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By P. Duwez, C. B. Jordan

A. J. SHALER*—I should like to congratulate the authors for having carried out such a precise set of experiments. It has been found useful, in sintering experimental compacts in vacuo, to make certain that the residual gas is not one which reacts with the metal. Since traces of oxygen can be kept away only with great difficulty, the technique is often adopted of using a "getter " of powder in the vicinity of the compacts, and, in addition, of permitting a small hydrogen leak to flow into the vacuum chamber. Did the authors use similar devices? This paper brings up a question concerning the definition of the word ' sintering.' The authors restrict its use to the adhesion between particles. Kuczynski, in a paper presented at this meeting, applies the word to the growth of areas of contact between particles. I have used it to mean both these phenomena and also the dimensional changes which continue to take place after the first two have run their course. May I suggest that we should come to an agreement on the use of these words ? Fig 1 and 2 show an interesting feature: extrapolation of the curves to zero time does not give a densification parameter of zero. The higher the temperature, the higher is the intercept on that axis. These observations agree with the concept of a practically instantaneous densification taking place while the compact is being brought to heat. Such a change may be brought about by plastic deformation and primary creep. The stress pattern causing this first rapid flow is, to my mind, due to the force of attraction between the surfaces of opposite particles in the regions immediately flanking their common areas of contact. The stress is not temperature-sensitive, but at room temperature plastic deformation only proceeds until the metal in the area of contact can support it elastically. As the metal is heated, the elastic limit falls, and further plastic flow occurs. At the higher temperatures, this is followed by primary creep, and finally by the steady-state rate-reaction which the authors are seeking. If they were to recalculate their densification-parameter values, using, not the initial density of the cold compact, but the density after the compacts have been brought to temperature, the systematic deviations from linearity in Fig 3 and 4 might be eliminated. Such initial densities might be obtained by extrapolating the curves of Fig 1 and 2 to zero time. I am naturally pleased to see that such a very well done series of experiments leads to a heat of activation (for the densification process in hydrogen) that is much higher than that for self-diffusion, in confirmation of the less elaborate results reported by Wulff and myself (Ind. and Eng. Chem., (1948) 40, 838). J. T. KEMP*—I would like to comment on Dr. Shaler's remarks. There are apparently different interpretations of the word "sintering." It seems to me that an accurate definition of our word is essential in all metallurgy. May I point out, in this connection, that in practical metallurgy the word "sintering" has been applied to a bonding process in the preparation of ores and flue dust for fur-nacing. It would be unfortunate if in the area of powdered metallurgy we should establish a definition that is essentially different in meaning. F. N. RHINES*—I think that I can answer the question by saying that I see no essential difference between the use of the term "sintering" in extractive metallurgy and in powder metallurgy; physically the same things are going on. I admit sintering is used for different end purposes in the two cases. When we resort to the sintering of lead ore mixture we are doing so to obtain a chemically reactive, loose texture of some rigidity. This is only a difference in use. After all, in powder metallurgy we sometimes deliberately produce a very porous material which has just a little strength, just as in the case of sinter cake. P. DUWEZ (authors' reply)—We agree that it would be helpful to have well-established definitions of such terms as "sintering." Since the question has now been raised, the time might be appropriate for its consideration by some suitable committee of one or more of the metallurgical societies. In answer to Dr. Shaler's first question, no getter nor hydrogen leak was used in our vacuum experiments, except insofar as the guard disks (used to reduce friction between specimens and trays) may have acted as getters. Dr. Shaler's statement that extrapolation of the curves of Fig 1 and 2 does not lead to zero densification at zero time apparently overlooks the logarithmic

