Search Documents

By R. M. Rose, K. A. Jones

Resistive measurements ulere made on superconducting niobium single crystals in transverse magnetic fields. Crystals were grouln in both high and ulfrahigh vacua, doped with stnall quantities of oxygen, and annealed in ultrahigh vacua at temperatures from 900' to 1350°C. Maxima in the fluxoid pinr~ir~g force were observedfor the [100] and [210] directions. The increase of the critical current density with dissoved oxygen was seen to saturate at relatively low concentration. This behavior, and the variation of J, and residual resistivity (as a function of oxygen content and annealing) of both clean and dirty gassy) crystals, is seen as a consequence of the formation of clusters with (210)~b habit planes and (200)ffo common boundaries. These suboxide clusters are apparenlly stable at high temperatures and very low oxygen concentrations. It is generally known that dissolved oxygen at concentrations well below the solubility limit sharply increases the critical current density of superconducting niobium.' Such a result would not be expected if Nb-0 solutions were random, not even as the result of segregation on the scale usually encountered in solid solutions. According to the Kim-Anderson theory of flux creep,' the critical transport current density is determined by the pinning force Fp associated with some feature of the microstructure. As the Lorentz force. a or (J X R), of the transport current in the magnetic field approaches Fp, flux creep and then flux flow occur. The pinning force is expected to be quite small if the heterogeneity involved is significantly smaller than tte range of coherency which for niobium is circa 250~.~ Although the strain field of an individual oxygen atom in the niobium lattice is relatively large, it does not seem plausible that individual atoms could be so effective as to account for the data. Also, ~ramer~ found that straining and strain aging specimens containing small amounts of oxygen on occasion decreased the residual resistivity. A possible explanation for the above behavior may be found in the work of van Ooijen and van der Goot,= who found that annealing changed J, for niobium foils containing oxygen, and they attributed the changes to ordering of the oxygen atoms. This phenomenon has been observed by other investigators using X-ray and PROCEDURE Cylindrical 4-in.-diam niobium single crystals with axial orientations [ill], [110], [112], and [oo~] were grown from pure niobium, see Table I for analysis, in an ion-pumped ultrahigh-vacuum system using the electron beam floating zone technique. Total pressure during growth was lo-'9 torr: the oxygen partial pressure was less than lo-" torr, as determined by a mass spectrometer. These crystals will be referred to as the "clean" crystals. Similar crystals were also grown in another system at a pressure of 5 X 10"6 torr. These crystals will be referred to as the "dirty" crystals. Specimens 14 in. long were cut from the as-grown crystals and one end was polished down to no. 600 carbide paper smoothness. A back-reflection Laue photograph was then taken in order to fix the crystallo-graphic directions transverse to the crystal. The critical current density J,, the current density necessary to produce a voltage drop of 1.0 pv between voltage leads placed a in. apart, was determined as a function of the magnitude and direction of the transverse magnetic field and of the oxygen concentration. The technique and experimental arrangement was essentially similar to that of Tedmon et al.' In the remainder of this paper, the azjmuthal angle $ for the field H is referenced to the [ I101 direction in all four crystals, and oxygen was added in small equal increments by anodization and annealing.7 The resistivity ratio, RR, of the resistance at room ternperature to that at 4.2"K (H =7.00 kG) was determined as well.

Jan 1, 1970

By Peter Beardmore, Michael B. Bever

The effects of the temperature of deformation and the degvee of deformation on the annealing spectrum of a Au-Ag alloy have been determined by vesistance measurements. Specimens were deformed in torsion at 4°, 78K and room temperature up to strains nd/l of about 1.0 and were isochronally annealed. Discrete annealing stages similar to those found for pure metals were observed. Stage A occurred below room temperature; the decrease in reszstance associated with this stage increased as the temperature of deformation was lowered or the strain was increased. Stage B manifested itself as an increase in resistance; this is attributed to the restoration of short-range order promoted by vacancy or vacancy aggregate migration. At temperatures above 48S0K, recrystallization or Stage C occurred. Stages A, B, and C in the annealzng curves of this alloy may be considered to correspond to Stages II, Ill, and V, respectively, in the terminology used to describe the annealing spectrum of pure metals. ThE annealing behavior after deformation below room temperature has been thoroughly investigated on pure metals, in particular gold and copper. The occurrence of several discrete stages in the annealing spectrum of these metals has been established, but the interpretation of some of these stages in terms of specific mechanisms is still controversial.' The annealing of alloys deformed below room temperature has been the subject of only a few investigations. In the investigation reported here, a Au-Ag alloy was annealed after deformation at and below room temperature. This continues a research program on the deformation and annealing behavior of Au-Ag alloys.2-8s EXPERIMENTAL PROCEDURE An alloy rod of composition 82.6 wt pct Au-17.4 pct Ag was reduced to wire, 0.0428 in. diam, by swaging and drawing. After a recrystallization treatment, the grain size was 0.031 mm, as obtained from the average linear intercept.7 The ends of wires about 6 in. long were flattened and sealed into short brass tubes with cold setting cement to form the grips of the torsion specimens. The equipment used for deformation has been described elsewhere.6 The specimens were deformed at room temperature, 78", and 4°K to various strains nd/l, where n is the number of turns, d the diameter of the specimen, and 1 its length between grips. The strain rate ?max was 0.1 min-' at the sur- face of the specimen except where noted otherwise. The specimens were annealed isochronally for 30 min at intervals of approximately 30°K from the temperature of deformation to approximately 800°K, except that after deformation at 4°K the lowest annealing temperature was 78°K. A potentiometric method was used to measure the resistance: all measurements were made at 78°K with the exception of some measurements at 4°K mentioned below. Data obtained with a single specimen yielded a complete annealing curve: in several cases duplicate specimens were used to confirm the reproducibility of the curves. Since the surfaces of the specimens were rough after deformation, their diameters could not be measured accurately. The resistance increments after deformation and annealing are therefore reported as percentages of the resistance of the same specimen measured after completion of the annealing, that is, after full recrystallization. The corresponding resistivity values can be calculated by obtaining the effective diameter of a deformed specimen from the ratio of its resistance after recrystallization to the true resistivity, which was determined with a smooth specimen of known dimensions. This method of calculation was used to obtain data shown in several of the figures. RESULTS AND DISCUSSION The isochronal annealing curves after deformation to various strains at 4", 78K, and room temperature are shown in Figs. 1, 2, and 3, respectively. The resistance increment of the as-deformed specimens as a function of strain is shown in Fig. 4. For the specimens deformed at 4°K. values measured at 78°K are plotted with the exception of those for the as-deformed

