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By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith's' concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman' who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By J. H. Smith, H. W. Paxton

X HE recent investigation of Butler, McCabe, and paxton' on the vapor pressure of manganese gas in equilibrium with Mn-Fe alloys has been extended to include the iron-rich solutions and alloys in the two phase equilibrium region. The study of the phase equilibrium by Kurnakov and Troneva2 and the extensive reviews of the Mn-Fe system by Hansen,3 and Hellawe114 are not in agreement with regard to the location and extent of the equilibrium between the solid phases of fcc y and complex P in the temperature range above the eutectoid temperature of approximately 975Kwhere 0 decomposes to y and bcc a. An evaluation of the existing equilibrium data is confronted with the conflicting results presented by various investigators who used techniques requiring a quenching treatment to retain the high-temperature equilibrium or encountered temperature hysteresis during thermal analyses. The difficulty of suppressing the transformation of the manganese-rich concentrations of the y-solid solution during quenching has been well etablished.' To avoid this uncertainty the phase equilibrium was investigated at temperature by measuring the partial pressure of manganese gas in equilibrium

Jan 1, 1962

By E. R. Gilbert, D. E. Munson

Creep of copper under 75 to 1.50 kg per sq cm stresses at temperatures near the melting point was found to he a complex reaction controlled by three mechanisms acting in parallel. In order of appearance with decreasing temperature, the auerage activation energies, Qc , are 168, 79, and 24 kcal per mole. Stress dependence of the minimum creep rate was found to he an exponential for the two high-Qc processes and a power law for the low-Qc, process. Transition of control occurs from one mechanism to another. The relative transition temperature depends upon the applied stress, and the range oiler which the transition occurs depends upon the difference in the activation energies of the mechanisms. The creep behavior at high temperature is explained by the climb of dislocations through thermally or mechanically formed jogs, CREEP in pure fcc metals at temperatures in excess of one half the absolute melting point is normally controlled by dislocation c1imb.1,2 A climb model which seems applicable, according to an extensive analysis of data,3 was derived by Weert-man.4 This model assumes jog-saturated dislocations and predicts an activation energy, Qc, nearly equal to that for self-diffusion, USd. Although the requirement of jog saturation is restrictive, agreement between theory and experiment seems adequate. Many other theoretical treatments, including an early model by Mott,5 include detailed consideration of jog formation as an initial requirement for climb. These models predict activation energies for creep which differ from those of self-diffusion. Seeger6,7 postulates an observed activation energy related to the stacking-fault energy. Thus, Usd <Qc<5Usd + Uj where Uj is the jog-formation energy. Seeger incorporated qualitatively the influence of the relative numbers of thermal and athermal jogs. Expanding this concept, Shoeck8 explicitly states a function based on formation mode and relative numbers of vacancies: e r ci exp {-uf/k T} exp {-Um/k T} [ 1 ] where Uf and Um are energies of vacancy formation and migration, respectively. The concentration of jogs, Cj, depends upon the manner of jog production. For intersection jogs, Cj is not sensitive E. R. GILBERT, Junior Member AIME, formerly with De- to temperature; for thermal jogs, Cj is proportional to exp {—Uj /k T}. Schoeck regards each mode as a distinct mechanism; therefore, the mechanisms may act together.299 The diversity predicted by theory, surprisingly, has not been substantiated by experimental results. A significant investigation must include the extremes in stacking-fault energy. Extensive creep studies of aluminum10 and nickel,11,12 high stacking-fault energy metals, have been made. Comparable studies on a low stacking-fault energy metal, such as copper, have not. It is the purpose of this paper to report the results of an investigation of the creep of copper under conditions which favor thermal jogs. EXPERIMENTAL Cylindrical compression creep specimens (0.240 in. in diameter by 0.400 in. long) were machined from cold-drawn rods of electrolytic tough-pitch copper containing 0.0007 Mg, 0.002 Fe, 0.001 Ni, 0.0005 Ag, Cd < 0.005, and Pb < 0.005 wt pct impurities. Undetected spectrographically was a nominal 0.04 wt pct 0, which occurs as a Cu2O constituent distributed discontinuously at grain boundaries. Vacuum annealing at 900°C for 15 min produced a stable 0.03-mm average grain diameter. Testing was carried out using apparatus similar to that described by sherby,13 modified by enclosing platens and a push rod in a vacuum cylinder. Normally this arrangement resulted in pressures less than 10 Only a slight surface tarnish, less than 0.0005 in. in thickness, occurred during the test. The applied stress, corrected for atmospheric pressure, was maintained within 2 pct of the desired true stress by the addition of lead shot at fixed strain increments. Creep strain was measured with dial gages as a relative displacement of the upper and lower platens; accuracy of measurement was 0.0001 in. Two creep-test methods were used, the differential or cyclic temperature14 and the isothermal, to obtain creep data at stress levels of 150, 100, and 75 kg per sq cm over the temperature range of 620° to 1032°C. Minimum creep rates were used from both test methods; this was considered proper because comparable temperature tests or cycling to the same temperature gave the same creep rate, within experimental error. The cold vacuum test chamber, with the unstressed specimen in place, was heated to temperature by placing a preheated furnace over the chamber. Temperature equilibrium was attained within 30 min. For the cyclic tests, the stress was removed during the 5 to 10 min necessary to effect the temperature change and re-