Jan 1, 1950

By R. E. Morgan, D. L. Douglass

The determination of phase relationships and solid-solubility limits can be performed by quantitative metallography in addition to the usual X-ray and metallographic techniques. For example, Beck and smith1 redetermined the ß/ß + ?, ß + ?/?, a/a + ß and a + ß/ß boundaries in the Cu-Zn system by measuring the volume fraction of second phase of several alloys and extrapolating the volume fraction-composition curves to 0 and 100 pct. A modification of this technique is suggested for certain alloy systems, in which it is not necessary to use several alloy compositions but merely one. A single two-phase alloy may be used to determine terminal solubilities in the following manner. The method consists of equilibrating samples of the alloy in a two-phase region adjacent to the desired solid solution, at three or more temperatures, quenching, measuring the volume fraction of second phase present, and applying an analytical treatment to calculate the unknown solid solution. However, two restrictions are inherent in this technique. They are: 1) only certain types of alloy systems are amenable to it, and 2) the general features of the system must be known. The first drawback to the new technique, i.e., that only certain types of systems may be studied, necessitates that the composition at one end of the tieline must either be constant with temperature or well established as a function of temperature. Either a pure metal or some intermetallic compounds fulfill the former. If it is assumed that the volume per gram-atom of a dilute solution is unchanged by the addition of element B to element A, the composition of the solid solution in equilibrium with the second phase may be determined by a material balance and is given by where X, = volume fraction of B in a solid solution Xc = volume fraction of B in compound c X = volume fraction of B in alloy f = volume fraction of second phase The composition by weight may then be determined by the use of tables in the Metals Handbook2 when the density ratio of the solid solution constituents is known. A possible alternative treatment involving the use of the lever rule is less precise than the above tech- nique. This may be used when the density of the solid solution is either known or may be calculated from X-ray data for several compositions. The following analysis is then made. The ratio of compound to solid solution (by weight) may be expressed as follows: x0 - x wc = xr-x = x0 - x r2i Xc -X where Wc = weight of compound w = weight of solid solution x, - alloy composition, weight percent x = unknown composition Xe = compound composition but where V, = volume of compound VA = volume of solid solution pc = density of compound p, = density of solid solution fc = volume fraction of compound fB = volume fraction of solid solution and fs = l -fc then If pc and xc are known, and f, is measured, then pB is the only unknown on the right side of Eq. [4]. The known densities of the solid solution can be plotted for various compositions and can then be expressed mathematically as a function of composition. The use of an expression of pB = f(x)reduces the equation to one unknown—the desired solubility. In the event that the densities are unknown, they may be calculated for various compositions from Vegard&apos;s law. The calculated values are then plotted and expressed analytically. The most accurate results are obtained for Eq. [4] when fc<< 1, i.c., when (x, -x,) - 0, &/l-f, - m; but as fc/l -fc - 0, (xl-x,)- (x, - x), and x - x,,. However, the accuracy with which fc can be measured decreases as f, decreases.3 Alloys for investigation must be selected by a compromise, which is based upon an error analysis of Eq. [4] and knowledge of the accuracy of volume fraction measurements. An examination of phase diagrams in the literature showed many which were amenable to the technique described here. The zirconium-copper system was selected in order to determine the solubility of copper in beta zirconium. Pieces of an alloy which was arc-melted three times were wrapped in tantalum foil and sealed under an argon atmosphere in Vycor tubes. The sealed samples were equilibrated at temperatures from 850" to 960°C for 3 weeks and quenched to room temperature by smashing the capsule in water. Several planes of polish were examined, and

Jan 1, 1960

By J. B. Clark, A. S. Yue

The zone-melting technique can be adapted for the de-termination of the eutectic composition in complex metal systerrzs. The application of this method is demonstrated in a simple eutectic system, Mg-AE, in which the eutectic composition is known and in a complex ternary system, Mg-Al-Zn, in which the literature is uncertain as to the composition of the ternary eutectic. The advantages and limitations of this unique approach for the determirution of the eutectic composition are discussed. ThE eutectic composition in phase diagrams is usually determined by thermal analysis of a series of arbitarily selected alloy compositions. The temperatures of the liquidus and eutectic arrests for each alloy are plotted and the eutectic composition is estimated by extrapolation to the entectic temperature of the curve formed by the liquidus arrest temperatures for the series of alloys. Although this approach readily yields the eutectic temperatures, several dekrminations are needed to estimate the eutectic composition, even in a simple system. In a complex ternary system, a great many determinations are often necessary to estimate, even approximately, the ternary eutectic composition. Thus, the conventional method is inherently tedious and time consuming. The application of zone melting provides a relatively efficient method of determining the eutectic composition.&apos; As an illustration, consider the zone melting of an alloy composition C, in the simple eutectic system A-B, shown in Fig. 1, under the ideal conditions of infinitely rapid diffusion in the liquid, no diffusion in the solid, and ease of nucleation of both phases. As the zone moves along the bar, the composition of the zone is enriched by solute rejected during the freezing of the a phase and the zone composition approaches the eutectic composition CE.Once the zone composition attains the lowest melting composition, i.e., the eutectic composition, it remains at this composition as the zone moves along the bar and finally freezes as such at the end of the bar. Chemical analysis of the end of such a zone-melted bar then should yield the eutectic composition CE of the system A-B. A corresponding analysis can be made for a ternary eutectic system. Under the ideal conditions noted above, only one pass of the molten zone is required to yield the eutectic composition. Experimentally, however, a solute-rich layer forms at the solid-liquid interface2 and the composition of the zone does not attain the eutectic composition as rapidly or as uniformly as in the ideal case outlined above. But with agitation of the melt, the ideal conditions can be approximated experimentally. Also, as shown below, zone melting permits a cumulative build-up of the solute at the end of the bar to the eutectic composition. The purpose of this paper is to demonstrate this unique method for determining the eutectic composition. The method is here applied to two systems: first, to the binary Mg-A1 system, in which the composition is well established, and second, to the complex Mg-Al-Zn system in which there is doubt concerning the composition of the ternary eutectic. EXPERIMENTAL PROCEDURE The zone-melting apparatus used in this study is described in detail elsewhere.3 Briefly, the binary alloy rods (5/8 in. in diam and 9 in. long) and the ternary alloy rods (5/8 in. in diam and 6 in. long), with the compositions given in Table I, were zone

