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By S. Leber, R. F. Hehemann

This investigation describes the kinetics of alloying in a (Cb-15 wt pct W. 5 wt pct Mo, 1 wt pct Zr) powder-metallurgy alloy. The degree of homogeneity obtained in hydrostatic ally pressed and vacuum-sintered samples is described by composition distributions resulting from analysis of X-ray dvfraction line profiles. Sintering variables and degvee of powder dispersion were evaluated. The utility of single-value parameters obtained from composition distributions is disaissed. The spatial distribution of composition, as revealed by anodically tinted metallographic sarrzples, was used to provide diffision models based on a concentric-sphere geometry. Diffusion equations developed from these models were found to be in general agreement with experimental results. The powder-metallurgy method for the production of refractory metal alloys has the ability to produce an inherently fine-grained, fabricable structure. The more general use of this method is inhibited, in part, by the presumed difficulty in obtaining homogeneity on a microscale. The degree of homogeneity therefore is an important, but usually neglected, variable in specifying the quality of a powder-metallurgy alloy. Convenient techniques for measuring the degree of homogeneity are now available,' and have been used to develop a model describing the process of alloying in a simple binary mixture.' In this investigation, the process of alloy formation has been studied in a more complex system. PROCEDURE The columbium-based F-48 mixture was prepared from the constituent powders shown in Table I. The particle sizes tabulated were provided by the vendors of the individual powders. Standard laboratory techniques utilizing a jar mill were employed for blending. The blended powders were hydro-pressed into 1-in. diam rods which were then sliced into thin discs for vacuum sintering. All samples were given a preliminary treatment at 1700°C for 2 hr. Varying degrees of homogeneity were obtained using additional treatments at higher temperatures. The degree of homogeneity obtained by a specific sintering treatment was evaluated metallographi-cally using the anodic-tinting technique described by olff,' and quantitatively by the analysis of X-ray diffraction line profiles using the X-ray diffraction technique developed by udman.' The diffraction technique is strictly valid only for binary systems. However, the relatively small difference between the lattice parameters of tungsten and molvbdenum when compared with columbium permitted the treatment of the complex composition of F-48 as a (W, Mo)-Cb pseudobinary. Calculations were weighted in accord with the W-Mo ratio in the F-48 composition. The contribution of the 1 pct Zr was ignored since it could not even be detected in the blended powder. Two factors are required to convert an X-ray line profile into a composition distribution. The variation of these factors with composition is shown in Fig. 1. Curve A was used to convert angular posi-

Jan 1, 1964

By D. E. Swets, R. C. Frank

It is well known that hydrogen is introduced into iron or steel as a result of many chemical processes (acid pickling, electrolytic cleaning, plating, etc.). One of the reactions that has been of recent interest1 is the reaction between an iron surface and water vapor. It was shown a few years ago2-4 that hydrogen can be introduced into steel at an accelerated rate during abrasion as a result of this reaction. Grun-berg and Scott have also observed that water in mineral oil lubricants increases pitting failure in ball bearings5 and they have suggested that hydrogen from the water is the primary cause of this effect.' In this laboratory, the question was raised as to whether or not hydrogen is also introduced into the metal surface of a bearing as a result of the decomposition of the hydrocarbon lubricant itself, and an experiment was performed to try to find a satisfactory answer. All steel parts contain some residual hydrogen. Therefore, it appeared that the best way to carry out this experiment without the need for highly accurate quantitative analyses was to use deuterium as a tracer. The natural abundance of deuterium in H2 is only 0.015 pct. The tracer was obtained in the form of deuteroparaffin (CD,(CDJ, CD,) and 0.25 g were dissolved in 20 cc of mineral oil to form the lubricant to be used in the tests. The bearings used were New Departure Type QOLOO ball bearings with a ball diam of 0.187 in. Prior to adding the mineral oil-deuteroparaffin lubricant, the bearings were cleaned in warm trichloroethylene to remove the packing grease. After packing with the new deuterated lubricant, the bearings were operated in a bearing fatigue test machine under a radial load of 190 lb and a thrust load of 190 lb at a speed of 3800 rpm. The expected life under these conditions is about 500 hr. Two tests were made; one for a period of 27 hr and the other for a period of 102 hr. The bearings achieved a temperature of 120o F during the tests. When the tests were stopped the balls were mechanically removed from the bearings and were immediately placed in liquid nitrogen to reduce degassing until the analysis for deuterium could be made. Before analyzing, the balls were warmed to room temperature and scrubbed with several degreasing agents to remove all traces of the deuteroparaffin mixture. This cleaning procedure was shown to be satisfactory by running a control test in which one ball bearing was subjected to all parts of the test except running in the fatigue machine. The hydrogen and deuterium were removed from the balls using a hot extraction apparatus attached to a mass spectrometer. Four balls from each bearing were analyzed. Each one was analyzed separately by removing it from a cold storage volume of the hot extraction apparatus and transferring it to the oven tube with a magnet. As the gases were evolved they were analyzed with the mass spectrometer. Since the hydrogen and deuterium pass through steel in the atomic form and since there are many more hydrogen atoms than deuterium atoms in the sample, the probability of forming an HD molecule is greater than forming a D2 molecule. For this reason the evolution of HD and H was followed as each ball was placed in the oven. The results showed that as each ball from the test bearing was dropped into the oven, the mass spectrometer recording of the HD evolution increased by about ten divisions. When balls from the control test bearing were dropped into the oven, the increase was about one division or less. The hydrocarbon background in the mass spectrometer was also monitored to see if hydrocarbons or deuterocarbons were given off when the balls were dropped into the oven, but no change in the hydrocarbon peaks was observed. Since the balls contained a fair amount of residual hydrogen, isotope ratio measurements were made on the gas obtained from each ball. The D/H value found for those balls which had been operated in the fatigue testing machine was consistently about 0.3

