Search Documents

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962

By J. M. Morkowitr

A. Sawatzky (Atomic Energy of Canada, Ltd.)—The detailed criticism by Markowitz of my simple treatment of the thermal diffusion of hydrogen in Zircaloy-2 indicates that my paper was not as lucidly written as it could have been. I would therefore like to reiterate several of the main points of my proposed mechanism and describe in more detail some of the features only implied in the original paper. The distribution equation derived in my paper was stated to hold only for the case where the volume taken up by the hydride was small compared to the volume taken up by the solid solution phase, subsequent work, mentioned below, having shown it to be out by only a few percent up to a hydrogen concentration of about 3000 ppm. Of course, hydrogen in the two-phase region alone is not conserved in my treatment as pointed out by Markowitz. On the contrary, one of the important features of my proposed mechanism is that in the presence of a temperature gradient a two-phase region cannot exist over the whole specimen. For example, if the specimen is entirely a + 6 initially, then on application of a temperature gradient, a single phase (a) region at the hot surface develops from time t = 0 onwards. As mentioned in my original paper, the interface between the a and a+d regions moves toward the colder surface of the specimen with a discontinuity in hydrogen concen- tration developing at the interface and increasing with time. This interface moves at such a rate that hydrogen in the specimen as a whole is conserved. It must be pointed out that my distribution equation (Eq. [5] in Markowitz&apos;s paper) holds only for linear geometry. It is easy to show that for the cylindrical geometry of Markowitz the assumptions used in my treatment lead to

Jan 1, 1962

By R. P. Marshall

This note describes positive evidence that hydrogen in titanium alloys diffuses under the influence of a thermal gradient. The experiments confirmed the expected similarity of this system to the H-Zr system and produced qualitative information on the magnitude of the heat of transport for hydrogen in titanium alloys. This effect has practical importance in applications where titanium alloys operate in a thermal gradient under conditions such that hydrogen embrittlement may develop within the expected lifetime of the structure, for example in supersonic aircraft service. The theories of thermal-gradient diffusion may be found in recent reviews and experimentation in this field by Shewmon,1 Sawatzky,2 Markowitz,3 and Darken and Oriani.4 The basis for Soret thermal diffusion is the "heat of transport", denoted by Q*. This is an energy term for the amount of heat (energy) transferred by atomic diffusion, and can be either positive or negative signifying a driving force for atomic diffusion to the cooler or hotter region, respectively. Experimentally, Q* is determined by plotting the natural logarithm of the point-to-point concentrations after exposure to a thermal gradient vs the respective point-to-point temperatures in units of the inverse absolute temperature scale. The slope of the straight line is Q*/R, R being the gas constant. For the titanium experiments, specimens (3 by 1 by 1/16 in.) of a) commercially pure titanium, b) the 8 Al-1 Mo-1 V titanium alloy, and c) the 6 A1-4 V titanium alloy were exposed to thermal gradients of 6° to 115°C per in. for 18 days at 250° to 550°C. The temperature gradient was in the direction of the 3-in. dimension. The hydrogen concentrations existing after exposure were determined on sections of the specimens by vacuum extraction. Three sections of unexposed sheet of each alloy were analyzed as standards to allow a check for hydrogen

Jan 1, 1965

By Mrs. V. J. DeCarlo, G. P. Salvo, H. W. Schadler, L. M. Osika

The lattice parameter of the inlerrnetallic compound Nb3Sn has been measured as a function of temperature from 80° to 1290°K. The results are compared with published data on the thermal ex- ThE recent interest in the intermetallic compound, Nb3Sn, as an engineering material for the production of superconducting devices has necessitated that certain engineering data be obtained. Because of the difficulty encountered in producing bulk pansion of niobium and indicate that the compound when made by diffusion of tin into niobium at 1000°C, would be subjected to a tensile strain of about 0.1 pct when cooled to room temperature. material which is single phase, the coefficient of thermal expansion has not been measured by dilata-tional methods. Therefore the lattice parameters of fine-grained samples of Nb3Sn produced on the surface of a niobium sheet by heating in molten tin at 950°C have been obtained as a function of temperature. The results are compared with published data on niobium2 and Nb3Sn3 and with lattice-parameter measurements made on small single crystals of Nb3Sn.

