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Albin, B. R Billings, Mont. Amster, Nathan L 25 Broad St., New York, N. Y. Bache, Jules S 42 Broadway, New York, N. Y. Barrett, C. P6338 Harper Ave., Chicago, Ill. Baum, Frank G Hobart Bldg., San Francisco, Cal. Bayless, Hon. William S Russ Bldg., San Francisco, Cal. Bean, Louis H., V.P., Dwight P. Robinson & Co., Inc 125 E. 46th St., New York, N. Y. Beatty, Ross J 1106 First National Bank Bldg., Chicago, Ill. Benwell, Oswald F 205 Colorado National Bank, Denver, Colo. Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. Bingham, Charles W 1542 Hanna Bldg., Cleveland, Ohio. Blumenthal, Hugo 44 Pine St., New York, N. Y. Boettcher, Charles Ideal Cement Bldg., Denver, Colo. Bowlus, Thomas H Iola, Kans. Bragg, E. B Carmel, Cal.

Jan 1, 1929

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1934

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10' to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969

By T. A. Read, S. W. Kitchen, H. I. Fusfeld

At the present time most artillery cartridge cases are used only a single time. Since the process of reshaping a fired cartridge case so that it may be used again is much simpler and cheaper than the original manufacture of the case, it is clear that important savings could be effected if such re-formed cases were used in place of new cases. Extensive use of reconditioned cases has been hindered in the past, however, by the deterioration of the brass which may occur in the period of time between the first firing and the reconditioning of the cartridge cases. This deterioration sometimes results in a dangerously high incidence of firing splits in groups of reconditioned cartridge cases. It appears that the mechanism of the deterioration is the season cracking of the brass, for season cracks, of varying degrees of severity, may frequently be found in the cartridge cases after their return from the field. There are, of course, severe practical limitations to the extent to which fired cartridge cases can be protected from corrosion under battle conditions, particularly since the powder residue in the case is itself corrosive. The present paper describes a rapid method of testing the sidewalls of artillery cartridge cases for the presence of season cracks. This method has been developed specifically for use in connection with the reconditioning of fired cases, and makes it possible to carry out 100 per cent inspection. This new method of inspecting cartridge

Jan 1, 1945

Albin, B. R Billings, Mont. '28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S 42 Broadway, New York, N. Y. '28 Barrett, C. P 5338 Harper Ave., Chicago, 111. '28 Bayless, William S Russ Bldg., San Francisco, Cal. '28 Bean, Louis, H 60 E. 42nd St., New York, N. Y. '28 Beatty, Ross J Room 604, 6 N. Clark St., Chicago, III. '28 Benwell, Oswald F Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher. Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H., Banker, Pres., Allen County State Bank Iola, Ran. '28 Brown, Colvin B Chamber of Commerce, Washington, D. C. '28 Burt, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1936