Jan 1, 1965

By R. A. Swalin, A. H. Geisler

THIS study represents an investigation of the effect of annealing temperature on the texture of drawn molybdenum, iron, and an iron alloy containing 14 pct Al. The effect of temperature on annealing textures has not been widely investigated in the past. One of the obstacles in making such a study using usual X-ray diffraction techniques results from the

Jan 1, 1957

By A. C. Fraker, H. H. Stadelmaier

WIENER and Bergerl reported the existence of the nitrides Fe3NiN and Fe3PtNwith a cubic L1&apos;2 structure. The present note shows that a similar nitride Fe3PdN can be observed and that the composition range between the iron nitride Fe4N and the nitrides Fe3NiN, Fe3PdN, and Fe3PtN is occupied by single-phase cubic nitrides with structures intermediate between L1&apos; and L1&apos;2. The materials used in this investigation were electrolytic iron of 99.9 pct purity, carbonyl nickel of 99.7 pct purity, sponge platinum of 99.95 pct purity, and palladium sheet of 99.8 pct. purity. Binary alloys of the transition metals were induction-melted in a crucible of fused alumina, powdered, and screened to a particle size of - 200 mesh. The powders were nitrided at 600°C in a gas mixture of ammonia and hydrogen, and the crystal structure was determined with the aid of a Wilson powder camera. The results are compiled in Table I together with information from the paper of Wiener and Berger.1 The compound at the nominal composition Fe3PdN has a diffraction pattern with prominent reflections of a face-centered cubic lattice (h2 + k2+l2 = 3, 4, 8, 11, 12, 16) and weaker superstructure lines (h2 + k2 + 12 = 1, 2, 5, 6, 9, 10, 13, 14). With decreasing palladium content the superstructure lines become weaker and approach the intensity of those of Fe4N. No analysis was made of the intensities, but it can be assumed that the structure is that found by Wiener and Bergerl in Fe3NiN and Fe3PtN, namely L1&apos;2 (perovskite structure) with both palladium and the interstitial nitrogen fully ordered. The dependence of the lattice constant upon the solute atom (Ni, Pd, Pt) content can be explained tolerably well by simple lattice expansion due to subsequent work confirms this suggestion, it will be of significance to order-disorder theory. The author is grateful to Lester Guttman for discussions on this topic.

Jan 1, 1961

By E. F. Adkins, R. I. Jaffee, C. T. Sims

The effect of oxide dispersions on mechanical proberties of cobalt and cobalt-base powder-metallurgy alloys was investigated. This study shows that oxide dispersions added to pure cobalt greatly improve the high-temperature creep resistance of the metal. Dispersions in powder-metallurgy .cobalt alloys were muck less effective. COBALT is extremely valuable as an alloy base for certain high-temperature applications. Important examples may be found in the widespread use of cast and workable alloys in aircraft gas-turbine engines. With the increases in cobalt production in recent years, greater use may be made of cobalt-base alloys for high-temperature applications, provided

