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By Lawrence H. Van Vlack

DISCUSSION, H. L. Burghoff presiding C. S. Smith (University of Chicago, Chicago)—The author is to be congratulated on his valuable contribution to the extremely meager absolute data on interface energies in metallic systems. It is interesting to note that the ratio between a and r iron boundary energies is approximately the same in the quaternary alloy with silicon, carbon, and sulphur as in the binary Cu-Fe alloy. A value for the copper grain boundary energy can be obtained from the author's data, Tables IV and VI, by utilizing the energy ratios of the following pairs of interfaces: copper-sulphide/copper, copper y iron, y iron/y iron, y iron/ copper, and copper/copper. This gives a value of 595 erg per sq cm for the free energy of the copper grain boundary. Despite this circuitous route and the assumption that the y iron boundary is identical in alloys with and without sulphur and does not change between 1105" and 100O°C, this figure is in remarkably close agreement with other values of the copper boundary energy, obtained by equilibration against lead and against the free copper surface. It therefore appears either that impurities do not greatly affect the grain boundary energies or that boundaries in even nominally pure metals are already sufficiently contaminated so that further change has little effect.

Jan 1, 1952

By P. E. Arnold, G. S. Ansell

RELAXATION in metals has been studied in detail by many workers in recent years.1-5 These studies have shown that there is an energy-loss peak observed in a metal placed in mechanical resonance at low frequencies which may be correlated with various metallurgical processes. These experiments have been largely used to study single-phase materials. In order to study the effect of a finely dispersed second phase in a metal matrix upon this phenomenon, the relaxation behavior of an aluminum-aluminum oxide SAP-Type alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions was investigated by the use of internal-friction measurements. The alloys studied, designated MD 2100, consist of a matrix of commercial-purity aluminum containing a finely dispersed second phase of aluminum oxide. The aluminum oxide is present in this alloy in the form of fine platelets approximately 130A units thick and several microns on edge. The mean free path betwen dispersed platelets is approximately 0.5 p. The grain size of this alloy is extremely stable at temperatures as high as the melting temperature of the aluminum matrix. In the as-extruded condition the grain diameter is several microns, while in the recrystallized condition it is several millimeters in diameter. The damping characteristics of the alloy samples were determined using a torsional-pendulum device. The internal-friction constant was determined for this alloy in both the fine-grained as-extruded and coarse-grained recrystallized conditions over the temperature range from 343" to 923°K at frequencies of 0.9, 1.3, and 1.8 cycles per sec. An internal-friction peak was observed in testing the fine-grained alloys which was not observed for the coarse-grained alloys. This peak, which might be associated with a type of grain-boundary relaxation, was observed at each of the three different test frequencies for the fine-grained sample. The temperature at which the relaxation peak occurred for each of the three different frequencies is shown in Table I. From these data an activation energy of relaxation for each pair of frequencies was determined by comparing the temperature shift of the relaxation peak with frequency between each of the test frequencies, assuming that an Arrhenius-type rate equation is applicable. The activation energy of relaxation determined from these data is also shown in Table I. The mean value of the activation energy was about 6 kcal per mole. The activation energy for the relaxation process determined in this investigation indicates that the relaxation associated with the grain boundaries in this aluminum-aluminum oxide SAP-Type alloy is quite a different process than grain boundary relaxation in single-phase aluminum alloys. In these latter alloys, the activation energy for relaxation has been found to be the activation energy for self-diffusion, approximately 36 kcal per mole1,2 Where the activation energy is the same as the activation energy for self diffusion, it has been proposed that the relaxation phenomena is dependent upon vacancy formation and motion. It is apparent therefore, that, in this aluminum-aluminum oxide SAP-Type alloy, the relaxation must be due to another type of atom transport. It has been shown previously in studies of the high-temperature, low-stress, steady-state creep behavior of as-extruded aluminum SAP-Type alloys, that the activation energy for steady-state creep is one that may be characterized by the nucleation of dislocations from the grain boundaries. It is proposed that the relaxation behavior observed here is due to a similar effect. In this case, the internal-friction peak is a resonance behavior due to the time-dependent nucleation of dislocations from grain boundaries in the sample. A process of this type would have an activation energy which is undoubtedly stress-dependent and of the form Q = Q, + (dQ/du)u

Jan 1, 1962

By W. C. Winegard, W. J. Bratina

Internal friction characteristics and temperature dependence of the torsion modulus for iodide zirconium containing 2.4 pct Hf were investigated, using a low frequency pendulum technique. The internal friction curve consists of a background which increases as the temperature increases, a maximum at 860°C apparently a background due to the al-lotropic transformation, a maximum due to grain boundary relaxation with an associated heat of activation of 58,000 cal per mol, and an anomaly below 350°C which may be associated with a precipitation perphenomenon, Oxygen in below small amounts reduces the grain boundary maximum substantially. The variation of the torsion modulus at 20°C was found to be 3450 Kg per mm2 for the zirconium used in the present work. IT is well known that small amounts of certain solutes materially affect the ductility of zirconium. Lely and Hamburger,&apos; as early as 1914, found that high purity zirconium exhibited a remarkable ductility, while Fast&apos; has shown that oxygen and nitrogen can cause substantia1 embrittlement. Treco" has recently demonstrated that the ductility decreases sharply with the oxygen content, and that 2 atomic pct O2 embrittles zirconium to such an extent that cold working is impossible. The marked decrease in ductility is difficult to understand in view of the fact that Domagala and McPherson4 report the solid solubility of oxygen in zirconium to be 29 atomic pct at 500 °C. Another metal which behaves much the same as zirconium in this respect is titanium. Pratt et al." investigated the internal friction characteristics of titanium and the effect of oxygen on the internal friction values. It is evident that internal friction measurements are of value for studying grain boundary segregation, as shown by Pratt et al. for oxygen in titanium, by Pearson for oxygen in copper, and by Maringer and Schwope for oxygen in molybdenum. With this in view, the internal friction characteristics of zirconium and the qualitative effect of oxygen on the grain boundary relaxation phenomenon were investigated. Materials and Experimental Procedure The zirconium used in the present work was supplied by the Foote Mineral Co. in the form of wire 0.05 in. diam. The analysis supplied by the manufacturer indicates the amount of hafnium as 2.4 pct, less than 0.01 pct O less than 0.01 pct N,, less than 0.02 pct H,, and less than 0.001 pct C. Additional spectro-graphic analysis indicates the other main impurities as follows: 0.01 pct Fe, 0.05 pct Si, 0.008 pct Cu, <0.005 pct W, <0.001 pct Al, <0.05 pct Mg, <0.001 pct Ni, <0.02 pct Ca, and <0.01 pct Ti. Microscopic examination of the material in the as received condition revealed very fine grains with numerous twins. Specimens were annealed either in situ in the internal friction apparatus or in evacuated silica tubes in an auxiliary furnace. When the specimens were annealed in the auxiliary furnace, they were wrapped in identical zirconium wire to prevent contamination by the container. Metallographic sections were taken in all cases. Some were taken from the specimens used for internal friction measurements after completion of the experiments, while others were taken from control specimens at intermediate stages of the experiments. lnternal friction values were obtained by measuring the free decay of a low frequency torsion pendulum (1 cycle per sec), the suspension of which was

