored it. He encountered some samples of brass that could not be rendered - magnetic by any treatment. Experiments in which these were remelted with iron additions gave negative results, and Cavallo concluded that iron impurity was not the cause of the magnetism. He worked with 50-grain (3-gram) samples melted under the blowpipe, hence cooled very quickly. Bennet5 made whole crucible charges from copper and zinc, and found _ the resulting brass ingots to be magnetic only when iron had been added and then only after cold-working. All these observations applied to material in the cast condi- tion, in which coring would produce a continuous spectrum of composition and cooling would result in varying degrees of precipitation. This knowledge of the subject seems to have been forgotten in the nineteenth century. The older brass was made by the calamine process and frequently contained iron in amounts of 0.5 per cent or more, absorbed from the impure ore with which the copper and charcoal were heated in making the brass. When metallic zinc became available in commercial quantities, calamine brass gradually disappeared, and with it the knowledge of its curious magnetic properties. Only when sensitive apparatus replaced the compass needle of the earlier investigators could the effects be detected in relatively pure metal. The effect of cold-working in inducing ferromagnetism was rediscovered by Bitter8 in 1930 in a sample of impure copper, and this was confirmed by Lowance and Constant: Honda and Shimizu, l0,11 and others. In the same year, Tammann and Oelsen12 showed that copper-rich copper-iron alloys after certain heat-treatments could be rendered ferromagnetic or made more strongly ferromagnetic by cold-rolling. Kussman and Seeman13 showed that the change of susceptibility of relatively pure copper on cold-working was associated with the iron content, and concluded that actual precipitation of iron was caused by cold-working, which is a satisfactory theory until one considers the improbably high rate of diffusion that this would involve. When studying precipitation phenomena in

Jan 1, 1942

By B. S. Tani, R. V. Schablaske, M. G. Chasanov

In the Ti-Cd system two intermediate phases, TiCd and Ti Cd, have been found and characterized by X-ray diffraction powder techniques. An earlier reference' had reported the existence of the compound Tisd. No structural details, however, were given nor was there any indication of the possible existence of other binary compounds. Studies of the solubility of titanium in liquid cadmium2 led to the discovery of both TiCd and Tisd. The solid phase in equilibrium with saturated solutions of titanium in liquid cadmium at temperatures below 620°C is TiCd, whereas TizCd is the equilibrium solid phase above 620°C. Both thermal analysis and X-ray studies show that a peritectic reaction between the y phase (~isd) and cadmium to form the 6 phase (Ti Cd) occurs at 620°C. X-ray diffraction powder photographs of material isolated from the ingots used in the solubility measurements as well as material prepared by a direct heat of the appropriate stoichiometric amounts of titanium and cadmium can be indexed on the basis of a tetragonal unit cell with a = 2.904 ± 0.002A, co = 8.954 * 0.004A, c/a = 3.083. No variation of lattice parameters indicative of a range of composition is evident. With four atoms in the unit cell the calculated density of the intermetallic is 7.05 g per cm3; the observed value is 7.07 g per cm3. The TiCd lattice is primitive as indicated by the fact that there are no systematic absences among hkl reflections. The absence of all hko reflections for which h + k = 2n + 1 is also evident. This systematic absence indicates the following two space groups, C\h — P4/n and D&~4/nmm; both groups, however, have the same two- and four-fold positions. Stoichiometry, symmetry and space group indicate two likely structure types. They are the PbO-litharge3 (B10) type and the Ti CU (B11) type. Spatial considerations favor the B11 structure with atoms placed in the following positions: 2Ti (c) 0, 1/2, Z; l/2, 0, Z 2Cd(c) 0, 1/2, Z; 1/2, 0, Z The TiCd structure may be summarily described as a layered structure in which double cadmium layers alternate with double titanium layers along the c-axis. The best agreement between calculated and observed intensities is obtained for the values ZTi = 0.608 and ZCd = 0.130. Calculated and observed powder intensities as well as other pertinent powder data are recorded in Table I. Interatomic distances for the proposed structure are recorded in Table II and are to be compared with the distances of closest approach for titanium and cad-