By C. G. Dunn, J. L. Walter

Secondary recrystallization to the (110) [001] texture in high-purity silicon iron occurs if low-oxygen material is annealed in a nonoxidizing atmosphere. Any departure from these conditions results in a growth of (100) oriented grains. The nature of the matrix and secondary recrystallization structures and textures and the nature of grain boundary interactions during growth show that the low gas-metal interfacial energy of the (110) surfaces provides the driving force for growth of these grains. A type of grain growth, characterized by a driving force which derives from energy differences of {hkl} surfaces at the gas-metal interface, has been treated in recent papers.&apos;-7 Secondary recrystallization to the cube text!:: in high-purity silicon iron provides one example. The present paper also deals with a surface energy driving force but the texture that results by secondary recrystallization is not the cube texture; it is a texture in which the (110) plane is in the plane of rolling and the [001] direction is in the direction of rolling. The phenomenon described in this paper is different from the impurity (dispersed phase)-controlled secondary recrystallization process in which the (110) [001] oriented grains grow under the action of grain boundary driving forces.8-12 It is also different from tertiary recrystallization,2 which also produces the (110) [001] texture in high-purity silicon iron, since the matrix textures and grain sizes are different. Finally, it is unlike any other form of secondary recrystallization reported in the literature. The possibility of obtaining the (110) [001] texture in high-purity silicon iron became clear in a study of the effect of impurity atoms on the energy relationships of (100) and (110) surfaces. In this study Walter and Dunn6 observed the migration of (100)/(110) boundaries, i.e., boundaries between two grains, one of which has a (100) plane and the other a (110) plane, respectively, parallel to the plane of the sheet specimen. At 1200°C the (100)/(110) boundaries advanced into (100) grains in a vacuum anneal, then reversed their direction and migrated into (110) grains in a subsequent anneal in impure argon. Finally, the direction of migration reversed once again with (110) grains growing into (100) grains in a second vacuum anneal. These results were explained in terms of a change in concentration of oxygen atoms at the gas-metal interface during the anneals. Thus, oxygen atoms were added to the surface during the anneals in impure argon to the point where ?100, the specific surface energy of the (100) oriented grains, was lower than ?110, the surface energy of (110) oriented grains. In vacuum, however, the oxygen concentration at the surface was lowered to the point where ?110 < ?100. Concerning the possibility of secondary recrystallization in high-purity silicon iron with a low initial oxygen concentration, the observed effect of adsorbed oxygen atoms has indicated6 that a good vacuum anneal would favor the rapid growth of matrix grains with the (110) plane in the plane of the sheet much more than grains in the (100) orientation. The growth of only (110) oriented grains of course would depend upon y110 being less than ?hkl, where hkl refers to any plane different from (110). The present paper is concerned with the application of the above ideas to secondary recrystallization to the (110) [001] texture in high-purity silicon iron. The matrix and secondary recrystallization textures and structures are defined and discussed. Observations of growth of nuclei for secondary recrystallization and of boundary interactions are included to provide direct information on the surface energy relationships between (110) and other (hkl) surfaces. EXPERIMENTAL PROCEDURE As before, 2,4-6 high-purity iron and silicon were melted and cast in vacuum to provide an alloy containing 3 pct Si with less than 0.005 wt pct impurities. The oxygen content of the ingot was lower than in previous ingots, being approximately 3 ppm (by weight). The carbon content of this ingot may have been slightly higher than was found for previous ingots. The same rolling and annealing schedule used previously2 was followed in this study to obtain samples 0.012 in. (0.3 mm) thick. These samples were electropolished prior to annealing. After rolling and polishing, the oxygen content of the material was approximately 6 ppm; material used in the previous studies contained about twice this amount of oxygen.

Jan 1, 1961

By G. C. Wallick, J. S. Aronofsky

This paper presents an experimental verification of numerical solutions of the differential equation describing the transient flow of an ideal gas through a porous material including gas slip effects. Several experiments previously proposed by one of the authors are described together with the correlation of the experimental results with the numerical solutions. Excellent agreement is shown between experiment and theory, thus demonstrating the validity of both the basic assumption made in the derivation of the differential equation and of the numerical solutions of the differential equation. INTRODUCTION In a recent paper,&apos; one of the authors has discussed a numerical solution of the differential equation describing the unsteady flow of an ideal gas through a porous material. This paper was primarily concerned with the effect of gas slip on the flow behavior. In steady state measurements, Klinkenberg2 and others have observed that the apparent gas permeability Kn of a porous material may be expressed as a linear function of the reciprocal average pressure 1/P of the form, ka = b + m/P........(1) where the intercept b is a constant for a given porous material and the slope m is a constant for a given porous material-gas combination. Aronofsky1 assumed that Equation (1) could be used to describe transient flow if P was replaced by the average pressure in an infinitesimal volume element. A number of numerical solutions of the resultant differential equation were presented and specific flow experiments were proposed as a means of testing the numerical solutions. The purpose of the present paper is to describe the results of several of these experiments and the correlation of the experimental data with the results of the numerical analysis. Reference should be made to the previous paper&apos; for details of the mathematical and numerical analysis. EXPERIMENTAL PROCEDURE A simplified schematic drawing of the experimental apparatus is shown in Fig. 1. An 8.89 cm diameter limestone core of length L = 14.82 cm was mounted in a conventional rubber sleeve permeameter cell. The external sleeve pressure in this cell was maintained equal to 500 psig during all experimental tests, thus permitting only longitudinal flow through the core. One end of the core, X = L, was connected to an adjustable cavity of volume V as well as a pressure gauge or manometer. The other end of the core, X = 0, was connected to a Nullmatic pressure regulator which was in turn connected to a nitrogen cylinder or vacuum pump. In each experiment, the core and adjacent dead volume were charged with nitrogen to a uniform gas pressure P1. The pressure at X = 0 was then suddenly raised or lowered to a constant pressure P, and the resulting pressure buildup or pressure decline at X — L was recorded as a function of the time. The porosity + and the permeability constants m and b were determined using the transient method which was suggested by the results of the numerical analysis and which was described in the earlier paper.&apos; The following average values for these constants were obtained as a result of 19 separate evaluations: 171 -0.259 2 0.005 md-atm; b = 0.374 5 0.008 md; and F = 0.098 ± 0.005*. It should be noted that in order that transient phenomena will be slow enough to be observed conveniently, it is desirable to use a porous material of very low permeability, e.g., less than I md. Moreover, it is in this low permeability range that the gas slip effects are most significant. Thus, such a low permeability sample is very suitable for use in an experimental verification of the numerical solutions previously described.