Jan 1, 1960

By J. S. Kirkaldy, D. G. Fedak

The extra degree of freedonz introduced by a second independetzt concentration in a tenzary system gives rise to the possibility of unstable planar phase interfaces in semi-infinite diffision layer couples. Diffusion paths which pass continuously in and out of too-phase regions of the phase diagram but which are not coincident with tie-lines give rise to super saturated zones which may be either adjacent to or isolated from planar phase interfaces, with corresponding nonisolated or isolated precipitates. Nonisolated precipitates are equivalent to morphological development of the interface. Selected couples in the ternary systems Fe-Ni-Cr and Cu-Zn-Sn have been examined nzetallographically and ifz the latter case both isolated and uo~zisolated precipitates have been observed. The diffusion path in one of the couples showing interface morphological developtnent has been examitled using electron probe microanalysis. IGNORING the spurious effects of preferential grain boundary diffusion and anisotropic crystal growth7 it can be unequivocally stated that it is impossible for a binary isothermal diffusion couple constructed of two unsaturated phases to sustain a nonplanar phase interface. Consider for demonstrative purposes the schematic phase diagram of Fig. l(a). Given an initial flat phase interface, semi-infinite boundary conditions and the internal boundary condition fixed by the constitution diagram, xB = xB(T), the unique solution of the diffusion equation requires a persistent flat interface. No other solution is possible. If, however, we anticipate the involvement of surface tension, then the internal boundary condition must be written xB = xB (T,Y) where r is the radius of curvature of a hypothetical nonplanar interface. The introduction of a new parameter such as r can be equivalent to the release of an internal constraint, so that a stable nonplanar interface may be possible after all. Consider a perturbation to the interface as indicated in Fig. 1(b). According to the Ostwald-Freundlich equation: which is applicable to a system of this constitution, the solubility of A in the matrix ß ,xB (Y), at a point of curvature r is given by where Va is the molar volume of the a-phase, R is the gas constant, and a is the interfacial tension. Since the right hand side is positive, xB(r) >xB cm, as indicated in Figs. 1(a) and 1(c). Accordingly, the perturbation will carry the interface concentration in a direction which is opposite to that which would sustain local equilibrium. Such a perturbation is necessarily moderated and the system is returned to its initial condition. This result is general for all binary couples since we can regard an interfacial perturbation as an attempt to precipitate within un-

Jan 1, 1962

By E. Parthe, J. P. Pemsler

TWO references can be found in the literature concerning the ternary system uranium-tantalum -carbon. C. H. Schramm, P. Gordon, and A. R. Kaufmam reported in this Journal1 on the existence of the ternary carbide "UTa10C4." They also report a second face-centered-cubic carbide phase in the system U-Ta-C, which they denote as "white" phase. The publication includes a reproduction of a Debye-Scherrer powder photograph of "UTa10C4" and a list of the sin2 0 values of this compound. H. Nowotny, R. Kieffer, F. Benesovsky, and E. Laube2 report the complete solid solubility between TaC and UC with a B1 structure. Since the ternary phase "UTa10C4" lies very close to the binary system Ta-C, and the established phase Ta2C with a C27 structure had not been mentioned by Schramm et al., it was thought worthwhile to compare the patterns of "UTa10C4" with Ta2C. The strong lines of the given pattern were indexed on a hexagonal unit cell with the approximate cell parameters a = 3.09A and c = 4.93A. These are the values reported for Ta2C in the literature.3 The correspondence between reported and calculated sin2 8 values may be studied in columns 4 and 5 of Table I. The agreement is fair, but there remain weak lines which cannot be assigned to the hexagonal unit cell. The extinctions correspond to those of Ta2C, but a comparison of the calculated and observed intensities of the Ta2C lines (columns 2 and 3) with those of the corresponding lines of "UTa10C4" (column 6) show occasional deviations. To clarify this situation, four new samples were prepared. The compositions of these samples were chosen in such a way as to observe any existing ternary phase in the system TaC-UC-U-Ta. The samples were arc melted in an inert atmosphere and annealed at 1100°C for 36 to 72 hr. Compositions of the samples determined by chemical analysis are given along with the results of X-ray investigations in Table 11. The following conclusions may be drawn from these data: a) No ternary compounds occur in the section TaC-UC-U-Ta of the ternary system Ta-U-C. The "white" phase reported by Schramm et al. corresponds to a solid solution between TaC and UC. Only one three-phase field exists: C27-B1-A2. (Both tantalum and ? uranium have body-centered-cubic A2 structures.) The a uranium observed in sample 4 transformed from the high-temperature ? phase on cooling. b) The phase Ta2C with a C27 structure extends into the ternary system. "UTa10C4" is, therefore, a uranium-enriched Ta2C. Good agreement is ob-