Jan 1, 1970

By S. K. Tarby, A. E. Rathke

A series of 0.21 pci carbon steel melts was processed under conditions which sinzulated industrial vacuum degassing practices. The results indicated that the efliciency of carbon deoxidation was not significantly increased by vacuunz degassing at chamber pressures below 100 torr. The two common phenomena of vacuu?rz carbon deoxidation, i.e.,an unaccountable carbon loss and nonequilibrium deoxidation, were observed in this study. Oxygen from adsorbed and chenzically combined water of certain refractory structures was probably responsible for the unaccourttable carbon drop. The nonequzlibrium deoxida-tion phenomenon was adequalely correlated by a bubble nucleation )mechanism. Although the major limiting factor in oxygen removal from these melts contained in alumina crucibles could not be eslablished with certainty, there was some evidence that melt-refractory interactions were not the most imp-portant limiting factor. CONSIDERABLE attention has been given to the use of carbon in conjunction with vacuum degassing* as a deoxidation technique. An advantage of utilizing the reaction: for deoxidation purposes is that the reaction product is gaseous and hence can be effectively removed from the melt. The pressure dependency of Eq. [I] is illustrated by the expression for the thermodynamic equilibrium constant, K: where pco is the partial pressure of carbon monoxide, and hc and ho are, respectively, the Henrian activities of carbon and oxygen in molten steel. The thermodynamic aspects of the C-0 reaction in molten Fe-C-0 alloys have been investigated extensively. Theoretical predictions based on Eq. [2] indicate that, at the chamber pressures reached in most vacuum degassing units, carbon is the most effective deoxidizer that can be obtained. ~ornak' has compared industrial values of carbon and oxygen contents with values calculated from theory, and has shown that on a commercial basis vacuum carbon deoxidation has not achieved the degree of success that is predicted from theoretical considerations of the C-0 reaction. The use of industrial units to determine the reason for this deviation is limited by economics and the difficulty in controlling critical process variables. Therefore laboratory-sized experiments in this area should yield valuable information. Investigations on vacuum carbon deoxidation have been made in experiments conducted under vacuum induction melting conditions where pressures in the low micron range, long treatment times, exposure to highly dynamic vacuum conditions, and relatively quiescent bath conditions have been maintained. Inve~ti~ators~~~ utilizing vacuum induction melting for the production of high-purity iron by carbon deoxidation have concluded that, under high vacuum conditions, melt-refractory interactions constantly supply oxygen to the melt. Thus, it has been suggested that refractory dissociation rather than the C-0 reaction establishes the lowest possible oxygen content of a melt. Thomas and Moreau4 and Bennett, Protheroe, and ward5 have studied carbon deoxidation of Fe-C alloys melted in magnesia crucibles under reduced pressures. The results of both studies differed considerably from those predicted by theory, and the limiting factor for lower oxygen contents was attributed to melt-refractory interactions. Because the refractory material used in both investigations was magnesia, no quantitative measure of crucible reaction could be made and the amount of carbon consumed during treatment was utilized as an indirect indication of the extent of crucible reaction. Studies concerned with the determination of the minimum oxygen content attainable in pure iron and Fe-C alloy material vacuum-induction-melted in various crucible materials have also been conducted."' The suitability of a crucible refractory for use under vacuum conditions appears to depend upon the major refractory constituent, the amount and type of impurity oxides, and the composition of the melt. Meadowcroft and Elliott9 have presented a theoretical review of the type and extent of various refractory reactions which should be considered in vacuum refining. ~eadowcroft'~ considered the vacuum degassing process to be dependent upon the "carbon boil" and has proposed that a part of the difference between the experimental and theoretical results for vacuum carbon deoxidation may be explained by the fact that the pco term in Eq. [2] is not the chamber pressure. Instead, the pressure necessary for carbon monoxide

Jan 1, 1970

By Eckhard Nembach

The phase diagram of the system Pb-In has been investigated between -27° and + 40°C, using nzainly X-ray dijfraction. In accordance with t her mo dynamic measurements by Heumann and Predel, a segregation occurs at low temperatures, though not in the form of a nziscibility gap. THE phase diagram of the system Pb-In has been the subject of extensive investigations,1&apos;1 but recently Heumann and prede13 concluded from their thermodynamic data that a new feature should occur below room temperature. These authors observed that the maximum values for the enthalpy and entropy of mixing, which occurred at a composition of 50 at. pct Pb, were +400 and —1.7 cal per g-atom deg, respectively. From this the authors estimated that a miscibility gap should occur below 30°C, centered at 50 at. pct Pb. Resistivity measurements seemed to support this view. These authors proposed the phase diagram outlined in Fig. 1. Three phases exist at 30°C: the tetragonal indium phase with c/a > 1, the tetragonal intermediate phase a, with c/a < 1, and the fcc lead phase. During an investigation of the superconducting properties of Pb-In alloys. it has been observed4 that aging a specimen with 50 at. pct Pb for 14 days at -18°C decreased the superconducting transition temperature about 0.13"K and tripled the transition width. In this paper, the results of an investigation of the Pb-In phase diagram in the temperature range from — 2T to +40°C are reported. Superconductivity and X-ray methods have been used. 1) SPECIMEN PREPARATION The materials were provided by the American Smelting and Refining Co. According to the manufacturer their purity was 99.999 pct. The weighed amounts of the constituents were sealed in quartz tubes under an atmosphere of 10 torr helium, mixed for 24 hr in a rocking furnace at 380°C, quenched in ice water, and homogenized at 20" to 30°C below the solidus line, established by Heumann and Predel. The annealing times were 144 hr for specimens containing Less than 30 at. pct Pb and 36 hr for the remainder. 2) SUPERCONDUCTIVITY EXPERIMENTS The specimens were quenched from the homogeniza-tion treatment into ice water and their superconducting transition temperatures T, measured. The procedure used has been described in Ref. 4. The transition was detected by the change of the mutual induc- tance of two coaxial coils containing the sample. T, was defined as the temperature at which 50 pct of the total change in inductance had occurred. The repro-ducibility with which T, could be measured was i0.002"K. Then the specimens with lead contents between 38 and 75 at. pct were aged for 7 days at temperatures between -30" and 40°C. If this treatment caused T, to change by more than 0.005"K or the width of the transition to increase by more than 0.002"K, it was concluded that the specimen had undergone a phase change and no longer consisted only of the fcc lead phase: as it did immediately after homogenizing. The result is shown in Fig. 2. From this one can estimate at what temperatures and concentrations phase changes occur. The X-ray measurements were based on these preliminary results. 3) X-RAY EXPERIMENTS Because of the softness of the material, relatively coarse powders. 75 p, had to be used, which were filed in a helium atmosphere from homogenized specimens. The powders were annealed at least 30 min at temperatures between 120" and 16OJC, depending on their concentration, and quenched in ice water. Then their X-ray patterns were taken at -178°C with a Picker diffractometer, model 3488K, and a cold stage. on which the specimen was in thermal contact with a liquid-nitrogen reservoir. In this way the following relation was established for the fcc lead phase: a = 4.697 + 0.00247C for 40 5 C 5 75 11 where n is the lattice constant (A) and C is the at. pct of lead. The coarseness of the powder made it impossible to use lines with 0 > 75 deg; therefore n was averaged from lines with 45 deg 5 0 5 75 deg. The results were reproducible to within i0.05 pct. Relation [I] is very similar to the one found by Heumann and Predel at room temperature. Following this, homogenized specimens with compositions between 15 and 56 at. pct Pb were aged for at least 10 days at temperatures between -27" and