Jan 1, 1955

By George A. Miller

THE outstanding characteristic of the American business man is that he likes to run his own business his own way, without any interference from his wife, his friends, his bankers, and least of all from his government. The oil man, like the miner, is an American business man in which this special characteristic is even more pronounced. It may be because he has been an explorer and is more nearly like those pioneering Americans who explored, developed, and built these United States.

Jan 1, 1944

U.S. Signs Pact With Miami Copper Miami Copper Co., of Arizona has agreed to mine lowgrade copper ores in an extension of its Globe-Miami mining district operations at a guaranteed price of 27.35[] per lb, under a contract signed with defense Materials Procurement Agency. Terms of the contract call for delivery of 230 million lb of refined copper between 1955 and 1962. DMPA said highgrade ore in the de posit will soon be exhausted and it is considered advisable to have Miami continue the operation. The Government has an option to buy 120 million lb of refined copper from present production at market prices. Miami will develop the new ore- body at its own expense-estimated at $3 million. If losses under the new contract reach a specified point, Miami may cancel the agreement. The company plans to use the block caving method in the underground operation.

Jan 4, 1953

By E. S. Fisher, L. C. R. Alfred

The elastic anisotropy factors, c4,/c6,, c3,/cll, and c12/cl,, for hcp metal crystals vary significantly among the dgferent unalloyed metals. Significant variations with temperature are also found. The effects of elastic anisotropy on the dislocation in an elastic continuum with hexagonal symmetry have been investigated by computing the elasticity factors for the self-energies of dislocations in fourteen different metals at various temperatures where the elastic moduli have been reported. For most of the metals the effects of the orientation of the Burgers vector, dislocation line, and glide plane are small and isotropic conditions can be assumed without significant error. Significant effects of anisotropy are, however, found in Cd, Zn, Co, Tl, Ti, and Zr. The elasticity factors have been applied in the calculations of dislocation line tensions, the repulsive forces between partial dislocations, and the Peierls-Nabarro dislocation widths. It is predicted that the increase in elastic anisotropy with temperature in titanium and zirconium makes edge dislocations with (a), (a + c), and (c) Burgers vectors unstable in basal, pyramidal, and prism planes, respectively. The probability of stacking faults forming by dissociation of Shockley partials in basal planes also decreases with increasing c4,/c6, ratio, when the stacking fault energy is greater than 50 ergs per sq cm. The widths of screw dislocations with b = (a) in titanium and zirconium increase very significantly in prism planes and decrease in basal planes as c4,/c6, increases. The effects of elastic anisotropy on various dislocation properties in cubic crystals have received considerable attention during the past few years. In the case of cubic symmetry the departure from isotropic elasticity depends entirely on the shear modulus ratio, A = 2c4,/(cl, —c12); i.e., the medium is elastically isotropic when A = 1. Foreman1 showed that an increase in the ratio A produces a systematic lowering of the dislocation self-energy for a given orientation and Poisson&apos;s ratio. ~eutonico~, has shown that large anisotropy can have a marked effect on the formation of stacking faults by the splitting of glissile dislocations in (111) planes of fcc and (112) planes of bcc crystals. ~iteK&apos; made similar calculations for (110) planes of bcc metals. Both studies of bcc metals showed that the large A values encountered in the alkali metals tend to reduce the repulsive forces between Shockley partial dislocations. In fcc metals, however, A does not vary over the large range encountered in bcc metals; consequently, the effect of A on the forces between Shockley partials is masked somewhat by the differences in Poisson&apos;s ratio between metals. The effect of A on the line tension of a bowed out pinned dislocation has also been investigated for cubic crystals, first by dewit and Koehler5 and more recent- ly by Head.6 In both cases the line energy model is applied and the core energy is not taken into account, thus making the conclusions somewhat tenuous with regard to the physical interpretation. Nevertheless, the fact that a large A decreases the effective line tension is clearly evident and the tendency for large A to produce conditions that make a straight dislocation unstable (negative line tensions) also seem evident. Head, in fact, shows visual microscopic evidence that stable V-shaped dislocations occur in 0 brasse6 For hcp metals the definition of elastic anisotropy is more complex and, furthermore, significant deviations from an isotropic continuum are found among a number of real hcp metals, especially at higher temperatures. The present work was carried out to survey the effects of elastic anisotropy on the elasticity factors, K, that enter into the calculations of the stress fields around a dislocation core. Some isolated analytical calculations have previously been carried out for several hcp metals but they are restricted in the dislocation orientations and temperature.8&apos;9 The present computations are based on single-crystal elastic moduli that have appeared in the literature and consider various orientations requiring numerical computations. The results are then applied to survey the effects of temperature on the dislocation line tension and dislocation splitting in hcp metals. PROCEDURE Anisotropy Factors. The degree of elastic anisotropy in hcp crystals cannot be described by a single parameter, such as the A ratio in cubic crystals. The following three ratios must be simultaneously equal to unity in order to have an elastically isotropic hexagonal crystal: The magnitudes of these ratios at several temperatures, as computed from the existing data for the elastic moduli of unalloyed hcp metals, are given in Table I. There are no cases of complete elastic isotropy, but the large anisotropy ratios encountered in the cubic alkali metals are also missing. There are, however, several significant differences among the hcp metals, the most notable being the relatively small A and B ratios in zinc and cadmium and the differences in the magnitudes and temperature dependences of A. It has been noted that the temperature dependence of A has a consistent relationship to the occurrence of the hcp — bcc tran~formation. For cadmium, zinc, magnesium, rhenium, and ruthenium, A is less than unity at 4&apos;~ and, with exception for rhenium, decreases with increasing temperature. In the case of rhenium, A has essentially no temperature dependence between 923&apos; and 1123"~, so that it is clear that A does not approach unity at higher temperatures. Cobalt is similar to the above-mentioned group of metals in that it also does