Jan 1, 1960

By J. E. Harris

By elimination of other possible nucleation processes, it has been demonstrated, for commercially pure magnesium and a Mg-Al alloy, that at stresses less than that necessary for triple-point cracking creep cavities are most probably nucleated heterogeneously at second-phase particles. Evidence for the existence of such particles is presented and the role of grain boundary sliding in the nucleation process is examined quantitatively. DURING creep deformation of polycrystalline magnesium and its dilute alloys in the temperature range 0.45 to 0.7 Tm (Tm = absolute melting temperature) cavities form mainly along grain boundaries oriented normal to the stress axis and failure eventually occurs by their growth and impingement.&apos; The possibility of low-ductility creep failure of magnesium-alloy reactor cans during service has prompted a number of studies of cavity formation in these materials.2-5 In this paper divergent theories of cavity nucleation6-10 are examined critically and conclusions drawn regarding the most probable mechanism of formation of cavities in magnesium. The paper is divided into two parts. The first section consists of the review and quantitative assessment of the possible role of grain boundary sliding in the nucleation process. In the second part an experimental program is described where an electron-microscope technique has been used to determine if second-phase particles exist in as-received commercially pure magnesium and in a magnesium alloy 1) THEORETICAL REVIEW Possible nucleation sites for creep cavities are: a) high-angle grain boundary triple points,11-14 b) subboundary/grain boundary intersections,15-18 c) ledges in the grain boundary, 19-25 d) second-phase particles. 9,26-30 Each of these possibilities is now considered with special reference to deformation of magnesium. 1.1) Triple-Point Cracking. The stroh31 condition to nucleate fracture is: " > vr [1] where ss = applied shear stress, ? = surface energy, C = shear modulus, L = length of sliding interface. This relationship is independent of the nature of the interface and it is possible to calculate the stress concentration at the end of a sliding high-angle grain boundary and thus deduce, approximately,* the minimum applied stress necessary to nucleate triple-point cracking. Such theoretical predictions for Nimonic alloys have been made by McLean13 and found to agree quite closely with the minimum stress determined by experiment. Stresses capable of nucleating triple-point cracking should also be sufficient to nucleate fracture at a grain boundary due to intragranular slip, for the lengths of sliding interface in the two cases are approximately equal. Thus the minimum stress for triple-point cracking should represent a demarcation between failure due to general "cracking" and that due to cavitation. Hauser, Landon, and Dorn32 have demonstrated that for polycrystalline magnesium in the temperature range 78° to 298°K the fracture stress is inversely proportional to the square root of the mean grain diameter. As pointed out by stroh31 this result indicates that Eq. [I] describes the fracture characteristics of magnesium at low temperatures. Heal3 has reported that for rapid deformation (112 pct hr-1) of polycrystalline magnesium the transition from cracking to cavitation occurs in the temperature range 175" to 275°C. He also presented the fracture-stress values for the same material tested under similar conditions. From Eq. [I] taking G = 1.3 x 10" dynes , ? = 600 ergs . cm-2,33 and L = 0.017 cm, a Stroh-McLean13,31 tensile stress of -266 kg. cm-2 is calculated, corresponding to a transition temperature of -190°C; this is in

Jan 1, 1965

By Stanley Rajnak, John E. Dorn

The saddle-point activation energy for the nu-cleation of a pair of kinks is estimated as a function of the applied stress, the lattice constants, and the height and shape of the Peierls&apos; hill by employing the line-energy model of a dislocation. The kinetics of disloration motion by the Peierls&apos; mechanism are discussed and the microscopic dislocation velocities and macroscopic strain rates are formulated by the Arrkenius type of approach in terms of the activation energy for the formation of pairs of PEIERLS was the first to illustrate that a straight-dislocation line has its lowest energy when it lies in a potential valley parallel to lines of closest packing kinks. The log of the dislocation velocity is found to be approximately proportional to the log of the local applied stress. It is also shown that the low-temperature mechmical properties of several bcc metals might be explained in terms of the Peierls mechanism, good agreement being obtained between theory and experiment for the flow stress us ternperature, activation energy vs stress, and activation volume us stress curves for these metals. of atoms on the slip plane. When such a straight dislocation is moved rigidly from one valley toward the next, the atoms in the vicinity of the core of the dislocation change their positions and bond angles, causing the energy of the dislocation to increase. Midway between two adjacent valleys, the disloca-tion energy reaches a maximum value and any additional small displacement will cause the dislocation to fall down the hill into the next valley. The maximum shear stress necessary to promote such