Jan 1, 1957

By Eric Kula, Åke Josefsson

L. J. Dijkstra and R. Sladek, (Ontario Research Foundation, Toronto, and Institute for the Study of Metals, Chicago, respectively)—This interesting paper confirms some results obtained some years ago in collaboration with Fast: namely the broadening of the nitrogen peak by the presence of small amounts of manganese. Later on a more extensive study of this effect was made at the Institute for the Study of Metals at Chicago. As the work has not yet been submitted for publication we wish to mention here briefly some of the results. The effect of about 0.5 atomic pct manganese, chromium, molybdenum, or vanadium on the nitrogen-peak in iron was examined. The broadening found previously in the case of manganese was even found to be more pronounced for chromium. In the case of molybdenum and vanadium a double peak was observed which seemed to justify the idea that in all cases mainly two relaxation times were involved: namely, the normal relaxation time as found in pure iron and a second relaxation time related to the existence of abnormal interstitial lattice sites introduced by the foreign metallic element. The analysis showed that for the normal nitrogen-peak as a reference at 22°C the abnormal peak was found at about 32°, 47°, 75°, and 87°C in the case of manganese, chromium, molybdenum, and vanadium, respestively. In the manganese alloy the free energy difference for a nitrogen-atom at an abnormal and a normal lattice site was estimated at 2800 cal per mol. This means that for temperatures above 100°C the solid solubility and overall diffusion rate of nitrogen is not much affected by additions of 0.5 pct Mn. We believe that the difference in rate of precipitation of nitrogen in pure iron and the manganese alloy is mainly a question of the number of potential nuclei available in the different steels. In studying the effect of these alloying elements on precipitation of nitrogen, a distinction must be made between the para reaction and ortho reaction, using terminology introduced by Hultgren.7 The ortho reaction in which the alloying metallic element participates in the diffusion under formation of nitrides occurs at high temperatures such as 600°C. The para reaction in which the alloying metallic element does not diffuse and in which the nitride inherits its alloy content from the matrix occurs at lower temperatures. To prevent the ortho reaction the alloys have to be quenched rapidly from the phase. It is not surprising that the authors find that the height of the peak indicates a lower nitrogen content than chemical analysis. In the first place the peak is not a single relaxation peak and secondly, the steels were not quenched from the phase after the nitrogen was introduced at 580 °C.

Jan 1, 1953

By R. G. Garlick, H. B. Probst

Tungsten single-crystal specimens of various orientations were deformed in tension at room temperature. Slip traces indicated both (112)(111) and (110) (111) slip; however, about 10 pct plastic dejormation was required bejore these traces could he seen. Resolzled shear-stress considerations indicated that at least some of the particular systems observed were not those on which slip initiated hut were secondary systems. This is highly probable, considering the high plastic strains involved. Analysis of the stress data with respect to possible slip systems indicated that slip must have been initiated at stresses below the proportional-limit stresses measured. ALTHOUGH there is general agreement that slip deformation in fcc and hep metals takes place on the plane of close packing and in the direction of close packing, there is no such agreement for slip in bcc metals. It is generally agreed that the close-packed direction (111) is the slip direction, but investigations have led to conflicting descriptions of the slip plane. As Hoke and Maddin1 point out, there are essentially four points of view. 1) Deformation in bcc metals is composite shear on (112) and (110) planes or on nonparallel (110) planes, and any apparent slip on other planes can be accounted for completely by slip on these planes. Chen and Maddin have reported this to be the possible case for molybdenum." 2) Slip occurs in the (111) direction and is limited to {110), {112), and (123) planes (the three closest packed planes of the lattice). 3) Slip occurs in a (111) direction, but not necessarily on planes of close packing (banal slip). 4) Slip occurs in those directions and on those planes for which ß, the ratio of Burgers vector to interplanar spacing, is a minimum. The slip systems of the bcc metal tungsten have never been fully determined, although several investigators have reported pertinent results.3"7 The present work was initiated to determine the active slip systems in tungsten at room temperature, the critical resolved shear stresses associ- ated with these systems, and the orientation dependency of operative systems. These features of tungsten deformation at room temperature have never been reported in the literature. The authors find this somewhat surprising, particularly in view of the availability of tungsten single crystals since the advent of electron-beam zone-melting techniques and the widespread interest in refractory metals. It would seem apparent that such work has been attempted but the results have not been reported, possibly due to the conflict with deformation theory. The results of the present work conflict with any straightforward description of deformation based on the proposed explanations of slip in bcc metals. Although these conflicts have not been resolved, a presentation of the problem seems in order and should be of value to others working in this field. MATERIALS AND PROCEDURE Single-crystal tungsten rods of 1/8-in. diameter were grown from undoped commercial rod by one-pass electron-beam zone melting in apparatus previously described by witzke.8 Representative analyses of the rod before and after melting are given in Table I. There was no detectable zoning of impurities during melting. Buttonhead tensile specimens, as shown in Fig. 1, were machined from single crystals. Two flats 90 deg apart were ground in the gage length of each specimen. These flat surfaces facilitated the analysis of slip traces. No attempt was made to position these flats with respect to the crystal orientation. The worked surface layer of the machined specimens was removed by electrolytic polishing in a NaOH solution. Tensile-axis orientations were determined by standard Laue back-reflection techniques. The sharpness of the Laue spots indicated that the crystals were free of strain.

Jan 1, 1964

By C. E. Birchenall

DaVIES and Richardson1 have measured composition changes for Mn1-Owith variation in the equilibrium partial pressure of oxygen at 1500°, 1575°, and 1650°C, where 6 is the deviation from the simple stoichiometric ratio. No trend in this relationship with temperature was observed, so these remarks apply to the whole temperature range. The experimental values and their spread are shown by the bounded straight-line segments in the figure. Davies and Richardson assume that the stoichiometric oxide shows Frenkel disorder, given by the equation Mn2+Mn2+ + Mn" [1] where Mn2+ is a normal lattice ion which moves into an interstitial site (Mni2+) leaving a vacancy (Mn,"). The superscript dashes indicate that there is an excess charge on the anions surrounding the vacancy. Schottky disorder, in which a perfect crystal acquires equal numbers of cation and anion (Ov") vacancies according to leads to equations of exactly the same form in the analysis below. In view of the neutron diffraction results of Roth,2 which shows extensive Frenkel disorder in Fe1-o, Eq. [I] seems more appropriate. The deviations from stoichiometric composition, MnO, result from the addition of oxygen according to In effect Davies and Richardson ignore the variation of Mn3+in constructing equilibrium constants. This approximation might not appear to be very serious if the excess positive charges are really free posi- tive holes (P+) and if the intrinsic conductivity is high as a result of the reaction where e- is a conducting electron. However, the calculations of Buessem and Butler3 indicate that the partition functions of the free charges make a large contribution to the equilibrium constant, and this approximation would not be a desirable one. Furthermore, Morin4 shows that the positive holes are probably localized in MnO and therefore are described better by the mass action principle than by a degenerate gas model. Davies and Richardson&apos;s considerations require that activity corrections be applied beyond a 6 value of about 0.005. It is proposed to show here that the dissociation pressure curve can be calculated reasonably well over the whole composition range studied without activity corrections by choosing appropriate equilibrium constants for reactions 1 and 2. As stoichiometric composition The mass action constant, Ks, for reaction [I.] and the equilibrium constant, K,, for reaction [2] are given by where the concentrations which do not change significantly have been absorbed into the constants. The brackets denote concentrations. The deviation from stoichometric composition is given by gardless of [Mni2 ]. Substituting Eq. [7] in [6]