Jan 1, 1969

By N. A. Gjostein

The self-diffusion coefficient D, for a surface near the (100) plane in copper was determined by means of the Mullins theory of thermal grooving, and was found to obey the Arrhenius relationship, and Do = 6.5 x 10&apos; sq cm per sec. Suppression of surface diffusion by chemisorbed impurities encounters difliculties as a satisfactory explanation for the large Q, and Do. Instead, a model is presented which indicates that Q,, as determined by a mass-transport technique, may involve both the energy needed to form an adsorbed atom from a ledge in the surface as well as that for the movement of the adsorbed atom.; LITERATURE reviews1-3 indicate that the mechanism of self-diffusion on metal surfaces is not clearly understood. The lack of experimental data on the temperature variation of the surface self-diffusion coefficient DJ has contributed greatly to this situation. Radioactive tracer techniques4-rn have been used to measure Ds, but for many years only Nicker-son and Parker8 had determined (for polycrystalline silver) an activation energy B, and a frequency factor Do for the surface self-diffusion process. Even in this case, a mechanism could not be clearly inferred because it was suspeted7 that a contribution from volume diffusion was not taken into account by the investigators. Some later work by Li and parkere on polycrystalline gold, in which they obtained essentially the same results as for silver and in which volume diffusion could be accounted for, seems to invalidate this criticism. In 1957, Mullins10&apos;11 developed the theory for the thermal grooving process. This advance has opened a new and promising technique for measuring the surface self-diffusion coefficient Ds. Recognizing that a thermal groove may form by several different mass transport processes, Mullins first consideredlo the cases where a) the groove forms by evaporation and condensation or b) by diffusion along the groove surface, in either case, in a system where a metal surface is in contact with only its dilute vapor phase. In a later paper," he extended the treatment to cases where the groove forms by volume diffusion into c) the solid phase or d) by mass transport through a passive gaseous phase at 1 atm pressure. The time dependence of the groove dimensions and the shape of the groove profiles predicted by Mullins&apos; treat-

