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By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By G. F. Bolling

Single crystals of each metal were deformed at 77°K and heated at constant rates, variously in the range 0.125" to 4o°Kper min from 77" to -390oK, while being monitored in an X-ray diffractometer. Changes in diffraction-peak heights and line breadths were used to ascertain the temperature ranges of recrystalliza-tion. The results were subjected to the analysis of nicholas' in order to obtain the rate-controlling activation energies,Q. In this analysis no recourse to a separate and distinct nucleation stage is required and the results of studying recrystallization proved consistent with the hypothesis of a constant number of nuclei or equivalent hypotheses. The values Pb = 5.5 ± 0.5 keal per mole Zn ~ 7.5 Sn - 5 Bi - 9. 5 correspond for lead, zinc, and tin to activation energies obtained elsewhere for grain boundary migration, and for bismuth and lead to previous studies of re-crystallization by Barrett.6 This correlation allows the conclusions that interference from recovery was minimal and that the observed recrystallization rates in these pure metals are effectively governed by grain boundary migration. Good agreement was not found between the results of this kind of study in zone-refined aluminum and previous work; and supplementary isothermral experiments involving hardness tests and metallography did not resolve the discrepancy. Nevertheless, at least a range,Q = 11.5 ± 2 keal per mole, can be assigned to the activation energy for boundary migration in aluminum. An experimental study of one aspect of the recrystallization process is presented here for four metals of different crystal structure. The metals chosen for study were all zone-refined to reduce impurity effects, but the attendant high purity presented a difficulty. For any reasonably high driving force a "re-crystallization temperature", TR, is in the range of 0.25 T,, where T, is the absolute melting point, and study was therefore restricted to lower temperatures. An X-ray technique under constant heating-rate conditions adequate above 90°K was devised for the study; in consequence, a newer type of analysis following Nicholas1 had to be used to obtain quantitative information about activation energies. The standard methods of studying recrystallization have involved the comparable analyses of Johnson and Mehl2 and Avrami3 which are reviewed by Burke and Turnbull.* The general analysis4 which is applied only to isothermal studies using any of various investigative techniques states:

Jan 1, 1968

By Henry E. Colton

NeaR the town of Christiansburg, Va., occurs a singular feature in topographical as well as geological structure, which may be said to have an important bearing on a large area to the southwest. The great water-shed ridge, which divides the waters flowing into the St. Lawrence from those flowing into the Atlantic ocean, coming southwestward, forms all of what was the boundary of Maine as agreed upon by the treaty of 1783, and a part of the present boundary, all of the northern New Hampshire boundary, and entering Vermont, continues south of Lake George. Passing irregularly through New York, it enters Pennsylvania, and there bifurcating, sends one prong to the west as a divide between the waters of the lakes and the Ohio, while the other becomes the steady, regular ridge which gave it the name of Alleghany, and thus passes on southwestward through Virginia. At no point has it ever been the geological divide. Its course, commencing in the Archean rocks, has passed through nearly every series of formation, and comes into Virginia in the Carboniferous strata. The geological divide—the line between the fossiliferous and the non-fossiliferous rocks—lies, in Canada, to the west of it, but from New York south into Virginia is far to the east. Reference to Dr. Hitchcock'k map will show this. But at the locality noted these positions are changed; the water-divide becomes the eastern chain, and the geological divide is the western, returning, it may be said, to the positions occupied in the region where they originated. These relations are shown on the large map accompanying the present paper. For several miles, the track of the Norfolk and Western Railroad

Jan 1, 1888

By J. C. Jaeger, G. A. Wiebols, N. G. W. Cook

It is usual practice in engineering to design a stable structure by ensuring that the stresses in the elements of the structure are always less than their strength, which may be defined as the yield stress, the ultimate stress, or the fatigue stress, according to the type of the load. Such restrictive design is not practical in the design of underground excavations since the rock surrounding such structures is usually failed, but only occasionally does this give rise to instability of the structure. Thus, while the usual criterion for the design of a stable structure is certainly sufficient, it is not necessary for underground excavations. A proper understanding of the conditions necessary for stability is vital to the useful application of rock mechanics knowledge to the design of underground structures. Most tests on the properties and strength of brittle rocks are disrupted at or near maximum load by the rapid release into the specimen of energy stored in the resilience of the testing machine. This is in contrast with a phenomenon, which may be observed frequently, where the rock immediately surrounding an excavation is both failed and subject to stress. By postulating a complete stress-strain curve for rock, it can be shown that failure is unstable or stable, depending upon whether the stress-strain curve of the rock lies inside or outside the stress-strain characteristics of the applied stress. Stability is, therefore, a function of the stiffness of the system applying the stress relative to that of the failing rock. Many workers have established that the strength of rock specimens under a lateral hydrostatic confining stress varies linearly with confining stress, in a way which may be expressed by the equation CT=Co+K[o]3