Jan 1, 1962

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Zinc difhsions in gallium arsenide having surface concentrations as low as 5 x 10&apos;&apos; atoms per cu cm have been attained. A multiple-difhsion sequence is employed during which zinc enters the gallium arsenide from a silicon dioxide film in a solid-to-solid diffusion step. The technique is illustrated for the case of a zinc surface concentration of -1 x 1017 atoms per cu cm and a junction depth of 1.2 p. Radiotracer measurements of -0.1-p layers of gallium arsenide are used to delineate the resulting profile. A diffusion coefficient for zinc in pyrolytically deposited silicon dioxide is reported. ZINC is frequently used as an acceptor impurity in gallium arsenide. As examples, p-n junctions are formed using zinc-diffused layers in solar cells, lasers, and varactor diodes. For these purposes surface concentrations of 10&apos;&apos; to over loz0 zinc atoms per cu cm are desired and readily obtained from a vapor source. Diffusion of zinc into gallium arsenide to yield surface concentrations of about 1017 atoms per cu cm, however, is more difficult. For instance, oldstein&apos; reports that large changes in the vapor density of zinc produce only small changes in surface concentration. Such low surface concentrations are necessary in forming the diffused base of a gallium arsenide double-diffused n-p-n transistor in order to obtain an adequate emitter efficiency. An alternative approach to zinc diffusion which can provide reduction in surface concentration of several orders of magnitude is the introduction of the diffusant from a solid source. This can be conveniently accomplished by using oxide films of the type generally employed for selective diffusion masking. Such oxides also serve to prevent the dissociation of the gallium arsenide surface at the high temperatures of diffusion. DIFFUSION PROCEDURE Fig. 1 illustrates the diffusion sequence which is employed for obtaining zinc surface concentrations in the range from 5 x lom to 1 X 10" atoms per cu cm. The description of technique will be given for the instance of -1 x 1017, which is typically utilized in double-diffused gallium arsenide transistor investigations at this laboratory. Tin- or germanium-doped gallium arsenide wafers drawn from crystals grown by horizontal Bridgman or Czochralski techniques are used, with bulk concentrations ranging from 1 to 3 X 10" carrier atoms per cu cm. Each wafer is chemically polished on the (iii) arsenic face using a mixture of five parts concentrated sul-furic acid, one part water, and one part 30 pct hydrogen peroxide at room temperature, followed by rinsing in deionized and quartz-distilled water. Pyrolytic silicon dioxide was chosen as the oxide coating because of the high quality of the films obtainable, the ease of their preparation, and the excellent control over film thickness and uniformity.

Jan 1, 1964

By Rodney P. Smith

The rate of motion of the boundary between a single-phase a-iron region and a two phase a-iron plus ?-iron, or a-iron plus cementite region has been measured on decarburization at several temperatures between 500" and 865°C. These data, together with data for the carbon content of a-iron at the boundary, yield the diffusivity of carbon in a-iron. The activation energy for carbon diffusion is 19.8 kcal per mole for the temperature range —50° to 150°C and increases to an average value of 23.0 kcaL per mole for the temperature range 727" to 865°C. AS part of an investigation of the diffusivity of carbon in iron using a steady-state method,&apos; the diffusivity of carbon in a-iron was determined at the temperatures 802" and 851°C. The diffusion constant thus obtained was larger, by nearly a factor of two, than that predicted from the combined results of stanley2 and of Wert.3 It seemed desirable, therefore, to continue the investigation. Since the temperature range in which the steady-state method can be conveniently used is limited, we have chosen a decarburization method, based on the laws of diffusion in metal accompanied by a phase change.4,5 If the initial carbon content of the Fe-C alloy is such that two phases coexist at the decar-burizing temperature* and decarburization is car- ried out such that the surface is maintained at substantially zero wt pct. C, the carbon distribution after a time, t, will be as shown in Fig. 1. The boundary between the single-phase and two-phase regions moves from y = 0 to y = x in the time, t, where x is proportional4 to tl". If the initial carbon (content of the sample is Ci, and CB is

Jan 1, 1962

By R. P. Smith

The diffusivity of carbon in iron, cobalt, and alloys of 89.7 and 79.3 wt pct Co has been determined by a decarburization method for the temperature range 850° to 1100°C. The Plots of log D us 1/T for the two Fe-Co alloys are linear through the region of the Curie temperature, showing that, unlike some cases of substitutional diffusion, carbon diffusion in these alloys is not affected by electron spin order. RECENT investigations1-&apos; have shown that for substitutional diffusion in iron the change in diffusivity with temperature does not follow an Arrhenius equation, at temperatures near the Curie temperature. Data on the diffusivity of carbon in a iron5"9 indicate that this anomaly does not exist for interstitial diffusion; however, this has not been definitely established. Since cobalt and Fe-Co alloys, 80 to 100 pct Co, have Curie temperatures in a temperature range convenient for carbon-diffusion measurements they are suitable systems for studying the relation of interstitial diffusion and the Curie temperature. EXPERIMENTAL The carbon diffusivity, D, was determined by a decarburization method. The diffusion cylinders, made from small vacuum melts of electrolytic cobalt and plastiron, were about 0.76 cm diam and 6.3 cm long. A small amount of carbon was added to each melt to keep the oxygen content as low as possible. The cylinders were first treated with a hydrogen-3 pct water vapor mixture at 1100°C to constant weight, then carburized to the desired initial carbon content with a suitable CO-C02 gas mix-

