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By E. J. Dulis, R. M. Fisher, K. G. Carroll

IT is well known that ferritic steels containing more than 15 pct Cr when subjected to temperatures in the range of 700" to 1000°F exhibit increasing hardness and decreasing ductility. The phenomenon has been widely termed the "885 °F embrittlement," after the temperature of most marked effect.'.' In view of the excellent review articles available in the literature3-6 only a brief account of experimentally established facts need be given here. The extent of changes in physical characteristics during embrittlement depends on chromium concentration and time at temperature, higher alloy content and longer time both promoting more rapid and extensive changes. In a 27 pct Cr steel, changes in impact strength and in angle of fracture in bending can be detected after only a 1 hr exposure at 885°F; after 50 hr this steel becomes quite brittle. Hardness increases slowly with time during thousands of hours exposure and may attain a maximum hardness number twice as large as that of the unexposed steel. Microstructural changes accompanying embrittlement have been described as an initial widening of grain boundaries followed by eventual darkening of ferrite grains. Embrittled steels etch more readily, e.g., the weight loss of a 27 pct Cr steel in acid solution may occur at a rate one hundred fold greater following exposure at 885 OF. Marked changes which accompany embrittlement have been observed in electrical resistivity, specific gravity, and magnetic coercive force. Changes in physical properties may be readily removed by heating at temperatures above the embrittling range, such as a treatment at 1100°F for 1 hr. It has frequently been noted that the 885 °F embrittlement suggests precipitation on a submicro-scopic scale of a chromium-rich constituent, the nature of which has not been revealed by X-ray diffraction. Progressive broadening of the body-centered cubic diffraction lines during embrittlement has been observed," and recent observations by Lena and Hawkes' upon single crystals have shown early asterism in X-ray photographs, disappearing within an hour at 900 °F. Many workers have ascribed8-13 the phenomenon to a precipitation of a phase (FeCr), which is known to cause embrittling effects at temperatures much higher than 885°F. Two general observations, however. suggest that a precipitation cannot be responsible for the 885°F phenomenon: 1—prior cold work greatly enhances a formation, whereas it scarcely affects the 885 °F embrittlement, and 2—the presence of an alloying element such as nickel or manganese may have an effect on the 885 °F embrittlement which is opposed to its effect upon a formation. The slight enhancement of a formation and 885°F embrittlement observed in the presence of elements with strong carbide and nitride forming tendencies' is probably a consequence of lessened chromium depletion of the matrix. The bar graph in Fig. 1 shows a typical example, taken from two 27 pct Cr steels used in this work, of the hardness after exposure for 10,000 hr at 900°, 1050°, and 1200°F. Steel A (0.03 pct C, 3.13 pct Mn) showed marked hardening at 900" and 1200°F, whereas steel B (0.12 pct C, 0.63 pct Mn) exhibited only the 900°F hardening. The cr phase was found in steel A at the higher temperatures but not in steel B. Presumably a formation is enhanced by the low-carbon and high-manganese concentrations in A," Thus there are two distinctly different hardening phenomena present which cannot both be ascribed to v precipitation without invoking a transition phase possessing remarkable properties. Materials A number of chromium steels exposed for long periods (5000 to 34,000 hr) at 900°F, as well as unexposed samples of one of the steels, were available for this investigation. Table I gives the chemical compositions and aging treatments of these steels. In addition to these steels exposed in the elevated temperature test furnaces of the National Tube Division, a number of high-chromium steels were heated for short periods in small laboratory air furnaces and lead baths. Supplementing these commercial steels, a sample of high-purity (0.018 pct C, 0.002 pct N) 28 pct Cr iron, exposed 1000 hr at 887°F. was furnished by the Union Carbide and Carbon Corp. In addition, an alloy of iron and chromium of high purity containing 46 pct Cr was used. This