Jan 1, 1962

By J. C. Uy, T. E. Davidson, A. P. Lee

The effects of hydrostatic pressures to 26 kbars on the micro structure of poly crystalline Cd, Zn, Bi, Sn, Zr, Mg, Cu, and Fe were examined. Pressure-induced microscopic plastic flow in the form of boundary migration, slip, multiple slip, or twinning has been observed either singly or in combination in cadmium, zinc, bismuth, and tin. No deformation was observed in zirconium, magnesium, copper, and iron. The occurrence of such deformation, in terms of its intensity and initiation pressure, relates directly to the degree of anisotropy in the linear compressibility. Pressure cycling does not significantly affect the residual tensile properties of a zinc alloy which exhibits pressure-induced deformation similar to that of Pure zinc. CLASSICAL elastic theory predicts that a superim-posed hydrostatic pressure will not induce shear stresses in an ideal material. Thus, in the case of homogeneous and isotropic materials plastic flow will not occur as a result of pressure exposure, regardless of the magnitude of the pressure, unless some form of phase transformation or permanent density change takes place. However, real materials, such as metals, often vary considerably from the condition of homogeneity and isotropy. For this reason, Vu and johannin' examined and observed hydrostatic pressure-induced microscopic deformation in polycrystalline cadmium and, zinc, but not in aluminum, to pressures of 9 kbars and indicated that its occurrence is related to anisotropy in the linear compressibility. In addition, Davidson and omaan' have reported pressure-induced deformation in polycrystalline bismuth below the 1-11 transformation pressure. It becomes apparent then that under certain conditions hydrostatic pressure can induce localized internal shear stresses in some metals of sufficient magnitude to cause plastic flow. In this work, eight pure single-phase metals of different lattice structures and degrees of elastic anisotropy were examined after pressure exposures of up to 26 kbars in order to establish the conditions under which such deformation occurs and the type of deformation as a function of pressure. The effects of pressure cycling on the mechanical proper-

Jan 1, 1965

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;',' however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3' The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962

By G. R. Frank, R. E. Willett, E. H. Hollingsworth

The most generally accepted equilibrium diagram for A1-Fe alloys has a eutectic system on the aluminum side with an essentially insoluble constituent of the formula, FeAl,, as the second phase. In 1938, Bradley and Taylor1 did report a phase change of FeAl,, but this change has never been confirmed. According to them, FeA1, is the stable phase only at higher temperatures; at lower temperatures, it is converted into Fe2Al7 and aluminum. It has now been found that there is, in fact, a phase change of the Al-Fe constituent on the aluminum side of the equilibrium diagram. This change, however, is not the one reported by Bradley and Taylor. The alloys used were cast by continuous processes and had these analyses: Fe - 1.98 to 2.02 pct, Cu-0.01 pct, Si - 0.01 pct, Mn - 0.01 pct, Mg - 0.00 pct, Zn - 0.00 to 0.01 pct, Cr - 0.00 pet, Ti - 0.00 to 0.04 pct. The constituent in these alloys was identified by X-ray analysis with a Guinier camera and by chemical and X-ray powder diffraction analyses. Two procedures were used to separate constituent for the last two analyses. In one procedure, it was separated by treating a sample with a solution of methanol saturated with iodine. And in the other procedure, it was separated by first applying, at 12 amp per sq ft in 15 pct sulfuric acid at 70°F, an oxide coating to a sample, and then dissolving this coating in a solution of 35 ml of 85 pct H3PO4 and 20 g of CrO3 per liter. Several observations directed attention to a phase change of the A1-Fe constituent. Differences that appeared too great to be accounted for by micro-structure alone were found in the voltages required to apply the same thickness of an oxide coating to products from rapidly and slowly chilled ingot. Even more striking was the difference in appearance of the coatings themselves. One applied to a product from a rapidly chilled ingot was dark gray in appearance, in fact, almost black, while one applied to a product from a slowly chilled ingot was essentially white. Also, even a short period of thermal treatment at an elevated temperature of products from rapidly chilled ingot led to the same anodizing behavior as that of products from slowly chilled in-

Jan 1, 1962

By P. K. Koh, L. S. Birks, J. M. Siomkajlo

Direct identification in situ of x and a phase precipitates in stainless steel is possible with the electron probe microanalyzer. Although particles in the 1 p size range are too small to yield absolute percent composition, the relative % Crfi Mo ratio can be used to distinguish the two phases with better than 95 pct confidence. Wet chemical analysis of extracted residues gives Cr/Mo ratios in good agreement with electron probe results extrapolated to the 4 to 5 p size range. WHEN stainless steels are subjected to extended heating in the temperature region around 1600°F, precipitation of the brittle 0 or x phases may occur and impair the properties of the material. Identi-