Jan 1, 1970

By Barry D. Lichter, Pierre Sommelet

High-temperature heat contents of InSb, GaSb, and AlSb were measured over the temperature range 400" to 1450°K using a diphenyl ether drop calorimeter. Smoothed ualues of the thermal properties, H$ - H:9s, have been derived and are tabulated at even temperature intervals. The heats of fusion of the three compounds were determined as, respectively, 5707 *100, 7780 * 100, and 9800 5 3011 cal per g-atorn at the determined melting points of 797" l°, 985" * , and 1330" * 5°K. The calculated entropies of fusion are, respectively, 7.16 0.12, 7.90 * 0.11, and 7.37 * 0.23 cal per deg per g-atotn. The heat capacities increase substantially on tnelting in contrast to the behauior of structurally related germanium and silicon. Deriations from the Kopp-Neumann rule are negative for solid compounds and positive for the liquid phases. Previously obsevrrd "post melting" in InSb is confirmed. The high-temperature thermal properties of 111-V compounds are presently not well-established, despite the technical importance of these semiconducting cbmpounds. Uncertainties in available heats of fusion and heat contents have seriously hampered thermo-chemical evaluations&apos; and thermodynamic analyses of phase equilibria2"" in these systems. This paper reports results of high-temperature heat content investigations of InSb, GaSb, and AlSb measured in the range 400" to 1450°K employing a diphenyl ether drop calorimeter. Similar measurements for InAs and GaAs will be reported in a following publication.~ EXPERIMENTAL PROCEDURES Samples. High-purity samples of the compounds InSb and GaSb were supplied in the form of crushed crystal fragments by Dr. Carl Thurmond of the Bell Telephone Laboratories and in the form of single crystals by Dr. A. Strauss of the M.I.T. Lincoln Laboratory. Single-crystal samples of semiconductor-grade AlSb were supplied by Dr. W. P. Allred of the Bell and Howell Research Center. Chemical analyses indicated that all compounds were stoichiometric to *0.1 at. pct, which is within the experimental uncertainties of the analyses. Samples were crushed, weighed, and encapsulated in evacuated, thin-walled, fused silica capsules. The capsules were nearly identical in external shape, 2 cm by 2 cm diam, but varied in weight due to differences in wall thickness. One sample of AlSb was contained in a thin-walled, high-purity alumina cup encapsulated in silica and used for heat content determinations of liquid AlSb. The capsule materials showed no visual evidence of reaction with any of the compounds. The sample and capsule weights are given in Table I. Calorimeter. A Bunsen-type calorimeter, similar in design to a previously described instrument6 but employing diphenyl ether (C6H5)&apos;0 as the calorimetric substance, was used for measurements of heat contents above 300.0°K, the melting point of diphenyl ether. Heat input to the calorimeter caused isothermal melting of diphenyl ether, and the resulting increase in volume was measured by displacement of mercury from the calorimeter into a 200 cm horizontal, calibrated capillary, 1.25 * 0.01 mm diam, or into a weighed beaker. The advantages of diphenyl ether over water have been previously pointed out7 and include: i) an increase by a factor of 3.5 in sensitivity as measured by the ratio of the volume change to the enthalpy change on fusion, ii) the smaller required extrapolation from the melting point to the standard temperature of 298.17"K, and iii) the positive volume change on fusion of diphenyl ether in contrast to the contraction which occurs on fusion of ice. Diphenyl ether was purified by fractional crystallization to 99.95 mol pct as determined from the melting point depression with fraction crystallized. During assembly of the calorimeter, the ether was repeatedly outgassed under high vacuum to remove dissolved air. The calorimeter receiving vessel consisted of an 8-in.-long by 1:-in.-diam copper tube with twelve horizontal 3-in.-diam radiator "fins" for dissipating heat to the surrounding mantle of diphenyl ether. Before forming the mantle the chamber surrounding the receiving vessel contained 3300 cu cm of liquid diphenyl ether above 250 cu cm of mercury which was

Jan 1, 1970

By M. J. Pool, with Appendix by Larry Kaufman, R. W. Krenzer

Thermodynmic properties of the Cu-Mn system have been deterrrzined in the temperature range 973" to 1273°K by measuring the vapor pressure of manganese in equilibrium with alloys of compositions varying from 0.13 to 0.91 rnole fraction manganese using the Knudsen effusion technique. Activities of manganese calculated from the measured vapor pressures show large positive deviations. Calculated heats and entropies of mixing are positive with a maximum occurring at approximately 0. 7 mole fraction manganese. ThE investigation of thermodynamic properties of binary systems involving transition metals is of considerable interest at the present time. The incomplete subvalency electron levels of transition metals lead to unusual behavior in some alloys, and considerable information can be obtained by determining the thermodynamic characteristics of these systems and relating the thermodynamic behavior to observed physical properties. The Cu-Mn system, shown in Fig. 1,&apos; provides an example of an alloy system in which the determination of the equilibrium phase diagram and various physical properties has received considerable attention, but very little work has been done on measurement of the thermodynamic properties. Elemental copper and manganese have comparable electronegatives, atomic sizes, and cohesive energies, but differ in crystal structure. They form a continuous series of solid solutions only at high temperatures and the structure varies in a continuous manner from fcc at the copper-rich end to fct at the manganese-rich end.&apos; The purpose of this investigation was to measure the vapor pressure of manganese over a series of Cu-Mn alloys and from these values determine the thermodynamic properties of the binary system. Vapor pressure measurements were made in the temperature range 973" to 1273"K, remaining within the solid-solution region for each alloy studied. EXPERIMENTAL PROCEDURE The relative thermodynamic properties of solid Cu-Mn alloys were determined from vapor pressure measurements by means of the Knudsen effusion tech- nique. Several discussions of the theory can be found in the literature. In the case of copper and manganese, it is assumed that manganese is the only component subliming, so the vapor pressure of manganese over the various alloys can be determined directly by measuring the weight loss of the effusion cell. This is a valid assumption since the vapor pressure of manganese is about four orders of magnitude higher than the vapor pressure of copper in the temperature region of interest. The vapor pressure of manganese over the alloys at any given temperature is then related to the weight loss of the effusion cell per unit area per unit time. An upper limit of 1.5 x 10"s has been measured for the ratio of polyatomic to monoatomic molecules for manganese vapor in equilibrium with solid manganese at 1180°K, so it was assumed that manganese vapor is monoatomic. The effusion cells, fabricated from high-purity alumina, are 26 mm high, 18 mm OD, and have a wall thickness of 1 mm. Three different sized holes of 2.03, 2.54, and 3.18 mm diam were drilled in the lids from the inside face to minimize chipping, and the lids were then slip-cast onto the cells to provide a gas-tight seal. Alumina was selected for this particular application both because of its resistance to thermal shock and reaction with manganese vapor. In the ideal case, the orifice of the effusion cell should have a knife edge so that effusion through the orifice