Jan 1, 1961

By E. S. Machlin, Morris Cohen

The isothermal formation of martensite in a 71 pct Fe, 29 pct Ni alloy is found to take place mainly by the nucleation of new plates rather than by the growth of existing ones, and is dependent on the temperature and time of the isothermal hold, the amount of atherrnal martensite present, the state of internal strain, and the application of tensile stress. The conclusion is reached that the isothermal nucleation is activated by thermal fluctuations superimposed on localized regions of very high strain. The reaction-path concept, involving martensite nucleation at strain embryos by athermal activation on cooling, or by thermal fluctuations on holding, reconciles the athermal and isothermal modes of transformation, and offers a unified picture of the kinetics of martensite formation. THE phenomenon of isothermal martensite formation has been the subject of considerable study lately,&apos;-&apos; and its reality has been thoroughly established. The existence of such isothermal transformation has been claimed to confirm the nucleation and growth hypothesis as applied to the martensitic reaction.1 " However, the isothermal formation of a martensitic phase is also compatible with the reaction-pathw escription of the transformation. The purpose of this investigation is to examine the isothermal mode of the martensitic reaction, both theoretically and experimentally, in order to test the likelihood of the above two mechanisms. Material and Methods The alloy used in this study contained about 71 pct Fe and 29 pct Ni. The complete analysis was 29.5 ± 0.2 pct Ni, 0.036 pct C, 0.02 pct N, 0.19 pct Mn, 0.09 pct Si, 0.008 pct P, and 0.006 pct S. The amount of isothermal transformation was determined by electrical resistance measurements using a Kelvin double bridge. The specimens were in the form of rods 1/16 in. diam x 4 in. long. Aus-tenitizing was performed at 1095°C for % hr either in a pre-purified nitrogen atmosphere or in an evacuated Vycor tube, followed by oil quenching to room temperature. After this treatment, the samples were completely austenitic, and the transformation studies were conducted at subatmospheric tempera- tures. Lineal analysis and X-ray determinations of retained austenite were used to calibrate the electrical resistance changes in terms of the percentage of martensite. The martensite range curve for this alloy is given in Fig. 9 of ref. 6. The M, temperature occurs at about -18°C (255°K). Reaction-Path Theory The nucleation and growth description of the martensitic transformation that occurs isothermally has already been given by Kurdjumow.&apos;,&apos;2 However, no comparable treatment exists using the reaction-path concept." Consequently this section presents the reaction-path description of the isothermal mode of the martensitic transformation. According to the latter theory, there is a reaction path (a strain) which describes the relative motion of the atoms during their transference from the austenitic to the martensitic state. The possibility exists, therefore, that the nucleation of a martensitic plate is accomplished by an embryo that comprises a state intermediate between that of austenite and martensite. This state may be attained within a finite volume by means of a homogeneous strain of the austenitic matrix. There is a free-energy barrier (F.) along the reaction path, corresponding to a critical strain in a critical volume. When activation is achieved, a spontaneous increase in strain and volume of the embryo takes place to generate the full-size martensitic plate. This mode of nucleation is to be distinguished from the more conventional mode involving embryos of the martensitic phase that merely grow in size by an interface motion. There are two ways whereby embryos in the austenitic phase can achieve the critical state of strain for isothermal nucleation: 1—through the formation of internal strains by plastic deformation or by stress; and 2—through thermal fluctuations, preferably superimposed upon existing internal strains. The activation free energy F,, must be supplied either mechanically by internal strains or thermally by energy fluctuations, or by a combination of both.

Jan 1, 1953

By A. Spilners, M. Simnad

The rates of formation of the different oxides on molybdenum in pure oxygen at 1 atm pressure have been determined in the temperature range 500° to 770°C. The rate of vaporization of MOO, is linear with time, and the energy of activation for its vaporization is 53,000 cal per mol below 650°C and 89,600 cal per mol at temperatures above 650°C. The ratio Mo03(vapor.lzing)/MoOS3(suriace) increases in a complicated manner with time and temperature. There is a maximum in the total rate of oxidation at 6W°C. At temperatures below 600°C, an activation energy of 48,900 cal per mol for the formation of total MOO, on molybdenum has been evaluated. The suboxide Moo2 does not increase beyond a very small critical thickness. At temperatures above 725°C, catastrophic oxidation of an autocatalytic nature was encountered. Pronounced pitting of the metal was found to occur in the temperature range 550° to 650°C. Marker movement experiments indicate that the oxides on molybdenum grow almost entirely by diffusion of oxygen anions. USEFUL life of molybdenum in air at elevated temperatures is limited by the unprotective nature of its oxide which begins to volatilize at moderate temperatures. Although the oxide/metal volume ratio is greater than one, the protective nature of the oxide film is very limited. Gulbransen and Hickman&apos; have shown, by means of electron diffraction studies, that the oxides formed during the oxidation of molybdenum are MOO, and MOO,. The dioxide is the one present next to the metal surface and the trioxide is formed by the oxidation of the dioxide. Molybdenum dioxide is a brownish-black oxide which can be reduced by hydrogen at about 500°C. Molybdenum trioxide has a colorless transparent rhombic crystal structure when sublimed, but on the metal surface it has a yellowish-white fibrous structure. It is reported to be volatile at temperatures above 500" and melts at 795°C. It is soluble in ammonia, which does not affect the dioxide or the metal. In his extensive and classic investigations of the oxidation of metals, Gulbransen2 has studied the formation of thin oxide films on molybdenum in the temperature range 250" to 523°C. These experiments were carried out in a vacuum microbalance, and the effect of pressure (in the range 10-6 yo 76 mm Hg), surface preparation, concentration of inert gas in the lattice, cycling procedures in temperature, and vacuum effect were studied. The oxidation was found to follow the parabolic law from 250" to 450°C and deviations started to occur at 450 °C. The rates of evaporation of a thick oxide film were also studied at temperatures of 474" to 523°C. In vacua of the order of 10- km Hg and at elevated temperatures, an oxidation process was observed, since the oxide that formed at these low pressures consisted of MOO, which has a protective action to further reaction in vacua at temperatures up to 1000°C. Electron diffraction studies showed that, as the film thickened in the low temperature range, MOO8 became predominant on the surface. Above 400°C MOO, was no longer observed, MOO, being the only oxide detected. The failure to detect MOO, on the surface of the film formed at the higher temperatures does not militate against the formation of this oxide, since according to free energy data MOO3, is stable up to much higher temperatures. At the low pressures employed, this oxide would volatilize off as soon as it was formed. Its vapor pressure is relatively high and is given by the equations" log p(mm iig) = -16,140 T-1 -5.53 log T + 30.69 (25°C—melting point) log p(mm He) = -14,560 T-1 -7.04 log T+1 + 34.07 (melting-boiling point). Lustman4 has reported some results on the scaling of molybdenum in air which indicate a discontinuity at the melting point of MOO, (795°C). Above the melting point of MOO,, oxidation is accompanied by loss of weight, since the oxide formed flows off the surface as soon as it is formed.5,6 Qathenau and Meijering7 point out that the eutectic MOO2-MOO3 melts at 778C, and they ascribe the catastrophic oxidation of alloys of high molybdenum content to the formation of low melting point eutectics of MOO3 with the oxides of the melts present. Fontana and Leslie -explain the same phenomenon in terms of the volatility of MOO,, which leads to the formation of a porous scale. Recent unpublished work by Speiser9 n the oxidation of molybdenum in air at temperatures between 480" and 960°C shows that the rate of weight change of molybdenum is controlled by the relationship between the rates of formation and evaporation of MOO,. They have measured the rates of evaporation of Moo3 in air at different temperatures and estimated an activation energy of 46,900 cal. This compares with the value of 50,800 cal per mol obtained by Gulbransen for the rate of sublimation of MOO, into a vacuum.