Jan 1, 1962

By R. G. Davies

WeERTMANI has shown that the high temperature steady state creep rate, i, in lead and indium-base alloys obeys an equation of the form where AH is the activation energy, o the applied stress, n the stress exponent, and R and T have their usual meanings. He observed a variation in n from 4.5 for pure metals to 3 for concentrated alloys, which he interpreted as due to Change in creep mechanism from the climb of dislocations in pure metals to a micro-creep mechanism in the alloys. The Cottrell-Jaswon microcreep mechanism of the moving dislocation taking its impurity atmosphere with it was considered to be the most likely process, although short-range order and the segregation of solute atoms to a stacking fault will also give a stress exponent of 3. Steady state creep has been investigated in a Au - 27 at. pct Cu alloy at temperatures above 1/2 TIM where TIM the absolute melting temperature. As the oxidation resistance of this alloy is excellent all tests were carried out in air with a furnace built to give a temperature variation of less than 1°C along the 60 mm gage length. A lever-arm arrangement applied the stress with a load being adjusted between each creep test to maintain a constant stress. As each test produced less than 0.5 pct creep strain, the variation in stress during the test was negligible. The creep strain was measured by a transducer at the end of one of the alloy-steel grips, with the out of balance potential being finally recorded on a variable speed chart recorder. A typical creep curve is shown in Fig. 1. The results, Fig. 2, confirm that n is nearer to 3 than to 4.5; the creep mechanism could be any of those given above. The activation energy, AH, which is independent of stress, is consistent with a diffusion controlled process; the activation energies for the self-diffusion of gold and for the diffusion of gold into Copper are both -45 kcal per ml., There is now considerable evidence, that, when the steady state creep is dependent upon diffusion, irrespective of the actual creep mechanism, the activation energy is independent of the stress. The author would like to acknowledge the financial assistance provided by the International Atomic Energy Agency, Vienna, and the Argentine Atomic Energy Commission.

Jan 1, 1962

By H. H. Podgurski, J. C. M. Li, Y. T. Chou, F. N. Davis, R. A. Oriani

When an Fe-2 pct A1 alloy is nitrogemted at 500ºC with a gus tnixture (NH3-H2) in which the nitrogen activity has been kept Lou] enough to avoid the formation of iron nitride, a two-phase alloy is generuled which consists of AlN particles and a ferrite phase cotaining a heavy network of dislocations. The amount of nitrogen contained in such an alloy, when equilibrated with the nitrogenating atmosphere, far exceeds both that needed to satisfy the normal solution requirements of a Fe and that needed to convert all of the aluninuwi to AlN. This excess nitrogen is accounted for as being trapped on dislocations, adsorbed at the ferrite -AlN interface, and as an en-Iuznced lattice solubility in strained ferrite. This excessive uptake of nitrogen had previously been attribuled by other investigators to the formation of a nonstoichiornetric aluminum nitride. Isotope exchange experiments revealed various amomts of exchargeable N14 present in the originally nitrided samples that could not be removed by reduction with HS at 500ºC. This exchangeable nitrogen has been identified us that bound to the AlN -ferrite interface. Estimates of inter facial areas in alloys containing -3 pct by weight of A1N are as high as 10 sq m per g of alloy. ThE first1 of this series of papers described the experiments forming the basis for the elucidation of the mechanism of the formation of aluminum nitride particles within an Fe-A1 alloy. It was found that not only are dislocations necessary for the nucleation of the AlN particles but also the nitriding reaction in turn produces a dense network of dislocations in the ferrite matrix. It was also observed that nitrogen in excess of that needed for the formation of stoichiometric AIN is taken up by the alloy without the formation of an iron nitride. The present paper is an analysis of the excess nitrogen sorbed by the nitrided Fe-A1 alloy which considers the structure generated by the formation of the aluminum nitride particles. Because of the high density of dislocations, this system has proved to be quite useful in studying nitrogen-dislocation interactions. Wriedt and Darken2 have already reported such studies in a cold-worked ferritic steel. EXPERIMENTAL Nitrogen Sorption. The specimens of this alloy were cold worked (50 pct reduction) to 0.011 in. thickness and chemically cleaned in a 2:1 concentrated phosphoric acid-50 pct hydrogen peroxide solution before nitrogenation. The flowing nitrogenating atmosphere (11 pct NH3-89 pct H2) was established before the ni- trogenating temperature was reached. The same gravimetric and gas-flow equipment described in an earlier paper1 was also used in this investigation. Changes in nitrogen concentration were followed gravimetrically when establishing the isotherms. In the isotope exchange experiments, concentration changes were followed volumetrically. In some instances chemical analyses (Kjeldahl method) were used to check for material balances in both the gravimetric and volumetric procedures. Our objective was to obtain reversible nitrogen sorption isotherms for alloys equilibrated with NH3-H2 gas mixtures over a large range of nitrogen activity* and temperature. The *Defined as equal to PN H /P3/2 ,where P corresponds to partial pressure in atmospheres. Actually the nitrogen activity, aN, in the alloy equals K PNH3 /p3/2H2, where K is the equilibrium constant for the reaction NH3 = N + 3/2H2. upper limit for nitrogen activity was below that which would produce iron nitride; for reasons which will become apparent later, most of the sorption studies were made in the temperature range between 400" and 500&apos;C. The alloy sample studied most extensively in this investigation was given a series of successive reductions (100 pct H2) and nitrogenating treatments at 500°C to attain a stabilized structure. Presumably some dislocations were lost during these treatments. Throughout most of the sorption studies, temperature was held at ± 1°C and the gas-phase composition was held to k0.2 pet NH3. Based upon the results of numerous diffusion experiments with this alloy* the &apos;Results to be published in a third paper of this series. times chosen for equilibration were considered more than adequate, Nitrogen Isotope Exchange. The first exchange experiments were carried out by circulating a measured quantity of H2 and NH3* (with a predetermined isotopic *The NH3 was synthesized over a synthetic ammonia iron catalyst using H2, and N2, enriched with N15. AS the NH3 was formed it was removed continuously from the gas phase by circulating the mixture through a refrigerated (78ºK) trap. When most of the nitrogen had been converted to NH3, it was distilled from the trap into a glass storage vessel. composition, N15/N14) over a nitrided specimen at 450°C in a closed glass system. Attempts to reach the exchange limit isothermally, i.e., an isotopic ratio (N15/N14) in the gas phase identical with the extractable nitrogen in the nitrided alloy, were futile. The exchange rate between the gas phase and the alloy was too slow, involving many days. To circumvent the slow exchange with the gas phase, measured amounts of N15 and N14 were introduced into the alloy by nitrogenating with an NH3-H2, mixture at 500°C containing an N15/N14 ratio of 7.76; the charged specimens were then sealed by allowing an oxide film to form over them in air, and in this final condition the specimens were subjected to 500°C in vacuum for various times during which isotope exchange was allowed to proceed within the specimen. It was estab-