Jan 1, 1964

By C. G. Durdaller, W. H. Robinson, G. M. Pound

The nucleation rate of the a (pay) to 0 (white) tin transformation was measured as a function of temperature and a tin particle size using an X-ray diffraction technique. The powder specimens of a tin were essentially monodisperse and the small dinzension of the particles of these specimens was varied from 13 to 75 p. Several types of nucleation sites of differing potency were fbund to be operative in the nucleation process, but it could not be determined whether these sites were on the free surface of the tin particles or within the volume. Assuming that they were on the free surface, the average density of the most potent sites was calculated to be 2.5 to 5.3 x 10&apos; sites per sq cnz through the application of a Poisson distribztion finction to the isothermal data. Analysis of the temperature dependence&apos; of the rate constmts at a given fraction transformed suggests that the active sites are regions of higher free energy and not catalytic interfaces. Appreciable induction periods were observed at the lower temperatures of transformation. Experimental studies1 of solid-solid phase transformations have led to the belief that the new phase nucleates at structural imperfections. The purpose of the present work was to learn more about the mechanism of nucleation in solids and the nature of the singularities at which nucleation occurs. In this investigation nucleation rates in the isothermal transformation of gray to white tin were measured by an X-ray diffraction technique using essentially monodisperse powders of gray tin. This particular phase transformation was chosen for study because it presented fewer experimental difficulties than most others. The experimental temperature-control problems were minimal because the two phases coexist in equilibrium at 13.3"C, and measurable transformation rates occur at temperatures only slightly above room temperature. The growth rate of the P phase into the a2 is sufficiently fast to make the measured transformation rate equivalent to the nucleation rate, provided that the particle size of the samples is small enough; for the experimental temperatures used in this study, the particle diameter must be less than 100 p. EXPERIMENTAL TECHNIQUE The P tin used in this study was obtained from Capper Pass and Son Ltd., North Ferriby, Yorkshire, England, and was of 99.999 pct purity. It was transformedS to the a phase and ground into a fine powder in an agate mortar. This powder was separated by a Roller air classifier into seven fractions whose dimensions, as determined by microscopic measurement of many thousands of particles, are given in Table I and whose distribution of size within each fraction is given in Figs. 1 and 2. The shape of the particles was roughly that of an oblate spheroid,

Jan 1, 1964

By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.&apos; From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author&apos;s previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954

By E. Buehler, J. E. Kunzler

High-pu.1-ity molybdenum has been heat treated, melted, and zone refined and the physical and chemical changes that are produced by these processes have been studied by making resistance ratio measurements. Pronounced effects are observed that are associated with recrystalliza-tion at about 1200°C and with melting. Melting alone is found to result in a substantial purification by the evaporation of impurities such as iron. Zone refining is found to be reasonably effective with four passes producing a three-fold decrease in resistance ratio and a minimum ratio of 0.0003. With the aid of low temperature measurenzents, it has been shown that the build-up of a deposit of the material being zone refined on the radio frequency coil used for heating can lead to contamination of the sample. CONSIDERABLE interest in high-purity refractory metals for the study of mechanical properties has developed during recent years. Also the need for highly pure metals in certain fundamental studies, such as electronic band structure, has become quite widely appreciated. Molybdenum can now be produced with sufficiently high purity to make it attractive for such investigations. The most suitable measure of chemical purity of metals used for many of these studies is its resistance ratio, R,.,o,/Ro, During the purification of molybdenum by zone refining and its subsequent evaluation by this technique, a number of informative observations were made. These observations concern the effectiveness of zone refining, the volatilization of impurities at the melting point, and the recrystallization of molybdenum and appear to be pertinent to other refractory metals. Also, the usefulness of low-temperature resistance measurements as an analytical tool for evaluating the presence of chemical impurities and physical defects in metals is again illustrated. Samples of high-purity molybdenum of known mechanical history were heated to various temperatures between 800°c and their melting point. Resistance ratios of the samples were measured after they had been given a specified treatment. The data were used, along with mass spectrographic analysis, as an aid in interpreting the nature of the processes that occurred in conjunction with each treatment. Changes in the concentrations of chemical impurities and physical defects are typical of things that effect the low-temperature resistivity. SAMPLES The starting material was obtained from Westing-house Corp., Bloomfield, N.J. It was in the form of molybdenum rods, usually 1/8 or 3/16 in. in diameter. These had been previously processed from bars, 5/8 in, in diameter, originally reduced from 4 in. diam arc-cast ingots, by hot swaging at about 1300°c. In the final step, the temperature was lowered to about l lOO°C which resulted in the production of elongated grains. Typical grains were about 0.03 mm thick and 0.6 mm long. The molybdenum was quite pure as is indicated by the results of mass spectro-scopic analysis1 given in Column 2 of Table I. Other nongaseous elements not listed in the table were not detected. ZONE REFINING AND THERMAL TREATMENT OF SAMPLES Several sample rods, 8 to 10 in. long, were zone refined or were heat treated at several temperatures. Both types of operations were performed using 3 me-