Jan 1, 1956

By F. D. Rosi, C. A. Dube, B. H. Alexander

WHEN a deformed polpcrystalline metal is heated to a sufficiently high temperature, a recrystallized structure develops which consists of small, essentially stress-free grains. This transformation is referred to as primary recrystallization. Under certain conditions, on prolonged annealing of the specimens, a type of grain coarsening occurs in which a small number of grains commence to grow at various points by devouring the neighboring finegrained primary structure, which, in itself, exhibits a marked stability toward normal grain growth. This grain coarsening process has been referred to by Burgers&apos; as "secondary recrystallization" or "exaggerated grain growth." Although much work has been done on recrystallization and growth processes, present knowledge of the factors which determine the occurrence and growth of secondary grains is inadequate for the advancement of a theory which accounts for the observed characteristics of this recrystallization phenomenon. In this respect, it would be important to make measurements of the velocity of growth of these large secondary grains. The early work of Feitnecht2 on aluminum showed that the size of secondary grains increased with temperature and time, suggesting that such measurements would be possible. More recently, Burgers1 found that the growth velocity of these grains in aluminum was constant over a large time interval, as is generally found for the growth velocity of primary grains in a uniformly deformed test piece.3-5 It is reasonable to expect that the determination of the activation energy of the secondary growth process might lead to a better understanding of the underlying atomic mechanism. This investigation, therefore, is one of a series primarily designed to measure the growth velocity of secondary grains at various temperatures for silver, copper, and aluminum. It is hoped that these studies along with those of orientation relationships, will establish a sound basis for theorizing as to the origin and nature of the secondary transformation. Experimental Procedure The metal used in the present investigation was high-purity silver (999.9 fine), which was supplied in the form of cold-rolled plates 0.250 in. thick. These plates were annealed at 500°C for 1 hr and then straight-rolled to a thickness of 0.04 in. in three reductions of approximately 45 pct, followed in each case by an anneal at 450°C for 1/2 hr. The 0.04 in. sheets were given a final reduction of approximately 50 pct, which resulted in a thickness of 0.02 in., thereby insuring two-dimensional crystal growth. Individual specimens of this material about 1x3 cm were used for all heat treatments, unless otherwise noted. The annealing was carried out under an atmosphere of argon in an Inconel tube furnace whose temperature was controlled to within -+2°C. Metallographic examination of the secondary transformation was accomplished by mechanically polishing the specimens on one side to approximately one half their thickness through 2/0 metallographic emery paper, and then electrolytically polishing in a solution of potassium ferrocyanide and sodium cyanide. With a current density of approximately 20 amp per sq dm, the time required to obtain a satisfactory surface varied from 3 to 5 min. Standard potassium bichromate was used to etch the electrolytically polished surfaces. A heavy etch with this solution produced a sharp contrast between the secondary grains and the fine-grained primary structure, darkening the latter while leaving the large secondary grains bright. All area measurements of the secondary crystals were made with a planimeter on enlarged tracings of the grains.

Jan 1, 1953

By J. W. Rutter, K. T. Aust

The migration of individual, large-angle grain boundaries has been studied as a function of tempereature and solute concentration in specimens of zone i.e filled lead containig very small additions of silver and of gold. Tile results are compared with various the-ories of grain boundary migration and with observations made prev.iorlsly of grain boundary migration in similar specimens of zone-refined lead containing tin additions. A previous investigation by the authors dealt with [he temperature dependence of grain boundary migration in bicrystals of zone-refined lead containing small additions of tin.&apos; It was shown that tin additions as low as a few parts per million cause a large decrease in the grain boundary migration rate at any given temperature, as well as a marked increase in the temperature dependence of the migration rate. It was found that existing theories of grain boundary migration. based on the motion of dislocations. or upon the concept of atom transfer in groups across the boundary (group process theory). or upon the control of grain boundary motion by volume diffusion of impurity atonls along with the boundary. are incapable of accounting for the observations. The single process theory of grain boundary migration. which is an absolute reaction rate calculation based on the transfer ui atoms singly across the moving boundary, was found to predict the migration rate reasonably well for a number of boundaries whose motion was shown to be very little influenced by impurities, but not for boundaries whose illation was influenced markedly by impurities. It was concluded that the elementary process of grain boundary migration involves the activation of single atoms during transfer across the boundary. and that inadequate knowledge is available to permit the influence of impurities to be properly taken into account. The present study was initiated to check the validity of the above conclusions with other alloy systems, namely high-purity lead with small additions of silver and of gold. Both silver and gold diffuse faster. and with a lower activation energy of volume diffusion. than does tin in lead;&apos; consequently, a study of the effects of silver and gold on grain boundary migration in high-purity lead offered a means of testing theories of boundary migration based on bulk diffusion of the solute (eg. ref. 3). In addition. it was hoped that the present work, in comparison with the results for tin in lead, would provide information concerning which factors are important in determin- ing the interaction between solute atoms and a grain boundary. EXPERIMENTAL PROCEDURE The preparation of bicrystals of zone-refined lead, with various silver or gold additions, was identical to that previously described for the lead-tin alloys.&apos;&apos;4 Each bicrystal consisted of a striated crystal which was grown from the melt. and an adjacent striation-free crystal which was introduced by artificial nucleation and growth.&apos;&apos;4 The striation or lineage substructure in the melt-grown crystal provided the driving force for grain boundary migration. During the preparation of striated single crystals by growth from the melt, it was found that silver or gold concentrations as low as 2 or 3 ppm by atoms were sufficient to cause formation of the hexagonal cell structure. which is due to the presence of impurity, during freezing. This structure is revealed on the solid-liquid interface by decanting the liquid during freezing. The hexagonal cell structure was observed previously4 in zone-refined lead crystals with tin contents above approximately 200 ppm by atoms. These concentrations of silver, gold, or tin are in agreement with the predicted amounts required for cell formation in lead,5&apos;6 under the present conditions of freezing.4 The absence of cell structure at decanted interfaces, therefore, served as a useful indication that the silver or gold contents were less than 2 or 3 ppm by atoms in the specimens as grown. It was found that grain boundary migration occurred only very slowly when the solute content approached that necessary for cell formation. As a result, the present experiments were conducted with silver or gold additions less than 1 ppm by atoms. This impurity level is well within the solid solubility limits for silver and gold in lead.7 The annealing treatments, measurements of grain boundary velocities, and orientation determinations were carried out as described previously.&apos; However. each bicrystal was also chemically polished in a solution consisting of 8 parts glacial acetic acid and 2