Jan 1, 1970

By H. A. Wriedt

At 500°C (932°F) the range of y&apos; iron nitride is from 5. 77 + 0.03 wt pct N (in coexistence with a iron) to 5.88 * 0.03 wt pct N (in coexistence with E iron nitride). Stoichiometric "Fe,N" (5.900 wt pct N) is near the upper extreme of possible compositiom. The depe-dence of nitrogen activity (expressed as pnh,/Ph,) on nitrogen content is described satisfactorily by a "Langmuir" isotherm: At even the highest nitrogen concentrations, less than 0.18 pct of&apos; the nitrogen atoms present are impositions of disorder. Past investigations1-4 of the Fe-N system have left only details of the thermodynamic behavior of the y&apos; nitride, "Fe,N9&apos;, to be studied. The present investigation was made to establish more precisely than hitherto the limits of composition and the relation between composition and nitrogen activity at 500°C. EXPERIMENTAL TECHNIQUE The compositions of nitrides in equilibrium with various NH, + Hz mixtures at 500°C were determined from the weights gained by 0.02-in.-thick (4.0 to 4.5 g) strips of purified iron* when the nitrides were formed A description of the gas generation and furnace system has been published.5 Cracking and blistering during conversion of the original solid iron at 550°C injected considerable porosity into the strips without causing their disintegration. The time for complete conversion was significantly lowered by periodically reducing partly nitrided specimens in hydrogen and then reexposing them to the nitriding gas. Gas mixtures producing single-phase were used in the equilibrations at 500°C. Equilibrium was regarded as existing when the specimen weight was not detect-ably affected by further exposure to the same conditions. The gas compositions and nitrogen activities at which y&apos; transformed to a iron (lower activity limit) and to E iron nitride (upper activity limit) were redetermined during the investigation. A specimen was equilibrated in an NH, + Hz mixture at 500°C and then exposed to a s1ightly different gas. When equi- librium had been reestablished the gas was again changed slightly. At each stage of this repeated process, while the specimen was reacting with the gas, the variation of its weight with time was observed. The onset of phase transition was marked by an abrupt change in the amount and rate of weight gain or loss. The specimens were weighed outside the furnace, in air and at room temperature, on a balance with 0.05 mg precision. When it was found that the specimens were oxidizing at a significant rate during the weighing, a series of timed weighings was made with each specimen, starting 1 min after its exposure to air. RESULTS AND ANALYSIS The gain in specimen weight from oxidation during weighing was linear in the logarithm of time between 1 min and about 2 hr, Fig. 1, later becoming linear in the cube root of time. In the logarithmic period, nitride specimens oxidized two to three times as fast as

Jan 1, 1970

By J. Serra, M. Turpin, R. Alberny

A new method is proposed to obtain automatically an unbiased estimate of the interdendritic spacing A. It is shown that the structure can be built by a random distribution of a rectangular basic unit. The usual definition of the interdendritic spacing yields a value 1 which, coupled with A, gives the shape of the basic rectangular unit. A study of the relationship between dendrite arm spacing and solidification rate was conducted as a part of a research program on dendritic solidification. For any comparison between theory and experiments to be meaningful, it is necessary to measure reproducible and clearly defined spacings. Fig. 1 shows clearly that even in a fairly simple structure such measurements are difficult. if we compare photos (a) and (b), we can hardly assess which one shows the larger spacing. Moreover, the quantity to be measured can be defined in several ways. On a small scale, dendrites seem to be distributed in a very regular and ordered way. However, on a larger scale, this regularity no longer exists. The usual way to measure spacings is to pick up some rows of dendrite stalks; such measurements are obviously biased since less orderly regions are not taken into account. A more objective method is to section the picture with randomly oriented straight lines and average the measured interdendritic spacings. The purpose of this paper is to show that such measurements, which can be conducted automatically, yield objective and reproducible results which are directly related to characteristic features of the dendritic structure. I) THEORETICAL ANALYSIS 1-1) Mathematical Morphology and Function of Co-variance. Matheronl and Serra2 enlarced- the definition and geometrical meaning of the notion of covariance to encompass problems in mathematical morphology. A brief review of part of their theory can be stated as follows. Let A&apos; be an isolated particle, and let us consider a group of two scanning points h is the vector joinlng these points, h its modulus, and a its direction. Let us also define a boolean function, k(x), whose value is 1 if x lies inside the particle and 0 if it 1s outside. The total number of events in which both points are inside A&apos; IS the covariance Ii&apos;,(h): is the measure of the intersection of A&apos; with the particle ALh obtained by translating A&apos; of -h Obviously K,(O) is the volume of the particle A&apos;, or its area if A&apos; is a two-dimensional body. The average value of K,(h), when the direction of a vector h of constant modulus is rotated, is: An important property of the covariance is illustrated on Fig. 2: if the shape of a particle shows some regularity along a direction a, K,(h) generally presents a maximum. We now consider a group A, made of many particles A&apos; distributed in space; then k(x) is taken as the realization of a stationary random f~nction.~ The volume fraction (or fraction of area if the problem is two-dimensional) occupied by A equals the average value q of k(x): meaning "average value of"). We also replace

Jan 1, 1970

By K. Tangri, B. Swaroop

Simultaneous measurements of lattice (elastic) strain by X-ray line shift method and total strain with an electrical strain gage have been carried out on polycrystalli,ne nickel with the help of a specially designed tensometer attachment for the X-ray dif-fractometer. During the initial stages of deformation, the rate of increase in lattice strain closely follows the total strain until the plastic strain sets in. From then onwards, the two strains deviate from each other and with further increase in afiplied stress the rate of increase of lattice strain eventually decreases. Depending upon the mode of unloading, both compressive and tensile strains have been observed in nickel deformed up to 0.29 pct strain. These results have been explained on the basis of the effects of clustering of dislocations and also the production and behavior of point defects during loading and unloading, respectively. POLYCRYSTALS deformed plastically in a uniaxial tension test show residual lattice strains (hereafter referred to as RLS), which broaden the X-ray line profiles and shift their peak positions.&apos;&apos;4 It is known that uniform straining of a crystal lattice (macrostrain) produced movement of ddfraction line peaks, whereas nonuniform straining (microstrain) causes line broadening.= Though the nature and origin of RLS in deformed metals is not yet clearly understood, these are believed to be due to the presence of some form of a locked-up stress system. Several possible detailed interpretations6&apos;" of the stress system have been proposed by various workers and common to all these interpretations is the assumption that different parts of the aggregate have different tensile yield stresses; e.g., that a part A yields under a lower applied stress than a part B. Therefore, during the deformation process, the elastic strain in A will be less than that in B, and, after completion of deformation, B will tend to contract further than A but will be prevented from doing so by the restraining influence of A. Thus, when equilibrium is reached, A will be in compression while B is in tension. Although there is general agreement on the correctness of this argument, controversy still exists as to the exact nature of the parts A and B in a deformed metal. In an alternative approach to the creation of parts A and B, many other investigators have assumed that the RLS observed in unloaded specimens are in some way connected with the lack of proportionality between lattice strain and applied stress in the region above the yield stress." cullity13 has prepared a schematic summary of the results of previous workers, mainly Smith and Wood,2&apos;11 which suggests that, above the elastic limit, the lattice strain may increase less rapidly with respect to strain, or may even decrease with increase in applied stress. If the applied stress is then decreased, the lattice strain would decrease along a line parallel to the loading line in the elastic region and thus produce a compressive residual lattice strain after unloading. At equilibrium, to balance these compressive stresses? there would have to be regions under tensile stress which may well be the grain boundaries or the substructure walls formed during deformation. The present investigation was undertaken to gain a better understanding of the nature and origin of RLS and also to experimentally verify the salient features of this hypothesis. EXPERIMENTAL Stress and strain determinations were made with a specially constructed tensometer attachment for the X-ray diffractometer, Fig. 1: which permits the following measurements simultaneously on a sheet specimen under uniaxial tension at various stress levels during loading and unloading: a) lattice strains, E=. in a direction perpendicular to the direction of pulling (x direction) from shifts in X-ray line peak positions; b) the total strain, ex, in the direction of pulling. with the help of an electrical strain gage affixed to the back of the specimen directly below the area irradiated by X-rays: and c) the applied stress, with the help of a load cell which consisted of a calibrated stainless-steel sample of dimensions identical to those of the specimen under investigation, and to which it was coupled. Because of its high stacking fault energy.I4 nickel