Jan 1, 1964

By E. W. Johnson, M. L. Hill

The dijfusiuity D was determined at 25° to 780°C- from hyd?-ogen evolution rates. Anomalous evolution from air-melted iron was att~zbztted to residual hydrogen, which is interpreted as a hydrogen compound that decomposes at a strongly temperature-(Ieperzdent rate above 500°C. Above 200°C, D = 0.0014 cm2sec-1 exp (-3200 cal per g atom/RT). Below, 200°C the diffusivity is anomalously low and represented by D = 0.12 cm2sec-l exp (-7820 cal per g atom/RT). It is postulated that at low temperatures the hydrogen in the metal is "trapped" with an energy 4.8 kcaL per g atom below- that of the interstitial hydrogen. 1 HE purpose of the present experimental study was to determine the diffusivity of hydrogen in a-Fe over an extended temperature range. As certain anomalies were encountered, attempts were made to understand the anomalies themselves. This research was in progress both before and after a determination of the diffusivity of hydrogen in nicke1.l The latter system was found to exhibit none of the anomalies of hydrogen in iron, and its description was far simpler. The experiments on nickel also

Jan 1, 1961

By John D. Verhoeven

A technique has been developed for carrying out normal freezing experiments with a current density of 2000 amp per sq cut passing through the solid-liquid interface. The equation relating the effective distribution coefficient to the equilibrium distribution coefficient in electric field-aided solidification, originally developed by Huckc et al.,1 has been modified for the case of concentrated solutions. Preliminary experiments on the Sn-Bi system give qualitative agreement with the equation. The data are analyzed by a slightly novel use of the normal freeze equation which allows one to determine the effective distribution coefficient more easily. Very extensive mixing in the liquid was found at these high current densities and it is postulated that the mixing results from a vertical component of the magnetic Lorentz force generated by the electric current. In the search for techniques of obtaining ultrahigh-purity metals the inefficient but very effective technique of electrotransport has received little attention. Electrotransport is most effective in the liquid state and a natural application, therefore, is to apply an electric field across the liquid zone of a zone-melting experiment. The present investigation was undertaken to study the effect of an electric field upon solidification of metals, so that the usefulness of electrotransport in such solidification experiments as zone melting could be determined. In zone-melting and normal-freezing experiments it is difficult to achieve complete mixing in the liquid in the immediate vicinity of the solidifying interface. Consequently a solute build-up will occur at the interface in the portion of the liquid where complete mixing does not occur (an equilibrium distribution coefficient, ko, less than one, and unidirectional atom motion will be implied throughout). This local solute build-up produces a corresponding rise in the solute concentration in the solid so that the ratio of the solute concentration between the solid and the bulk liquid is larger than the equilibrium distribution coefficient. This ratio is defined as the effective distribution coefficient, k,. The differential equation describing the solidification process may be derived by applying the continuity equation to an expression for the net solute flux at the interface. The solution to this differential equation then allows one to determine the solute distribution in the liquid and the relationship between k0 and ke. One of the most useful solutions to this equation was first derived by Burton, Prim, and Slichter,&apos; in which they assumed that a) the equilibrium distribution of solute was maintained on the plane of the interface, 11) the solute build-up ahead of the interface in the liquid disappeared at a distance 6 from the interface, and c) the solute distribution in the liquid was invariant with time. The following well-known relation between ko and ke was then obtained, where R is the rate of solidification and D the diffusion coefficient of the solute in the liquid. This equation appears to correlate the data from a number of different types of solidification experiments very well. Application of an electric field across the solid-liquid interface can produce an additional flow of solute atoms as a result of the electrotransport. When the polarity of the field is such as to direct the electrotransport flux away from the interface the solute build-up may be diminished, even to the point of producing a solute depletion and a consequent ke smaller than ko. The quantitative description of this process and the resulting form of Eq. [I] was first given by Hucke et al.1* and then inde- where E is the electric-field intensity and U is the differential mobility, i.e., the velocity of the solute atoms with respect to the solvent atoms per unit electric field. Both authors follow the method of Burton, Prim, and Slichter in their derivation, the only difference being the additional electrotransport term in the flux equation. It has been pointed out1,3 that Eq. [2] predicts the possibility of a noticeable increase in the purification of materials by solidification in an electric field. The validity of Eq. 121 has not been checked experimentally and it is possible that other factors&apos; arising from the presence of an electric field across

Jan 1, 1965

By G. Sandoz

A simple diffusion-couple experiment was carried out for the purpose of determining whether chromium in sufficient amounts would cause the cementite phase in cast irons to become thermodynamically stable with respect to graphite and austenite at 1750°F. The implications of the results to some current theories on graphitization mechanisms are discussed. The literature abounds with evidence that chromium retards the decomposition of cementite to graphite and austenite or ferrite, for example during first-stage and second-stage graphitization in malleabilizing white cast irons and the subcritical graphitization of steels. Efforts to explain this retarding action of chromium have been conjectural, however, because the mechanisms controlling graphitization kinetics in the absence of chromium have never been clearly established. Concerning rate control, there are basically two schools of thought: 1) that graphitization rates are limited by diffusion potential (the stability of cementite relative to graphite, and 2) that graphitization rates are limited by diffusivity of Fe, C, Si, vacancies, and so forth.5&apos;10 Chromium then, is thought either to increase the stability of cementite or to retard some critical diffusion process.