Jan 1, 1962

By D. M. Wade, F. F. Redfield

PRODUCTION at Aguilar started in 1936 and by 1942 the mine had reached a peak of 25,000 tons a month. Present production is only about 60 per cent of this capacity because of difficulties in railroad transportation and the rationing of fuel oil brought about by the war. In the early years, cut-and-fill stopes were tried, but square sets were found to be the most practical method in the southern section of the mine, where blocky, treacherous ground and greater mining widths are prevalent. Square sets and opencut mining were the rule until 1942, when it became increasingly difficult to get mine timber. The ore beds in the northern section of the mine were found amenable to cut-and-fill stoping as the rock was firmer and the veins narrower. At present 69 per cent of the ore comes from cut-and-fill stopes, 27 per cent from opencut, and only 4 per cent from square-set stopes. Massive galena and sphalerite with comparatively little quartzitic gangue constitutes the higher-grade ore. The gangue minerals that can be detected by eye in low-grade ore are rhodonite, wollastonite, and pyrrhotite. Wall rocks range from shale to quartzite, with occasionally a little limestone.

Jan 1, 1947

By Walter McKee

WHEN mixed with common cast steel in quantities ranging from 11 to 13 ½ per cent. and properly treated, manganese increases the ductility of the metal and adds greatly to its toughness and resistance to abrasive action, which properties comprise the distinctive characteristics that make manganese steel so valuable for many purposes at the present time. Manganese steel has been manufactured for about 26 years. .It was first made in a small way in England and subsequently produced in the United States in 1892. At present the manganese-steel foundries of this country have an annual capacity of about 60,000 tons and most of the growth has occurred within the past 10 years. In the early days of the industry it was impracticable to make manganese castings weighing over a few thousand pounds, but at present crusher heads, rolling-mill pinions, and similar castings weighing up to 30,000 lb. each are produced, and it does not appear that the limit of weight has been reached by a considerable margin. Manganese steel is similar in analysis to ordinary first-class converter metal except that it is high in carbon and contains from 11 to 13 ½ per cent. of manganese. From one standpoint manganese steel is similar to malleable iron in that the casting as it comes out of the sand is hard and brittle and must be made ductile by a heat-treating process. The heat treatment is an essential part of the process of making manganese-steel castings and must be properly carried out to secure satisfactory results. The necessity for heat treatment limits the thickness of sections which may be made of manganese steel. Originally the annealing depth was comparatively small, but researches carried on during the past few years have resulted in an increase in the thickness of section up to 5 ½ in., which it is possible to treat successfully. Large castings are cored out to a minimum thickness of 5 ½ in., thus not only eliminating some of the internal stresses which are invariably set up in a very thick casting, but also reducing the weight and inertia of the piece, an

Jan 12, 1915

By AIME AIME

FEATURES of the second fall meeting of the Petroleum Division for 1941, held at the Ambassador Hotel, Los Angeles, Oct. 29-30, were the forum on the Paloma Plan on Thursday after- noon, the large attendance from east of the Rockies, and the dinner on Wednesday evening sponsored by the Southern California Section and at which President Suman spoke on the strategic minerals and metals situation. The attendance was large and the technical fare uniformly good ; the presiding officers had the proceedings well in hand at all times and kept things humming. Some- times it was necessary to taper off the discussion because of pressure on time. All this was due to careful groundwork before the respective sessions. These presiding officers deserve citation: L. W. Huebel, Howard Pyle, E. K. Parks, Carlton Beal, E. G. Trostel. R. W. French, Jr., John Dodge, and H. N. Marsh. The Los Angeles local commit- tees and the Southern California Section deserve much credit for the arrangements, which were recognized by suitable resolutions at the end of the meeting.

Jan 1, 1941

C. P. BOWIE, San Francisco, Cal.-In my work with the U.S. Bureau of Mines, I have been detailed to report on oil storage containers, and in going around the country I have, been much interested in, the possibilities in the use of concrete for such containers. In talking with a good many people, I have discovered that concrete is being used A good deal for a wide variety of oils ranging from 14° to as high as 40° Bé., especially, by some of the western railroads:, If any member has had experience, in storing gasoline in concrete, I should like to learn of it. DORSEY HAGER, Tulsa, Okla.-Mr. M J. Munn, formerly .with the U. S. Geological Survey, acid connected with the Gypsy Oil Co., until a short time ago, has invented a invented a method for the application of concrete to the storage not only of crude oil but of refined products:. The Cosden Oil Co., of Tulsa, is now working on that plan, and, expects to store refined products in concrete tanks. THE CHAIRMAN (I.N. KNAPP, Ardmore Pa.).-I have had considerable experience in building masonry tanks for gas Holders. I do not believe it is possible to build a concrete or masonry tank of any kind. With hydraulic cement, mortar, which will be absolutely water-tight, unless the bottom and inner wall, after completion are waterproofed with some impervious material. The same will be true of oil tanks, the bottom and inner face of which must be made impervious to oil. Masonry tanks are intended to be sunk in the ground. All that the wall of the tank then amounts to is a retaining wall to keep the excavation in shape and to receive an impervious coating. The bottom of, a; tank, when empty, must be protected by a relief valve from any hydraulic: pressure acting from below. At ordinary prices, for sheets, a tank 100 ft. diam by 20 ft. deep can be built of steel much quicker and cheaper than of masonry. Several years, ago I saw very large oil storage tank under construction in California the bottom and sides being concrete. The sides were, sloped at about the single of repose for the material excavated: If you build a steel oil tank, you can get. .men for the work who do nothing else, and you, are likely to get a satisfactory job; but if you wish to build a concrete or masonry tank it is almost: impossible to find men skilled in building absolutely water-tight masonry Work. The general idea is that any laborer can mix up concrete in any old way and make a,