Jan 1, 1972

THE Johnson award for 1926 was given to T. L. Joseph for his experimental work on blast-furnace operation. When the Bureau of Mines undertook its experimental blast-furnace investigation in 1919, a number of operators and metallurgists were doubtful as to the practicability of small-scale tests. Several pre-vious attempts, outside the Bureau, to operate small furnaces had been unsuccessful. However, pig iron was produced in three and four-ton furnaces during the first half of the nineteenth century. The operation of a small furnace did not therefore seem an impossible task. This point of view, together with a realization of the importance of problems connected with the pro-duction of pig iron, prompted the Bureau to undertake this work. Such problems as the feasibility of using charcoal briquets as a fuel, the application of oxygen enriched blast, and the use of new ores and raw ma-terials, in general, can be investigated only at consider-able cost on full sized furnaces, while with an experimental furnace they can be conducted at a com-paratively ;small, cost. The results of small-scale tests are sufficient to determine whether the problem. War-rants the expenditure required for a trial on a com-mercial scale. The accompanying photographs and chart show the various stages of the experimental furnace development. Some idea of the size and shape of furnaces which were tested can be had from the development chart. In oper-ating furnaces A to F, a series of changes were made to increase hearth temperature. Perhaps the most im-portant change was the position of the tuyeres with respect to the bottom of the hearth. The height of the tuyeres above the hearth was gradually increased and the hearth diameter decreased. It was shown by this series of furnaces that metal and slag are the chief source of heat supply to the crucible. For this reason there is a minimum rate at which these materials can be brought into the hearth of a small furnace if it is to function properly. The rate of slag "and metal fall are determined by the burden on the furnace and the rate of blowing. Due to lack of funds necessary to provide ample blowing equipment, hot blast stoves, essential mechani-cal features, and to meet operating expenses, it. was necessary to work with much smaller furnaces, such as G to K shown in the chart. The particular object of these tests was to study the extent to which reactions could be speeded up by decreasing the size of the stock. One decided change, noticed at the beginning of this series of tests, was the effect which coke size had on the production of a strongly reducing gas. Furnace G, 22 in. high, operating on coke crushed to pass 10 mesh, made a gas richer in carbon monoxide than did fur-naces A to F, operating on run-of-the-oven coke.

Jan 3, 1927

By ALEC CROWELL

Mississippi has had oil production for only the past six years and natural gas production of minor magnitude since' 1926. The search for oil and gas commenced in 1903 and 1496 wells had been drilled in search of oil and gas up to Jan. 1, 1946. As the year 1945 ended, 659 wells were producing oil and gas from 23 separate reservoirs. The production for the year was 8,353,719,000 standard cubic feet of natural gas measured on a pressure base of 15.025 lb. per sq. in. abs., 15.316,009 bbl. of oil¬field water and 19,093,766 bbl. of crude oil and condensate. Production for the year 1944 was 2,636,067,000 standard cubic feet of gas, 14,979,793 bbl. of salt water and 16,420,346 bbl. of crude oil and condensate.

Jan 1, 1946

By Rex O. McLellan

The formation of a monovacancy in a metal is simulated in an elastic model by the displacement of the surface of a small spherical cavity in a large elastic continuum. The application of linear elasticity to this distortion results in a well- known formula for the energy and an expression for the concomitant entropy change due both to the shear strain in the continuum and also to the dilation of the solid resulting from the boundary conditions at the surface of the solid. Elastic data (the sliear modulus and its temperature coelficient) are used to calculate the entropy and energy of formation for many metals. Despite the simplicity of the assumptions involved, the agreement between the calculated entropies and energies and experimental values is remarkably good. In recent years there has been a large increase in measurements of the absolute concentration of mono-vacancies in metals as a function of temperature. Hence new data for both the energy and the noncon-figurational entropy of formation of monovacancies has become available. Recent measurements&apos; of the anomalous (non-Arrhenius) self-diffusion in many bcc metals has also focused interest on the prediction of the thermodynamic parameters of mono- and multi-vacancies in those metals for which no data are available. Damask and Dienes&apos; have discussed the various theoretical calculations of the energy of formation EL, of a monovacancy. These include simple models involving the breaking of atomic bonds on moving atoms from the interior of a crystal to the surface, models combining elastic calculations with surface-energy terms and detailed quantum mechanical calculations. The simler models give the correct order of magnitude of &, but tend to overestimate it by a factor of about two. The quantum mechanical calculations4"7 have been carried out for the noble and alkali metals with generally reasonably good agreement with the available Ef data. The calculation of entropy of formation Sfv14 lnvolves a fundamental calculation of the perturbation of the phonon spectrum caused by the creation of a vacancy. Huntington, Shirn. and wajda8 have given an approximate evaluation of sJV by considering an Einstein model for the localized vibrations in the immediate neighborhood of the defect and then using elastic theory to calculate the entropy associated with the shear stress field in the distorted crystal (as originally proposed by Zenerg). They also included a term due to the dilation of the crystal. They obtained a value of 1.47k for copper, in good agreement with the experimental value (1.50k). However, Nardelli and Tetta- manzi1° have recently shown that neglecting the coupling between atoms (Einstein Model) may lead to a serious error so the agreement may be somewhat fortuitous. In this work simple linear elastic theory is used to calculate the entropy and energy of formation of mono-vacancies. Despite the simplicity of some of the assumptions involved, the agreement with the available experimental data is remarkable. However. the reasonable degree of success in the application of linear elastic calculations to the excess entropy of a solute atom in a dilute solid solution1&apos; indicates that the application of elastic theory to vacancies. where the interaction of different atomic species is not involved, may not be inappropriate. THE ELASTIC MODEL The metal is assumed to be a spherical elastic continuum. A small spherical cavity of volume V = 4i;v:&apos;/3 is cut from the center. removed. and dissolved rever-sibly in the bulk of the material. TO a good approximation no net atomic bonds are broken and the material does not undergo a volume change although the externally measured volume of the body would increase by V. The radius of the sphere of metal is much larger than r Next a negative pressure is applied to the cavity causing its surface to be displaced inward by an amount simulating the relaxation of the lattice around a monovacancy. In this model the energy and entropy accompanying the distortion are taken as 4, and <. As a first approximation the equation of state for the solid is taken as: r = ro(i + *~D LiJ where K is the bulk modulus. P the hydrostatic pressure. Vo the volume of the material at 0°K and zero pressure. and d+/dT = 30. where 0 is the linear thermal expansion coefficient. The variation of entropy with hydrostatic pressure is given by the Maxwell equation: These equations give the entropy change resulting from increasing the hydrostatic pressure from 0 to P as: and since • we have: This is the entropy arising from the dilation resulting