Jan 1, 1960

By E. G. Schempp, W. A. Morgan

The influence of modifications in the molybdenum, vanadium and, to a limited degree, carbon and boron content to a basic composition of 5 pct Cr, 0.75 pct Mo, 1 pct V hot-work tool steel composition, was studied in respect to hardenability, grpain- coarsening temperature, and tempering charactevistics. Tensile, impact, and fatigue pvoperties were studied for the most promising compositions. An alloy with a typical composition of 0.43 pct C, 4.97 pct CI-, 0.33 pct Si, 2.25 pct Mo, and 1.00 pct V uas found to offer the most favorable combination of properties in respect to high-strength applicntions when tempered at 1100°F. MANY 5 pct Cr high-strength steels are at present being manufactured in North America which fit well into the classification of the AISI-SAE system. Much interest has been shown in these materials as ultra-high-strength steels for use at elevated temperatures. The limiting temperature of use lies at the point where the steels begin to soften rapidly. Although a great deal of information has been made available in the past two years on the properties of selected alloys in this series, little information exists on the effect of systematically varying the ccntent of one or more elements in the 5 pct Cr-base alloy. This paper presents the results of an investigation of the effect of variations of the carbon, molybdenum, vanadium, and, to a limited extent, the silicon, manganese, boron, and niobium content of a 5 pct Cr steel to the AISI H-13 base analysis. EXPERIMENTAL PROCEDURE All experimental heats were melted in a 50-lb. induction furnace. The melting stock consisted of

Jan 1, 1962

By J. T. McGrath, R. C. A. Thurston

Poly crystalline specimens of copper, and copper with various additions of zinc, were tested in plane-bending fatigue. In tests performed at a constant stress, the fatigue life of copper increased slightly with the addition of up to fifteen per cent zinc. There was a sharp increase in fatigue life as further additions of zinc of up to 35 pct were made. Surface observations showed that the coarse slip bands that are characteristic of fatigue became narrower as the concentration of zinc increased. The rate of crack propagation also decreased with increasing zinc content. It is suggested that the fatigue behavior is controlled by cross slip processes. CROSS slip occurs when dislocations move from one primary slip plane to another along a connecting or cross slip plane. The primary and cross slip planes have a common slip direction. Wide stacking faults, having low energy, tend to make cross slip more difficult. According to recent theories, the ability of a material to cross slip is important to the formation and propagation of fatigue cracks. McEvily and Machlin2 have examined this concept experimentally by fatiguing single crys tals of lithium fluoride, sodium chloride, silver chloride, and KRS-5.* The latter two materials ex- hibit easy cross slip, while the former two do not. Normal rapid fatigue failure was obtained in the silver chloride and KRS-5 specimens, whereas it was much more difficult to achieve in sodium chloride and lithium fluoride crystals. Furthermore, numerous slip band extrusions and intrusions were found in silver chloride and KRS-5 crystals, whereas only one isolated extrusion was found in lithium fluoride and none was found in sodium chloride. McEvily and Machlin also consider that there is no clear-cut demarcation between crack initiation and propagation. The intrusion-extrusion process, which initiates crack formation, continues ahead of the cracks to allow propagation of these cracks along slip bands. The process of cross slip is therefore important not only to crack initiation, but also to crack propagation. Holden4 postulates that fatigue crack growth is dependent upon cross slip and thus upon stacking-fault energy. Using an X-ray microbeam technique, he found a cyclic subgrain structure in fatigued aluminum and a-iron. Holden suggests that micro-cracks develop in the densely-packed sub-boundaries ahead of the main crack front, and when sufficiently numerous join up to promote crack growth. The ease with which a subgrain structure could form would depend upon the ability of the dislocations to cross slip, and thus upon the stacking-fault energy. Hence in aluminum, which has a high stack-ing-fault energy and in which cross slip is easy, Holden found that the relative rate of fatigue crack propagation was considerably greater than in stainless steel, a low stacking-fault energy material. It has been shown by a number of investigators that the probability of forming deformation stacking faults in copper increases as zinc is added.5-7 Cross slip should, therefore, become more difficult as the zinc concentration is increased. In order to check the validity of the foregoing theories, it was decided to test copper and copper with various additions of zinc in plane bending fatigue, and determine to what extent their fatigue properties are dependent upon their ability to cross slip. EXPERIMENTAL PROCEDURE Fatigue tests were carried out on polycrystalline OFHC copper and various copper-zinc alloys with 5, 15, 20, 30, and 35 wt pct Zn. The Cu-Zn alloys were obtained commercially in sheet form. Test specimens, as shown in Fig. 1, were machined from sheet that had been reduced to an approximate grain size of 0.040 mm, the heat-treatment procedure being similar to that of Feltham anc copley.8