Jan 1, 1970

By M. S. Burton, J. E. Ritter

The sessile-drop technique was employed to study the effect of atmosphere and alloy additions of titanium and chromium on the surface tension and contact angle of nickel on sapphire substrates at 1500oC. Shear tests were conducted on the solidified sessile drops. The liquid-gas surface tension of pure nickel on sapphire was found to be 1747 ergs per sq cm, with a contact angle of 109.6 deg. The surface tension and contact angle were not affected significantly by the four atmospheres, vacuum, impure argon, pure argon, and pure hydrogen. Small additions of titanium and chromium decreased the contact angle and for the same alloy content, contact angles were lower in pure argon than in pure hydrogen. On the basis of shear-test results , the most probable cause for adhesion in the Ni-Al2O system is the formation of NiO:Al2O3 spinel at the interface; in the titanium alloy-Al2O3 system adhesion is thought to be due to a mechanical interlocking effect; in the chromium alloy-Al2O3 system adhesion is believed to be the result of solid-solution formation involving Cr2O3 and Al2O3 at the interface. In the last few years there has been considerable interest in reinforcing metals with ceramic whiskers. It has been postulated that, by reinforcing nickel with sapphire whiskers, high-temperature strengths su- perior to those of the best current nickel alloys can be achieved.&apos; To fabricate a whisker-metal composite having optimum density and strength, understanding of wettability and adherence in the system is of prime importance. Although there has been some previous research in this a a need for further studies has been cited4-8 to understand better the effects of impurities, alloys additions, and atmosphere on the wetting and bonding of metals to metal oxides. The purpose of this research was to investigate the factors involved in the wetting and adherence of nickel/nickel alloys to sapphire (single-crystal a Al2O3). Sessile-drop experiments were conducted in vacuum, impure argon, pure argon, and pure hydrogen, to determine the effect of atmosphere on the contact angle of the metals on sapphire, and the liquid-gas surface tension of pure nickel. The solidified sessile drops were sheared from the sapphire substrate to measure the bond strength between the metal and ceramic. The alloy additions chosen were titanium and chromium since both enhance the wetting of nickel on sapphire.2, 3c Also, titanium is commonly used when brazing metal-to-ceramic seals to improve adherence. Since chromium forms an oxide that is completely soluble in sapphire, it was thought that the oxide could serve as a transition phase to promote bonding between the Ni-Cr alloy and sapphire. I) EXPERIMENTAL APPARATUS AND PROCEDURE The sessile-drop apparatus was a horizontal furnace, with an induction-heated, cylindrical molybdenum susceptor in a water-cooled Pyrex chamber. This apparatus was patterned after that of Williams and Nielsen.7 A flat Pyrex window at each end of the furnace allowed temperature measurements to be made at one

Jan 1, 1968

By P. S. Rudman

Crystal-structure occurrences in binary phase diagrams of fifth- and sixth-period elements, zirconium through palladium and hafniun through platinum, are surveyed with the conclusion that average .group number GN is the dominant correlative. This is interpreted in terms of curves of enthalpy differences between competitiue structures that are continuous func -tions of GN. It is further reasoned that the absolute formation energies may also be continuous functions of GN and if so can be simply obtained from the regatives of the heats of sublimation of the elements. It is shown that from such a heat of formation-GN plot the heats of mixing of alloy systems can be quantitatively predicted. For example, for sixth-period alloys very large exothermic heats of mixing are predicted for systems that span GN = 6 (i.e., Hf-Pt, Ta-Os, ...). Thermodynamic data with which to test these predictions do not appear to be available. If in the latter transition (A subgroup) elements we eliminate from consideration the fourth period where magnetic terms contribute to crystal-structure stability, as shown in Table I, there is a very regular sequence of structures. Using the group number (GN) assignments of Table I, which differ from the usual assignments of 8 to the elements listed as 8 through 10, it is perhaps trivial to say that the phase occurrence is a unique function of GN. However, the interesting aspect of alloys from among these elements is that the alloy structures also appear to correlate with GN. The GN for an alloy is given as GN = SixiGNi, where xi and GNi = atomic fraction and GN of component i, respectively. It is difficult to credit anyone in particular with having discovered this correlation, so many people have implicitly or explicitly employed it in the last 10 years. However, Bloom and Grant&apos; in their correlation of s-phase occurrence with total number of d + s electrons were certainly one of the first to appreciate the correlation and Hume -Rothery2 appears to be responsible for the use of average GN as defined above. Only in the last few years have the phase diagrams of enough alloy systems been determined for this correlation to be surveyed with any degree of completeness. We shall here, in an abbreviated format, summarize the available phase-diagram literature and discuss some consequences of the GN correlation. BINARY DIAGRAM SURVEY In Figs. 1 to 3 the phase occurrences are summarized. In Fig. 4 the occurrence limits for the more common structures are summarized. That the GN of an alloy falls within the occurrence limits of a particular structure is a necessary but not a sufficient condition for the appearance of that structure. The preceding figures certainly illustrate that GN is a dominant correlative for structures of these elements. Many of the diagrams have complications, with ordering and other phase changes occurring in intermediate phases, that cannot be clearly accommodated in such a schematic survey and have hence been left out. Such omissions cannot, however, negate the GN correlations discussed here. Relative atomic size is also an important crystal-structure determinant and since atomic size varies quite regularly with GN for these elements it is possible that the apparent GN correlation is basically a size correlation. In Fig. 5 relative size occurrence limits are given for intermediate phases and extended terminal solutions. The relative volume, ?v/(v) - 2(vA - vB)/(vA + uB), has been taken as the measure