Jan 1, 1970

By M. J. Mullikin, J. B. Conway

Several different equation forms were studied to determine the extent to which each particular equation type yielded an accurate representation of a given set of first-stage creep data. Specially developed least-squares computer programs were employed to obtain unique solutions for the creep-equation constants. In studies of creep data for lead at 14.5"C, nickel at 70OCC, and arc-cast tungsten at 2400°C consistently good representations were afforded by a third-degvee polynomial in t113. Other effective correlations were obtained with the Andrade, Cottrell-Aytekin, and de Lacombe equations along with a third-degree polynomial in t112. A newly proposed creep equation involving a hyperbolic-sine term in t1&apos;3 was also found to yield very satisfactory results. This appears to be the first use of such a functional relationship in the analysis of transient creep behavior. In general, the deformation behavior of a material subjected to a tensile load is described in a strain-time plot. Experiments have shown that, following the instantaneous elongation which results on loading, the instantaneous slope (i.e., creep rate) of the strain-time curve decreases gradually with time and approaches what appears to be a constant value. Equations, therefore, which are proposed to provide an analytical representation of such first-stage or transient creep behavior must be consistent with these observations. In other words, at time zero, these equations must yield a finite deformation value corresponding to the elongation on loading. Furthermore, the first derivative of these equations must exhibit a fairly high although finite value at time zero, and then values which decrease with time. It is also preferable, in general, that the derivative eventually assume a constant value at high time values. Although many studies of first-stage creep behavior have been made and numerous equation forms have been proposed for expressing this type of deformation behavior, it is still not possible to state with any assurance which functional relationship will be adequate for a given set of measurements. Parabolic relationships have been employed most extensively although logarithmic expressions have been shown to be applicable in some instances. Combined forms1 have been studied in considerable detail and have on occasion been found to be very effective. One such expression is that of iXndradea and involves a modified parabolic expression: where 1 is the instantaneous length, lo is the length immediately following load application, t is the time, and p and k are constants. Another combined form has been proposed by weaver3 as follows: where E is the instantaneous strain, is is the linear creep rate, t is the time, and a and b are constants.

Jan 1, 1967

By J. P. Zannaras

Referring to the article by R. J. Charles and P. L. de Bruyn, let us assume that W = weight of glass bar; P = weight of hammer; e = total deformation; K = unit of deformation; K = potential stress energy; E = modulus of elasticity; L = length of the bar; 7 = coefficient of inertia; h = height, ft; V = velocity, fps; and a = cross section area. The portion of kinetic energy which is effective in producing stress energy in a fixed bar struck horizontally is given by the formula" 1 + 1/3 W/P K =1+1/3w/p/(1+1/2w/p)2 P.V2/2g = Ph where 1 + 1/3 W/P ? (1 + 3W/P/(1=1/2w/p)2 [8] Putting e e = W/P =------------ From the above equation it can be seen that the maximum transfer of kinetic energy to stress energy is when e = 0 or W/P = 0 which indicates that the weight of the hammer must be very large as compared with the weight of the impacted rod. Eq. 8 diametrically opposes the conclusions reached by the authors of this article. In fact, if their suggestions were followed to the extreme when e = co when P = 0, there would be no transfer of kinetic energy to stress energy at all, as 7, becomes zero. Eq. 8 presumes that the velocity with which the stress is propagated through the bar is infinite, whereas the authors claim that the compression waves reflected are reaching the struck end of the bar prior to the complete transfer of the kinetic energy to cause such modification of the conditions there as to make them reach the reverse conclusions demonstrated by the above formula. That such interference exists is unquestionably demonstrated by the authors and others. However, if my observations are correct, such interference for this specific experiment and also for practical comminu- tion is insignificant, and the conclusions of the authors are in error and must be reversed to comply with Eq. 8. Eq. 5, w. = AE 2/2, given by the authors on page 51, is derived from the following equation (Eq. 9): K = 1/2Pe, where P = Sa, S = ?E, e = EL, and L = 1. The above formula, Eq. 9, cannot be applied in this case. This formula is applicable for static loads where the load increases from zero up to its final value, P, in such a way that the deformation at different instants is proportional to the loads acting at those instants and actually represents the area of a right triangle in the strain load diagram of base e and height P. The typical photographs shown in Figs. 3 and 4 represent the familiar strain load diagrams, and since the line of the wave marks the existence and intensity of the strain with the unquestionable conclusion that such strain has been caused by the action of a load acting continuously all along the wave until it reached the horizontal axis, the work stored at this point is represented by the area under the wave line and the horizontal axis and not by the area of the fictitious triangle given by the authors. Then if this is correct, even visual estimation of these areas at gage stations given in the typical photographs of Figs. 3 and 4 suffice to contradict the authors&apos; calculation given in Figs. 6a and 6b and Figs. 7a and 7b. The typical photographs presented by Charles and de Bruyn show a considerable variation of the intensity of the strain at different stations but very small variation of areas which actually represent the stress energy at the corresponding stations. And, apparently, by squaring the small quantities, the authors magnified their error tenfold. J. M. Frankland&apos;s paperV iscusses the relative strain intensity and not the total energy for different types of impact loading. He states in his paper, "The reader is explicitly warned not to confuse the results in this report with those obtained when the load is applied by a blow as from a hammer. In this case the peak load rises to very large but mostly unknown values. The accompanying large deflections and stresses are the result of high values of P, not of the dynamic load factor n. According to Frankland "the dynamic load factor" is the numerical maximum of the response factor. It therefore appears that the authors followed the same procedure in obtaining the relative strain energy ab-