Jan 1, 1963

By J. M. Hodge, H. M. Reichhold, R. D. Manning

The work reported in this paper represents the first of a series of investigations of the factors governing notch toughness in ferritic materials. This paper is concerned with two of these factors, namely, the effect of ferrite grain size, and the effect of an alloy content of 3.64 pct nickel. Every effort has been made to hold other variables constant in order to isolate the effects of these two. The compositions chosen for study were 0.02 pct carbon in order to eliminate the variable of carbide distribution, one steel being a plain carbon steel and the other alloyed with 3.64 pct nickel. Both steels were fully killed with silicon, without an aluminum addition, so that the variable of deoxidation practice was held constant. Finally, all samples were water quenched from 1200°F and tempered 24 hr at 300°F in order to hold the quench aging variable constant and to decrease the tendency for grain boundary carbide precipitation. The ferrite grain size was varied by heat treatment over the range of A.S.T.M. grain size numbers of about 2 to 6 in each steel so that the effect could be evaluated individually and the notch toughness of each steel could be compared at comparable ferrite grain sizes. Materials and Experimental Procedure MATERIALS The materials for this investigation were obtained from Battelle Memorial Institute as 250 Ib induction melts which were forged into 134 in. square bars and then rolled into 0.6 in. square bars. Both steels were deoxidized with silicon, the aluminum content being held to a minimum. Check analyses of these materials are shown in Table 1. HEAT TREATMENT FOR GRAIN SIZE The grain size was varied by varying both the cooling rate and the austeni- tizing temperatures. The heat treatments used and the corresponding grain size values are tabulated in Table 2. A semicontinuous network of grain boundary carbide was observed in the microstructure of both the plain carbon and nickel steels in the as rolled condition and an additional heat treatment was necessary to eliminate this variable. Therefore, all samples were water quenched from 1200°F and tempered 24 hr at 300°F as a final treatment before testing. This heat treatment served to eliminate to a great extent the grain boundary carbide network and to hold the quench aging effect constant. IMPACT TESTING Standard keyhole Charpy impact tests were machmed after heat treatment. A bath of acetone and dry ice was used for refrigeration of the samples down to temperatures of —94°F (—70°C) and a bath of either methyl-cyclohexane or isopentane, cooled by

Jan 1, 1950

By J. F. Butler

The degree and type of carbide dispersion resulting from changes in the cooling rate from austenite determine the amount of carbon remaining in solution after slow cooling- from a subsequent subcritical annealing treatment. A difjusion model has been proposecl to explain the effect of carbide dispersion on the amount of carbon retained in solution and the amount of carbon in solution has been related to the degree of carbon strain aging. COTTRELL and Leak&apos; have shown that the rate of strain aging in low-carbon steels is dependent upon the amount of carbon and nitrogen in solution. Carbon can be effectively removed from solution as Fe , C by quench aging at temperatures of 200" C or lower; however, the relatively higher solubility of nitrogen at these temperatures prevents sufficient removal of nitrogen as iron nitrides. For this reason, nitrogen in solution has been considered the major cause of strain aging in rimming grades of commercial low-carbon steels. Nitrogen can be effectively removed from solution and nonaging steel produced through the addition of aluminum to form the stable nitride, AlN; however, the aluminum also causes deoxidation resulting in a killed steel. III an attempt to produce a rimmed steel which was also nonaging, Morgan and Shyne 2 investigated tile strain-aging properties of low-carban steels containing boron and found that strain aging was suplx-essed in steels containing as little as 0.007 pet B. The original purpose of this investigation was to determine the mechanism of strain-aging suppression by boron. Early in the study, the function of boron was discovered to be much like that of aluminum in that the formation of a nitride, BN, removed the nitrogen from solution.&apos; However, during the course of the investigation, an effect of heat treatment upon the strain-aging properties and the amount of carbon in solution was found which could be related to the microstructure of the steel. The purpose of this paper is to examine these relationships among heat treatment, microstructure, carbon in solution, and strain aging in steels where nondetectable amounts of nitrogen are present in solution. EXPERIMENTAL PROCEDURE The investigation was carried out using 0.030 in. by 12. in wire specimens which had been cold swaged and drawn to the final diameter. Table I lists the compositions of the low-carbon steels used. Those with &apos;V&apos; designations were vacuum melted and cast; the alloys designated &apos;AISI&apos; were prepared from high-purity iron obtained from the American

Jan 1, 1962

By K. M. Rolls, R. M. Rose, H. B. Shukovsky

Studies of the phase structure, critical current density, and resistive critical magnetic field of a 45 pct Nb-55 pct Zr superconducting alloy after final-size heat treatments are reported in this paper. A combination of optical metallography, X-ray diffraction, and electrical-resistivity measurements were used to determine the phase structure. Superconductivity measurements, made with heat-treated wires, are correlated with microstructure. Although no quantitative relationship between microstructure and critical current density is found, it is shown that SINCE Kunzler1 as well as Berlincourt, Hake, and Leslie2 first described the high-field, high-current-density superconductivity of Nb-Zr alloys, it has be- the critical current density is highest when the microstructure is finely divided by fibering, coring, precipitation, or fine-scale phase dispersions. The resistive critical field is very sensitive to the compositions of the phases present. Since the alloy investigated here is near the maximum resistive critical field for the Nb-Zr system, any phase decomposition results in a lower H,. Elimination of the effects of cold work lowers H, also. A possible interpretation of the latter in terms of internal surface superconductivity is suggested. come apparent that the resistive critical field and the current-carrying capacity of such alloys are, in large measure, dependent on composition and processing. The resistive critical magnetic field (Hr) for low current densities has been found to increase progressively with zirconium content until a flat maximum is reached between 50 and 65 pet Zr.3 For any single composition, a characteristic maximum value of H, is attained by heavily cold-drawn wire.4 critical current density (J,) depends not only upon cold work but also, apparently, upon microstructure. Heat treatments of cold-worked wires generally