Jan 1, 1961

By R. M. Waterstrat

X-ray diffraction and metallographic examination of binary Mn-rich alloys with Ti revealed the presence of intermediate phases in this system. A binary R phase has been identified and also a phase having an a-Mn type structure. The X-ray pattern of the phase TiMn3 is presented and a tentative phase diagram for the Mn-rich portion of this binary system has been constndcted. MANGANESE-rich alloys with titanium have been subjected to thermal analysis at temperatures down to 1100°C by Hellawell and Hume-Rothery.1 Their results indicate the existence of an intermediate phase TiMn3 in this binary system. This phase appears to coexist with the Laves phase TiMn2, and with terminal solid solutions based on the allotropes of manganese, at least down to 1100°C. The above investigators did not attempt to determine the crystal structure of this phase, however. Since, by analogy to the binary systems Mn-V and Mn-Cr3 one might expect to find a phase in this region of the diagram, it seemed desirable to obtain X-ray diffraction patterns of alloys in the concentration range in question, in order to ascertain whether the sigma phase or related structures occur. EXPERIMENTAL PROCEDURES Alloys were prepared by arc-melting electrolytic manganese and iodide titanium in a water-cooled copper crucible under a helium atmosphere. Excess manganese was added to each melt in order to allow for losses incurred during melting. The alloys were then wrapped in molybdenum foil and sealed in evacuated quartz tubes for annealing at various temperatures, as shown in Table I, followed by quenching in cold water. Although the inside of the tubes showed evidence for some loss of manganese from the specimen during annealing, there was no evidence of any reaction between the specimen and either the molybdenum foil or the quartz tube at these temperatures. It was later found that the manganese loss was considerably reduced by annealing these alloys in sealed quartz tubes containing one atmosphere of purified argon. As an added precaution the surface of each specimen was ground off before crushing the alloys to -270 mesh powder, using a hardened steel mortar and pestle. X-ray powder patterns were obtained using either FeKa or CrKa radiation in an asymmetrical focusing camera, which gave excellent dispersion of the closely spaced lines. Pictures were also obtained using a Debye camera of 5-cm radius which provided data in the angular region not covered by the focusing camera. The alloy specimens were polished and examined metallographically, using an etchant consisting of 60 pct glycerine, 20 pct nitric acid, and 20 pct hydrofluoric acid. The 10-g buttons were in each case broken in half and found to be well-melted and free of any gross segregation. One half of certain alloy buttons was submitted to chemical analysis in the "as-cast" condition. No appreciable change in composition seemed to occur during annealing . RESULTS The X-ray pattern of alloy Ti1.17Mn0.83 was found to agree well with that of the ternary R phase which was first found in the Mo-Cr-Co system,' and re-

Jan 1, 1962

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 B. F. Oliver, F. Garofalo

Gas-metal heterogeneous reactions and zone-lrelting were sinultarneously employed to produce several high-purity irons with low interstitial contents in a levitating- zone melter. Successive zone-tneltitzg pusses were made in carious sequences of atmospheves which included prepuvified tank hy-drogeta, water vapor hydrogen, palladiuril-purified hydrogen, and vacuunm of 2 x 10-6 Torr. Different irons ranging in purity from 99.89 to 99.996 pct with residual curbon contents of 17, 8 to 10, and 3 to 5 ppm have been Drepared. No measuvable gradient in the residual carbon content was observed along the entire zone-melted length (6-10 in.) in I-ilz.-diameter bars. The absence of a carbon-concentration gradient in the solid indicates an apparent distvihution coefficient of 1, an unusual condition. Internal friction, solid-state extraction, and hot-hardness results indicate that the level of mobile carbon in a iron depends on the gas-metal heterogeneous reactions employed. Purification under an oxidizing atmosphere resulted in the immobilization of nearly all of the carbon present at leuels of 10 ppm or less. Continuation of purification in a reducing atmosphere veturued the carbon to a state of mobility which was aguin reversed by further purification in all oxidizing atmosphere. The immobilization of curbon at "vesidual levels " is believed to be associated with a strong interaction between carbon and oxygen atoms. frons with low carbon and nitrogen contetzts which did not exhibit a hot-hardness peak were produced after zone ynelting in vacuum. CARBON, nitrogen, and oxygen have strong and well-known effects on many properties of iron. These effects persist even at concentrations of 5 to 20 ppm. The intent of the present investigation was to establish procedures for the preparation of high-purity iron with concentrations of these elements in the range of 5 to 20 ppm and lower. The results reported here deal with the procedures employed to prepare high-purity iron, and with observations on the behavior of certain elements at "residual levels": particularly carbon. The details of the (levitating) zone melter in which the final purification steps are performed and the necessary control of the pertinent solidification variables have been described previously.1,2 MATERIALS AND PROCEDURES Commercial electrolytic iron was induction vacuum-melted and cast into 30-lb ingots. Melt additions and ingot analyses for carbon, oxygen, and nitrogen are noted in Table I. All ingots were melted in stabilized zirconia crucibles conditioned with one iron wash heat. Middle sections of the ingots were forged to 1-1/4-in. rounds, machined to 1-in.-diameter bars, then cut to 36-in. lengths. The zone-melting operations were performed on six iron bars (A to F) at a freezing velocity of 2 in. per hr with the freezing interface rotating2 at 200, 300, or 400 rpm. Liquid zones were passed through the bars in various sequences of atmospheres, Table 11, including prepurified tank H2, palladium-purified Hz, wet H2, and system vacuum of 2 x 1018 Torr. Wet-Hz atmospheres were obtained by bubbling palladium-purified Hz through water exhibiting a resistance of 3 megohms. This water was heated with a platinum-immersion heater and was degassed prior to use. Zone melting in a wet-HZ atmosphere resulted in oxidation of the elements which are oxi-dizable with respect to iron. Fine oxide particles were observed on the surface of the liquid zone, and were encased in the bar surface with the passage of the molten zone. Between each zone pass, the surface of the bar was removed by filing and deep etching; this was continued until the oxide formation ceased. The filings were magnetically separated and the residues analyzed by optical spectroscopy. These were especially high in silicon and manganese. Samples were removed from the iron bars, with few exceptions, following each zone-melting operation. A 0.08-in.-thick disc was cut with an Al2O3 cut-off wheel at a point 1/2 in. above the beginning of freezing. Material from each disc was used for hot-hardness measurements, resistivity-ratio measurements, and carbon, nitrogen, and oxygen analyses. Analyses for most other elements were