Jan 1, 1957

By Harry C. Gatos, Frank J. Bachner

It was shown through high-pressure experiments that tin loss by volatilizatim is necessary for the degrada-tion of the superconducting transition temperature of Nb,Sn associated with high-temperature annealing. Crystallochemical analysis of the degraded Nb3Sn showed that it constitutes a new phase with ordered niobium-site vacancies, created by the migration of niobium atoms to vaccnt tin sites. This new phase was found to form when 4 pct Nb-site vacancies were present. It has a transition temperature of 6&apos;K and a lattice parameter of 5.283A. A similar degradation effect was observed in Nb,Al. Its superconducting transition temperature dropped from 16.5" to 8" K following a high-temperature annealing. The superconducting temperature degradation in these 0-tungsten structure compounds is attributed to the disruption of the interchain d bonding by the periodic interruption of the niobium atom chains. By annealing the degraded Nb, Sn at 1000 C in nitrogen its normal superconducting behavior is restored most likely due to the incorporation of nitrogen atoms causing the elimination of the ordered vacancies. HANAK et al.&apos; have observed low superconducting transition-temperature values (T, - 9"K) in some NbsSn samples deposited from the vapor phase. They attributed such low T, values to disorder in the 0-tung-sten structure. Much lower T values (down to 5.6"K) were reported by Reed et al.zC for NbsSn samples annealed at high temperatures. These authors also attributed this degradation effect to disorder (random occupation of the A and B sites by niobium and tin) but pointed out that such disorder could be brought about (by high-temperature treatment) only in samples containing niobium in excess of the stoichiometric composition NbsSn. Both groups reported that the normal superconductivity behavior could be rever-sibly restored by appropriate heat treatment. Courtney et al., also found that degradation in NbsSn requires excess niobium brought about by the loss of tin during the treatment. However, these investigators proposed that the degradation is due to niobium-site vacancies resulting from the migration of the niobium atoms to the vacated tin atom sites. They did not consider the reversibility of the effect. The present study attempts to establish the nature of the above degradation phenomenon. EXPERIMENTAL PROCEDURES All compounds prepared for this investigation were made from the powders or filings of the elements which were intimately mixed, cold-pressed into a cylindrical pellet at approximately 50,000 lb per sq in., and then submitted to the desired heat treatment. The samples annealed under high pressure were placed in a MgO sample container which was mounted in a pyrophyllite tetrahedron designed for a tetra-hedral-anvil press. Details of the experimental arrangement are given elsewhere. This setup allowed heating at 1800°C or above under pressures in excess of 30kbars for 3 hr. The samples annealed in a vacuum were prepared in a high-temperature vacuum furnace which could reach temperatures up to 2400°C under a pressure of 2 x lo-&apos; Torr. For annealing in a reactive atmosphere, a quartz tube was placed in a clamshell furnace and the desired gas ambient passed through the tube. Lattice parameters were determined using a Debye-Scherer 114.6-mm camera. Cohen&apos;s method, programmed for the IBM 7094 computer, was used to calculate the lattice parameter from the measured d spacings. X-ray integrated intensity measurements were made on several samples. These samples were ground to -400 mesh and the powder mixed with a solution of collodion in amyl acetate. The mixture was poured into a depression milled in a bakelite disc. When the mixture dried, the surface of the disc was ground flat leaving a diffraction surface defined by the face of the disc. The disc was mounted in a Philips rotating specimen holder which allowed the rotation of the sample in the plane of the diffraction surface and the integrated intensity measured using a scintillation counter and a pulse-height analysis sys-tem. The superconducting transition temperatures were determined by means of self-inductance techniques.&apos; EXPERIMENTAL RESULTS AND DISCUSSION The Role of Tin Loss in the Degradation of Super-conductivity. The loss of tin during high-temperature annealing can be effectively suppressed by annealing under high hydrostatic pressures. Accordingly, a series of experiments were performed under pressures of approximately 30kbars. This pressure was the minimum under which high-temperature experiments could be safely performed in the particular pressure apparatus employed. Experiments were also designed to test high-pressure effects on the superconductivity behavior of NbJSn. The results of the high-pressure annealing experi-ments are summarized in Table I. All samples were prepared as described earlier. They were reacted and homogenized at 1000°C for 24 hr under argon at-