Jan 1, 1954

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

A simple reproducible method was developed for determining the ignition temperatures of magnesium and magnesium alloys and by this method magnesium and over 100 magnesium alloys were measured. The ignition temperature of magnesium was determined in O2-SO2, O2-N2 mixtures and in O2 from 0.166 to 10 atm pressure. The ignition temperature of magnesium is generally lowered by alloying and increased by an increase in oxygen pressure. WITH the expanded use of magnesium alloys in industry, ignition temperatures are of considerable importance, especially in heat treating and for service at elevated temperatures. Magnesium alloys exhibit a relatively slow linear oxidation rate up to temperatures near the melting point.' At some critical temperature the rate of oxidation becomes extremely rapid. This high rate of oxidation is accompanied by the emission of light and additional characteristics suggesting a flame. The literature concerning the ignition temperatures of magnesium and magnesium alloys is relatively incomplete and the values reported by various authors are not in agreement. The most probable reasons for this are: 1—The absence of a suitable definition of ignition, and 2—the need of a standardized method of determining the ignition temperatures of inflammable metals and alloys. The exact date of the discovery of the fact that magnesium will ignite and burn is unknown. It is likely that H. Davey encountered this property of the metal during its preparation in 1808. The first reference in the literature specifically on ignition of magnesium is by Lenze, Metz, and Rubens.' They investigated the inflammability of certain magnesium alloys. Brown3-' reported that magnesium ribbon will ignite in air at 507 °C by what was called the rising temperature method. Hartman, Nagy, and Brown" reported that magnesium powder ignites from 475" to 560°C depending on particle size. According to Guise, Mars, and Wilson prolonged heating in air at 427°C of common casting magnesium alloy causes it to ignite. Samples of magnesium alloys were placed directly in the flame of a torch by Carapella and Shaw.' These investigators obtained some evidence of melting prior to ignition. For commercial magnesium, they reported an ignition temperature of 650°C. Their values varied from 450" to 800°C for magnesium alloys. Willmore and Peterson" studied the effect of air velocity, humidity, rate of heating, and foreign metal contact on the ignition temperature of magnesium. They conclude that melting is not a prerequisite for ignition and that the conditions which influence ignition are complex and difficult to analyze. The only quantitative theoretical treatment of the ignition temperatures of magnesium and magnesium

Jan 1, 1952

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 W. M. Hirthe, E. H. Greener, D. R. McCann

It has been proposed1'2 that, at low temperatures, point defects are a strengthening factor in inter-metallic compounds whereas, at high temperatures, the deformation is diffusion-controlled and, therefore, an increase in the concentration of point defects tends to soften or increase the plasticity of a compound. More recent investigations, including those of Bloem and Kroger' on PbS, Kramers and smith4 on TiO, and Nadeau5 on LiF, have extended this concept to ionic crystals. Rutile (TiO2) is a tetragonal transition metal oxide which has a defect structure over at least the compositional range. The defect in near-stoichiometric rutile is either an oxygen ion vacancys or a titanium ion interstitial.' This investigation does not contribute to resolving the defect question but either defect would satisfy the results obtained. Six specimens having the same orientation, see Fig., 1, utilized in an independent investigation1' were cut with a diamond saw from a single-crystal boule purchased from the Linde Co. Three specimens were annealed in air at 1200°C for 4 hr and slowly cooled to room temperature in a period of 12 hr. The remaining specimens were reduced in a vacuum of l0 mm Hg at 1200°C for 4 hr and cooled at the same rate in vacuum. The reduced specimens were weighed before and after reduction and, assuming the weight loss to be oxygen, the corresponding oxygen-to-metal ratio is 1.998. All specimens were chemically polished and etched utilizing the techniques described by Hirthe, Adsit, and Brittain." The specimens were embedded in acrylic resin and mounted on a leveling vise in a Kentron micro-hardness tester. A 200-g load was applied to a Knoop indenter with a descent time of 18 sec and a dwell time of 20 sec. Eight indentations were made on a near (171) surface, approximately 3 deg from the (lii) plane, for each orientation of the major axis of the indenter relative to the crystal structure. The dependence of microhardness on orienta-