Jan 1, 1964

By Rex B. McLellan

Studies of the eyuilibrzum between ferrite and austenite with gas mixtures (CO + CO2 and H2 + CHe) have been used as a means of deducing the energy and vibrational entropy of carbon atoms in dilute interstitial Fe-C solutions. A simple model for dilute interstitial solutions is given which enables a solubility equation for the equilibrium between the gas mixtures and the solid to be deduced. This solubility equation is used to estimate the partial In this work measurements of the equilibrium between dilute solid solutions of carbon in iron and gaseous mixtures of CO2 + CO and CH4 + Hp have been analyzed using theoretical solubility equations deduced from a knowledge of the thermodynamic parameters of the gas mixtures and an appropriate model for the solid solution. The solubility equations are deduced by equating the chemical potential of carbon atoms in the gas thermodynamic functions of dilute Fe-C solutions from the measured equilibrium between the solid and the gas mixtures. It is shown that the vibra-tional entropy of a carbon atom in a and y iron is smaller than the corresponding entropy 01. a nitrogen atom in solid solution inferrite or austenite and that there is little difference between the vibrational entropies of both nitrogen and carbon atoms in ferrite and austenite. and solid phases. The chemical potential of carbon in the gas is found from a simple statistical mechanical analysis of the gas mixtures utilizing spec-troscopic data while that for carbon in the interstitial solution is found from a model in which the carbon atoms act as bound oscillators distributed in a random fashion in the solution. The solid solution is dilute enough to enable solute-solute interactions to be ignored. Thus the configurational entropy of the solution is ideal but the mixing entropy contains additional excess terms due mainly to the vibrational changes occurring on solution formation. The partial excess entropies (and the partial energies) do

Jan 1, 1965

By Rex B. McLellan, M. L. Rudee, T. Ishibachi

A modelfor dilute quasi-regular interstitial solid solutions is proposed in which the solute atoms can occupy both the octahedral and tetrahedral interstices in the bee solvent lattice. The distribution function, according to which the solute atoms are apportioned between the two kinds of sites, is calculated. The partial thermodynamic functions of the solution are calculated from the distribution function. It is shown that such a solution model can explain the deviation from linearity of the Arrhenius plot of the temperature variation of the diffusivity of carbon through a iron. The published difiusivity data is analyzed to obtain numerical values for the distribution function. Finally it is shown from the numerical values of the distribution function that the possibility of dual-site occupancy will have a negligible effect on the solution thermodynamics for this system. DeSPITE the large amount of experimental data available on the thermodynamics and diffusion kinetics of dilute solid solutions of carbon in a iron, many of the elementary properties of these solutions are not understood due to real or apparent discrepancies in the experimental data. Basically there is a lack of agreement between the solubility and diffusion data obtained by anelastic damping techniques and by bulk chemical thermodynamic methods. SPecifically the heat of solution of cementite in ferrite estimated from thermodynamic measurement1, 2 is about twice as high as that determined from anelastic damping measurements.3 Furthermore the diffusion coefficient D of carbon in a iron in the range -40" to about 150°C (covering about ten orders of magnitude) determined from anelastic damping techniques is such that an Arrhenius plot of In D vs 1/T is linear. However in the range of about 300o to 850°C where mass flow measurements of D have been made (covering about four orders of magnitude), although the data merges with the low-temperature data, the Arrhenius plot departs from linearity. The object of this paper is to present a more refined model of dilute ferrite solutions in which the solute atoms can occupy two kinds of interstitial sites. The experimental data is analyzed in the light of this model and it is believed that thereby some of the anomalies can be resolved. snoek4 explained the room-temperature internal-friction peak (usually referred to as the Snoek peak) in iron as the stress-induced ordering of interstitial carbon and nitrogen atoms occupying the octahedral (0, 0, 1/2) interstices in the bee lattice. From the consideration of a hard-sphere lattice model the (0, 1/4, 1/4) tetrahedral interstices are larger than the octahedrons but their symmetry would not produce the strain dipole necessary to give rise to the Snoek peak. Thus the presence of the Snoek peak is direct evidence that the octahedrons are occupied. Since the publication of Snoek&apos;s explanation, most workers have assumed that all of the carbon and nitrogen in the a solid solution was located in the octahedral sites. This assumption of universal octahedral occupancy has been implicit in the theory of wert5 for interstitial

Jan 1, 1965

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,&apos; a pure metal and its vapor,&apos; and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