Jan 1, 1967

By M. D. Banus, M. B. Bever, A. K. Jena

The heals of formation at 78", 195, and 273°K of the ternary compound h3SbTe2 based on the elements and based on the binary compounds In Sb and [inTe have been measured. The heats of formation at these temperatlcres of the binary compounds In Sb and In Te based on the elements have also been determined. Heal contents and free energies of the three compounds have been calculated from 0° lo 80I)°K. The free energies of joyrrzalion, heats of formations, and entropies of formation at 298°K have also been calculated. The results shown that the tertnary compound is metastable with vespecl to InSh and ln Te below 696 °K. bul is slable above that temperature. The weaker bonding of results in a positice entropy of formation which with incrensirzg temperature makes increasing negative conlvihtclions to the free energy and above 696°K renders the compound slable. THE ternary compound In3SbTez occurring in the quasi-binary system In Sb- In Te&apos; forms on cooling at 829°K by a peritectic reaction.&apos; Observations at 673" and 573 K have shown that this ternary compound decomposes slowly into the binary compounds InSb and1n~e.l&apos;&apos; It has not been possible to analyze the metastable behavior of the ternary compound because up to the present time data on its thermodynamic properties have been lacking. Some information on the binary compounds, however, is available. The heat of formation of InTe at 273°K and its free energy at 673°K are kn~wn.~&apos;~ The heats of formation of InSb at 78", 273&apos;, 298", and 723°K have been measured5-&apos; and its heat capacity between approximately 12" and 300"Kg9l0 is also known. In the investigation reported here the heats of formation at 78% 195% and 273°K of the ternary compound In3SbTez have been measured. The heats of formation of the binary compounds InSb and InTe at these temperatures have been obtained by combining new calorimetric results with previously published data. The heat contents and free energies of the three compounds at various temperatures from 0" to 800°K have been calculated. Against the background of this information, the metastability of the ternary compound will be discussed. 1) EXPERIMENTAL 1.l) Preparation of Specimens. The materials used consisted of the elements indium, antimony, and tellurium, the binary compounds InSb and InTe, and the ternary compound In3SbTez. The elements, obtained from American Smelting and Refining Co., had a nominal purity of 99.999+ pct. The compound InSb was Cominco semiconductor grade; the compound InTe was prepared from the elements by melting under a vacuum of 10-h m Hg followed by slow cooling. Three batches of specimens of the compound In3SbTez were used. One batch was prepared by melting appropriate amounts of the elements in an evacuated and sealed Vycor tube. The melt was held at approximately 100°K above the liquidus for about 8 hr, shaken repeatedly, and quenched into a mixture of ice and water. The specimen was annealed in vacuum at 760°K for 4 weeks. In preparing a second batch, a mixture of the component elements was melted and quenched in water. The resulting ingot was powdered. The powder was pressed into pellets, which were annealed in vacuum at 748" to 773°K for 4 weeks. A third batch was prepared in the same manner as the second, except that the starting materials were InSb and InTe rather than the elements. Metallographic examination of samples of the three batches and X-ray diffraction examination of a sample of the second batch did not reveal evidence of microsegregation or a second phase. The results obtained with the three batches showed no systematic differences. 1.2) Calorimetry. The calorimetric method has been described in detail." Samples of the compound In3SbTez, mechanical mixtures of InSb and InTe in the proportion of 1:2, and mechanical mixtures of indium, antimony, and tellurium in the proportion of 3:1:2 were added to a bismuth-rich bath at 623°K in a metal-solution calorimeter. These additions were made from 78°K (liquid nitrogen), 195°K (dry ice and acetone), and 273°K (ice and water). The heat effects of the additions were measured. The difference in the heat effects of the additions of a compound and the additions of the mixtures of its constituents, adjusted for differences in the concentration of the bath, is the heat of formation of the compound. In the concentration range not exceeding 1.5 at. pct solute, the heat effect of the additions was a linear function of concentration. The heat of formation refers to the temperature from which the additions were made, namely, 78", 195", or 273°K. Several calibrating additions were made in each calorimetric run. The calculated heat capacity of the calorimeter and hence the calculated heat effects of the additions of samples depend upon the values adopted for the heat contents of the calibrating substance. In this investigation bismuth at 273°K was used and a value of 4.96 kcal per g-atom was taken for (HGZ3"k . 2) RESULTS AND DISCUSSION 2.l) Heats of Formation. The heats of formation of the ternary compound In~SbTez from the component elements indium, antimony, and tellurium and from