Jan 1, 1963

By R. L. Rickett, W. C. Leslie

The influence of deoxidation practice, prior thermal history, and aging time and temperature on the strain-aging behavior of low-carbon open-hearth steels was investigated. The criterion of aging employed was the increase in yield strength in the tensile test, after straining and aging. Composition, prior heat treatment, and aging conditions were all found to be important in governing the strain-aging characteristics of these steels. THAT deoxidation changes the strain-aging propensities of low-carbon steels has been known for a long time, but there has been little agreement, and even contradiction, between results obtained by different investigators and between results obtained in the laboratory and in the mill. This investigation was begun in the hope that some of the uncertainties connected with the strain aging of commercial steels could be eliminated. In considering this problem, it was necessary to define strain aging and to examine the methods used to measure this property. Strain aging can be defined as the changes in properties of a metal or alloy with time, after cold working. The rate at which these changes occur increases as the temperature is raised above atmospheric. The requisite plastic strain is the principal distinction between strain aging and quench aging, the latter being due to precipitation from supersaturated solid solution. Strain aging is also characterized by rapid attainment of maximum hardness at high aging temperatures and lack of softening (overaging) at low aging temperatures. Several possible criteria of strain aging have been listed by Sachsl and by Davenport and Bain.' Because changes in mechanical properties are the most easily measured and the most commonly used, consideration of methods to be used in this investigation was confined to three tests: tensile, notch-impact, and hardness. Hardness tests are the most economical and easiest to perform, but produce only one measure of strain aging. Also, as pointed out by Felmly, Hartbower, and Pellini,³ hardness changes due to aging are not pronounced for steels containing more than 0.15 pct C. Notch-impact tests require careful preparation of large numbers of specimens. Above and below the transition temperature the test lacks sensitivity; furthermore, it is extremely difficult to impart a uniform strain to the specimens, followed quickly by aging and final testing; machining must generally take place after straining. For these reasons, the tensile test was selected for use. Although this test requires a considerable expenditure of time, labor, and money in preparation of the specimens and performance of the test, more information can be gained than from any other single mechanical test, information which includes upper and lower yield points, yield-point elongation, tensile strength, strain-hardening exponent, reduction of area, and elongation. Low and Gensamer' and Schwartzbart and Low5 lso used the tensile test, taking the increase in flow stress after straining in tension and aging as a measure of strain aging. In our work, as in theirs, each specimen was strained an arbitrary amount, sufficient to pass through the

Jan 1, 1954

By M. E. Nicholson

The effect of boron on the austenitic transformation rate of iron is smaller than on low carbon steels. The influence of austenitizing temperature on B-Fe is the reverse of its influence on steels. THERE have been many studies made of the influence of boron on the hardenability of steel, but apparently none has been made of its influence on the y-a transformation of pure iron. There are several facts suggesting that boron should have a pronounced effect on the transformation rate of iron. First, Simcoe et a1.l indicated that boron reduces the nucleation rate of ferrite and bainite. Second, they showed, along with others,', " that the lower the carbon content of steel the greater the influence of boron on hardenability. If this trend extends to pure iron, the influence on rate of ferrite formation should be considerably greater for iron than for medium carbon steels. According to Rahrer and Armstrong," the multiplying factor for boron in pure iron should be about 2.40, compared with 1.50 in a 0.35 pet C steel. According to an extrapolation made by Grange and Mitchell,' the effect should be even greater, and the multiplying factor should be about 3.5 in iron. Many investigations of the boron influence'.7, 2, 5 indicated that boron is effective only when in solid solution. On the other hand, Chandler and Bredig" suggested that boron increases hardenability by combining with nitrogen, thereby preventing formation of AlN, which catalyzes the decomposition of austenite. If their hypothesis is valid, boron should have no effect on an alloy free from nitrogen. Digges et al." showed that so far as low nitrogen high purity Fe-C alloys are concerned this is not the case. No experiments, however, have been made on low nitrogen iron. To determine whether or not boron has an effect on low nitrogen iron and, if an effect exists, to determine whether it is as large as predicted from the investigations of boron treated steels, the following work was performed. Because of the rapidity with which iron transforms from austenite to ferrite at even a moderate degree of supercooling, it was decided to study the influence of boron on the transformation rate of iron by determining the effect of quenching rate on the temperature of the beginning of transformation. The technique, essentially that used by Greninger' and Duwez,H consisted of heating small specimens, 0.1 in. sq and 0.010 in. thick, in an atmosphere of purified helium with a resistance heater coil, and then quenching the sample in a jet of helium gas. At the time the jet was applied, the heating coil was removed from around the sample. The sample was suspended in the furnace on 30 gage chrome1 and alumel wires, one welded to each side of the specimen, which also served as a thermocouple for measuring the specimen temperature. Specimens were prepared from vacuum-melted iron obtained from the National Research Corp. which was rolled to a thickness of 0.060 in. and then decarburized in wet hydrogen for 51/2 hr at 700°C. This treatment also removed any boron present in the iron. The resulting iron contained 0.001 pet C. 0.0002 pet N, and 0.005 pet 0. One half of the piece was then boronized by surrounding it with 325 mesh boron powder and heating it for about 2 hr at 900°C in H,. The boronized iron was then homogenized at 1100°C for 24 hr. The iron boride case formed by boronizing was removed by grinding 0.010 in. from each side of the plate, and the piece was finally rolled to a thickness of 0.010 in. The resulting alloy contained