By R. Rocca, M. B. Bever

THE adiabatic elastic deformation of a body is accompanied by a change in temperature. This phenomenon is known as the thermoelastic effect. Under adiabatic conditions the temperature of a metal bar is decreased by an elastic elongation and is increased by an elastic compression. All materials which elongate on heating behave in this manner. The sign of the thermoelastic temperature change is reversed for the few materials which have a negative coefficient of thermal expansion. The following equation for the thermoelastic effect can be derived from fundamental thermody-namic theorems, as shown in the Appendix: dT8 =-a1/cs T dss [1] Cs In this equation, T is the absolute temperature, S is the entropy, a, is the coefficient of linear thermal expansion, cs&apos; is the heat capacity per unit volume at constant stress and s is the stress (positive in tension). Eq 1 can be applied to small, but finite changes in stress in the following form: ?Ts =- a1/cs T?ss [2] The sign of the temperature change AT is opposite to that of the change in stress s for materials which have a positive coefficient of thermal expansion. Eq 2 has been verified for many different materials and stresses at room temperature. No previous publication appears to have been devoted to an in- vestigation of the thermoelastic effect over a range of temperatures. Review of Literature Lord Kelvin (W. Thomson) presented a general theory of the thermoelastic effect in 1851&apos; and later applied it to a solid, subject to an arbitrary system of stresses&apos;. His analysis was based on a cycle of isothermal and constant-strain transformations and led to Eq 2 above. Even today, one of the clearest expositions of the thermoelastic effect is found in Lord Kelvin&apos;s article on elasticity in the Ninth Edition of the Encyclopedia Britannica (1878). R. ROCCA, Junior Member, and M. B. BEVER, Member AIME, are Research Assistant in Metallurgy and Associate Professor of Metallurgy, respectiuely, Massachusetts Institute of Technology, Cambridge, Mass. AIME New York Meeting, Feb. 1950. TP 2760 E. Discussion (2 copies) may be sent to Transactions AIME before APT. 1, 1950, and is scheduled for publication Nov. 1950. Manuscript received Oct. 15, 1949.

Jan 1, 1951

By Daniel D. Pollock

The il&apos;lott and Jones theory of thermoelectricity predicts that the absolute thermoelectric power of alloys of transition and noble metals should be a maximum when the concentration of the noble metal is approximately 55 to 60 at. pct. An examination of the emf of a series of relatively pure alloys of copper and nickel shows that the predicted maximum occurs at about 57 at. pct Cu. This excellent agreement with the theory is considered to substantiate the Mott and Jones theory of thermoelectricity for binary alloys of transition elements. This theory is extended to show that the emf behavior of dilute, ternary copper-nickel base alloys, which contain approsimately 60 pct Cu and 40 pct Ni, may be described in terms of a scattering mechanism. The scattering effect of a third element is demonstrated to be a function of its valence and its period in the periodic table. Small amounts of solute elements have additive scattering effects upon the emf of the Cu-Ni base. The Mott and Jones equation is modified to include this scattering parameter. This adaptation accurately describes the thermoelectric behavior of ternary and quaternary CLL-Ni base alloys. An empirical form of the modified Mott and Jones equation is derived which permits the calculation of thermoelectric power with an average error of less than 0.4 pct at 500 "C. CONSTANTAN has long been used as a thermocouple element. Its approximate composition varies from 50 pct Cu, 50 pct Ni to 65 pct Cu, 35 pct Ni. Small amounts of manganese, iron, and other elements have been used to modify the composition in order that the resultant emf vs platinum conforms to nationally accepted table. Adjustments of this type are made on a purely empirical basis. Constantan was originally made in Germany and was imported into this country for thermoelectric and electrical resistance purposes. During World War I, the supply of this material became seriously depleted. The work of Bash4 was done in this period in order to develop a satisfactory substitute for the imported material. Bash&apos;s empirical work on Cu-Ni alloys is still the basis for all commercial constantans made in this country. No reexamination of the electrical properties of this system has been made, despite the fact that it is now well known that Bash&apos;s alloys contained impurities which strongly affected their thermoelectric behavior.

Jan 1, 1962

By D. D. Pollock, G. P. Conard II

Equations of the form of the Mott and Jones equations for the absolute thermoelectric powers of metals are derived primarily from a thermodynamic approach. The behaviors of transition thermoelements in common use are then examined and compared with this simple theory. MOTT and ones&apos; derived a general expression for the absolute thermoelectric behavior of metals and alloys using the approach of the solid state physicist. This expression was then applied to specific cases.1,2 The present work develops equations of the same form principally by a thermodynamic approach. These relationships are then employed to gain some insight to the behavior of the transition thermoelements in common use. I) DERIVATION OF AN EXPRESSION FOR ABSOLUTE THERMOELECTRIC POWER First consider a metallic conductor which is maintained in a temperature gradient with no current flowing. At constant pressure, there will be a gradient of the free energy (F,) given by:

Jan 1, 1963

By R. H. Ernst, H. R. Ogden, D. J. Maykuth

AT present, no theories exist which allow prediction of the effect of alloying additions on the thermoelectric properties of metals. Nevertheless, Battelle and others1 have observed that, at high temperatures, the peak thermal electromotive-force output (relative to a platinum standard) occurs with metals in Group VI of the Periodic Chart. The authors suspected that this peak was associated with the fact that maximum electronic bond stability is achieved with these metals which have six bonding electrons per atom. On the basis of current electron-concentration theory for transition metals and alloys:&apos; it was surmised that the addition of valency electrons to metals of Groups IV and V (accomplished by the addition of metals from Groups VI, VII, or VIII) should progressively increase the thermoelectric-power output of the resulting alloys until an alloy composition is reached at which the number of valency electrons per atom is six. A further increase in the ratio of valency electrons per atom should then decrease the thermoelectric power. In contrast, the addition of bonding electrons to Group VI, VII, or VIII metals should decrease their thermoelectric power since the electron per atom