Jan 1, 1968

By R. C. Padfield

Experience over a 3-year period in Bethlehem Steel Corporation&apos;s plants has demonstrated the reliability of open-hearth roofs of bonded sprung-arch constructzon with burned basic brick. The design principles lor constructing these roofs include a minimum hot-strength requirement for the basic brick, expansion allowances that extend the full roof thickness, structural members to control arch contour, and a specified minimum roof rise. The greater stability of bonded roofs is explained in terms of the basic stress patterns of ring constrution and bonded construction. PRIOR to the development of successful sprung-arch roofs of basic brick, the majority of open-hearth furnaces in the United States were operated with sprung-arch roofs built of silica brick. Although many silica roofs used on open-hearth furnaces were ring-arch construction, Bethlehem Steel Corp. used bonded-arch construction because of its greater stability. In ring construction, each ring of brick is separately keyed and comprises an independent arch with the straight joints between rings traverse to the longitudinal axis of the furnace. In bonded construction, the bricks are laid in rows starting from the skewbacks so that the straight joints run parallel to the longitudinal axis of the furnace. Each brick in a given row is laid so that it spans the joint between two bricks in the row beneath it. Thus, the transverse joints across the arch are broken and the arch rings are thereby interlocked or bonded. When basic roofs were first being developed, the basic brick that were available had low hot strength. Such brick could not be safely used in sprung-arch construction without some means of suspending them. With the development of higher firing techniques by brick manufacturers and the recently introduced direct bonded bricks with high hot strength, the use of burned basic brick in sprung-arch roofs became feasible. The availability of high hot strength basic brick coupled with the potentially lower cost and proven stability of bonded construction prompted Bethlehem&apos;s Research Department to study the possibility of using basic brick in bonded roofs. With the full cooperation of plant ceramic engineers and open-hearth superintendents, particularly in 3 years of fur-nace trials, we developed the design criteria for bonded roofs and the corresponding property requirements for the basic brick that are discussed in this paper. DESIGN PRINCIPLES OF SPRUNG-ARCH BRICK ROOFS Stresses in Fixed Arches. A sprung-arch open-hearth furnace roof is generally built on rigidly held skewbacks. The constraint of the fixed support at each end adds a bending moment to the horizontal and vertical reactions at the ends of the arch. Fig. 11 shows the positive direction of forces acting on an arch fixed at both ends. Fixed arches can be analyzed when the members are continuous and have elastic properties. However, brick are inelastic, and arches built with individual brick segments cannot carry tensile stresses. Therefore, for practical solution of brick arches, empirical formulas have been derived from elastic theory that place design restrictions on arch dimensions to avoid development of tensile stresses. McDowell2 cites three main conditions for stability in sprung brick arches: 1) the thrust line of the arch should be maintained in the middle third of the thickness to avoid tensile stresses and resulting open joints in inner and outer curves of the arch; 2) the angle between the line of thrust at any joint and a line perpendicular to the joint must not exceed the angle of repose between brick; and 3) the maximum pressure at any point must not exceed the strength of the arch materials at furnace operating temperatures. The first and third conditions are particularly important in designing sprung-arch basic roofs because of the comparatively low hot strength of basic brick. According to McDowell&apos;s equation, if the thrust line is maintained within the middle third of the arch thickness, the unit pressure is obtained as follows: where p = unit pressure in psi, F, = resultant thrust normal to skewback in pounds per foot, t = arch thickness in inches, and z = distance in inches of thrust line from arch axis. When the resultant thrust normal to the skewback acts along the arch axis, z equals zero and unit pressure is simply the thrust divided by the cross-sectional area. If the thrust line moves to the limits of the middle third of the arch thickness, beyond which tensile forces would develop, z then equals one-sixth of the arch thickness and the unit pressure is double that when the thrust line is acting

Jan 1, 1968

By Ray W. Carpenter, Ralph Hultgren, Raymond L. Orr

Heats of formation of Au-Zn alloys of compositions Au3Zn and AuZn were rneasured at several temperatures by liquid tin solution calorimetry. The data for Au3Zn show that much smaller heat and entropy effects are associated with the a2- a1 transformation than for the a1 - a transformation. This result is consistent with reported X-ray diffraction studies which indicate that the a1 and (a2 phases have ordered structures which only slightly differ, whereas the a phase is disordered. The heat of formation of AuZn(ß&apos;) does not change significantly between 322o and 8000 K, confirming that the ß&apos; alloy remains highly ordered to high temperatures. Not many measurements have been made of the energies of order-disorder transformations in alloy phases. In many cases these energies may be conveniently determined by measuring heats of formation as a function of temperature. Many alloy phases approximately obey Kopp&apos;s law of additivity of heat capacities; as a consequence their heats of formation do not change with temperature. In ordered alloys, however, a decrease in degree of order with increasing temperature will contribute an endothermic component to the heat of formation. Thus, for ordered phases where other anomalous contributions to heat capacity in the alloy or its pure components are absent, a measured change in the heat of formation may be attributed to the energy of disordering. A portion of the Au-Zn phase diagram1" is shown in Fig. 1. The composition AuZn(ß&apos;) has a well-ordered superlattice structure of the CsCl type at room temperature. The alloy is considered to remain ordered to its melting point,1 although, from X-ray diffraction data and electromotive force measurements of zinc activities, Terpilowski3 concluded that considerable disordering began at -673°K. The Au3Zn composition is a disordered fee solid solution (a) at high temperatures. Between 693o and 543oK, the ailoy orders to form the a1 phase, having a structure based on the L12(AuCu3) type, but with a regular distribution of ordering faults in the c direction, making it tetragonal. Below 543oK, the alloy orders further by means of slight atomic shifts, without diffusion, yielding a complex long-period orthorhom-bic superlattice structure, a2.4-7 Heats of formation of Au3Zn(a2) and AuZn(ß&apos;) were measured at 363°K by Biltz et al.8 by aqueous solution calorimetry. Heat capacities of several alloys between 14.9 and 38.4 at. pet Zn in the range from 373" to 723°K were measured by Iwasaki ef al.6 Stoichiometric Au3Zn, however, was not included in the alloys measured, the nearest composition being 26.1 at, pet Zn. Also, the heating rate used for the measurements, 2 deg per min, may not have permitted equilibrium to be reached in the neighborhood of the transformations. Heat contents of solid and liquid AuZn were measured between 488o and 1138°K by Kubaschewski.9 It was decided to determine the ordering energies of Au3Zn and to check on the possible disordering of AuZn by measuring the heats of formation of these alloys at several temperatures. The present paper reports measurements by liquid tin solution calorimetry of the heats of formation of the three phases of Au3Zn at temperatures within their regions of stability, and of AuZn at a low (322°K) and a high (800°K) temperature. EXPERIMENTAL Alloy Preparation and X-Ray Examination. Ten-gram ingots of Au3Zn and AuZn were prepared by melting weighed amounts of gold (99.95 pct Au) and zinc (99.99 pet Zn) together in sealed evacuated Vycor tubes at 1060°K, followed by rapid quenching. The resulting ingots were homogenized at 900°K for 10 days. The Au3Zn alloy lost no weight in preparation, the loss from the AuZn alloy was enough to introduce an uncertainty of only 0.1 at. pet in its composition. Filings for X-ray examination were taken from various parts of each ingot and strain-annealed at 723°K for 20 min in vacuo. The Au3Zn filings were quenched rapidly to retain the disordered phase. Diffraction patterns were determined with an X-ray dif-fractometer using copper Ka radiation.