Jan 1, 1957

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff' have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

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

E. A. ANDERSON*—At the outset, I note that you are using a humid atmosphere containing ammonia but that you make no reference to the variable of carbon dioxide content. Edmunds in his work in this laboratory found very marked effects on the rate of failure due to variations in carbon dioxide in the environment. This point is, of course, strongly related to the overall corrosion rate problem since the role of the carbon dioxide seems to be to permit the formation of hygrogroscopic salts which give a controlled moisture film on the specimen surface, which in turn seems to support the intergranular penetration more consistently than would otherwise occur. (2) Your results with various copper binary systems are very striking. It is curious, however, that the time-to-failure minima all occur at percentages of the alloying element which are considerably below the solubility limits as given in the conventional equilibrium diagrams. If your theory regarding the presence of these impurities in some concentration in the grain boundaries is correct, then either the existing diagrams are not accurate in the room temperature region, or there is a difference in solubility in the grain boundaries as compared -with the grains. A study along these lines might be very revealing. (3) The undesirable effect of silicon in copper calls to mind our own observations on the influence of silicon on the stress corrosion cracking resistance of alpha brass. In this case, silicon was found to have a very marked beneficial effect, particularly when a heat treatment capable of producing a grain boundary constituent was used. I should appreciate it if in the discussion of your paper this point should arise, you would attempt to clarify the difference between the copper-silicon binaries and the copper-zinc-sili-con ternary alloys. D. H. THOMPSON and A. W. TRACY (authors' reply)—(1) We have no data on the constancy of the carbon dioxide content of the air used for the test atmosphere but have believed that the normal carbon dioxide content of the air was as constant as could be obtained by using Edmunds' method of removing carbon dioxide from the air and then adding a measured quantity. In any event, the test atmosphere was the same for all specimens in a test run. We agree with Mr. Anderson that the carbon dioxide content is important in the formation of a hygroscopic film on specimens. (2) We can imagine that there could be a concentration of solute atoms at the grain boundaries which would be so small that present methods would not detect it even if it exceeded the solubility limit of the alloy. There could be somewhat greater solubility at the grain boundaries for an interstitial solute. There is a possibility that phosphorus dissolves in this way but we believe that none of the other solutes studied does. In our present studies we hope to find out something about conditions at the grain boundaries of some of the systems mentioned in the paper. (3) Mr. Anderson points out that silicon brass, which has had a high temperature heat treatment followed by a quench. is highly resistant to stress-corrosion cracking. Although the test conditions used by Anderson* et al were different from our test conditions, it is noted that the silicon brasses which had not had the special heat treatment were less resistant to stress-corrosion cracking than copper containing approximately equal amounts of silicon. G. R. GOHN†—Nonferrous metallurgists and particularly, materials engineers, have been accustomed to thinking

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 N. Brown, M. Herman

ORDERING'S effect on the creep strength and other plastic properties of metals is unknown at the present time. Sachs and Weerts' attempted to compare the mechanical properties of the ordered and disordered state by comparing a quenched specimen with one annealed for a long time at a low temperature. This experiment is unsatisfactory because it introduces a possible effect from quenching. Barrett' used a hot impact test, but his method was not sufficiently sensitive to indicate any discontinuity in plastic behavior in the neighborhood of the critical temperature. On the theoretical side, Fisher9 as suggested that short range order would strengthen an alloy, but he gives no conclusions as to the effect of long range order. Cottrell" has discussed the interaction between long range order and dislocations, but does not indicate whether slip in a completely ordered alloy without domain boundaries is appreciably more difficult than slip in the disordered state. Because order exists in so many alloy systems, it is most important to prove experimentally whether long range order weakens or strengthens a metal. This investigation used -brass because: 1) it orders