Jan 1, 1918

By H. Scott

IN a paper read before the Institute of Metals, Rosenhain 1 described a new type of furnace designed primarily for the thermal analysis of metals by the inverse-rate method and used by him in the metallurgical department of the National Physical Laboratory with considerable success. In his discussion of this furnace, Rosenhain pointed out some difficulties met with in its operation, such as uniformity of rate of heating or cooling being inadequate for the degree of accuracy aimed at. To overcome this difficulty, he suggested, in place of motor propulsion, a gravity drive controlled by a"hydraulic cylinder with a relief valve whose width of opening can he regulated to allow of any desired rate of motion." The authors, in constructing a thermal-analysis furnace of Rosenhain's type, have therefore followed this suggestion and also added certain features that increase somewhat the convenience and simplicity of its operation. Requests for information regarding this furnace and the highly satisfactory results obtained from its use, it is believed, justify describing its construction and operation in sufficient detail to make possible its duplication or improvement. Description of Furnace.-The details of the furnace construction are shown in Fig. 1, which is drawn to scale. The heating tube is of /4 in. (6.35 mm.) wall "alundum" heated at the upper end by seventeen turns of 0.52 mm. platinum wire, which is coated with "alundum" cement supplied for this purpose. The cement coating is essential when a high temperature (over 1000° C.) is required, as it prevents hot spots with the resulting burning out of the heater. This platinum-wire winding, unlike "nichrome," is entirely satisfactory for temperatures of at least 1000° C. It has been maintained at that temperature continuously for 2 months and shows no signs of deterioration. This temperature is maintained by a current of 5 amp. drawn from 30 volts potential, so its necessarily continuous operation is quite economical.

Jan 8, 1919

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

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

Jan 1, 1952

By M. L. Holzworth, Philip R. Sperry, Paul A. Beck

INTRODUCTION THE basic work of Z. Jeffries1,2,3 has long ago established the main features of grain growth in the presence of a dispersed second phase. Working with sintered specimens of initially fine grained tungsten, to which various amounts of thoria have been added, Jeffries found that grain growth was inhabited, that is, practically prevented, up to a certain annealing temperature. When this temperature, which increased with the thoria content, was exceeded, extremely large grains developed abruptly from the fine grained matrix. Such a "coarsening temperature" was later found by Gross mann13,14 in certain types of steel, while Bain showed" that in other steels grain growth was gradual, without inhibition and abrupt coarsening. Later work16,17,18,19,21 demonstrated the connection between coarsening and aluminum additions. The viewpoint that the direct cause of inhibition and coarsening in aluminum killed steels is a fine dispersion of aluminum oxide21 appears to be held quite generally, although some doubts have been voiced even very recently.20 In steels with Ti additions the titanium carbide phase is considered responsible for the inhibition effects found.20 The coarsening temperature increases, with the titanium content. That coarsening may occur, as a result of certain heat treatments, even in low carbon rimmed sheet steel, was shown by Samuels,22 He also detected coarsening in a steel ingot of similar composition, after giving it the same heat treatment as that used by him for the sheet material, In this instance the identity of the inhibiting phase has not been determined, However, Tangerding found 23 that even the few small carbide particles, which occur in carbonyl iron, have a very marked inhibitive effect. As a result of an oxidizing anneal at 850°C, large grains begin to form at the surface of the carbonyl iron specimen, and gradually grow inward as the subsurface oxidation of the carbide particles progresses and eliminates the obstruction, The carbide particles can be removed also by annealing in hydrogen, with similar results. But if the oxidizing anneal of 10 hr at 850°C in air, is followed by annealing in hydrogen for 75 hr at the same temperature, grain growth is more spectacular; usually the whole specimen is transformed into a single crystal (approx. 1,5 cm X 5 cm). The reversed procedure, that is, hydrogen annealing followed by oxidizing annealing leads to smaller grains. Tangerding arrived at the logical conclusion that there must have been in his specimens some additional obstruction to grain growth resulting from a minor impurity, other than carbon. It seems likely that this obstruction was caused by an oxide formed during the oxidizing anneal and gradually reduced during the subsequent hydrogen-annealing. Other instances of grain growth inhibition of varying severity, associated with a dispersed second phase, have been described by several authors. Notable examples: lead with 0.06 pct Cu or Ni,24 cartridge brass with 0.12 pct Cr,25 or with up to 0.15