Jan 1, 1968

By Donald C. Barton

The theory of gravitation is based on Newton&apos;s law that any two bodies exert a mutual attraction which is proportional to the product of their masses and inversely proportional to the square of the distance between them; i. e., A = KMRm2 (1) where K is a constant, M and m are the respective masses of the two bodies, and R the distance between them. In the earth&apos;s gravitational system, the earth is one of the bodies; the other may be any body within or without the earth. In theoretical discussions and calculations,in regard to gravity, that other body usually is taken as a unit of mass: in the C:. C:. S. system, a body of one gram in mass. Gravity and Level Surfaces Gravity is defined in geophysics as the force of attraction exerted by the earth, towards itself, on a body of unit mass. The intensity of gravity is usually expressed in dynes of force or in centimeters of acceleration In geophysical work in America, most commonly it is expressed in dynes (per gram) with the "per gram" understood and not directly expressed. In geophysical work in Europe, most commonly it is expressed in centimeters per second per second (cm. /sec.2) and less commonly lrierely as centimeter-gram-second units (c. g. s). At sea level, the intensity of gravity amounts very nearly to 980 dynes. The vertical is the direction along which the attraction of gravity is exerted at any point. In most cases, it is very nearly, but not quite, perpendicular to the earth&apos;s surface. The path that would be taken by a body falling freely through space toward the earth is vertical at each point and may be spoken of also as (&apos;the vertical," or as the line of the vertical, or as a line of force of gravity. At the earth&apos;s surface it comrrlonly is very nearly, but not quite, a straight line.

Jan 1, 1929

By G. S. Ansell, J. Weertman

The creep behavior of an aluminum alloy hardened with a finely dispersed phase of aluminum oxide was investigated. The as-extruded alloy shows an approximate steady-state creep in which the creed rate depends exponentially on the applied stress. The activation energy of creeb is abbroximately 150,000 cal per mole. The recrystallized alloy shows no steady-state creep. ONE method of improving the creep resistance of a metal is to introduce a finely dispersed second phase into the metal matrix. The improvement of the creep resistance has been qualitatively explained by assuming that the dispersed second-phase particles act as obstacles to dislocation motion. If the main effect of second-phase particles is simply to hinder dislocation motion then it is possible to derive a high-temperature creep equation for a dispersion-hardened alloy in a straightforward manner. In the Appendix of this paper such an equation is derived from a creep model which works very well for pure metals. Recently, F. V. Lenel has fabricated, for the first time, powder extrusions of aluminum-aluminum oxide in a large-grained recrystallized form. This alloy, designated as MD 2100, consists of a fine dispersion of aluminum oxide plates in a matrix of commercial purity aluminum. A considerable amount of investigation has been carried out concerning the microstructure and physical properties of this alloy.&apos; ) The aluminum oxide is present in the form of flakes 130A units thick and 0.3 u on edge. They are dispersed in the aluminum matrix with an average spacing of approximately 0.5 jx. The spacing varies in the range of 0.05 to 1.5 µ. The alloy structure is extremely stable at high temperatures. For this reason the alloy offers a unique opportunity for a fundamental study of creep of a very finely dispersed two-phase alloy. Lenel supplied specimens in both the unrecrystallized and recrystallized condition. This paper reports high-temperature creep experiments carried out on these specimens. The results obtained were rather unexpected. No steady-state creep was observed in the recrys-tallized material. In fact, after some transient creep which takes place upon loading, the creep rate is essentially zero ( < 10-8per min). If the second-phase particles acted solely as obstacles to the motion of dislocations, measurable steady-state creep would be expected. Since none is observed it appears that the main effect of the fine dispersion in the recrystallized material is to inactivate the dislocation sources themselves, rather than hinder the motion of dislocation loops created at these sources. EXPERIMENTAL DETAILS Specimens were tested in wire form, 0.087 in. in diam for the as-extruded alloy, and 0.035 in. in diam for the recrystallized alloy. These samples were held in friction-type wire grips; a gage length of 2.5 cm was used for all the creep tests. The specimens were held at 600°C in the test apparatus for at least 15 hr prior to each test. The tests were run under the condition of constant loading and, since the creep strains were small, can be considered as constant stress tests. The temperature of testing was held constant within 3°C. Elongations were measured with an optical cathetometer which was capable of measuring strains as smaIl as 0.00012. This allowed the measurement of strain rates as low as l0-8&apos;per rnin. In addition to the creep tests optical micrographs were made in order to determine both the grain size and microstructure of these materials. RESULTS Fig. 1 shows a few typical creep curves obtained from the as-extruded material. The elongations were somewhat erratic, but each curve shows a region of quasi-steady-state creep from which an approximate steady-state creep rate can be obtained. In general the higher the stress at a given temperature, the greater the total elongation before fracture. The lower the applied stress, the longer is the region where the creep rate is almost constant. Summary data from the creep tests of the as-extruded material are listed in Table I. The steady-state creep data of the as-extruded material for a range of stresses at a constant temperature follow a creep equation of the type creep rate = K&apos; = A exp (&) [11 where A and B are constants, k is Boltzmann&apos;s constant, T is the absolute temperature, and a the stress. The standard error of estimate of the data received is less than one order of magnitude. As shown in Fig. 2, if one compensates the creep-rate data for the effect of temperature over the range of test temperature, the steady-state creep data roughly follow a creep equation of the type Temperature compensated creep rate = K* = A exp