Jan 1, 1957

By H. D. Kessler, R. J. Van Thyne

Phase diagrams of the titanium-rich portion of the ternary systems from 0 to 10 wt pct Al and 0 to 1 wt pct 0, N, and C were determined. Micrographic analysis of annealed high purity arc melted alloys was the principal method of investigation and was supplemented by X-ray diffraction. TITANIUM-ALUMINUM alloys exhibit excellent properties, particularly for elevated temperature use. For this reason, the Materials Laboratory, Wright Air Development Center, sponsored an investigation of the effect of the interstitially soluble contaminants, oxygen! nitrogen, and carbon, on the Ti-A1 system. Using high purity arc melted alloys and micrographic analysis of annealed samples as the chief method of investigation, titanium-rich partial phase diagrams were determined for the ternary systems. Experimental Procedure Materials: The titanium used in the preparation of the alloys was iodide crystal bar (99.9+ pct pure) produced by the New Jersey Zinc Co. and Foote Mineral Co. The aluminum was obtained from the Aluminum Co. of America in the form of sheet. The given analysis was: Si, 0.0006 pct; Fe, 0.0005; Cu, 0.0022; Mg, 0.0003; Ca, <0.0006; Na, <0.0005; and Al, 99.99. High purity titanium dioxide purchased from the National Lead Co. was used in the preparation of the oxygen-bearing alloys. The spectrographic analysis of this material was as follows: SiO,, 0.07 pct; Fe,O,,, 0.002; A1,0,, <0.001; Sb,O,, <0.002; SnO,,, <0.001; Mg, <::0.001; Cb, <0.01; Cu, 0.0004; Pb, 0.002; Mn, <0.00005; W, <0.01; V, <0.002; Cr, <0.002; Ni, <0.001; and Mo, <0.002. Special spectroscopic graphite rod purchased from the National Carbon Co. was used in the preparation of the Ti-A1-C alloys. Alloy Preparation: Alloy ingots weighing 10 grams were melted in a nonconsumable tungsten electrode arc melting furnace using water-cooled copper hearths and a helium atmosphere. The arc was struck on a tungsten stud in the copper block to minimize contamination from the electrode. Details of the techniques have been reported.&apos;, &apos; Each ingot was inverted and remelted a minimum of four times to insure homogeneity, without opening the furnace. Remelting small control ingots of iodide titanium under similar conditions resulted in no measurable hardness increase, indicating contamination-free melting conditions were used. The alloy charges and resultant ingots were weighed to the nearest milligram. Only small weight losses were obtained upon melting, indicating that the actual compositions were very close to the nominal compositions. Check analyses substantiated this. Oxygen and nitrogen were added during ingot preparation as master alloys. An oxygen master alloy containing 25 wt pct 0 was prepared by melting iodide titanium and pressed titanium dioxide (40 pct 0) powder. The Ti-25 pct 0 alloy is more easily handled during weighing and charging than the pressed TiO, powder. Chemical analysis indicated that titanium-nitride received from an outside source contained large amounts of impurities (2.7 pct Ca). Therefore, a master alloy containing approximately 12 pct N was prepared by melting nitrided sponge titanium. As the sponge melted with difficulty, the alloy was diluted by addition of titanium to lower the melting point. The chemical analysis of the final alloy was 6.69 pct N. Both master alloys are friable and were used as —8 +16 mesh lumps resulting from crushing the ingots. NIelting the Ti-A1-0 and Ti-A1-N compositions five times produced homogeneous ingots. The preparation of homogeneous carbon-bearing alloys caused considerable difficulty. Alloys containing less than 1 pct C were prepared using spectrographic graphite rod, 1/8 in. diameter by 1/8 in. long. However, the graphite did not dissolve even with long melting times and many remelts. The ?/s in. pieces of graphite were used rather than powder because the low density powder is troublesome in arc melting.