Jan 1, 1968

By D. S. Tannhauser, I. Bransky

Measurements of the electrical conductivity, the thermal electromotive force, and the deviation from stoichiometry by thermogravimetry were made on ferrous oxide (wüstite) single crystals as well as on poly-crystalline samples in the temperature range of -900" to 1330°C. In the region defined by T 2 1000°C and 1.05 5 O/Fe 5 1.10 the electrical conductivity was shown to be proportional to the sixth root of- the oxygen partial pressure and to be linearly dependent on the deviation from stoichiometry. The absolute Seebeck coefficient of single and polycrystalline wüstite was shown to be independent of temperature in the above region and a p to n transition of the Seebeck coefficient was observed at O/Fe = 1.09 in polycrystalline wüstite. Analysis of the results showed that the predominant defects in wüstite in the above region were doubly ionized cation vacancies. The analysis also ruled out the existence of complexes of the type postulated by Roth, except that below 1000°C there is some evidence of &apos;association of defects. Of the three oxides of iron (FeO, Fe3O4, Fe2O3) only FeO (wüstite) can exist within a wide range of the ratio O/Fe. This has been shown by several investigations of the phase diagram using for instance chemical analysis of quenched samples&apos;-4 or thermogravimetric measurements. 5,8 Darken and Gurry&apos;s1 data for example in the temper- ature range 1100o to 1400°C show that the lowest O/Fe ratio obtainable for FeOl +. is about 1.045 and that the existence range extends to O/Fe = 1.20 at 1400oC. On the basis of detailed analysis of thermogravimetric measurements made by Vallet and Raccah6 the existence of three varieties of wüstite at elevated temperatures was suggested by these authors and by Kleman. It is well-established that wüstite has a NaCl structure with vacant cation sites.3, 8 From a neutron-diffraction study of wüstite samples quenched to room temperature Roth9 concluded that defects in wüstite are mostly complexes composed of two cation vacancies and one interstitial cation in a tetrahedral site. The atomic arrangement in the vicinity of such a defect is similar to that in magnetite, where each occupied tetrahedral site is surrounded by four vacant octahedral positions disposed at the corners of a tetrahedron, so arranged that each vacancy is shared by two tetrahedral cations. Thus there is an average of two vacancies per interstitial. Recent X-ray diffraction measurements made by Smuts10 on quenched wüstite samples confirmed the results of Roth&apos;s neutron-diffraction experiments. Roth&apos;s model of defects in FeO can be regarded as a solid solution of Fe3O4 in FeO; salmon1&apos; used this defect model to calculate the activity of Fe3O1 in FeO at high temperature and claimed good agreement with the results obtained experimentally by Darken and Gurry.&apos; Each missing cation in wüstite is accompanied by two trivalent cations, thus preserving charge neutrality. The "holes" which differentiate between the Fe 2+ and Fe3&apos; states of the ions in octahedral positions can overcome the attractive field of the cation vacancies, and are then free to move through the crystal as charge carriers. A similar picture holds for COO, NiO, andMnO.l2, 13 Localization of the charge carriers in transition

Jan 1, 1968

By Harold M. Feder, Robert V. Schablaske, Irving Johnson, Ewald Veleckis

The stoichiometry, structure, and stability of the internzediate phases formed between zinc and some of the rare earth (RE) metals were systematically exarnined by means of a recording effusion balance and X-ray diffraction analyses. In the La-, Ce-, PY-, Nd-, and Y-Zu systems, at or below about 600 C, the following sequences of phases (REZnx) were found: La, x = 1, 2, 4.0, 5.25, 7.3, 17/2, 11, and 13.0;&apos; Ce, x = 1, 2, 3, 11/3, 4.3, 5.25, 7.0, 17/2,* and 11; Pr,x = 1,2, 3, 11/3 ,* 4.3, 5.3(?), 7.0, 17/2,* and 11; Nd,x = 1,2, 3,* 11/3,* 4.3, 6.5, 8.5,* and 11; Y,x = 1,2,3, 11/3, 4.5, 5.0, 17/2,* and 12.* The structure types of all these phases were classified. In addition, lattice parameters were obtained for the first time for the pluses denoted by asterisks. In the absence of de tectable valency or electronegativity effects the systesnatic trends in the results have been ascribed to the effects of&apos; the lanthanide contraction. For example, the maximum number of zinc atoms in the coordination polyhedron surrounding the RE atom decreases from twenty-four to twenty-two to twenty as the size of the RE atom decreases. THE structures and compositions of a great many intermetallic phases (e.g., the Laves phases) are known to be based primarily, but not exclusively, on the space-filling efficiency of various modes of packing together atoms of different sizes. The valencies and electronegativities of the constituent atoms are, however, also influential. In extreme cases hypothetical intermetallic phases which fulfill the efficient spacefilling requirements may not be present in the constitutional diagram because of thermodynamic instability brought about by the operation of valency or electronegativity factors. Hence, for a detailed study of the influence of atomic size on alloy structure and composition, it would be desirable to minimize variations of valency and electronegativity. The intermetallic phases formed by the rave earths (RE) with some common partner offer an excellent opportunity for isolating the effects of size from those of valency and electronegativity. The rare earths exhibit a large, but smooth, decrease in size (the lanthanide contraction) in the series from lanthanum to lutetium when inter comparison is made for a common valence state, e.g., isolated atoms or trivalent ions. The elements yttrium and scandium are frequently included as pseudo rare earths; their sizes place them in the vicinity of dysprosium and lutetium, respectively. The electronegativities of RE elements vary by less than 10 pet. The trivalent state is the most common; however, the well-known tendency of cerium, praseodymium, and terbium to achieve higher valencies, and of samarium, europium, and ytterbium to seek lower valencies, requires that caution be exercised in the assumption of equal valencies. In the present study the existence, constitution, and structure of each of the numerous intermediate phases formed by zinc with lanthanum, cerium, praseodymium, neodymium, or yttrium were examined systematically and in detail. The investigation was conducted by a recording effusion balance technique and by X-ray diffraction analysis. The results enrich our knowledge of the phase diagrams of these systems. In addition, they present some clear-cut evidences of the operation of the size factor alone. EXPERIMENTAL PROCEDURE Apparatus. The mode of operation of the recording effusion balance and its application to phase studies have been discussed in detail elsewhere.&apos; In this work, an effusion cell containing a finely divided alloy was suspended within an evacuated tube from the beam of an analytical balance. The tube was immersed in a massive molten salt bath whose temperature was controlled to within 0.5o C during each experiment. The loss in weight of the alloy owing to effusion of zinc* was continuously recorded. Two effusion cells, 1/2 in. diam by 1 in. high, were machined from tantalum rods. Two orifices were drilled laterally into the walls of each cell. The orifice areas were determined by calibration with pure zinc: cell A had a total orifice area of 6.5 x 10-41 sq cm, and cell B an orifice area of 9.8 x 10-3 sq cm. By appropriate choices of orifice area and temperature the wide range of volatilities from pure zinc to pure rare earth metal could be investigated. X-ray diffraction powder photographs were made at room temperature with a 114.6-mm Debye-Scherrer camera with both filtered CuKa radiation and filtered CrKa radiation. Lattice parameters were refined by a computer-programmed least-squares analytical treatment which incorporated appropriate extrapolation techniques.2 Frequent use was also made of a special computer program3 designed to generate a powder pattern from an assumed structure in order to verify structural assignments. Materials. Lanthanum, neodymium, and yttrium were purchased from the Lunex Co., cerium from the Cerium Metals Corp., and praseodymium from the St.