Jan 1, 1965

By F. Weinberg

In developing a mechanism for the solidification of metals from the melt, it has been proposed that solidification proceeds by the growth of platelets parallel to close packed planes. The evidence for this is based primarily on observations of decanted interfaces of lead1,2 and tin on which platelets 1 to 10 µ thick4 were observed. In recent observations of decanted eutectic alloys, 5,6 it was found that the eutectic structure on the decanted surface was markedly different than that of the bulk material, with the surface structure extending approximately 10 µ behind the interface.&apos; This suggested that, at least for these experiments, a residual liquid layer 10 µ thick had been left on the decanted interface, which solidified subsequent to decanting. If a similar thickness of residual liquid was left on the decanted surfaces in the lead and tin observations referred to above, then it is questionable to what extent the observed platelets can be related to the solid-liquid interface before decanting. The purpose of the present investigation was to measure the thickness of the residual liquid layer on a decanted surface of tin, using relatively standard decanting procedures. The technique used was to add approximately 200 ppm of Tl204 (PI) to the melted portion of a high purity (99.999 pet) bar of tin, which was being progressively melted from one end, and then decant during melting. Since only the melt contained the radioactive tracer, the activity emanating from the decanted surface could be used as a measure of the thickness of the residual liquid layer. Progressive melting was carried out in the same fashion as single crystal growth, namely, in a horizontal graphite boat, in an argon atmosphere, using a moving furnace. The decanting was done in two ways; 1) removing the furnace and suddenly dropping the melt end of the boat, and 2) suddenly jerking the solid away from the liquid by the action of a falling weight (estimated peak acceleration 3 x 105 cm per sq sec), using a split graphite container. In all cases the melt was vigorously agitated by bubbling argon through it. The activity of the decanted surface was measured through an aperture 1.5 cm by 0.5 cm in a lead shield with an Anton tube geiger counter. Assuming that the active layer on the surface had the same concentration of Tl204 as the decanted liquid, the thickness of the layer could be determined from the measured activity of the decanted material, and the relationship between activity and material thickness. The latter was determined by rolling some of the decanted material into foil and measuring the activity of multiple layers of the foil. The activity At of material of thickness t (in mm) was determined to be A, = Ao(1 - e-22.5t) where Ao is the activity of the bulk material. The results of the measurements of the thickness of the residual liquid layer for six decants are given in Table I. The variation in t is attributed to variations in the decanting procedure and the rate of melting, the latter being difficult to control because of the vigorous agitation of the liquid. The rate of melting was in the order of 2 cm per hr, estimated from the position of the solid-liquid interface during melting. The results indicate that a residual liquid layer of the order of 10 µ in thickness is left on the decanted interface in agreement with the observation on eutectic alloys referred to above. If the mixing of the liquid during melting is not complete, as was

Jan 1, 1962

By A. Kelly, S. Sato

Tensile tests have been performed on aluminum single crystals of 99.99 pct purity at 196°K. The resolved shear stress when the stress-strain curve becomes concave to the strain axis depends on orientation, being always higher for crystals with an initial orientation close to the sides of the unit triangle. Observations have been made, with the optical microscope, of the appearance of slip lines on polished surfaces of the crystals. Particular attention has been paid to the first appearance of cross-slip. It is confirmed that marked cross-slip is first seen when the stress-strain curve becomes concave to the strain axis. Measurements are reported of the lengths of the slip lines observed on top and side faces of the crystals at various stages of the deformation. The lengths of the slip lines vary inversely as the flow stress for all crystals, independent of crystal orientation. From measurements of the lengths and separations of the slip traces it is possible to estimate the number of dislocations which are annihilated at each cross-slip site. It is concluded that the annihilation of screw dislocations of opposite sign is the most important cross-slip process occurring. FRIEDEL1 recently pointed out that the stress-strain curve of many pure metals of face-centered-cubic structure can be considered as composed of three stages. Plastic flow commences with a region showing a small rate of hardening which is approximately linear. This has been called "easy glide*. It is followed by a region of more rapid hardening in which the slope of the curve is again approximately constant and this, in turn, is superseded by a final part of the curve which is concave to the strain axis. Following Diehl2 we may designate these regions as stages I, II, and III respectively. The onset of stage 111 occurs at lower stresses at higher temperatures. The appearance of the slip lines formed during these various stages has been described by a number of workers?-5* The object of the present work was to make detailed observations of the lengths and separations of slip lines for a number of crystals of different orientations deformed at the same temperature and strain rate. Although much previous work has been published on the deformation of aluminum single crystals the importance of measurements of these quantities has only recently been realized—they are essential for experimental tests of recent theories of work hardening.&apos; 9 In aluminum, deformed at room temperature, stage 11 of the stress-strain curve is very weakly marked, as the stress for the onset of stage 111 is attained soon after the end of easy glide. In the present experiments it was decided to use a temperature lower than room temperature so that stage II of the curve was better developed. However, at temperatures as low as 90°K slip lines are not measured easily with the optical microscope.5 For this reason 1960k was chosen as a suitable temperature. Even at 1960k however, stage III of the curve commences at glide strains of 6 to 10 pct and hence