Jan 1, 1970

By M. E. Wadsworth, C. H. Pitt

Nickel corrosion in sulfuric acid solutions at elevated temperatures and oxygen wer-pressures was imestigated. Weight loss was 1inear with time and varied directly with oxygen concentration. Independent variation of the possible active species in solution indicated that the undissociated sulfuric acid molecule plays an important part in the corrosion mechanism. The rate determining step was considered to be the adsorption of oxygen on a site containing adsorbed H2SO4. THE tendency for a metal to go into solution depends on a number of factors some of which are: 1) the position of the metal in the electrochemical series; 2) the type and concentration of corroding species in solution; 3) the concentration of oxygen in solution; 4) the type of film formed at the liquid-metal interface; and 5) the physical state of the metal. The corrosion of a metal in an aqueous solution may be considered to be a heterogeneous reaction that occurs at the liquid-metal interface. The reaction is generally considered to occur as a result of electrochemical potential differences within the system. Little work has been published in the literature concerning the corrosion of pure nickel. A great deal has been publistled dealing with the experimental and theoretical aspects of the over-all corrosion process. Evans,1 Uhlig,&apos; and recently Todt 3 and Tomashoff,4 have published books which review the results of experiments which have been conducted on corrosion, and have developed some of the basic ideas of the more widely accepted theories of corrosion. Friend5 states that. nickel does not readily discharge hydrogen from any of the common nonoxidiz-ing acids and that a supply of some oxidizing agent is necessary for appreciable rates of corrosion. He further notes that at temperatures between atmospheric and close to boiling, corrosion rates tend to vary with concentration, temperature, and aeration in acid concentrations up to 25 pct. Whitman and Russel6 studied the effect of dissolved oxygen on a number of metals in acid solutions and found that oxygen accelerates the rate of corrosion of nickel in sulfuric acid. Flowers and Kelley7 in studying the action of dissolved CO, on electroplated nickel postulated that nickel dissolves as NiHCO3 in the presence of CO, and air. It was found that oxygen was necessary for corrosion to take place and that the rate increased with increasing amounts of oxygen in solution. Flowers and Kelley attributed the oxygen effect to cathodic depolarization. MacGillavry, Rosenbaum, and wensson&apos; determined metal solution potentials of nickel in various electrolytes. They found that nickel has no tendency to corrode in alkaline solutions in the presence or absence of air. In acid solutions in the presence of air, metal solution potential increases in the order of 1/2 v were observed. This increase was attributed to probable chemisorption of oxygen on the nickel surface and the corrosion mechanism suggested was the interaction of H+ ions with the nickel oxide formed at the surface. Delahay9 observed the reduction of oxygen on various metals. A polarograph was used to measure the course of the reaction. With some metals hydrogen peroxide was produced as an intermediate compound. However, nickel was not considered to be a hdrogen peroxide producer. Van Rysselberghe 10,11 and associates attributed the accelerating effect of carbon dioxide on the corrosion process to the presence of percarbonic acid produced in solution reacting with the hydrogen peroxide. The percarbonic acid can be reduced at less negative potentials than hydrogen peroxide and as a result accelerates the reaction. EXPERIMENTAL Since a complete description of the apparatus used can be obtained elsewhere,12&apos;13 no attempt will be made here to describe the equipment other than to note that it consisted essentially of an autoclave unit from which samples could be withdrawn periodically without disturbing the interior state of the autoclave. A titanium autoclave liner was used to protect the autoclave from the solution.