Jan 1, 1965

By A. Josefsson

The transition temperatures of 0.01 to 0.02 pct carbon steels are shown to be strongly influenced by cooling rate in the a range, quenching from A, causing a very low transition temperature even after strain aging. In a titanium-stabilized steel and in a steel with 0.05 pct C this effect is absent. NORMAL mild structural steels usually show a structure of more or less pure ferrite, as a matrix, in which cementite grains or pearlite are embedded. Of these components, ferrite is by far the most interesting one as far as ductility and brittle (cleavage) fracture are concerned. Obviously, pear-lite and carbide are by no means necessary for a cleavage crack to nucleate and grow in the ferrite, as steels with a very low carbon content (Armco iron with 0.02 pct C) have an impact transition temperature just as high as semikilled steels with 0.26 pct C.1 Although it has been argued that a very embrittling effect is to be expected from cementite, precipitated as continuous films along the ferrite grain boundaries,'. " the micrographic evidence for a direct causal connection between the brittleness and these films does not seem to be very convincing. On the other hand, it has been stated that cementite particles in ferrite are able to stop ferrite cracks.4,5 In any case, the properties of the ferrite itself seem to be of overwhelming importance to the ductility of steels, justifying a thorough study of steels consisting of ferrite of different compositions, but principally free from pearlite, which means a carbon content below 0.02 pct. Such investigations have been carried out using the impact transition temperature as a criterion of the tendency to brittle fracture and have given some rather unexpected results. One result is the profound influence of carbon on the transition temperature of the steel in normalized condition. If the carbon content is reduced from 0.02 to 0.015 pct and below, a nearly discontinuous decrease in transition temperature appears even with high percentages of such elements as phosphorus and nitrogen present. This will be reported elsewhere." The present paper deals with another effect of carbon upon transition

Jan 1, 1955

By H. H. Johnson, Eric W. Johnson

A newly developed ac technique was used to measure the electrical-resistivity changes associated with both cyclic stressing and subsequent annealing of high-purity and OFHC copper. The early stage of push-pull fatigue was explored at 293° and 4.2°K, with stresses chosen for an expected fatigue life of 2 to 8 X 105 cycles. For high-purity copper, fatigue at 293°K was accompanied by an initial increase in resistivity. After about 5000 stress cycles, no further increase was observed. Annealing studies showed that the resisticity increment could be accounted for solely in terms of an increased dislocation density, to about 2 x 1010 disl pev sq cm. Fov 42°K fatigue, however, the resistivity increased continually, with no evidence of saturation, as approximately (No. of stress cycles)1/4. This is intevpreted to result from both dislocation multiplication and vacancy production; estimated vacancy concentrations are 10-4 to 10-9. The continuous resistivity increase was inhibited by interspersed annealing treatments at 293°K, which also raised the level of the stress-strain curve. These effects are attributed to annealing of vacancies into dislocation loops. In contrast, OFHC copper fatigued at 4.2°K showed saturation of electrical vesistivity after only a few hundred cycles, and it appeared that vacancies annealed out completely between 77° and 293°K. MaNY observations suggest that both dislocation multiplication and point-defect production are important aspects of fatigue deformation. An increase in dislocation density with number of stress cycles has been demonstrated or implied by several experimental techniques, including optical metallography with lithium fluoride,' electron microscopy with copper,2 thermal conductivity of Cu-Zn alloys,3 and peak-stress measurements during cycling at constant plastic strain amplitude.4,5 At low amplitudes and/or stresses saturation of fatigue hardening and dislocation density occurs early in the expected fatigue life,4-6 frequently by a few hundred cycles. The evidence for point-defect production is somewhat less extensive, but it is nonetheless persuasive. Rosenberg7 reported briefly that, for equal stresses, copper fatigued at liquid-hydrogen temperature displays an increase in electrical resistance some ten times that which accompanies unidirectional stressing. Further, the extra resistance saturates after a few hundred stress cycles, and does not anneal significantly until a temperature of about 170°K is attained.' Point-defect production during fatigue is also suggested by 1) the softening during cyclic stressing of initially strain-hardened polycrystal-line copper9, 2) the strong temperature dependence of the yield strength of fatigue-hardened mono- and polycrystalline copper,579"0 and 3) the influence of intermediate annealing upon slip-band formation in copper fatigued at 90°K.8 It is evident that characterization of the fatigued state requires a knowledge of both point-defect and dislocation densities. For this purpose electrical-resistivity measurements are useful, but they are difficult to perform because of geometric limitations. Push-pull fatigue is necessary to obtain a macroscopic ally uniform deformation over the specimen cross section; however, the specimen must then have a low slenderness ratio to avoid plastic buckling, while the standard dc resistivity technique requires a very slender specimen for