Jan 1, 1962

By D. L. Creighton, S. A. Hoenig

The field-emission microscope has been adapted for the study of microcrack growth during the early stages of fracture in metal wires. Cracks as small as 6 1 in length can be detected and their growth can be followed to specimen failure. The system is quite useful in searching for microcracks since only sharp-edged surface defects will emit electrons under the experimental conditions. THE conditions leading to brittle fracture were discussed a number of years ago by Griffith1 and the term Griffith Cracks is often used for the small surface cracks which are responsible for brittle fracture. Griffith&apos;s theory has been modified by stroh2 and more recent results on metals are discussed by Allen,3 pp. 123-40. At present the phenomenon is not completely understood but there is general agreement that at least in certain materials the sequence leading to brittle fracture involves several stages. The initial microcracks are present because of cooling or working stresses, Hahn et al.,3 p. 95. When a stress is applied to the specimen the cracks grow slowly until the release of stored elastic energy is large enough to accelerate the crack and provide the necessary surface energy for crack growth. At this point the growth rate appears to increase rapidly to some new equilibrium velocity, and failure occurs. Since the microcracks are usually about the size of a single metallic grain (Ref. 3, p. 99) it is not easy to find them and it is very difficult to follow their growth under stress. This paper will report on the use of a cylindrical field-emission microscope for observation of the formation and growth of microcracks. I) THE FIELD-EMISSION MICROSCOPE The field-emission microscope (FEM) has a high magnification and resolution and is almost uniquely suited for observations of microcracks. Since the FEM is relatively new as a metallurgical instrument, a short description will be given here. Normally metals at room temperature do not emit electrons; however in the presence of a strong electric-field gradient, electrons can tunnel out through the reduced potential barrier. Since this tunneling is a function of the local field gradient and the local work function, the emitted electrons can be used to produce a highly magnified image of the surface by allowing them to strike a phosphor screen. Because the electron emission is dependent upon the local field gradient, smooth surfaces emit few electrons except at very high fields. On the other hand cracks, extrusions, or other surface defects, having sharp edges, emit strongly since the field gradient is very high in the vicinity of these defects. This indicates that the FEM should be most useful for detection of microcracks on otherwise smooth surfaces. A field-emission microscope was first used by Muller4 in 1936 for observation of metal surfaces, and recent reviews have been given by Muller5 and Gomer.6 The instrument has been used for metallurgical studies in the area of surface diffusion,= recrystallization,7 and grain growth 8 (Ref. 8 is directed specifically at metallurgists). In the work of Muller4,5 and Gomer 6 the specimen was in the form of a sharp metal point at the center of a phosphor-coated glais sphere. The impact of the emitted electrons on the phosphor produced a highly magnified image of the specimens. Such a system is not practical for applying a controlled stress to the specimen and a cylindrical geometry has been used in this investigation. This allowed the application of a controlled tensile stress to the wire specimen. Normally a cylindrical FEM geometry produces magnification only in the radial direction. This is the case because a smooth wire at the center of a cylinder produces a purely radial electrical field. However, if there is a break in the smooth surface of the inner cylinder, the field near the break becomes three-dimensional and the area of the break is highly magnified. The reason for this is clear if it is recalled that the field gradient depends on the relative radii of the inner and outer cylinders; if a crack forms, its edge radii are of atomic dimensions and a very high field gradient is formed near these crack edges. Since the electrons receive most of their acceleration near the crack edge and are always traveling perpendicular to the field lines, they tend to spread out and produce the magnified image observed in the cylindrical field-emission microscope. 11) BRITTLE-FRACTURE STUDIES A) Experimental Apparatus. The geometrical arrangement chosen was that used earlier by Gifford