Jan 1, 1961

By Eugene A. Stephenson

In most instances the fluids produced from underground reservoirs have been described as they appear at the surface, and usually it has not been necessary to distinguish between surface and reservoir phases. More recently it has become imperative to recognize the fact that changes in phase may occur between the reservoir and the receiving unit. The simple terminology of "wet" and "dry" gases and "crude petroleum oil" served our needs fairly well in the shallow, low-temperature and low-pressure fields. It has been left to the legislatures, regulatory commissions, and courts to decide whether a field is or was a gas field, an oil field, or both. This they have done by direct definition and also by implication. For example, in Texas:&apos; (d) The term "gas well" is any well (a) which produces natural gas not associated or blended with crude petroleum oil at the time of production, or (b) which produces more than one hundred thousand (100,000) cubic feet of natural gas to each barrel of crude petroleum oil from the same producing horizon, or (c) which produces natural gas from a formation or producing horizon productive of gas only encountered in a well bore through which crude petroleum oil is also produced through the inside of another string of casing. (e) The term "oil well" is any well which produces one (1) barrel or more of crude petroleum oil to each one hundred thousand (100,000) cubic feet of natural gas. In the state of Louisiana, the same general result is achieved largely by the following paragraph :* Wells producing both oil and gas shall not waste or blow into the air an amount of gas of more value at three cents per thousand cubic feet, than the market value of the oil recovered. The Commissioner of Conservation shall allow a reasonable time to determine the status of any well. This means that for wells making both oil and gas, if n represents the price of oil in dollars, and x the allowable gas waste expressed in M cu. ft. Per day,

Jan 1, 1938

By W. F. Cloud

The data and information compiled under Part I of this report are the results of experiments performed in the petroleum engineering laboratory under the supervision of W. F. Cloud, Associate Professor of Petroleum Engineering and William Schriever, Professor of Physics, University of Oklahoma. Problems Being Studied Most of the time has been spent in trying to determine the rate of flow and pressure gradient in a 4-in. flow tube 10 ft. long, which was packed with sand of various grain sizes. To date, only two kinds of sand have been packed in this tube: 60 to 80-mesh Canadian river sand, 60 to 80-mesh and 80 to 100-mesh Simpson sand. The original intention was to follow the same procedure and use the same types of crude under identical saturation pressures of both air and gas, as well as unsaturated (dead) oil, flowing the various crudes through several different sizes of both Canadian river and Simpson (Wilcox) sands, but lack of time has prevented such an intensive study of the problem. Some additional time has been spent flowing saturated and unsaturated crudes, similar to those used in the 4-in. tube, through 1-in. tubes, one of which was 2 ft. long and one 5 ft. long. The results obtained have been checked against those obtained by using the 4-in. tube, to obtain the relation of diameter and length of tube to rate of flow in similar sands. Laboratory Equipment Saturation Tank.—A heavy steel cylindrical saturation tank, capacity about 42 gal. was mounted on a platform of bricks, then a galvanized tin temperature bath was built around the saturation tank. This contained

Jan 1, 1930

By D. W. Fuerstenau

The United States is rapidly approaching an acute shortage of minerals. According to some observers, this situation may even be more severe than the energy crisis because the US consumes nearly 30% of the world&apos;s mineral production. With the mounting competition for world mineral supplies, we can no longer take for granted that foreign mineral products will be available to the US as abundantly as in the past. In 1973, US consumption of mineral raw materials was $35 billion. Of this, $7 billion consisted of imports. Without a drastic reorientation towards the mining of domestic mineral resources, the 1973 $7 billion deficit might mushroom to $100 billion by the year 2000. Thus, a return to domestic sources of raw materials will become absolutely necessary-and will be bucking the trend of the past 25 years, characterized by capital investment for growth in multinational overseas mining operations.