Jan 1, 1960

By D. B. Hunter, H. W. Rosenberg

The titanium-rich portion of the Ti-Pd system was investigated from 0 to 75 wt pct Pd by metallo-graphic and X-ray techniques. A 0 eutectoid occurs at 24 wt pct Pd and 1190°F. Two compoutzds are indicated in the region below 75 wt pct Pd, Ti,Pd and Ti2Pd3. The solubility of palladium its a titanium is low, probably less than 1 pct. In 1960 Rudnitskii and Birunl published a complete version of the Ti-Pd phase diagram. However, their work was in disagreement with the earlier literature in that they reported only one inter metallic compound, whereas three had been reported earlier. In view of these discrepancies, it was therefore necessary to redetermine those portions of the diagram of immediate interest. The following account describes our work on the system over the range of 0 to 75 wt pct Pd. MATERIALS AND METHODS Distilled titanium sponge and elemental palladium were used in the formulation of the alloys; the chemistry of these materials is detailed in Table I. The alloys were prepared as 10 to 50 g blended compacts that were melted into buttons by arc melting under gettered argon on a water-cooled copper hearth. Weighing of the ingredients before and after melting showed that negligible weight changes occurred. Therefore, no analyses were undertaken and the compositions of all alloys are nominal. All alloys were fabricated by hot rolling at 1700°F to 0.070-in.-thick sheet. Scale was removed by sandblasting and pickling in a 5 pct HF-35 pct HNO,, balance H20 solution. For metallographic examination, specimens were mounted after heat treatment transverse to the rolling direction, ground on silicon carbide papers of increasing fineness to 600 grit, and then electro-polished using a solution containing 600 ml me-thanol, 60 ml perchloric acid, 360 ml butyl cello-solve, and 2 ml "Solvent X". Unless otherwise specified, etching of alloys containing up to 42 pct Pd was carried out by swabbing with a 12 pct HN03-1 pct HF aqueous etch where a bright etch was required, or by a 1 pct hydrofluoric in saturated oxalic acid solution where contrast between phases was required. The Ti-52.8 Pd alloy was etched with a solution of 25 ml HF, 40 ml glycerine, 35 ml methanol, and 18 g benzalkonium chloride. For X-ray examination, 1/2-in.-square speci- mens of sheet were mounted flat in a standard 1-in. metallographic mount and ground and polished as above. X-ray diffraction was performed using a Norelco type 12045 Diffractometer, employing CuKa radiation with a nickel filter at 40 kv and 20 ma. Specimens were rotated about the sheet normal during exposure. Although this procedure did not remove the effects of sheet texture from the relative intensities, it had the advantage that oxidation or contaminants entering during preparation of powder samples could not confuse the patterns obtained. RESULTS AND DISCUSSION Fig. 1 illustrates the Ti-Pd phase diagram according to Rudnitskii and Birunl with the work of the present authors superimposed. Both interpretations agree that the system is of the 0 -eutectoid type with an extensive 0-phase field, and that the eutectoid temperature is just below 1200°F. There is also agreement that the solubility of palladium in a titanium is restricted. Our work would indicate that the a solubility of palladium is low, probably less than 1 pct. However, whereas Rudnitskii and Birunl place the eutectoid composition at 41 wt pct Pd, this investigation shows it to be at about 24 wt pct Pd. Moreover, this investigation confirms the existence of compounds at Ti2Pd and Ti2Pd3, whereas Rudnitskii and Birun report only a single Berthol-lide phase covering the TiPd to TiPd, range. Laves et a1.&apos; and Wallbaum, whose work was summarized by Maykuth , reported the existence of Ti2Pd3 and TiPd, in addition to Ti2Pd. More recently, Nevitt and Downe~&apos; have reported the structure of