Jan 1, 1965

By H. E. Biber

DURING the production of tin plate a thin layer of FeSn2, is formed at the interface between the steel sheet and the protective tin coating. Because excessive amounts of this alloy layer are undesirable, the kinetics of its formation is a subject of interest in the tin-plate industry. A recent study of this subject at our laboratory uncovered a relationship which should be of general interest to anyone studying kinetics of reactions in metallic systems. It had been previously concluded that, at any given temperature in the range 175" to 330°C, the Fe-Sn alloy layer would have a parabolic growth rate.1,2 However, our studies showed that this rule apparently holds only when the tin plate is heated very slowly to the "reaction" temperature; when the tin plate is rapidly heated, considerably different growth rates occur. An example of this effect of heating rate on growth behavior is contained in the accompanying results of alloy-layer growth measurements at 240°C in oil baths stirred at 10,500, 1800, and 0 rpm. The heating curves for these three conditions are given in Fig. 1, and the growth data are presented in Fig. 2. With the rapid heating rate, provided by the stirring at 10,500 rpm, the alloy layer had three distinct stages of growth. In the initial stage, which persisted well beyond the time required to heat the tin plate to bath temperature, the alloy layer formed very rapidly. The growth followed a rate law of the form w = ktn where n > 1. This initial stage was followed by a growth-retardation stage of about 50-sec duration in which little additional alloy was formed. In the third stage the growth again followed a rate law of the form w = ktn, but here « =0.3. With the intermediate heating rate provided by stirring at 1800 rpm, the three-stage nature was less pronounced and the slope of the third stage increased (i.e., n > 0.3). With the slow heating rate provided by the unstirred oil bath, the alloy layer grew in two stages. The initial rapid-growth stage persisted only until the specimen was heated to bath temperature, no growth retardation was observed, and the slope of the main portion of the plotted data was greater than in the stirred baths, having a value of almost 0.5. Similar results were obtained for other bath temperatures in the range 200" to 300°C. This effect of heating rate on growth behavior may be due to changes in the rate of nucleation of FeSn, crystallites. The iron and tin are in contact from the onset of heating. Thus the initial formation of FeSn, occurs not at the "reaction" temperature but rather while the tin plate is being heated to that temperature. Because nucleation is in general temperature-dependent, different heating rates could cause different over-all nucleation rates, which in turn could cause different growth behaviors. A more detailed discussion of the growth of Fe-Sn alloy layer and the effect of heating rate will be published shortly.

Jan 1, 1965

By D. Krammer, E. S. Machlin

The effect of a brior high-temperature creep strain on the low-temperature ductility of commercially pure nickel has been evaluated. The low-temperature (-196°C) ductility decreases linearly with an increase in prior high-temperature (920°C) creep strain. The effect is experimentally correlated to the formation of inter crystalline cracks and voids during the prior high-temperature creep strain. The magnitude of the effect is also believed to be a function of the notch sensitivity of the material. SEVERAL mechanisms have been presented to explain the process of inter crystalline cracking in metals undergoing high-temperature creep. zenerl has suggested that grain boundary relaxation of shear stresses could build up high stresses at ob- stacles to grain boundary shear and thereby nucleate a crack. Chang and rant&apos; have experimentally demonstrated that cracks do form at obstacles to grain boundary shear such as lines where three grains meet. The role of vacancies in the mechanism of high-temperature inter crystalline cracking has been explored by Machlt with the conclusion that the nu-cleation of voids by vacancy condensation is almost

Jan 1, 1960

By B. C. Allen, R. I. Jaffee, D. J. Maykuth

Wrought unalloyed iodide chromium, containing 39 to 95 ppm total interstitials, has a tensile transition temperature of —15°C. Re crystallizing at 1100°C causes the transition to rise to 90° to 390°C, depending on the purity, grain size, and cooling rate after annealing. At about the 100 ppm level, individual additions of carbon or nitrogen raise the transition of both wrought and recrystallized chromium by as much as 210°C, while oxygen has a lesser effect, and sulfur essentially no effect. High transitzon temperatures are exhibited by recrystallized and quenched chromium, and appear to be associated with the amount and distribution of inter-stitials. The latter cm be either in solid solution or in the form of precipitates within the grains or at the grain boundaries. Quench hardening in chromium is primarily caused by nitrogen. The hardness, re crystallization, and grain growth behavior of chromium with and without impurity additions were also investigated. BECAUSE of low density and good oxidation resistance, chromium-base alloys are potentially useful for elevated-temperature applications. The main deterrent to the use of chromium in structural applications is its lack of low-temperature ductility, especially in the recrystallized condition. Accumulated evidence has shown that the ductility of chromium is sensitive to purity. The objective of the current study was to determine the effect of common nonmetallic impurities on the tensile properties of high purity chromium. The separate effects of carbon, oxygen, nitrogen, and sulfur additions on the ductile-to-brittle transition were evaluated for wrought and recrystallized material after various cooling rates. EXPERIMENTAL WORK Unalloyed iodide chromium and seven impurity alloys containing individual carbon, oxygen, nitrogen, or sulfur additions were prepared in rod form. Nominal additions were 100 ppm C, N, and S, and 100 to 500 ppm O. The additions were about a factor of ten greater than the residual amounts in the unalloyed material. The seven alloys and two unalloyed compositions were consolidated into four-pound ingots by conventional consumable arc melting of pressed and welded electrodes under 0.5 atm of helium. Impurity additions were made to the electrode in the form of crushed master alloys. The impurity alloys were double melted to improve homogeneity. The ingots were broken down by extrusion at 1200°C in evacuated steel cans at a reduction ratio of 18 :1, using a molten borosilicate glass lubricant and a ram speed of 80 in. per min. The cans were removed by acid pickling, and the chromium core ground free of surface undulations. Cut lengths were sheathed in mild steel and swaged at 900°C until the core was about 1/4 in. in diam. Two additional 15-lb ingots of unalloyed chromium (ICr-3, ICr-4) were prepared by arc melting and broken down by 26:1 extrusion at 1250°C without a steel can. The billet was lubricated and protected from contamination by a coating of molten glass. The resulting extrusion was then sheath swaged as described previously. Representative chemical analyses of each of the materials, after removal of a 10-mil surface layer