Jan 1, 1961

By R. Ruka, E. A. Gulbransen

ONE of the interesting questions in the understanding of the reaction of iron with oxygen is the kinetics and the mechanism of the crystal structure changes occurring in the formation and breakdown of the oxide film. In a recent work&apos; the electron diffraction method was applied to the study of the solid phase reactions occurring internally in the oxide film on iron above 570°C and under vacuum conditions. The higher oxides which form under oxidizing conditions are reduced internally by the diffusion of iron into the oxide leaving the bulk of the oxide FeO (wüstite). This paper will ask and consider three questions. These are: (1) What is the nature of the depressed transformation temperature for the Fe3O4 + Fe ? 4Fe0 reaction in very thin oxide films?; (2) What is the mechanism of the forward transformation of Fe3O4 to FeO at or near 570°C?; and (3) What is the nature and mechanism of the slow reverse transformation of FeO to Fe3O4 and Fe below 570°C?. The composition of the oxide as well as its electrical, magnetic, mechanical, and chemical properties depends upon the kinetics of these reactions. Literature Survey The composition of the oxide film on pure iron at temperatures up to 570°C has been studied extensively by the electron diffraction method. Nelson,&apos; Jackson and Quarrell,3 and Gulbransen and Hick-man4 have shown that Fe3O4 and a-Fe2O8 are formed in the temperature range of 225" to 570°C, while y-Fe,O, is most likely formed below 225°C for long oxidation times. In very thin films FeO (wüstite) is found to form at temperatures as low as 400°C, and its existence depends essentially upon the extent of initial oxidation. FeO is not found in the formation of thick films below 570°C. On the other hand X-ray5 and micrographic8 studies show that Fe3O4 may exist as the main com-ponent in thick films up to 650°C, well above the equilibrium temperature for the reaction Fe3O4 + Fe ? 4FeO. The kinetics of the forward and reverse trans-formations of the reaction Fe3O4 + Fe ? 4FeO have not been studied in oxide films. However, analysis of the data of Gulbransen and Hickman4 on the heat-ing and cooling of iron oxide films of known thick-nesses in high vacua shows that the forward reac-tion proceeds rapidly even for a 4000 A film at temperatures of 575" to 600°C. The reverse reaction or decomposition of wüstite (FeO) occurs at tem-peratures below 450°C. Thus, there appears to be a slow process in the decomposition which is in marked contrast to the rapid forward reaction. The decomposition of a bulk sample of FeO free from the metal has been studied extensively by Chaudron, Benard and coworkers using the micro-graphic, X-ray diffraction, and thermomagnetic methods. Chaudron7,8 first observed that the de-composition of FeO (wüstite) below 570°C occurs by the reaction 4FeO ? Fe3O4 + Fe. Later work by Chaudron and Forestier5 showed that the rate of de-

Jan 1, 1951

By D. Turnbull, J. H. Hollomon, J. C. Fisher

Application of the concepts of nu-cleation and growth to the analysis of experimental transformation data has led to valuable descriptions of phase transformations, an outstanding example being the transformation austenite —* pearlite which has been examined with particular care by Mehl and co-workers.&apos;-5 In addition to the pearlite transformation, the proeutectoid fer-rite and proeutectoid carbide transformations are known to proceed by nucleation and growth. Martensite, on the contrary, until recently was thought to form by a mechanism involving neither nucleation nor growth; however, extension of standard nucleation theory6 suggests that martensite, bain-ite, and the other products of austenite decomposition all grow from nuclei in the parent phase. The theory that martensite forms by nucleation and growth is strongly supported by recent experimental work of Kurdjumov and Maksimova.7 The concepts of nucleatioli and growth have been fruitful also in providing a sound basis for quantitative theoretical treatments of the kinetics of phase transformations. For example, Volmer and Weber8 and Becker and Döring9 developed the theory of nucleation from fundamental considerations to a point where excellent agreement was obtained with the results of experiments on the condensation of supercooled vapors. As a result of their analysis, the kinetics of vapor-liquid transformations now can be predicted. It seems probable that application of the theories of nucleation and growth to a quantitative study of austenite decomposition similarly will clarify the nature of the individual transfor: mations involved, and will enable the calculation of austenite transformation kinetics. In the present paper, the theories of nucleation and growth are applied to the austenite ? martensite transformation in steels. The analysis begins with a discussion of nucleation in single component systems. Martensite appears to be coherent with the parent austenite, hence the nucleation theory is modified to include the effects of elastic distortion. Nucleation in the two component iron-carbon system then is discussed, for most steels are primarily alloys of these two elements. Finally, M. temperatures and martensite transformation curves are calculated for each of several alloy steels of varying carbon and chromium content, and are compared with those determined experimentally by Lyman and Troiano10 and Harris and Cohen.11 Nucleation Theory NUCLEATION IN SINGLE COMPONENT SYSTEMS6,12-14 The work required for reversible formation of a region of phase within the parent a phase is expressed conveniently as the sum of two terms: W1 = Aa, the product of the area of the interface and the interfacial free energy, and W2 = VAf, the product of the volume of the region and the free energy increase per unit volume associated with the transformation. The total work is therefore W = Aa + VAf. When a is more stable than ß, Af is positive and W increases without limit as the volume increases. The transformation a ?ß does not occur. It is nevertheless true that small regions of phase ß enjoy temporary existence here and there in the a. The equilibrium number of ß regions of given size is proportional to exp(— W/kT) per unit volume of a, assuring that larger (ß regions occur with diminishing probability. When a is less stable than ß, Af is negative and W passes through a maximum as V increases. Assuming for simplicity that regions of ß are spherical, as is true when the interfacial tension is isotropic and there are no elastic strains, W = 4r2a + (4/3)*r3Af The maximum value of W is W* = 16iro3/3Af2 [1] for regions with radius r* = -2o/Af. [2] For single component condensed systems it has been shown14 that the steady rate of nucleation of 0 per unit volume of untransformed a is nearly proportional to exp[- (W* + Q)/kT] where Q is the activation energy for the unit processes of adding or removing one atom from an embryo or nucleus. If To is the temperature at which a and ß are in equilibrium, the rate of nucleation is a maximum at a temperature 0 < T < To where (W* + Q)/kT is a minimum. P regions smaller than critical size are called embryos; they tend to grow smaller and disappear, only exceptionally growing larger. Regions equal to or larger than critical size are called nuclei. A critical size nucleus may grow indefinitely large or may shrink back to a, either process decreasing the free energy of the region.

Jan 1, 1950

By J. S. Kirkaldy, G. R. Purdy

THE formation of ferrite in supersaturated aus-tenite has been the subject of considerable speculation and investigation. Aaronson has recently reviewed the data pertinent to this reaction.&apos; Since these data in all cases refer to ternary or high-order alloys it is not possible to put them to the test of simple binary diffusion formalism. It has not, therefore, been possible to make a certain statement as to the controlling mechanisms in the process. An assessment of the difficulties inherent in the conventional statistical metallographic approach suggested that a study of the problem by means of a macroscopic two-phase diffusion couple might contribute useful information. Accordingly, such a couple was synthesized, and the rate of motion of a ferrite-austenite phase boundary (the growth of an austenite layer at the expense of a ferrite layer) was determined. Wagner originally produced a diffusion solution applicable to the motion of a planar phase interface in a binary diffusion couple, assuming local equilibrium throughout the diffusion zone. This solution, which is stated free of typographical error* in Ref. where a is the position of the interface in A space (A = x/fi), C; and CL1 are the equilibrium inter-facial concentrations in phases I and 11, C: and C*1 are the initial bulk concentrations in phases I and 11, and & and are diffusion coefficients (assumed constant). If a diffusion couple consisting of homogeneous layers of ferrite and austenite in equilibrium is raised to a higher temperature, the austenite layer will grow at the expense of the ferrite. Provided that the thickness of the ferrite layer is much less than the diffusion length of carbon in ferrite, we can set , so that Wagner&apos;s solution reduces to