Jan 1, 1965

By H. Warlimont

In recent investigations of the microstructure and crystallographic features of martensite by electgon microscopy,', '9 thin films (about 50 to l000A in thickness) have been used as specimens. It was found by W. Pitschl ,2 that the lattice relationships between the supefiaturated fcc matrix and the martensite formed in thin films were different from those observed after transformation in bulk material. Corresponding differences are to be expected in nucleation and in reaction kinetics in the formation of martensite in thin films, but have not yet been reported. In the course of the preparation of thin films of iron-base alloys for investigation by electron microscopy it was observed that films of alloys, whose martensite formation temperature (Ms) was below room temperature, formed martensite during the electrochemical thinning process conducted at or above room temperature. The chemical compositions and approximate bulkM,-temperatures of the three materials on which this observation was made are listed in Table I. The alloys were vacuum-melted from high-purity metals. It can be seen that the effect occurred in alloys that contain only sub-stitutional components as well as in alloys that contain carbon as an interstitial solute. The appearance of martensite formed in this manner is illustrated in Fig. 1, which represents a polished film of alloy No. 1 at XI0 magnification. The martensite plates can be recognized by their surface relief effects. In addition, heavily strained (owrinkledo) austenite can be seen near the edges of the film where it is thinnest and transformation stresses or strains can be accommodated by plastic deformation most easily. The nonuniform distribution of transformed regions is probably due to the varying thickness of the film. These observations were common to all materials listed in Table I. Because effects of supercooling or straining can

Jan 1, 1962

By Herman Blumenthal, Ronald Silverman

lnfiltrability of a porous Tic compact, produced by powder metallurgy technique, depends on the capillarity of the compact and the surface condition and nature of the individual particles. Capillary forces raise the liquid metal infiltrant into the interconnected pores of the compact and the complete filling of these pores is a function of their geometry as well as the wettability of the Tic particles. The paper deals especially with the improvement of this wettability through surface conditioning of the Tic particles. INFILTRATION, a technique for preparing dense powder metallurgy parts by filling the void spaces of a porous body with a liquid metal, has been used for the manufacture of titanium carbide-base cermets. Although the infiltration process was

Jan 1, 1957

By I. Tamura, J. O. Brittain, T. Mura

Plain carbon steel in the cold worked or marten-sitic conditions has an internal friction peak at about 250 oC at a frequency of I cps. The influence of substitutional alloying elements on this peak was examined experimentally. The alloys were vacuum melted Co-, Cr-, Mo-, Ni-, and Si-iron (about 3 pct alloying elements), and carburized Si-iron. The internal friction of the alloys in the temperature range 30o to 500 OC was determined by means of a torsion pendulum. The 250 oC peak of the cold-worked alloys was lower in height than that observed in plain C-iron and steel. Carburized Si-iron in the quenched condition had a peak which occurred at a slightly lower temperature than in quenched plain C-steel, but the height of the peak was substantially greater than that found for the same alloy in the cold-worked condition. The activation energy of this peak for martensitic Si-steel was about 35 kcal per mol. ANNEALED a iron has two internal friction peaks due to nitrogen and carbon at 20o and 40o C respectively, at a frequency of 1 cps. If a iron is cold worked, these diffusion peaks become smaller and a new peak appears at about 250o C. The activation energy for the 250o C peak is in the range of 32 to 44 kcal per mol and has an average value of 38 kcal per mo1. It has been experimentally verified that both interstitial solute atoms and dislocations are necessary for the 250o C peak. 3 Wert has also shown that an incubation period precedes the appearance of the 250 C peak.4 With regard to quenched martensitic steel, Ke et al.596 observed two peaks at around 130o and 250o C. They conjectured that the 250o C peak in martensite was due to the same mechanism as the 250°C peak in cold worked a iron, and the 130°C peak was due to the nature of tempered martensite. They did not report the activation energy for these peaks. Chernikova7 found only one peak at about 200° C in tempered martensite. In a previous paperS we reported an activation energy of approximately 40 kcal per mol for the 250° C peak in plain carbon martensitic steels. Ichiyama8 found the activation energy to be about 36 kcal per mol for the 250° C internal friction peak in steels in the martensitic condition. The present authors proposed a theory for the 250°C peak for cold worked and quenched iron and steel.= The theory for the peak is based upon the addition of a strain-energy term to the free energy for the formation of a carbide precipitate due to the presence of a disclocation. The model employed for the relaxation process consists of the growth and solution of a carbide precipitate of critical size as a consequence of an oscillating dislocation. In this report, the influence of substitutional alloy ing elements on the 250° C peak is examined and the experimental results are discussed in terms of our theory for the peak. Most of the experimental work on the alloy steels was confined to the Fe-Si-C alloys.