Jan 1, 1965

By John D. Roach

DURING an investigation of the yttrium-hydrogen system aimed at producing solid yttrium hydride specimens containing various amounts of hydrogen, it was observed that yttrium containing approximately 2 wt pct H exhibited a tendency to crack and crumble to a powder on standing in air at room temperature. It was also observed that longer hydriding times, at a given temperature, increased this susceptibility to powdering without an increase in hydrogen content, also that moisture in the air is necessary for the observed effects to occur. Even if cracking did not occur, there was a continual formation of a light gray powder on the as-treated surface of the hydrided yttrium and this reaction continues until the entire hydrided piece has been reduced to a powder. Storing the hydrided specimens in the absence of air or removing the surface either by machining or grinding were effective means of preventing this disintegration of hydrided yttrium. In an attempt to determine the reason for this powdering phenomenon, the surfaces of a number of as-hydrided yttrium specimens were examined by X-ray techniques. In all cases the X-ray pattern obtained showed the major phase to be yttrium hydride (YH2) as would be expected since the specimens contained 2 to 2.2 wt pct H. In some cases a trace of yttrium oxide was observed. There was also a third phase present on the surface of these hydrided specimens which could not immediately be identified. This unknown phase was a face-centered cubic material, NaC1-type structure, with a lattice parameter of 4.855 and a calculated density of 5.914 g per cc. Very slight hand polishing of the surface of the hydrided yttrium specimens completely removed both the unknown phase and the traces of oxide so that only the yttrium hydride pattern remained. Based on the X-ray patterns the quantity of the unknown phase on the surface of the hydrided yttrium appeared to be directly related to the susceptibility of the material to powdering. Work at the Denver Research Institute on the yttrium-nitrogen binary system showed that yttrium nitride (YN) is a face-centered cubic material with a lattice parameter of 4.878A and a density of 5.890 g per cc. They also noted that this compound rapidly disintegrated to a powder on standing in air. The unknown pattern observed in the above specimens corresponds very closely to that of the nitride—fcc structure, 4.885 parameter, and density of 5.914 g per cc. The presence of this thin film of nitride on the surface of the hydrided specimens probably accounts for the observed powder formation and crumbling. The nitride reacts with the water vapor in the air (verified by private communication from Dr. C. Huffine, General Electric Co.) to yield yttrium oxide and ammonia. Ammonia is readily detected when hydrided yttrium specimens were allowed to stand in bottled moist air. The powder formed on the surface of the hydrided specimens was shown by X-ray analysis to be yttrium oxide. This reaction appears to occur primarily at the grain boundaries since discrete particles of yttrium hydride separate from the specimens during this powdering process. The reaction of yttrium nitride with water vapor is believed to be as follows: 2YN + 3H2O - Y203 + 2NH3. Despite the fact that this nitride is present only as an extremely thin surface film, if the above reaction is not prevented by removing this film from the surface either by machining or grinding, the reaction continues until the entire hydrided piece has been reduced to a powder. To account for this continuation of the reaction, it is believed that the following reactionalsooccurs: 2YH2 + 2NH3 -2YN + 5H2. The nitride produced by the latter reaction reacts in turn with water vapor. The reaction therefore becomes autocatalytic and continues until the hydride has been consumed and the entire piece reduced to oxide powder. The amount of nitride required to initiate this reaction is quite small and this nitrogen contamination can occur from a number of sources—hydrogen gas employed, minute leak in the hydriding apparatus or even from degassing of the reaction vessel itself. Longer hydriding times increase the possibility of nitrogen contamination and this is especially true when a dynamic gas system is employed in the hydriding process. The production of stable, solid hydrided yttrium is dependent on the complete absence of nitrogen contamination during processing. If such contamination does occur, powdering of the hydrided product can be prevented by removing the nitride from the surface e.g. grinding or by preventing access of air to the pieces e.g. sealing in wax or plastic. The author wishes to express his appreciation to General Electric Co. for sponsoring this research and for permission to publish the results of work under Subcontract AT-93.