Jan 1, 1963

By E. A. Gulbransen, K. F. Andrew

THIS paper. will present the results of our studies on the kinetics of the gas phase reactions of co-lumbium and tantalum with O2, N2 and H2. Studies on zirconium and titanium have been previously reported.9,11 Due to their high melting points and their many excellent physical and chemical properties, colurn-bium and tantalum have been finding their places as useful metals in science and industry. Chemically the metals are very inert to gas and liquid phase corrosion at room temperature. However, at moderate temperatures of 250°C and higher the metals react readily with oxygen and hydrogen. It is of interest to study the gas phase reactions of these metals for the following reasons: (1) to compare the rates of the several reactions with those of other metals and to correlate the rate data with theory and structure predictions, (2) to add basic information on the practical difficulties of the reduction, refining and working of columbium and tantalum, (3) to anticipate new uses for the metals and (4) to understand the role that the metals play as components in high temperature alloys. Literature Survey A number of papers exist in the literature on the gas phase reactions of columbium and tantalum with O2, N2 and H2; however, only fragmentary data have been reported on the kinetics of these reactions. Although the free energy of formation of the oxide Ta2O520at 25°C has been determined and some thermodynamic work has been reported on columbium and its oxides, the data are not sufficient to make equilibria calculations at elevated temperatures. Oxidation: 1. Kinetics: The rate of oxidation of columbium and tantalum has been studied by McAdam and Geil23 using the interference color method. Tantalum is reported to oxidize more slowly than columbium, zirconium and iron. The amounts of oxidation of columbium after 20 hr in air for several temperatures are reported by the Fansteel Metallurgical Corporation.36 Columbium starts to oxidize in air at about 200°C. The oxide is said to be adherent and prevents further oxidation until the temperature is raised. Columbium is reported not to become brittle on heating in air for short periods like tantalum because the oxide film prevents further reaction. The columbium oxides dissolve into the metal when heated in a vacuum at temperatures between red heat and 1200°C. Above 1200°C the oxides are reported to evaporate. Columbium, in the oxide free state, is an active getter in vacuum tubes. 2. Preparation and Structure: G. Grube, O. Kuba-schewski and K. Zwiauer15 have studied the decomposition of Cb2O5 in argon. They find that CbO2 is formed slowly at 1150° and rapidly at 1300°C. Cb2O5 can be reduced to CbO2 by moist H2. The reduction of this dioxide to the lower oxides is rapid. By varying conditions CbO2, Cb2O3, CbO and Cb2O can be formed. CbO2, CbO and Cb2O have independent lattices while Cb2O3 is a stoichiometric mixture of CbO and CbO2. In a later paper O. Kuba-schewski" has shown that CbO is cubic and that CbO2 has a rutile type of lattice. The most exhaustive work on the oxides of columbium is that of G. Brauer.8 The number and constitution of the solid phases in the binary system Cb-O were investigated by the preparative, analytical and X ray methods. He indicates that only the oxides Cb2O5, CbO2 and CbO exist with limited regions of homogeneity. The solid oxide Cb,O, exists

Jan 1, 1951

By Jack Washburn, E. R. Parker

Kinking in zinc single-crystal tension specimens was observed under conditions of low stress and high temperature. Kinking is discussed in relation to other plastic bending phenomena on the basis of dislocation theory. Experiments on the stress-induced motion of small angle boundaries are reported. KINKING was first reported by Orowan1 as a new deformation mechanism. He observed the phenomenon in cadmium single crystals loaded in compression. Glide lamellae in a local region of the rod were observed to snap over suddenly to a tilted position, resulting in a sudden shortening of the specimen. Between the tilted portion and the rest of the crystal there were fairly sharp boundaries, with the slip plane assuming approximately mirror image positions on opposite sides of these boundaries. Orowan considered the boundaries to be regions where dislocations had concentrated. Hess and Barrett&apos; observed the formation of kinks in critically oriented zinc compression specimens. It was found that the sudden snapping over of the tilted region was not an essential part of the kinking phenomenon but rather was associated with the method of loading. Kinking was explained on the basis of the accepted mechanisms of slip and flexural glide. It was also suggested that a kink can be considered as a special type of deformation band. During a recent investigation of the effect of surface condition on creep of zinc single crystals," a similar phenomenon was observed in crystals which were loaded in tension. The specimens were 0.4 in. diam cylindrical rods with a free length of 4 in. between end connections. All of the crystals were tested at a constant load. adjusted to give an extension rate of approximately 0.05 pct per hr. Kinking, as shown in Fig. 1, occurred in some of the tests performed at temperatures above 200°C. Kinking was observed in specimens varying widely in initial orientation, scattering about a 45" angle between the slip plane and the specimen axis. The condition leading to kinking in tension appeared to be non-uniform distribution of flow along the gage length combined with the restraint imposed by the tensile load. At low temperatures and fast strain rates, the distribution of strain throughout the midsection of tension specimens was generally quite uniform; therefore, bend planes developed only near the ends as described by Miller.4 However, at high temperatures under creep conditions it was difficult to obtain specimens in which the distribution of flow was uniform. Some of the factors which may have caused differences in flow stress along the length of the crystals are: Nonuniform distribution of impurities, accidents of growth (lineage structure), slight bending or other damage during handling, surface conditions, and strain-aging characteristics due to dissolved nitrogen." Plastic flow, once started in a local region, often continued to a relatively large strain before other parts of the gage length became active. Under these conditions a series of kinks, such as those in Fig. 1, were produced. Fig. 2 illustrates how a nonuniform distribution of slip produces bending moments which- are responsible for kink formation. If no plastic bending were to occur while the rod extended by pure slip in two separate sections of the rod, it would assume a shape such as that in Fig. 2a. A specimen having this shape and being subjected to a tension load would have concentrations of stress at the concave surfaces C and lower than average stress would exist at the convex surfaces D. Therefore a bending moment is superimposed on the average stress in the regions between C and D. The positions of potential bend planes under these conditions are shown as dotted lines. Actually no such shape as Fig. 2a develops because plastic bending in the region C-D occurs simultaneously with pure slip in the intervening regions. The observed structure of a tension kink is indicated by Fig. 2b. Perhaps the best approach to an understanding of kinking as well as other related plastic bending phenomena, such as the bend planes discussed by Miller,&apos; cell formation studied by Wood et al.,6 and polygonization,7 is consideration of the dislocation model of a bent lattice. Current theories of the slip process postulate generation or multiplication of dislocations at certain lattice imperfections. The mechanism proposed by Frank and Read8 results in continuous generation of concentric dislocation loops which spread out