Jan 1, 1962

By J. W. Freeman, E. E. Reynolds, A. E. White

Fram a study of 63 systematic alloy modifications it was found that molybdenum, tungsten, and columbium, added individually or simultaneously, and increases in chromium cause major improvements in 1200°F rupture strengths of Cr-Ni-Co-Fe base alloys. Rupture strengths were a function of the effect of composition modifications on both the inherent creep resistance and the amount of deformation the alloy would tolerate before fracture. THIS paper describes the results of an investigation of a series of alloys with systematic variations of the chemical composition of the following basic alloy: C, 0.15: Mn, 1.7; Si, 0.5; Cr, 20.0; NI, 20.0: Co, 20.0: Mo, 3.0; W, 2.0; Cb, 1.0; N, 0.12; Fe, 32.0 pct. The 62 modifications of this alloy were produced under conditions which minimized all factors influencing properties at high temperatures except composition. Melting, fabrication, and heat treatment were carefully maintained constant. Stress-rupture properties at 1200°F were used as the primary criteria of evaluation of the alloy. The objective of the study was to obtain data for determining the fundamental role of the influence of alloying elements on properties of heat-resistant alloys at high temperatures. In addition the results should be useful in determining optimum chemical compositions, the sensitivity of properties to variations in composition, and the degree to which alloy content could be reduced while retaining worthwhile properties. It is difficult or impossible to develop correlations between properties at high temperatures and systematic variations in chemical composition from published data for wrought heat-resistant alloys developed for gas turbines.' ' The main reason for this is the extreme dependence of the properties on conditions of treatment of the alloys." In most cases variation in final treatments between alloys so influences the properties that the influence of chemical composition is obscured. In addition it is recognized Table I. Basic Alloy and Some Modifications Used Basic AllOy, Variations in Element Pct Composition, Pct C 0.15 0.08. 0.40. 0.60 Mn 1.1 0.03,0.25.0.50,1.0,2.5 S1 0.50 1.2, 1.6 Cr 20.0 10, 30 Ni 20.0 0, 10,30 Co 20.0 0. 10, 30 MO 3.0 0. 1.2.3, 5, 7 W 2.0 0, 1, 5, 1 Cb 1.0 0.2,4,6 N 0.12 0.004, 0.08, 0.18 Fe 32.0 that variations exist between heats of the same alloy which are related to melting practice and that there is a strong possibility that conditions of hot working influence response to final treatments. The development of heat-resistant alloys has been based on the gradual accumulation of data roughly related to composition from extensive testing programs. There is every reason to believe that in most cases the optimum compositions have been achieved by this procedure in the alloys commercially available. There are, however, very little data showing the influence of systematic variations of composition free from the influence of other factors, particularly for alloys of the type investigated. Several investigators of cast alloys have demonstrated compositional effects, notably Grant,1-6 Epremian,t Guy,8 and Harder and Gow.9 Sykes10 eviewed the work on the wrought alloy Rex 78 and the systematic variations of carbon, copper, molybdenum, and cobalt leading to the development of the stronger Rex 337A alloy. From the papers by Wilson11 and Henry12 it is possible to deduce the beneficial effect of substituting cobalt for iron in 0.45 pct C-20 pct Cr-20 pct Ni-4 pct Mo-4 pct W- 4 pct Cb alloys. Wilson mentioned but did not present the extensive compositional studies involved in developing these alloys. Binder" showed optimum properties for 3, 2, and I pct, respectively, for molybdenum, tungsten, and columbium in 20 pct Cr-20 pct Ni-20 pct Co-30 pct Fe alloys for limited systematic variations of these

Jan 1, 1953

By D. Coutsouradis, L. Habraken, P. Nicolaides

The TTT curves of 0.1 pct C, 13 pct Cr steels containing up to 12 pct Co have been determined in order to establish whether the effect of cobalt is similar to that observed m plain carbon steels. It is shown that cobalt increases the incubation time and decreases the transformation rate, though not in an uniform way. The bainitic transfornation is displaced to lower temperature and overlaps partially the martensitic zone. ThE effect of cobalt on the transformation of a plain carbon austenite has been studied by many investi-gators.'-3 It was shown that cobalt displaces the TTT curves to shorter times and diminishes the harden-ability. The interpretations given for this effect of cobalt are conflicting. According to E. Houdremont,4 cobalt increases the transformation rate of austenite because it increases the diffusion of carbon as shown in the experiments of E. Houdremont and H.Schrader,' R.Smoluchowski,5 and M. Blanter.6 On the other hand, M. Hawites and R. Mehl3 deny on the basis of their own experiments any effect of cobalt on the diffusion of carbon and they assume that an explanation should be found in an eventual effect of cobalt on the mechanism of nucleation and growth of pearlite. W. C. Hagel, G. M. Pound, and R. F. Mehl7 have shown by calorimetric measurements that cobalt increases the free energy of the austenite-pearlite transformation in an eutectoid steel and this result explains qualitatively the observed effect of cobalt on the rate of nucleation and growth of pearlite. The purpose of this research was to see by determination of TTT curves, if this same effect exists in 13 pct Cr steels. EXPERIMENTAL PROCEDURES The preparation of the alloys was carried out in an