Jan 1, 1948

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By W. F. Rochow, W. C. Burke

Numerous designs of linings and accessories, including dams, lifters, and heat exchangers, contribute greatly to kiln efficiencies. Greater conductivity is achieved with basic brick than with fireclay and high-alumina refractories, depending largely upon the use of steel plates in radial joints between adjacent brick to increase heat transfer through the lining. Refractory lifters expose all portions of the load to radiant or convective heat and raise some portions to higher temperatures by cascading the load down through the path of the hot gases.

Jan 3, 1955

THE 125th meeting of the Institute was held in New York, Feb. 20-23, 1922, inclusive, and was the most successful annual meeting of the Institute ever held; there was a larger registration, there were more sessions of importance, and a greater number of sessions, than in any previous year. The total registration was 1331, comprising 351 New York members, 393 visiting members and 587 guests. At the annual business meeting of the Institute, held on Tuesday, Feb. 21, with President Ludlow presiding, there was a much larger attendance than usual. The report of the tellers was read and the following officers were declared elected: Arthur S. Dwight, Director and President-District 0 J. V. W. Reynders, Director and Vice-president-District 0 A. R. Ledoux, Director and Vice-president-District 0 Charles F. Rand. Director-District 0 George D. Barron, Director-District 0 William H. Bassett, Director-District 1 Thomas B. Stearns, Director-District 8 William Kelly, Director-District 5

Jan 3, 1922

By S. B. Twiss, P. R. Basford

The relationship between areas of iron powders, briquettes, and sintered compacts and tensile strength has been determined. It has been found necessary to distinguish between two types of areas which exist in such powders—a macroscopic area due to the shape and size of particles and a microscopic area due to pores and cracks in the surface. Only the macroscopic area, specifically the area due to particle irregularity, contributes to tensile strength; the microscopic area cannot be forced into contact with adjacent particles ond does not participate in bond formation. Of the two methods of area measurement employed in this study—permeability to liquids and gas-phase adsorption—only the former is useful for determining the roughness factor. A measure of this roughness, (area measured by permeability to liquid) -f- (orea of powder with the same size distribution, but made up of spherical particles), is shown to be uniquely related to tensile strength at constant density. The other important factors in determining the strength of sintered-metal compacts are the density and presence or absence of surface oxide. THE manufacture of metal parts by the process of powder metallurgy is an important and rapidly growing industry. Progress has been rapid and continuous, largely because of the excellent research in the field. Nevertheless, the process remains inherently complex and empirical. Several investigators have shown that the properties of the final compact must depend on many variables; namely, shape,' size distribution,"-" nd compositiona of the original particles, the pressure necessary to compress to the desired density, the density of the compact, the time and temperature of sintering, and so on. Through the application of some new techniques to the study of powders and compacts, and the correlation of a number of observations of known variables, the present paper attempts to clarify and simplify the underlying theory of the powder-metallurgy process. Any theory must start with the obvious fact that the strength of a compact, its most useful property, is due to the formation of welded areas between adjacent particles, and attempt to deduce what effect other variables will have on (a) the area and (b) the intrinsic strength of these welds. Such welded areas can be demonstrated by electron micrographs, as in Fig. 1. It was believed that (a) could be most directly studied by means of surface-area measurements on the original powders and on the compacts made from them; the area decrease should be related closely to the welded area. A representative group of eleven iron powders from commercial sources, and made by a variety of processes, was chosen for this study. In addition to the surface-area measurements, correlations were established between the tensile strength and all the known variables which might possibly affect it. The results are quite unexpected. They indicate that the situation is much simpler than the authors had anticipated. The strength of the sintered compact is determined, indeed, by no more than three variables; viz., the irregularity of the original particles, the density of the compact and, in exceptional cases, the amount of surface oxide. All three had been recognized previously as having some effect on the tensile strength, but in the absence of the special techniques and interpretations to be developed here, there could be no suspicion that they were the only relevant variables. Materials and Methods Material—All the iron powders were commercial products obtained from the Amplex Division of Chrysler Corporation. Powders A, B, C, and J were very pure electrolytic iron. Powder D was made from oxidized scrap reduced by heating with an excess of cast iron. Powder E was a high-grade iron ore reduced by hydrogen. Powder I was prepared by atomizing molten cast iron in an air blast, quenching the droplets in cold water, and crushing the coarse powder. Mill scale (oxide) is added and the mixture heated to reduce the high carbon content. The other powders were all prepared by reduction of iron oxides, such as mill scale. They