Jan 1, 1965

By R. J. Evans, A. G. Revesz

Silicon films have been grown by chemical reaction on (111) silicon substrates. The surfaces were examined by various microscopic and interfero-metric methods. Surface structures are classified into two groups depending on whether the angles between the bounding planes and the (111) surface are small (<3 deg) or large (> I0 deg). A layer-gvowth mechanism is postulated to explain the topography and the influence of growth parameters. Growth proceeds by lateral expansion of the (111) layers in (211) directions, thereby forming steps. The step edges are perpendicular to the direction of expansion and are thus along (110) directions. Step bunching md surface nucleation both play an important role in modifying the flow pattern and in the step regeneration. These are influenced ver?) much by impurities, especially oxygen. Although the growth is a result of a surface-controlled ga: reaction, it is very similar to growth from an impure solution. OVERGROWTH ("epitaxial growth") of silicon is important and widely used. During the past years several investigators have observed various topographical features or so-called faults on the grown films. A study of the surface morphology gives some insight into the growth mechanism. I) EXPERIMENTAL Silicon films have been grown on silicon substrates by a method described by Theuerer.&apos; Silicon is formed by reduction of SiCl, in hydrogen. The rate of incidence of SiC1, was varied between 5 x 10"6 and 2 x 10&apos;4 moles min-&apos; cm-&apos;. The mole fraction of Sic4 in the Hz-SiCL mixture was about 5 x X Both the rate of incidence and the mole fraction were calculated on the assumption that the Hz bubbling through the SiC1, reached equilibrium saturation. Assuming uniform velocity distribution, the linear velocity of the gas in the reactor tube was estimated to be 2 cm sec-l. The temperature of deposition was varied between 1070" and 1260°C. Chemically polished p-type silicon wafers of 20 to 100 ohm cm resistivity were used as substrates. These were within 1/2 deg of a (111) orientation. The thickness of the grown n-type film was determined by two methods: a) measurement of the depth of the p-n junction taking into account the junction shift due to diffusion, b) measurement of the traces of stacking-fault tetrahedra on the (111) plane.&apos; The agreement between the two methods was better than 20 pct. The rate of growth varied between 0.2 and 4.0 pmin-&apos;. The formed films were examined by reflection and light-section microscopy, and by multiple-beam interferometry. Phase-contrast illumination revealed height differences of about 30A. For measuring heights greater than 1 p a light-section microscope3 was used. The resolution by multipke-beam interferometry4 was between 50 and 100A. Crystallographic directions on the surface were determined by X-ray and from the orientation of etch pits and stacking faults as revealed by Dash etch (I part HI?, 3 parts HNOJ, and 12 parts CH3COOH). Some specimens have been investigated by electron microscopy. Platinum-shadowing and carbon-replica techniques were used to show the fine topography and reflection diffraction to determine the structure of the grown layers. 11) RESULTS The topographical features can be classified into three groups. he first group is comprised of fine ridges (striations). The second group consists of structures, which are bounded by planes making angles of less than 3 deg with the (111) surface. They are, therefore, vicinal planes. Structures which closely resemble growth or etch pyramids from the third group would normally be bounded by perfect low-index crystallographic planes. In this case they are deformed. The angles between the bounding planes and the (111) surface are generally larger than 10 deg. The fine ridges are present, even on the smoothest surfaces, as shown in Fig. 1. They are along a (110) direction. The height differences could not be resolved with interferometric techniques. The basic characteristic structures of the second group are depressions and hillocks. These are bounded by three planes, two of them with larger slopes than the third one. The edges between the planes, as projected to the (111) surface, point in (211) directions. Various habits of these structures are shown

Jan 1, 1964

By W. A. Backofen

THE preferred orientations, or textures, resulting from many of the various methods for testing and forming metals have been the subject of numerous investigations.1,2* Despite this large amount of work, however, only a few limited studies have been made of the texture that is developed by torsional deformation. Ono3 found that in severely twisted wires of copper and aluminum a [Ill] direction lies parallel and a [1101 direction perpendicular to the longitudinal axis of the wire. Sachs and Schiebold4 have reported that a double-fiber texture exists in a twisted aluminum wire with both the [Ill] and [loo] directions parallel to the axis of the wire. Twisted iron wires have also been examined by Ono.8 Both the [1101 and [1121 directions were reported as parallel to the axis of the wire. Goss5 concluded from a study of twisted rods of a low-carbon steel that the preferred orientation existing at fracture is quite complex, but that many grains have a [1101 direction parallel to the axis of the wire. In addition to the earlier experimental work, some suggestions have been made about the possible nature of the torsion texture. These suggestions are based on the results of many experiments which indicate that the cold-working texture of a particular metal is largely determined by the geometrical change in shape that the metal undergoes during plastic deformation.1,6 Hibbard and Yen7 have considered the problem of deformation textures and have presented an analysis which is able to explain why equivalent changes in shape should yield similar textures. Therefore, a knowledge of the principal strains associated with torsional deformation would seem helpful in the interpretation of the torsion texture. The necessary analysis has been made of the state of strain in an element of metal lying in the surface of a cylindrical rod or tube that has been subjected to pure torsion.8,9 This analysis shows that the directions of the principal normal strains rotate continuously within a torsion specimen while it is being twisted. After the first infinitesimal amount of twisting, these directions make angles of 45" with the longitudinal axis of the bar. They rotate from this position as twisting proceeds, and after an infinite amount of twisting, the direction of the principal tensile strain is perpendicular, and the direction