Jan 1, 1968

By J. C. Bokros, A. S. Schwartz

The irradiation-induced densification of pyrolytic carbon has been shown to take place by a simple first-order rate process. The values of the densification constant, kd, for isotropic carbons are 1.0 x 10-22, 1.4 X 10-22 and 2.8 X 10-22 (nut)-1 at irradiation temperatures of 520o, 670°, and 1000oC, respectively. The apparent activation energy obtained from the temperature dependence of kd for isotropic carbons is about 0.2 ev. Estimates of the maximum stresses that develop in isotropic carbons owing to shrinkage onto an unyielding support show that stresses in excess of 15,000 psi may be avoided during irradiatian at 600" and 1000°C if the initial coating density is kept above 1.5 and 1.9 g per cu cw, respectively. If a carbon coating on an unyielding support is not completely isotropic, stresses may continue to build up at high neutron exposures after densification is complete because of continued anisotropic distortion. Stresses in excess of 15,000 psi from this source may be avoided during irradiation at 1000°C if&apos; the Bacon anisotropy factor is kept below 1.3. A variety of applications of carbon and graphite in nuclear technology has stimulated numerous studies of the effect of neutron irradiation on these materials One of the most interesting problems associated with the use of carbons and graphites in the high fast neutron fluxes of nuclear reactors arises as a consequence of the neutron-induced dimensional changes that occur during irradiation. Energetic neutrons displace car- bon atoms from their lattice positions; and, depending on the temperature, the interstitials and vacancies produced migrate to form clusters, recombine, or are annihilated at dislocations or crystallite boundaries. The competition of various sinks for the point defects results in structure-sensitive bulk-dimensional changes that vary with temperature in a complicated way. This paper deals with the neutron-induced dimensional changes in turbostratic carbons that are being used as coatings on nuclear fuel particles. Details of the structure of these carbons and the variations of their structure with deposition conditions have been reported.&apos;-3 It has been shown in previous work that the neutron-

Jan 1, 1968

By W. Bonfield

The microstrain characteristics of a polycrystal-line Cu 1.9 wt pet Be precipitation-hardening alloy have been determined for various conditions of aging. The friction stress remained constant for all the conditions investigated, whereas the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-8 in. per in.) and the three-stage stress-strain curve in the microstrain region were sensitive to changes in dislocation and precipitate distribution. Correlations between the measurements of microplasticity and electron-nzicroscope observations of substructure are considered. ALTHOUGH the macroscopic mechanical properties of Cu 1.5 to 2.0 wt pet Be precipitation-harden ing alloys were established&apos; in some detail, there has been no previous investigation of the nature of microyield-ing in these alloys. This paper describes a high-sensitivity extensometer determination of microplasticity in polycrystalline Cu 1.9 wt pet Be, in which the friction stress, the microscopic yield stress (the stress to produce a plastic strain of 2 x 10-6 in. per in.), and the rate of strain hardening in the micro-strain region were measured for various conditions of precipitation. The structural changes accompanying aging in this alloy were examined using transmission electron microscopy, a study which differed from previous investigations as, in order to minimize grain boundary precipitation effects,&apos; the solution-treated alloy was cold-rolled to 40 pet reduction prior to aging. Hence the extent of recovery and recrystalliza-tion, as well as the variation of precipitate morphology and distribution, were assessed. From these results possible correlations between the microstrain characteristics and the observed precipitate and dislocation structure are considered. EXPERIMENTAL PROCEDURE The material investigated was a commercial copper beryllium alloy (Berylco 25), which had a com- position of 1.9 wt pet Be and 0.2 wt pet Co. The alloy was solution-treated at 800°C, quenched in water, and then cold-rolled to 40 pct reduction. Tensile specimens of gage length 1 in. and rectangular cross section of 0.18 by 0.06 in. were prepared from the solution-treated, cold-rolled material and aged for 15 min, 2, 24, and 100 hr at 315°C and 24 hr at 425°C to produce a range of precipitate structure. The hardness values associated with these conditions are listed in Table I. It can be seen that a maximum value is obtained after 2 hr at 315oC, which decreases with continued time at temperature to a minimum after 24 hr at 425°C. For comparison some as-solution-treated specimens were also aged for 2 hr at 315°C. The specimens heat-treated to a given condition were examined in two ways. First, the nature and distribution of the precipitate and dislocation structure was characterized using transmission electron microscopy. Thin foils were obtained from the specimens by electrolytic polishing in a 30 pet nitric acid-alcohol solution at -20oC, and were examined in an RCA EMU 3 electron microscope. Second, the mi-croplastic behavior of the specimens was measured with a Tuckerman strain gage, using the load-unload technique previously described2, 3 to determine the friction stress, the microscopic yield stress, and the variation of plastic microstrain with stress. RESULTS 1) Structural Changes During Aging. a) Annealing Processes. The solution-treated, cold-rolled Cu 1.9 wt pet Be had an irregular dislocation-cell structure,

Jan 1, 1968

By R. D. Pehlke, J. V. Gluck

A study was made of the effect of small additions of metallic solutes on the thermodynamic activity of zinc in dilute solution with molten bismuth in the range 450o to 650°C. The experimental measurements were made in a multielectrode galvanic cell using. a fused LiCl-KCl electrolyte. The activity of zinc in binary solution exhibited a strong positive deviation from Raoult&apos;s law and obeyed Henry &apos;s law to at least 0.050 mole fraction. The ternary addition of lead, gallium, or indium increased the activity of zinc. Cadmium or tin additions slightly decreased the zinc activity. Copper, mercury, silver, or antimony caused moderate decreases, while gold strongly decreased the zinc activity. The results are expressed in terms of Wagner&apos;s interaction parameter ejZn and a second-order cross-interaction parameter. The interactions for copper, gold, silver, and antimony showed a linear dependence with reciprocal absolute temperature, while the other interactions were essentially independent of temperature over the experimental range. Since tin and antimony decreased the zinc activity, the hypothesis of a purely periodic variation with atomic number was rejected. A semiquantitative explanation was possible with a free-electron model when relative electronegativities were used to express changes in the electron/atom ratio caused by the solute addition. Random solution and quasi-chemical models correctly predicted the majority of the interactions for which binary data were available to apply them. A knowledge of the thermodynamic interactions in liquid (and solid) metallic solutions is of considerable theoretical and experimental interest in the formulation of quantitative thermodynamic relations for metallurgical processes. The approaches to defining the interactions may be either phenomenological (i.e., "What mathematical function adequately describes observed behavior and permits extrapolation to new situations?") or theoretical, such as a specific model

Jan 1, 1968

By E. Furubayashi, T. Taoka, S. Takeuchi

Recrystallization textures developed from artificial nucleation around indentations were compared with spontaneously recrystallized textures in two rolled 3 pet Si-Fe single crystals with (111)[112] and (100) [011] orientations. Orientation of individual grains in some stages of their growth was also directly determined by a microetch-pit method. In both the crystals, the recrystallization texture was characteristic of each orientation regardless of any nucleation conditions, artificial or spontaneous, though artificially nucleated grains were more randomly oriented in finer stage. These results support the concept that the process of selection of growing grains controls the formation of the prejerred recrystallization texture. Discussion is given on the factors controlling the mobility of grain boundaries. Recrystallization textures are formed through a number of stages which are customarily called by the terms recovery, nucleation, and grain growth. Many experiments have been done to clarify the mech- anism of formation of recrystallization texture but no fully successful explanation has been proposed. The texture consists of oriented grains which nucleate at many sites of the deformed matrix and grow at the expense of the matrix during annealing. The current theories on the formation of recrystallization texture are based on the following two extreme hypotheses: 1) the oriented nucleation theory by Burgers et al.;1, 2 2) the oriented growth theory by Beck et al.3-5

Jan 1, 1968

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.&apos; The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968