Jan 1, 1960

By D. H. Thompson, A. W. Tracy

Season-cracking is a type of failure of brass that results from the simultaneous effect of stress and certain corrodants. The object of this paper is to present data that will aid in a more complete understanding of the mechanism of season-cracking and related phenomena. Results presented show that certain high copper alloys are susceptible to season-cracking or stress-corrosion cracking, and possible explanations are discussed. Starting at least as far back as 1906, many papers have been devoted to this subject but the symposium1 held in Philadelphia in 1944 is the richest source of information. In order to study season-cracking, several of the many variables were held constant so as to learn the effects of others. Season-cracking is generally understood to refer to the corrosion cracking of brass having internal stresses;²,³ it is a special case of the general stress-corrosion cracking. Inasmuch as applied stresses are more readily produced and controlled, they were used exclusively in this research and the resulting phenomenon must he called stress-corrosion cracking.²,³ Only constant tensile stresses were used. The agents believed to be most frequently responsible for season-cracking are ammonia. amines and compounds containing then]. Both moisture and oxygen also appear to he necessary. Therefore, an atmosphere containing ammonia, water-vapor and air was selected for these tests. Briefly, the work consisted of exposing sheet metal specimens, having a reduced section ¼ by 0.050 in., of copper-base alloys to the effect of static tensile stresses between 5,000 and 20,000 psi and simultaneous contact with a. continuously renewed atmosphere containing 80 pct air, 16 pct ammonia and 4 pct water vapor at 35°C. The gas mixture and the speci- mens were maintained above the dew-point. The time-to-failure in minutes was the primary measure of results. In order to limit the experiment to finite time, it was considered that a specimen which had neither failed nor undergone microscopically detectable cracking in 40,000 min. (4 weeks) while under a stress of 10,000 psi or more could be considered immune to cracking. This is merely a convenient limit and is not to be considered proof of immunity. Supplementary tests in the absence of stress using weight loss or microscopical appearance as measures of attack were made. Apparatus The apparatus used in this research is shown in Fig 1. To facilitate the description it may conveniently be divided into six parts: stress-producing units, test chamber, gas train, electrical controls, timers and gas analysis device. A stress-producing unit is shown in an exploded view at the left in Fig 2. At the right is an assembled unit with a specimen in place in the lower portion; it is this part that remains in the ammonia atmosphere during a test. The upper part contains a spring, a central threaded rod, a large nut and necessary washers, pins, and so forth. Stress is produced in the specimen by screwing down the top nut against the spring, thus putting a tensile load on the central rod and so on the specimen. The wrench that turns the nut by extending through the upper cap, is seen at the upper right of the figure. The magnitude of the load is gauged by measuring from the pin that extends through the side of the tube, to a fixed point on the large flange. Measurement is made with a vernier beam caliper, shown at the right of the figure. The necessary spring compression to give a desired stress is calculated from the calibration curve of the spring and the dimensions of the specimen. The test chamber, center Fig 1, consists of a thermally insulated steel box 32 in. long by 10 in. high by 7 in. wide. A horizontal baffle reaching nearly to each end divides the chamber equally. Below this baffle are inlets for air and ammonia, a heating coil and a fan. Thus the gases are warmed and mixed in the lower level and flow past the specimens in the upper level. A thermo-regulator and thermometer project into the upper space. The top is pierced by 12 ports flanked by 3/8 in. threaded studs. A test starts when a port is opened and a unit containing a stressed specimen is thrust through it and bolted down against a neoprene gasket. The test chamber is held at 35°C. The gas train, right rear Fig 1, carries ammonia and air continuously to the test chamber. Tank ammonia passes through two reducing valves, a needle valve, a flow meter and into the test chamber. The air from either the plant compressor or a small laboratory compressor passes through wool towers and flow controls to the flow-meter. It then bubbles through water at 34°C and through a heated line to the test chamber. Electrical controls, left rear, Fig 1, provide rectifiers and mercury relays for the test-chamber and humidifier-heating-control circuits and outlets for