Jan 1, 1953

By S. S. Cole, D. L. Armant

The smelting of titaniferous ores for the past hundred years has not been successful because of thickening of the slags in the furnaces. The interest in the utilization of these iron bearing materials has been due to the extensive deposits which have been found in various parts of the world.1 The literature contains references2 to the use of titaniferous ores in blast furnaces. None of these attempts has met with success due to the lack of sufficient information as to the cause of failures and to economic considerations. Evaluation of the published information, as to the probable cause of failure in various attempts, has indicated that the presence of lower valence titanium oxide and formation of titanium carbide contributed to the failure. It was apparent that severe reducing conditions which are present in a blast furnace had been one of the factors for such failures. The previous smelting operations had as a primary objective the recovery of iron from these ores. Under these conditions the highest recovery of iron could only occur with severe reducing conditions. Application of Melting Point Data The application of the melting point data, from the system CaO-MgO-Al2O3-TiO2 reported in another paper,3 to the smelting of titaniferous ores required an extrapolation of these melting points due to the presence of other impurities from the ores. Likewise, a study of the effect of varying FeO and reduced titanium content of the slag was necessary before the data could be fully applied. The melting point data under oxidizing conditions had clearly indicated that a fluid slag with a melting point in the temperature range of 1370°C could be obtained. The smelting of a titaniferous ore had as a primary objective the production of a high titanium slag which was fluid and substantially free of iron and low in trivalent titanium. Since production of a high titanium slag was of primary importance, rather than the recovery of iron from these ores, the smelting concept could be altered to a marked degree. The ferrous oxide could be maintained at higher levels than is the normal practice in iron ores slags without being detrimental to the slags, although a loss in iron recovery resulted. During the reduction of the molten mixtures of ferrous iron and titanium, carbon acts as the reductant for changing the valence of the titanium and iron. The reaction can go further than in the case of the reduction which occurs in iron-titanium solutions. The formation of metallic iron removes iron from the system, so that the titanium oxide can be reduced to trivalent and divalent titanium oxides and also form titanium carbide which removes the titanium from the slags as a soluble constituent. The problem, therefore, resolves itself into maintaining the proper amount of ferrous iron in the slag thereby avoiding the formation of appreciable amounts of trivalent titanium and no divalent titanium oxide or titanium carbide. The latter two have been found in the viscous

Jan 1, 1950

By K. A. Jackson, G. A. Chadwick, A. Klugert

The diffusion field ahead of a lamellar interfnce is analyzed using an electrical analog. A self-consistent solution is obtained for the shape of the interfnce and the diffusion field by an iterative process. The solutions presented here are for a 50-50 eutectoid or eutectic, The shape of the interface is found to he independent of growth velocity and lamellar spacing, and to depend on the relative values of interfacial free energies at the phase houndaries . The mode of growth of lamellar eutectics and eutectoids has been a subject of much interest for many years.1-4 Mehl and Hagel 1 have shown photomicrographs taken by Tardif when he attempted to determine experimentally the shape of an advancing pearlite interface; the results are completely ambiguous. Brandt&apos; and schei13 have made approximate calculations of the composition ahead of a lamellar growth front. The shape of the advancing front and the composition distribution ahead of the front are difficult to calculate because one depends on the other. It is the purpose of the present paper to describe a method by which this calculation has been done. Lamellar-eutectic growth usually occurs under conditions where the growth is fairly rapid, and the interface temperature is close to the eutectic temperature. The growth rate is usually determined by heat flow. Eutectoid growth, on the other hand, can best be studied by quenching to some temperature, and allowing growth to proceed isother-mally. In both cases the growth is believed to be controlled by diffusion* rather than by the atomic kinetics of the transformation. This being the case, a single treatment of the diffusion equation will apply to both cases, provided the region of the interface in a eutectic may be considered to be isothermal. If a part of the interface could appreciably change its thermodynamic driving force by advancing ahead of or lagging behind the mean interface, then the two cases would not be similar. Eutectics normally grow in temperature gradients of the or-der of a few degrees per centimeter. The normal eutectic spacing is the order of a few microns. Part of the interface would have to extend many lamellar spacings ahead of the mean interface before it experienced sensibly different conditions. The interface temperature is usually a few tenths of a degree below the eutectic temperature so that temperature differences of the order of one-thousandths of a degree (a displacement of one lamellar spacing) would be unimportant. Protrusions large compared to the mean spacing do occur when one phase only grows into a eutectic liquid. This is usually a dendritic type of growth, and easily distinguishable from the lamellar mode of growth. A single treatment of lamellar growth will apply equally well to both eutectic and eutectoid decomposition. At the interface, which as shown above is essentially isothermal, the difference between the equilibrium eutectic temperature Teu and the actual interface temperature Ti, can be divided into two parts: 1) the composition varies across the interface, so that the local equilibrium temperature is not Teu; and 2) the interface is curved, so that the local equilibrium temperature is depressed according to the Gibbs-Thompson relationship. This undercooling can be written as Teu-Ti =?T = mAC(x) + a/r(x) [1] where ?C(X) is the departure of the composition at a point x on the interface from the eutectic composition, see Fig. 1, r(x) is the local radius of curvature at a point x on the interface, m is the slope of the liquidus line on the phase diagram, and a is a constant given by where s is the interfacial free energy, TE is the equilibrium temperature, and L is the latent heat of fusion. The calculations in this paper will be made only for the case where the phase diagram is symmetric, that is, the eutectic occurs at 50 pct, the liquidi have the same magnitude slope m at the eutectic temperature, and C,, the amount of B rejected when unit volume of a freezes, see Fig. 2(a), is the same for both phases. As shown in Fig. 2(b), the composition ahead of the a phase will be rich in B, the composition ahead of the ß phase will be rich in A. The composition at the phase boundary is the eutectic composition. The difference between the local liquidus temperature and the actual tempera-

Jan 1, 1964

By B. Ramaswami, U. F. Kocks, B. Chalmers

The latent hardening of silver and an Ag-Au alloy was investigated by lateral compression, overshoot in tension and cormpression, and the stability of multiple-slib orientations. The latent hardening of a secondary slip systenz depends on its relation to the primary slip system. For most secondary slip systems the latent hardening is larger for Ag-10 at. pct Au than for pure silver. The maximum increase in. flow stress on a secondary slip system over that of the primary slip system was 40 pct. The work hardening during the lateral-compression test on the latent system after prestress on the primary system is iuterbreted in terms of the preferential distribution of barriers to dislocation movement with respect to the active slip system in work-lzardened fcc crystals. The work-hardening in fcc crystals is mainly due to the dislocation interactions and the barriers to dislocation movement formed as a result of reactions between dislocations of different slip systems. The operation of sources on the latent system depends on the flow stress of those systems; hence, the increase in flow stress of a latent system due to glide on an active system, which is called latent hardening, is an important element in understanding the phenomenon of work hardening. The problem of latent hardening has attracted the attention of many investigators in the past. For example, a theoretical study of the elastic latent hardening of the latent systems due to glide on an operative system has been made by Haasen&apos; and ~troh. These calculations, however, neglect the stress required for the intersection of forest dislocations by the glide dislocations, a factor which would be important for producing macroscopic strains on the secondary slip systems. The importance of this factor will become evident from the results presented here. Attempts have also been made to determine the latent hardening of different slip systems by experimental means by the methods summarized in Table I.3-9 The experimental methods used have been subject to certain limitations. For instance, in the method used by Hauser,9 frictional constraints between the specimen and the compression platen were not eliminated by proper lubrication (see Hos- ford10). Secondly, with the exception of Kocks,6 Hauser,9 and Rohm and Kochendorfer,11 latent-hardening studies have been made on only one of the slip systems, i.e., on either the conjugate or the coplanar slip system; hence, extensive results are not available on the latent hardening of different slip systems in the same materials, with the exception of aluminum.6 It was therefore decided to study the latent hardening of the conjugate, critical and half-related slip systems in silver. Similar experiments were done in Ag-10 at. pct Au to study the effect of solute (gold) on the latent hardening of silver. Lastly, indirect evidence can be obtained by a study of the orientation stability of crystals of multiple-slip orientations in tension and compression. This method has been used by Kocks6 to supplement his studies of latent hardening in aluminum. Similar studies were made at room temperature in single crystals of silver. EXPERIMENTAL PROCEDURE The single crystals of the desired orientations were grown and the tensile test specimens were prepared as described in Ref. 12. The compression tests were made on 1/4-in.-cube specimens. The specimens were cut from single crystals, in the Servomet spark-erosion machine.13 The two cut surfaces were planed using the lowest available planing rate in the machine to minimize the deformation layer. A brass strip was used as the planing tool. This method of preparation ensured plane parallel faces for the compression tests. The deformed material was removed by prolonged etching in a weak etching solution. A weak etching solution was used to prevent pitting of the surfaces and to ensure uniform etching. About 25 to 50 µ of material were removed from all faces by the etching treatment. The specimens were then annealed for 24 hr at 940°C in oxygen-free helium and cooled in the furnace to room temperature over a period of 7 hr. After annealing, the orientation of the specimens was determined by Laue back-reflection technique to make sure that no recrystallization had occurred on annealing. The compression-test technique and setup are described in Ref. 14. The Laue back-reflection technique was used to study the overshoot in tension, the overshoot in compression, and the stability of the axial orientation in tension and compression. The tests were interrupted after every few percent strain to determine the axial orientation. In investigating the overshoot in compression, the operative system was determined by studying the asterism of the Laue spots.