Jan 1, 1959

By J. Chipman, N. J. Grant, J. H. Walsh, T. B. King

WITH the development of adequate sampling and analysis techniques, much information has been obtained concerning the behavior of hydrogen in the steel bath during the course of steelmak-ing operations. From studies of this type it has become clear that the slag has an important role to play in determining the hydrogen content found in commercial products. A knowledge of the behavior of hydrogen in slags is necessary to round out our knowledge of hydrogen in steelmaking practice; with this information we are better able to assess practical methods of control. In this paper a method developed for analyzing slags for hydrogen content, studies of the solubility of hydrogen in synthetic slags, and studies of the variation of hydrogen content in slag and steel in industrial heats will be described. Previous Work—While very little has been done in the past to determine the hydrogen content of metallurgical slags, measurements have been made on such slag-like materials as geologic magmas and glasses. Goranson as made extensive studies of the solubility of water in natural and synthetic granites. Many workers have investigated the solubility of gases in synthetic and commercial glasses, but the recent work of Russell" is the most extensive. Russell found that the solubility of water in glass was proportional to the square root of the water vapor pressure in water vapor-oxygen mixtures. It was found that the solubility could either increase or decrease with temperature depending on the glass composition. Wentrup, Fucke, and Rief,' and Piper, Hagedorn, and Backes' have extracted hydrogen by holding a slag at 1300" and 800°C respectively in vacuum. Wentrup et al. reported hydrogen and water vapor as evolved together while Piper et al. passed the evolved gases from the hot extraction treatment over hot ferromanganese to reduce the evolved water vapor to hydrogen and, therefore, reported the analyses in terms of total dissolved hydrogen. Yavoiskii has reported hydrogen and nitrogen analyses on steelmaking slags. Dobrokhotov, Povol-skii, and Khan have studied the hydrogen content of basic open hearth steel under slags of varying viscosity. These authors reported that the hydrogen content of the steel bath increased as the fluidity of the slag was increased by the addition of bauxite. They recommended that a viscous slag be used and the steel tapped without deoxidation in the furnace to ensure a low final hydrogen content. Analysis of Slags for Hydrogen Development of Apparatus—The vacuum fusion analysis equipment described by Shields, Chipman, and Grant" was modified for the analysis of slags." This method depends upon the reduction of water in the slag to hydrogen, which is readily determined by the method used for hydrogen in steel. Preliminary experiments were made with a eu-tectic ferrosilicon melt as the reducing agent. Other experiments included the use of graphite and molybdenum crucibles. The ferrosilicon alloy bath was found to produce a thick coating on the furnace tube which could adsorb hydrogen. Graphite produced CO by the reduction of FeO, MnO, and SiO2 in such quantities that analysis for hydrogen was virtually impossible. Molybdenum, while giving a low blank value, could reduce the slag sufficiently to produce a volatile oxide which again was found to adsorb hydrogen. The arrangement finally adopted is shown in Fig. 1. The molybdenum sheet served as the induction-heated susceptor, and was separated from the escaping gases by alumina guide tubes. An outer jacket of alumina protected the quartz furnace tube, and alumina and quartz stools completed the assembly. The falling sample is shown wrapped in aluminum foil, 0.002 in. thickness, which acted as the reducing agent' This foil was careful'~ washed in acetone and an d and then dried in hot air before wrapping the weighed slag sample for charging into the apparatus. Investigation of the hydrogen content of the aluminum foil itself showed that a small quantity of hydrogen was released in vacuum, but had no relation to the weight of the aluminum charged. This quantity of hydrogen was

Jan 1, 1957