Jan 1, 1951

By E. P. Klier, S. M. Grymko

The transformations in eutectoidal systems have been extensively studied as they occur in steels.&apos; As a consequence of these studies the martensite, bainite and pearlite reactions found for most steels are widely recognized. Further, because of the work of Smith and Lindlief2 and of Greninger and Troiano3 these reactions, except for the bainite reaction, are considered as typical for all eutectoidal systems. The primary alloy studied by Smith and Lindlief2 was a CuAl alloy of near eutectoid composition as was the alloy more recently studied by Mack.4 The transformations in these alloys were, for the most part, studied metallo-graphically, while an X ray analysis of structures was essentially wanting. It has appeared desirable, therefore, to investigate selected CuAl alloys at and slightly away from eutectoid composition. For this purpose three alloys were prepared containing 10.5,11.9 and 13.5 pct A1 respectively. The results of a metallographic and X ray analysis of structures obtained for isothermal transformation of the ß-phase are reported here for the 11.9 and 13.5 pct A1 alloys. Introduction The phase equilibria in the CuAl alloys of immediate concern are indicated in the equilibrium diagram section presented in Fig 1.5 The equilibrium and transition structures which have been reported in this system are as follows: a = copper rich terminal phase (f.c.c.) ß = high temperature eutectoidal phase (b.c.c.) r2 = aluminum-rich intermediate phase (r-brass structure) a&apos; = modified a-phase postulated by Bollenrath and Bungnrdt.26 ß1 = ordered ß (b.c.c.) ß&apos; = martensite structure: A1 < 13 pct (near h.c.p.) ß" = ß&apos; of Smith and Lindlief2 7&apos; = martensite structure: A1 > 13.5 pct (h.c.p.); ß2 of Bollenrath and Bungardt.26 The eutectoid transformation can be suppressed at sufficiently high cooling velocities. The ß-phase is then retained to about 500°C where ordering sets in. The ordering interval is not satisfactorily known but indirectly appears to be non-suppressible. Subsequent to the ordering reaction and consequently at lower temperatures, the ordered ß1 decomposes to a marten-sitic structure. The kinetics of these reactions and in particular those of the martensite reaction have an important bearing on the results obtained in this investigation. Since some confusion exists concerning certain reported aspects of these reactions, they will be considered in some detail. THE MARTENSITE REACTION The martensitic structure is formed on cooling through a critical range6

Jan 1, 1950

By D. K. Deardorff, H. Kato

THE transformation temperature of hafnium from hcp to bcc is 1750° + 20 °C in contrast to previously published values by Duwez and fast2 which are believed inaccurate. The Bureau of Mines determined this value by measuring the temperatures at which a sudden decrease was observed in the electrical resistance of hafnium alloys containing up to 18 at. pct Zr, and then extrapolating the temperatures to 0 pct Zr. Duwez1 previously reported a transformation temperature of 1310°C, obtained by use of a rapid-cooling thermal-analysis technique. Later, Fast2 published a much higher value of 1950° 100°C based upon: a) his own determination of 1690°C for the beginning of the transformation range for hafnium containing 5.7 at. pct Zr, and b) his belief that lattice parameters reported3 for Duwez&apos; hafnium indicated i contained 19 at. pct Zr and that the 1310°C value should be associated with that composition. Russell4 subsequently stated that Duwez and Fast probably were reporting their lattice parameters in different units and reassigned a value of 6.0 at. pct Zr to Duwez&apos; hafnium. If this assumption were true, Duwez&apos; hafnium was of approximately the same purity as Fast&apos;s, but his transformation value was considerably lower. The reason for this divergence is not known. Fast&apos;s value for hafnium containing 5.7 at. pct Zr agrees well with our data. McGeary5 determined a transformation value of 1660°C by metallographic examination of heat-treated specimens, but the zirconium content of his hafnium was not definitely established. The specimens used in this investigation were 1/8-in.-diam rods 6 1/2 in. long, fabricated by hot-swaging bars cut from arc-melted buttons. These buttons were melted from crystal bar hafnium and crystal bar zirconium. The chief impurity in the hafnium