Jan 1, 1962

By J. Gurland

THE microstructure of sintered carbides consists of particles of metal carbides, such as WC and TiC, embedded in a metallic binder which is usually a cobalt—or nickel-rich solid solution. One of the important factors influencing the strength of the alloys is the degree of dispersion of the carbide particles in the binder matrix. While it is generally accepted

Jan 1, 1960

By D. W. Levinson, L. E. Tanner

DURING the course of an investigation of the zirconium-iron-tin system the zirconium-iron system was reexamined up to 55 pct* Fe. The alloys pre- visible melting3 and X-ray diffraction studies were made of samples of the alloys. The ferromagnetic properties of ZrFe2were determined by Professor P. W. Selwood* using a modified Faraday balance.4 The zirconium-rich portion of the phase diagram is presented in Fig. 1 and compared with the work of Hayes et al.1 The maximum solubility of iron in ß is somewhat decreased while the eutectic temperature is raised. There seemed to be no change in the eutectic composition of 16 pct Fe. Since the base material was so low in iron content, it was possible to establish the maximum solubility in a between 0.017 and 0.025 pct Fe at the eutectoid temperature. The observation of fine ZrFe, particles in the micro structure of a specimen of 0.012 pct Fe alloy quenched from 700°C indicated that the solubility drops below this composition at 700° C and lower. Further study was made of the intermediate phase ZrFe2. wallbaum5 identified the compound initially as ZrFe2 with a C 15 (MgCu2) structure, placing it at 55 pct Fe stoichiometrically. Hayes et al.1 believed they found the phase at about 47.2 pct Fe and called it Zr2Fe3 but reverted to ZrFe, in the discussion of their paper.6 Jordan and Duwez7 confirmed Wallbaum&apos;s work as well as finding the same single-phase structure to about 62.3 pct Fe or Zr0-61 Fe2-18. In order to establish the ternary phase relations in the zirconium-iron-tin systema the exact position of this phase had to be known. This was accomplished by X-ray diffraction, visible melting, and metallographic techniques. Elliott8 obtained a single-phase ZrFe2 X-ray diffraction pattern from an alloy of about 55 pct Fe. This was confirmed in the present study with an alloy of 54.81 pct Fe. However, extra lines (attributable to a or ß zirconium) were found in diffraction patterns of the 47.42 and 49.83 pct Fe alloys. The melting characteristics of these same alloys were studied by suspending 47.42, 49.83, and 54.81 pct

Jan 1, 1960

By H. Margolin, E. Ence

In order to understand the effect of zirconium on properties of Ti-Cu-A1 alloys, Ti-Zr alloys were examined for the presence of ordering or compounds at the following compositions in weight percent: 24.1 pct Zr (lZr:GTi), 32.2 pct Zr (lZr:4Ti), 38.8 pct Zr (lZr:3Ti), 49.0 pct Zr(1Zr:ZTi). Alloys were prepared as 15-g buttons by non- consumable arc melting under argon atmosphere from Bureau of Mines titanium (Bhn 63) and Reactor Grade zirconium (Bhn 150). Weight losses during melting did not exceed 1 pct of the initial button weight. Prior to heat treatment, buttons were hot-rolled at 600" to 700°C to rods of about 6 mm diam. Contamination after hot-rolling was found to extend to a depth of less than 0.5 mm. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. Annealing times were as follows: 700°C — 7 days; 600°C— 14 days; 575°C-1 and 2 months; 525°C-2 months; 500°C-2 months. Prior to heat treatment, all Ti-Zr alloys were vacuum annealed at 900°C to remove hydrogen. The reanneal of 575°C specimens for an additional month produced no observable microstructure changes. The results obtained by microstructure and X-ray diffraction are shown in Fig. 1, together with data of Hayes et al.&apos; No other phases than a or P were found. Small amounts of retained P were detected by X-ray in the 49 pct Zr alloy. The data of the present investigation suggests that ß and a transus boundaries are at considerably lower temperatures than those of Hayes et al. The work of Hayes et al. is based on sponge titanium and Bureau of Mines zirconium, both of which contained 0.15 pct 0. Since melting was performed in

Jan 1, 1962