Jan 1, 1950

By R. H. Frazier, C. H. Lorig, F. W. Boulger

This investigation establishes the effect of ferrite grain size resulting from various heat treatments on the transition temperature of a semikilled steel plate. Different austenitizing temperatures and various cooling rates were used. The ductile-brittle transition temperatures were determined by the Navy tear test and the keyhole Charpy test. THE data presented in this paper deal with quality characteristics of ship-plate material which were investigated in a research project sponsored at Battelle by the Bureau of Ships, Dept. of the Navy. Specifically, the object of this investigation was to establish the effect of ferritic grain size (resulting from various heat treatments) on the so-called transition temperature of ship-plate steel. Transition temperature is not a fixed property of steel. It is derived from a series of static or dynamic tests made at various temperatures and is qualified by specifying the type of test employed as well as the testing criteria. Because in earlier investigations of ship-plate quality1,2 the so-called Navy tear test and standard notched-bar tests (keyhole Charpy) proved to be useful in interpreting instances of brittle behavior of ship plate in service, these tests were used in the investigation reported in this paper. By definition,' in the Navy tear tests the highest temperature at which one or more of four specimens breaks with a brittle fracture (that is, when less than 50 pct of the fracture area has a dull fibrous texture) is termed "transition" temperature. In the Charpy tests, the 12 ft-lb level of energy absorption was used as a criterion indicating the "transition" temperature, although other levels of energy absorption were also used for comparison. Earlier work" on ship-plate steels indicated that the temperature at which ship plate is finished has a very significant effect on its notched-bar properties. Plates rolled in the laboratory, where the finishing temperature can be carefully controlled, showed a 16°F decrease in tear test transition temperature when the finishing temperature was lowered 200°F (from X" to Y°F). The same plates showed a drop of 10°F in the keyhole Charpy transition temperature from the same decrease in finishing temperature. Commercially finished plates' exhibit a similar trend. When the ferrite grain size of the hot-rolled laboratory plates was determined, a close relationship was found between the ferrite grain size and the notched-bar transition temperature." " he indicated relationship between grain size and transition temperature was in agreement with the findings on low carbon steels of Hodge, Manning, and Reichhold' despite the differences in composition of the steels. The cooling rate after rolling varies from one steel plant to another. This variation changes the micro-structure" and appears very likely to affect the notched-bar properties of the steel plates. In the investigation summarized in the present paper, heat treatments simulating finishing practices in the hot rolling of ship plate were used in order to vary the ferritic grain size. It is believed that the indicated relationship between grain size and transition temperatures of the ship-plate material will prove useful in estimating the effect of rolling temperature and of cooling rates from rolling temperatures on the notched-bar properties of semikilled steel plate. Material The semikilled steel plate used in this investigation was a ¾ in. hot-rolled plate from an open hearth heat. Other plates from this heat have been used on many other studies performed for the Ship Structure Committee," "," and the heat has been identified as project steel "A". The chemical composition of the plate1 was 0.25 pct C, 0.49 pct Mn, 0.011 pct P, 0.045 pct S, 0.04 pct Si, and 0.004 pct N.

Jan 1, 1956

By Howard Reiss, C. S. Fuller

A theoretical and experimental study has been made of those interactions between holes and electrons which influence the solubilities of donors and acceptors in semiconductors. The major portion of the work concerns the solubility of lithium in silicon doped to varying degrees with boron. This solubility increases with increasing boron content in a manner predicted by theory and exhibits the expected temperature dependence. A qualitative experiment in germanium is described which demonstrates, in accordance with theory, that doping with a donor decreases the solubility of another donor. SEVERAL authors have discussed the possibility that holes and electrons behave like chemical entities and influence the solubilities of ionized impurities, Wagner was the first to invoke this concept in connection with his studies on nonstoichio-metric oxides. He used it again in explaining the solubility of hydrogen in molten binary alloys. In a theoretical paper,' Reiss drew attention to the fact that solutions of impurities in semiconductors

Jan 1, 1957

By N. J. Grant, K. M. Zwilsky, J. T. Blucher

DISPERSION strengthening has been studied in a number of metal-metal oxide systems. To date those pure metals available as fine particles (less than about 5 p) have received most of the attention whereas solid solution alloys, generally unavailable as fine powders, have not been examined in detail. The present work was undertaken as a preliminary study to evaluate combined effects of solid solution and dispersion strengthening. The technique used was that of dry mixing of elemental powders with the oxide, followed by a diffusion treatment to obtain the solid solution. The average particle size of the powders used was: Ni, 3.2 p (1nco B); Mo, 1.3 p (Fansteel Metallurgical Corp.); and y alumina, 0.027 \i (G. L. Cabot, Inc.). The particle size of the metal powders was determined by Fisher subsieve measurements while the size of the alumina was calculated from a surface area determination. Prior diffusion studies on small compacts pressed from mixtures of nickel and molybdenum powders with and without 7.5 vol pct A1203 indicated that diffusion was complete after sintering for 100 hr at 1800" , or 50 hr at 2250", or 20 hr at 2550° F. The progress of diffusion was followed by microstructural examination and micro-hardness measurements. Two observations made during the diffusion experiments were: 1) That diffusion proceeded faster in the presence of alumina, confirming similar findings by Seith and Loepman on "SAP'';4 2) That diffusion at temperatures above 1800°F resulted in coarsening of the alumina in agreement with results of other authors reporting on the growth of alumina in nickel above 1800"F. Similar experiments in the Ni-Cr system using 6 and 20 p Cr powders of 0.7 and 0.025 pct 0, respectively, did not result in significant solid solution formation even after long time exposures at 2550° F. It must be concluded that chromium oxide films around individual particles interfere with normal diffusion. A nickel alloy containing 5 wt pct Mo and 7.5 vol pct alumina was fabricated by dry mixing of powders, isostatically compacting at 30,000 psi, diffusing for 120 hr in dry hydrogen at 1800" F, and extruding at 1950"~ with a 30 to 1 reduction of area ratio. The resulting structure, presented in Fig. 1

Jan 1, 1963