Jan 1, 1955

Using 5-p Ni powder and 0.018 ,u A1203, oxide dispersion strengthened nickel alloys were prepared by mechanical mixing of powders, followed by compaction, sintering and extrusion. Processing variables such as cooling of the powder during mixing, electrostatic discharging, mixing time, amount of oxide, and so forth, were studied to determine the effects on room-temperature tensile and high-temperature creep-rupture properties and on the reproducibility of alloys. MECHANICAL mixing of metal and metal oxide powders provides one of the simplest and most inexpensive methods for preparing dispersion strengthened metal-metal oxide alloys;" however, because of large differences in specific gravity, powder particle diameters and other variables, difficulties have been encountered in reproducing alloys and alloy properties. Using 5-p Ni powder and 0.018 p A1203, the following variables were investigated: a) Blending techniques b) Blending time c) Volume fraction of oxide for the selected pow- ders d) Sintering of compacts before extrusion Cooling of Powders During Blending— Cremens and Grant had indicated that dry ball milling of the powder mixture gave superior results over other procedures. When ultra-fine metal and oxide powders became available and comminution was unnecessary or offered little gain, the use of dry mixing in a Waring Blendor gave optimum results.&apos; In the current study, observations of the powder mixtures indicated that considerable heat was generated due to the high speed of the Waring Blendor (15,000 rpm). This heating appeared to produce some degree of clustering and pelletizing. To minimize such agglomeration, a Pyrex cooling coil was installed in the mixing vessel. A double coil, water cooled, proved to be quite satisfactory, providing a fair degree of cooling along with good erosion resistance. Discharge of Electrostatic Charge—Electron-microscopy showed that agglomeration was minimized by the cooling procedure but was not entirely eliminated. It appeared that some of the ag- glomeration had to be explained on the basis of an electrostatic attraction due to the high-speed blending operation. These charges had the effect of promoting the growth of alumina clusters. At the end of the blending procedure such clusters had an effective size which was as much as 50 times that of the individual powder particles and were very tightly bunched. Several methods were utilized to try to discharge the electrostatic forces to minimize the clustering. One successful method, utilized in alloy 17, involved continuous exposure during blending to a radium source of 50 millicuries at a distance of 1.5 ft from the container. A number of other methods were noted to work equally well. Fig. 1 shows the more open oxide structure which results from such a treatment, permitting the matrix metal to penetrate into the cluster more effectively. The combination of powder cooling and discharging led to noticeably improved structures. Fig. 2 shows a cross and a longitudinal section in alloy M-17, one of the best alloys, illustrating the marked decrease

Jan 1, 1961

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

THERE are both advantages and disadvantages in using semikilled steels in place of killed steels. One advantage of semikilled steels is they provide a higher ingot-to-product yield. This is especially important to shipbuilders in the time of national emergency. By using semikilled steel for hull plates, a greater number of ships can be built from the same ingot tonnage. Consequently, if semikilled steel plates are adequate for the service, the advantage of the higher product yield is of considerable importance. The performance of hull plates is closely associated with the ductile-to-brittle transition temperature, and this, in turn, is strongly dependent on the composition of the steel. A low transition temperature is desirable because it indicates that the steel is less likely to fail at low ambient temperatures. Killed steels are known to have lower transition temperatures than semikilled steels. It is believed that the better qualities of killed steels in this respect are due mainly to the low oxygen contents of the steel. The principal deoxidizers, aluminum, silicon, and manganese, lower the oxygen content. Fundamental studies1-0 have shown that the oxygen content remaining after the addition of one of these three elements is influenced by the residual amounts of the other two present. In the current study, therefore, various amounts of silicon and aluminum were added to steels containing different manganese contents for the purpose of studying the influence of silicon and aluminum on the notched-bar properties of hot-rolled steels. Eleven types of steels were studied. The temperature at which the plates were finish-rolled was care- fully controlled at 1850°F. All plates were rolled to ¾-in. thickness, and tested in the as-rolled condition. The total number of steels prepared in the laboratory for this study was 95. The charge consisting of ingot iron and ferrosilicon equivalent to 0.10 pct Si was melted in a 200-lb induction furnace under an atmosphere of argon to insure low, uniform nitrogen contents. After the charge was melted and the desired temperature was obtained, the melt was partly deoxidized with either silicomanganese or aluminum. Aluminum was used for this purpose in only those steels with very low silicon contents, where the finished steel was to contain some aluminum. This initial deoxidizing addition was made to obtain consistent recoveries of subsequent additions of ferro-manganese, ferrosilicon, and aluminum. Carbon, in the form of graphite, was added, either just prior to tap or to the final aluminum addition. The entire heat of 200 lb was poured directly into a 6x6-in. big-end-up mold. The ingots of semikilled steel were capped with a steel plate. The killed steels, on the other hand, were poured with a hot-top containing 14 pct of the total volume of the ingot. The ingots were processed by heating to 2250°F, followed by forging to slabs 1¾ in. thick and 6 in. wide. After reheating to 2250°F, the slabs were rolled to 0.9-in. gage, using reductions of approximately 1/6 in. per pass. The 0.9-in. thick plates were immediately recharged in a furnace held at 1850°F. After 30 min in the furnace at 1850°F, the plates were rolled to ¾ in. in one pass. Following the final pass, the plates were stacked on edge on a brick floor, with a brick separating one from another, where they were allowed to cool in air. Drillings for chemical analysis were taken from the plates at locations corresponding to the top and bottom of each ingot. Carbon, manganese, silicon, phosphorus, sulfur, and nitrogen contents of each sample were determined. The analysis of each steel was carefully controlled so that the contents of