Jan 1, 1960

By M. K. Yen, W. R. Hibbard

Previous studies of plastic deformation of metals have emphasized the important role of bending and constraints during strain under relatively pure stresses.1"5 Some new phenomena such as early conjugate slip6 and polygonization7 are intimately concerned with the relief of bending stresses, the former by slip and the latter by a process analogous to re-crystallization. However, few analyses of the bending deformation of single crystals were found in the literature, and those8,9 are sufficiently previous to the modern interpretations of slip to invite further investigation in this area. The transverse bending mode of testing, using the two-point loading method, was selected because the center portion of the specimen may be considered as under a theoretically pure bending stress with a uniform bending moment. Considerable attention was given to both the lattice distortion and flow characteristics of the crystals during deformation. Experimental Proeedare A specimen under the action of equal and opposite couples at both ends is said to undergo pure bending. The shear and moment diagrams of a specimen under the two-point loading method of transverse bending are shown in Fig 1. The moment over the middle-third of the span is equal to PL/6, and the vertical shear is zero. Fig 2 (A) illustrates the stress distribution in the elastic range on a plane across the middle of the specimen. It can be seen that the normal stress has a maximum value at the extreme surfaces on the tension and compression sides, and decreases proportionately to zero as it approaches the neutral plane. However, when the plastic range is reached, the stress distribution is no longer a straight line relation, but changes in a manner which can be best illustrated as shown in Fig 2(B). The following calculation and stress analysis are mainly in accordance with the works reported by Timoshenkol0 and Kochendörfer.9 From the simple beam formula, the maximum normal stress will occur at the surface of the specimen. For a round specimen with a radius r and for a rectangular specimen with a height 2h and width 2b, the maximum normal stress, Sp, will be given by the following formulas: For round specimen: 2PL Sp = 3pr3 [1] For rectangular specimen: Sn = 8bh2 [2] Since it is reasonable to consider that slip takes place under the same conditions as in uniaxial loading, the resolved shear stress S?, along the operative slip direction will be as follows: For round specimen: 2PL sin x cos ? Sp = 3pr3 sin x cos ? [3] For rectangular specimen: PL S8 = 8bh2 sin x cos ? [4] where X is the angle between the specimen axis and the slip direction and X, the angle between the specimen axis and the major axis of the glide ellipse. It was also reported by Kochenclorfer9 that the critical bending moment, that is, the bending moment exerted on the specimen to initiate slip, should be higher than the value given by the equations stated above. Based

Jan 1, 1950

By S. Isserow

RECENTLY, a description of the wartime work in this laboratory on the U-Si phase diagram was published. This diagram was available earlier in the open literature; as were Zachariasen&apos;s crystal structure identifications for the compounds in the system. The uranium end of the phase diagram is shown in Fig. 1. The most recent work on this system has emphasized the peritectoid E phase, of particular interest for a number of reasons. The early work provided evidence of this phase&apos;s resistance to corrosion in water and of its slight ductility. Further information on these properties has been obtained here. Work elsewhere4 has provided evidence of stability under irradiation. This body-centered-tetragonal phase is relatively isotropic compared to the more usually applied a or ? uranium phases. Unlike the other compounds in this system, it contains no Si-Si covalent bonds.3 In addition, consideration on the basis of Pauling&apos;s concepts leads to the conclusion that in the E phase, uranium has a higher valence than in any of the other phases. Definition of the composition of the ? phase has been of prime concern in the study of this alloy. Evidence is presented below that its silicon content is slightly higher than that of stoichiometric U8Si, the composition frequently assigned this phase on the basis of Zachariasen&apos;s identification. This work on the composition required careful attention to the method of dissolving the alloy for analysis, since apparently low silicon contents could be found under certain conditions, see Appendix. Preparation: Melting, Casting, and Heat Treatment—Almost all the samples were from castings with a diameter of 13/4 or 2 in. and about 1 ft long, weighing 10 to 15 lb. The U-Si charge was melted by heating to about 1650°C in an induction heated vacuum furnace. Beryllia crucibles were used at first, but were replaced by zirconia-washed graphite as the technique of keeping the carbon content low enough (about 500 ppm) was mastered. The alloy was bottom-poured at about 1650°C into graphite molds. A few small buttons, weighing no more than 50 g, were prepared in a small arc melting unit.&apos; Since cast material has a preponderance of uranium and U8Si2, heat treatment is necessary to ob-tain the ? phase by the solid-solid peritectoid reaetion. Once obtained, the ? phase is stable to room temperature, obviating the need for speeial attention to the method of cooling after epsilonization, see Fig. 1. It was found desirable to epsilonize at 800°C for a week. For some purposes, in which residual uranium and/or U8Si2 are tolerable, shorter periods may be adequate. The temperature of 800°C is not critical, since essentially the same results were obtained from 785° to 825°C. Further departure from this epsilonization range is inadvisable.

Jan 1, 1958