Jan 1, 1963

By Charles Wurms, Robert Steinitz

DURING an investigation to determine the compatibility of several metals with tungsten, the degree of reaction between tungsten and lead was determined. A literature survey showed considerable disagreement between the results of various earlier investigators. Information presented by M. Hansen1 states that, according to S. Inouye,2 tungsten has very poor resistance against attack by molten lead, even at the low temperature near the melting point of lead. A phase diagram in the same reference indicates a solubility of 30 wt pct W in molten lead at 1300°C. Contrary evidence was shown by Parkman and shepard3 in their investigation of materials for use in heat transfer systems containing liquid lead alloys; they performed experiments at 980°C for times up to 50 hr without noticing any appreciable attack on the tungsten. Tungsten sheet was immersed in molten lead contained in Vycor tubes evacuated to at least 10-4 mm Hg. R. Bernard4 and R. I. Jaffee5 also indicate that no reaction occurs between molten lead and tungsten. However, no experimental data were included in these reports. In order to settle the question of the solubility of tungsten in molten lead, tungsten powder with an average Fisher subsieve particle size of 6µ was pressed in a double-acting die at 6 tsi to small compacts. They were then sintered in an atmosphere of hydrogen for 2 hr at 1700°C, resulting in a sintered density of 64 pct of theoretical with final dimensions of 0.260 in. in height and 0.245 in. in diameter. For all tests, the tungsten pellets were immersed in molten lead. Table I is a summary of the experimental procedures showing atmospheres, temperatures, and times. The first experiments were performed at 650°C; at this temperature, the liquid lead should wet the porous tungsten better than at its melting point, and penetrate into the pores. The lead was heated in a graphite crucible with a graphite cover. No protective atmosphere was used, as it was expected that the formation of CO would be sufficient to prevent oxidation. This, however, proved to be wrong, and all tungsten samples showed a slight oxide film after treatment. The tungsten samples were immersed in the molten lead for times of 5 min, 10 min, 1/2 hr, 1 hr, and 2 hr. After this time, the melt was poured into a form and the

Jan 1, 1962

By J. L. Brimhall

Slip-line formation during bending has been studied on neutron-irradiated molybdenum single crystals. For equivalent strains, the slip lines are coarse and distinct in the irradiated molybdenum and not resolvable in the unirradiated molybdenum. The slip lines have been directly correlated with dislocation channels present in the irradiated and deformed thin foils. The heterogeneous distribution of the dislocations during deformation in the irradiated material results from dislocation interaction with the dejects produced during irradiation. Impurities , in the form of&apos; carbides, affected the dislocation channeling Principally by acting as dislocation sources. ALTHOUGH the mechanical behavior of irradiated materials has been studied extensively, the precise mechanism of irradiation hardening has not been established. Some information on the microstructural species responsible for hardening of irradiated materials has been derived from direct and indirect observations. The direct observation of the structure of deformed irradiated metals, particularly by transmission electron microscopy, is a relatively new and unexplored area. Slip-line studies in fcc metals have been restricted primarily to copper.1-3 Very coarse slip lines, representing slip on many closely spaced planes, have been observed in deformed, irradiated copper. Coarse slip lines have also been observed in irradiated aluminum.4 Clear channels in irradiated copper caused by dislocation motion through the defect structure have been seen by transmission electron microscopy and correlated with slip lines.5-6 To date, little work has been reported on the irradiated bcc metals. Eyre described the slip lines around hardness indentations on irradiated iron and found them to be more distinct than lines in unirradiated material.&apos; Mastel et al.&apos; have observed channels in deformed irradiated molybdenum similar to those reported in copper. As part of a program concerned with the effect of neutron irradiation on metals, the slip-line

Jan 1, 1965

By O. N. Carlson, K. E. Solie

The brittle-ductile transition temperatures of single and poly crystalline chromium metal were studied as a function of nitrogen concentration and chromium nitride distribution. It was observed that In recent years there has been an increasing interest in chromium-base alloys for high-temperature applications. The principal disadvantages, however, have been the difficulties of fabrication and the design problems associated with a material of such limited ductility. Various studies have been the effects noted in the poly crystalline material are essentially reversed in the single crystals. These observations are discussed in terms of existing theories for the brittleness of chromium. conducted recently directed toward a determination of the cause of this brittleness and to find ways for minimizing its effects. Allen et al.,&apos; Wain Abrahamson and rant,&apos; and weaver4 have carried out studies on the effects of interstitial impurities on the brittle-ductile transition of chromium metal of various degrees of purity. These investigations have shown that oxygen has little or no effect on the transition temperature of chromium in all conditions studied but that carbon increases the transition temperature under all conditions tested. Nitrogen was found to increase the transition temperature in the wrought condition and in the quenched or cast conditionS but reportedly has no effect in the furnace-cooled condition.

Jan 1, 1964