Jan 1, 1957

By F. Bonaccorso, G. Venturello, C. Antonione

A study of the effect of small amounts of interstitial impurities on recovery and re crystallization in high-purity iron (99.995 pct) has been undertaken. This paper gives results on the effect of carbon, introduced in small-dosed amounts @om 0.0005 to 0.0086 wt pct) by heating iron specimens of high purity m a static atmosphere of CO + ,. The materials prepared in this way, cold-worked 80 pct and subjected to a series of isochronal and isothermal annealings, were submitted to examinations by X-rays, micrographs, and hardness tests. It was observed that effect of carbon is remarkable in the sense of blocking recovery of mechanical properties up to the temperature at which re crystallization begins. On the contrary, carbon has a negligible effect on primary re crystallization temperature, when compared with the known effect of substitutional impurities. This is in agreement with the high mobility of interstitials. In effect, only a slight decrease, -20 pct, of the grain-boundary motion rate was noted, due to the interaction between the grain boundary and the carbon atoms. On the other hand, in the samples in which the carbon content is above the solubility limit at the temperature at which re crystallization occurs, a slight increase of nucleation frequency is noted due to the presence of precipitated carbides. ThE effect of purity on recovery and recrystalli-zation phenomena has been known for a long time; however, recently, new attention has been given to the problem since new methods for obtaining metals with extremely low impurity contents have become available. Most of this research work essentially concerns the effects of impurities which cause precipitates or give rise to substitutional solid solutions. The works of Bolling and winegard1 and Aust and utter&apos; on lead, and Vandermeer and orddon&apos; on aluminum, 01sen4 on nickel, and Abrahamson and Blakeney on iron should in particular be referred to. On the effect of this type of impurities a quantitative theory has been formulated by Detert and Lucke6 and has lately been discussed critically by Cahn7 and Gordon and vandermeer.&apos; Interstitial solid solutions in iron have not as yet been studied. As the study of the effect of interstitials is of great interest both from a theoretical and practical standpoint, it was deemed useful to examine the effects of carbon, nitrogen, and boron on recovery and primary recrystallization of iron. There already is some work by Chaudron et al.,1-" on the effect of interstitials on iron; their work, however, mainly concerns secondary recrystallization. The present paper refers in particular to the effect of carbon. EXPERIMENTAL PART Preparation of Materials. The pure iron used for this research was obtained from FeCIS recrystal-lized and purified by extraction with isopropylic ether. From the ferric chloride purified in this manner, hydroxide was precipitated with a solution of very pure ammonia, and, by calcination in pure sintered alumina crucibles, oxide was obtained. Reduction of the oxide to iron sponge was performed in sintered alumina tubes with very pure hydrogen at 650°C; at the end of the operation temperature was increased to 900°C. Specimens for the experiments were obtained by sintering the sponge at 1480°C in pure Hz after a pre sinter ing treatment at 900° C. It is important to note that the treatment at 1480°C in Ha produces a further purification from more volatile elements such as zinc, cadmium, arsenic, lead, and tin. Details on the preparation and characteristics of this type of very pure iron are given in a previous work.&apos;&apos; Only the complete analysis performed by neutron-activation methodsz3 is given here, Table I. Some of the specimens prepared in this way were carburized in the 0 region with very low amounts of carbon by treating them at 700°C in a static atmosphere of Ha containing a definite amount of CO. The set-up used is described in Fig. 1. A gas-tight quartz tube containing the specimen to be carburized and an internal friction control specimen, after being evacuated, was filled with Hz

Jan 1, 1963