Jan 1, 1965

By L. Zwell, H. A. Wriedt

X-ray Lattice parameter and bulk density measurements were made at room temperature on solid solutions of nitrogen in purified a, iron, containing from 0 to 0.053 wt pct N. When nitrogen is dissolved in a, iron, the fractional increase in unit cell volume (X-ray diffraction) and the fractional increase in volume per gram of iron (bulk density measurement) are the same within experimental error. The two sets of results when averaged show that the unit cell edge of a, iron increases linearly by 3.2 X 10-2 A per wt pct N dissolved and that the partial gram-atomic volume of nitrogen at infinite dilution in a, iron is the same as it is in nitrogen-martensite, that is, 5.90 cm3. RECENT reviews17&apos; of literature dealing with the lattice parameter of ferritic iron-nitrogen alloys indicate that the dilating effect of dissolved nitrogen on the bcc unit cell of a iron is not known with confidence. Five investigations3-7 either revealed no effect of nitrogen or were inconclusive. Among other investigations, where quantitative data were obtained, the results of Osawa and Iwaizumi8 indicate too large an effect, and those of Eisenhut and Kaupp9 show the lattice parameter of ferrite varying with the nitrogen content at concentrations far beyond the known solubility limit. It is not clear in Burns&apos;10 data what value should be used for the lattice parameter of nitrogen-free ferrite in calculating the dilation. Burdese11 shares with Burns the shortcoming that the iron-nitrogen alloys were solution-treated and quenched with undissolved nitride present. The consequence is that the un- certainties in the solubility limit1 are added to those in the lattice parameter measurements when the variation of lattice parameter with nitrogen content is computed. For a system of such widespread interest, we felt that a new investigation was merited. Both X-ray diffraction and bulk density measurements were used to determine the dilation of the , a iron lattice by dissolved nitrogen. EXPERIMENTAL PROCEDURE Material. The bulk density and X-ray diffraction experiments were both made with specimens of a purified iron (denoted as "B iron")- from Battelle Memorial Institute. The impurity contents were as follows: As, C, Cu and Pb—50 ppm; Ag, Al, Co, Ga, 0, Ti-11 to 50 ppm; B, Be, Ca, Cd, Cr, Mg, Mn, Mo, N, Ni, S, Sb, Si, Sn, V, W-10 ppm or less. The vacuum-cast ingot was hot-forged and annealed. Pieces of the forged stock were machined and cold-rolled to give strip stock 0.08 and 0.002 in. thick for density and for X-ray measurements, respectively. Preparation of Specimens. Starting with a piece of the cold-rolled iron stock, the general sequence of operations, after an initial recrystallizing anneal, was to measure the density or lattice parameter, nitrogenize, remeasure the property, age or denitrogenize, and again measure the property. Duplicate analyses for nitrogen were made by a modified Kjeldahl method on portions of the actual density specimens and on pieces nitrogenized to equilibrium alongside the X-ray specimens. Annealing of the density specimens was performed by sealing the pieces with the as-rolled surfaces removed by filing into evacuated "Vycor" capsules and treating for 1 hr at 750°C followed by furnace cooling. (TO check the effect, if any, of annealing procedure, a specimen also was

Jan 1, 1962

By M. Kaufman, D. Rosenthal

IT would be of great importance to our understanding of the phenomena of fracture in metals if a unique relationship could be established between stress and some easily measurable parameter of deformation up to the fracture. It is known that no such relationshir, has been found when the parameter was the mechanically measured strain,&apos; the major part of which is plastic. The present investigation was initiated to determine, among other things, if the X-ray or lattice strain" might be a • For the definition of lattice strain see ref. 2. more suitable parameter. To this end, annealed stress free*&apos; specimens of 61s aluminum alloy were ** Freedom of stress in this particular case means absence of those stresses which can be checked by the technique employed. tested at room temperature and liquid nitrogen temperature (—195OC), by first maintaining the same temperature from the beginning until the end of the test, and then with crossovers from one temperature to the other. Three major factors had to be taken into consideration in designing the specimens and testing equipment. The test setup must allow X-ray pictures to be taken while the specimen is under load (for as much as 2 hr at a given load). Provision must be made for maintaining the test specimen at the temperature of liquid nitrogen as well as at room temperature. In addition, the specimen must be able to rotate to allow the X,ray beam to take in as large a sample of grains as possible, to maintain centering, and to correct for effects of large grains. The final design of the specimen and equipment is shown in Figs. 1 and 2. The specimen and grips are hollow, enabling liquid nitrogen to be poured in through a funnel-container arrangement while the specimen is rotating. The diameter of the specimens at the 2 in. gage section is 5/16 in. with a 3/16 in. diameter hole through the center. A small pilot valve in the lower grip allows a very small stream of liquid nitrogen to escape, thus assuring circulation of the liquid at all times. A low temperature silicone grease-tissue paper packing is used to seal all joints. The specimen is held in the grips by a pin. Spherical socket joints at top and bottom are used to allow for proper alignment. The grips are connected to the thrust bearings by means of plastic couplings to decrease the heat flow. Rotation is accomplished by means of a motor which drives a plastic gear (integral with the lower coupling) through a semiuniversal joint to allow for deforma- tion of the specimen. The torque applied to the specimen is very small. The maximum stress caused by this torque at the highest loads reached was found to be less than 200 psi, The whole unit was mounted in a 10,000 Ib testing machine. An insulation cage was placed around the specimen to cut down air circulation, and consequent frosting of the specimen, and also to reduce radiation and convection heat losses. A narrow window, covered on both sides with a thin plastic materiai allows the X-ray beam to reach the specimen. Thermocouples placed just outside the pilot hole at the lower grip, in the bottom of the funnel container and near the top of the funnel container permitted checks of the

Jan 1, 1955