Jan 1, 1960

By George W. Neumann

The mines and concentrator of Brunswick Mining and Smelting Corporation are located in the northern part of the province of New Brunswick, approximately 20 miles distant from the City of Bathurst. Discovery of the No. 6 orebody by diamond drilling in 1952 was followed by the finding in March 1953, of the larger and higher- grade No. 12 orebody, approximately six miles to the north of the No. 6 deposit. Original development was financed by St. Joseph Lead Co., and included a small open-pit operation with a 10C ton per day pilot mill at No. 6 orebody, shaft sinking and underground development at No. 1; orebody, and an extensive program of laboratory and pilot plant metallurgical research on No. 12 ore. These operations were suspended in May 1958, and remained in standby condition until June 1961, when the equity of St. Joseph Lead Co. was purchased by a group headed by M. J. Boylen, K. C. Irving, Maritime Mining Corporation, and the Patino Corporation. Construction of a mine plant and concentrator at the No. 12 mine commenced in October 1962 and the concentrator was placed in operation in March, 1961b. Preparation of the open pit mine for production, construction of the No. 6 Concentrator to produce bulk Pb-Zn-Cu-Ag concentrate from No. 6 ore, and construction of an Imperial Smelting Process smelter at Belledune were started in 1964 and placed in operation in September 1966.

Jan 1, 1970

By William E. Ford, Edward Salisbury Dana

34. Axial Ratio, Axial Plane. - The crystallographic axes have been defined (Art. 22) as certain lines, usually determined by the symmetry, which are used in the description of the faces of crystals, and in the determination of their position and angular inclination. . With these objects in view, certain lengths of these axes are assumed as units to which the occurring faces are referred.

Jan 1, 1922

By N. A. Gokcen

THE data of Chaudron,1 Tonosaki,2 and Collins³ on the thermodynamic properties of MOO, disagree widely. These authors, by using essentially similar methods, studied the following reaction: 1/2MoO2(s) + H2(g) == i/2Mo(s) + Ph,o H2O(g),K = —----- [1] Ph2 Tonosaki used a vacuum system consisting of a furnace containing MOO, and a water saturator whose temperature was kept at 25 °C with a thermostat. After repeated evacuation, hydrogen was admitted slowly into the system. The experiments were based upon the fact that at a constant furnace temperature and constant partial pressure of water, the total pressure of gas mixture over MOO? + Mo is constant. Any attempt to vary the pressure by external forces would vary only the amounts of MoO2, and Mo, after which the pressure should return to the equilibrium value in accordance with the equilibrium constant of reaction 1. The actual value of K was determined from the total equilibrium pressure (sum of Ph2o + Ph2) at each temperature. The total pressure of gas was varied within the range of 80.2 to 125.4 mm Hg, within a temperature range of 645" to 823 °C. The results were summarized as log K = 0.9413 — 1444.6/T for reaction 1. The ratio of H2O/H2 was considered to be uniform in spite of the presence of a thermal gradient across the static gas phase. It was shown by Rosenqvist and Cox,&apos; however, that in somewhat similar circumstances the error resulting from thermal diffusion may be large. Collins³ improved Tonosaki&apos;s method by attempting to avoid thermal diffusion errors. His equilibrium data were obtained at 700°, 800°, and 900° C, and the result for reaction 1 was expressed as log K = 1.258 — 1822/T. The purpose of this investigation was to study reaction 1, avoiding the thermal diffusion errors, and to obtain equilibrium data in a considerably wide temperature range for the reliable extrapolation of the resulting thermodynamic functions. Experimental Procedure The diagram of the apparatus is shown in Fig. 1. Tank hydrogen was passed through a tube containing platinized asbestos at 425 °C in order to convert a trace of oxygen into water vapor. The flow rate was carefully controlled with a capillary-type flow-meter B and a bubbling column D. The gas was then presaturated sufficiently at P and led into a condenser system immersed in a thermostat, controlled to within ±0.002C. The temperature of the thermostat was measured with a thermometer calibrated against a certified standard. The temperature of P was adjusted to avoid the condensation of unduly large amounts of water as judged from the rate of flow out of the capillary tube M. Argon was purified by passing it through magnesium chips kept at 630°C. After passing through the flowmeter B&apos;, it was mixed with moist hydrogen emerging from the thermostat. The resulting gas mixture was then led into the hot zone of the furnace through the heated glass tubing and the silica tube S, thus insuring the same ratio of PII2o/Ph2 from the condenser to the reaction chamber, thus avoiding thermal diffusion. The entire gas system was of all-glass construction, except at the magnesium train. The furnace comprised a glazed alumina tube over which a 15-in. platinum coil was wound. The lower end of the alumina tube was tightly closed with a brass bottom and a silicone rubber gasket, and the upper end with two glass disks, each with a hole of 1/16 in. in diameter, through which the gas mixture escaped into the atmosphere. A back-up coil of kanthal wire facilitated the temperature control of the furnace. A coil of annealed molybdenum strip of 99.99 pct purity, 0.005 in. thick and 0.050 in. wide, and weighing 17 g was hung in the furnace with a 0.010-in. platinum wire attached to one end of a sensitive analytical balance. The temperature of the furnace was measured with a Pt-Pt-10 pct Rh thermocouple checked against a standard. The experimental procedure consisted of heating the gas purification trains, adjusting the gas flow rates, attaining a constant thermostatic temperature, flushing the entire system for 2 hr while heating the furnace to well above the expected equilibrium temperature and then cooling it at a rate of 0.3°C per min during which time the change in the weight of molybdenum was observed on the balance. For a given thermostatic temperature, i.e., a constant Prr,o/Px,, molybdenum oxidized upon cooling slightly below the equilibrium temperature. The procedure was then repeated by heating the furnace and thus reaching a temperature slightly above the equilibrium value. The average of the two temperatures, differing by 2" to 3"C, was considered to be the true equilibrium temperature. In order to determine the stoichiometric composition of the oxide phase present in this investigation,

Jan 1, 1954

By J. P. Morris

PREVIOUS investigations1,2 have shown that alloying elements in liquid iron influence the thermodynamic activity of sulphur and thereby affect the partition of sulphur between metal and slag in the desulphurization process. For example, the greater efficiency of desulphurization in the blast furnace as compared to the open hearth can be attributed in part to a higher level of sulphur activity in blast-furnace metal due to the higher concentration of carbon and silicon. In the present investigation, a short study was made of the influence of manganese on the activity of sulphur in liquid iron and iron-carbon alloys. In contrast to carbon and silicon, manganese was found to decrease the activity coefficient of sulphur; and in iron-carbon alloys it counteracts to some extent the influence of carbon. However, at manganese concentrations normally present in the blast furnace or open hearth, the effect of manganese is small. Since manganese sulphide has a limited solubility in iron, manganese can act, under certain conditions as a desulphurizing agent. Considerable data on the manganese-sulphur product in carbon-saturated melts were obtained in the investigation and have been included in this report. The experimental procedure was the same as that used in the earlier investigations on the effect of silicon&apos; and carbon&apos; on sulphur activity. Briefly, the method was as follows: The molten alloy, contained in a graphite or sintered alumina crucible, was brought to equilibrium at a constant temperature with a mixture of hydrogen and hydrogen sulphide of constant composition by bubbling the gas through the metal. Samples of&apos; the melt were taken for analysis at regular intervals by suction through a 2 to 3 mm bore silica tube dipped into the metal. The experiments were run in a graphite spiral resistance furnace with melts weighing 50 to 60 g. The gas bubbling tubes were made of sintered alumina and were 5/16 in. OD, 1/16 in. ID, and 24 in. long. Equilibrium was assumed to have been attained when the sulphur content of the liquid metal reached a constant value. During an experiment there was a rapid loss of manganese from the melt by volatilization. To offset this loss, small additions of manganese were made periodically. The rate of manganese addition needed to maintain a constant manganese concentration was determined in preliminary tests. In all of the experiments, deposits of manganese sulphide formed above the melts in a cooler region of the furnace. Apparently, these deposits resulted from a reaction between manganese vapor and hydrogen sulphide in the gas. To prove that manganese sulphide did not volatilize from the melts to a measurable extent, an experiment was run in which helium was bubbled through liquid iron containing both manganese and sulphur. Although manganese volatilized rapidly in this test, there was no appreciable loss of sulphur. Volatilization of manganese sulphide from a melt would have led to an apparent equilibrium condition in which the sulphur content of the metal was lower than the true equilibrium value. The experimental results are shown in the first seven columns of Table I. The data in the last two columns were obtained from the previous work on the effect of carbon&apos; and show what the results would have been in the absence of manganese but with temperature, gas composition, and carbon content of the metal remaining the same. Comparison of the last four columns show that, in the presence of manganese, the sulphur content of the metal increased at equilibrium and the activity coefficient of sulphur decreased. However, the results show that, for manganese concentrations below 3 pct, the effect of manganese is small. The values for activity coefficient of sulphur given in Table I were calculated from the following relations: S (in liquid metal) + H2 (gas) = H2S (gas) [l] K ph2s/?s X %S X phg = 0.00251 [2] where K is the equilibrium constant for the reaction, PH2S and ph2 are the partial pressures of hydrogen sulphide and hydrogen, respectively, and ?s is the activity coefficient of sulphur. The standard state for sulphur was taken to be a 1 pct solution of sulphur in pure iron. The numerical value for K at 1600°C was determined in the earlier work. For the purpose of showing graphically the results of the tests run at 1600°C, the activity coefficients of sulphur were recalculated so as to correspond to a manganese concentration in the metal of 2 pct in each case. In the calculation it was assumed that the increase in sulphur content of the metal at equilibrium caused by the presence of manganese

Jan 1, 1953

By Harvey Brooks

Jan 1, 1963

By Bernard H. Coyle, Robert N. Anderson, Judith A. Koperski

Between 6 and 8 million cars are shredded annually in the U.S. This shredded material is magnetically separated leaving a mixture of nonmetallics and nonferrous metals which can be further separated into its metallic and nonmetallic constituents. The metallic portion is a mixture of metalr; and alloys containing predominately zinc, and some aluminum, copper, and residual iron. Hydrometallurgical strategies are proposed for recovering the aluminum, copper, and zinc. The thermodynamic and kinetic behavior of the most promising alternatives to separation are discussed.

Jan 1, 1978