Jan 11, 1975

By Albert E. Wood, Edgar R Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as &apos;&apos;308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By Albert E. Wood, Edgar R. Shepard

The interest of the Federal Government in improvement of waterways dates from 1820, when Congress appropriated $5000 for making a survey of the Mississippi and Ohio Rivers and assigned this work to the Corps of Engineers of the Army. Since that time the Government has gradually assumed increasing jurisdiction in the matter of improvement and control of inland waterways until, by the River and Harbor Act of Jan. 21, 1927, Congress assigned to the Secretary of War and to the Chief of Engineers the duly of making surveys, in accordance with House Document No. 308, 69th Congress, to formulate plans for the most effective improvement of the navigable streams of the United States and their tributaries, for navigation, development of water power, control of floods, and the needs of irrigation. Virtually all the preliminary investigations and surveys required by this act have been completed. The reports made to Congress have been published and often are referred to as &apos;&apos;308 Reports." The map shown in Fig. 1 is merely a skeleton distribution of the projects covered by these reports, but it serves to indicate the magnitude of the proposed undertaking. In many instances, a single character on the map stands for a major development involving several dams and reservoirs or many miles of canals or levees. The devastating floods of 1936, and the need for worthy public works to take up the slack in employment, gave further impetus to this program and in 1936 led to the enactment of a bill authorizing a large number of these projects. The National Flood Control Act of 1936 specifically authorizes some 270 flood-control projects in 31 states, and affecting nearly every state in the Union, with an estimated construction cost of about $300,000,000. In addition, the 1936 Act directs the Secretary of War to make preliminary examinations and surveys for flood control in some 230 additional localities, and to continue surveys and studies of 18 reservoir sites. The Corps of Engineers is proceeding rapidly with foundation investiga-

Jan 1, 1940

By J. F. Butler

Boron nitride, BN, has been identified in boron low-carbon steels by means of light microscopy, electron microscopy and diffraction, and chemical analysis. This boron nitride is responsible for strain aging suppression in these steels through the removal of nitrogen from solution; however, small oxidizing potentials which result in deboronization In the austenitic temperature range also result in boron nitride decomposition and the subsequent occurrence of nitrogen strain aging. THE addition of boron to low-carbon steels is an effective means of eliminating the detrimental effects of strain aging;&apos;,&apos; however, the mechanism by which boron suppresses strain aging has not been established. In studying the effect of heat treatment on the strain aging of boron low-carbon steels, Butler3 found that no detectable nitrogen was present in the ferrite solid solution after various heat treatments even though the total nitrogen analyses of the steels were 0.003 pct N. Apparently the function of boron in suppressing strain aging is the removal of nitrogen from solution to form a relatively stable second phase. A clue to the identity of this phase was found by Speight4 who extracted from an aluminum-killed boron steel an acid insoluble residue which contained boron and nitrogen in proportions corresponding to the compound, BN. Shyne and Morgan5 found that the addition of nitrogen to a hardenable boron steel lowered its hardenability in a manner which suggest-d the presence of nucleating particles (presumably BN) even at high austenitizing temperatures. Although this indirect evidence for the presence of boron nitride in boron steels has been found, the compound was not identified metallographically as a separate phase in these steels. Because boron has an affinity for oxygen comparable to that of silicon,5 boron steels must be thoroughly killed with aluminum in order to prevent the reaction of boron with oxygen.7 The affinity of boron for oxygen also is demonstrated through the ease of deboronization of a boron steel in an oxidizing atmosphere. Digges, Irish, and Carwile8 found that a mixture of wet natural gas and air caused both deboronixation and decarburization of a boron steel at 1900°F. The boron content rose at the surface of the steel due to the formation of boron oxide. Shyne and Morgan9 encountered deboronization at much lower oxygen potentials; loss of boron occurred in steels treated at 1750o F under argon purified to 0.0014 pct 0, even though decarburization did not occur. Boron oxide, B2O3, is much more stable than the nitride, BN, as is indicated by the standard free energies of formation at 980oC: -235 kcal per mol of B2O3 (liquid) and -28 kcal per mol of BN (crystal). It is evident that the oxygen potential must be kept low in the presence of BN in order to prevent its decomposition and the subsequent formation of B2O3&apos; The purpose of the work described in this paper was to identify the nitride phase responsible for the removal of nitrogen from solution and to study its stability under oxidizing conditions. IDENTIFICATION OF BN In order to identify the phase containing boron and nitrogen, several alloys high in boron and nitrogen were made up in a small vacuum furnace. In alloys 3 and 4, Table I, electrolytic iron was used as a charge material. Boron additions were made in the form of 18 pct B ferro-boron after the iron was molten. In the case of alloy 3, the charge was solidified at this point; for alloy 4, nitrogen at 1 atm pressure was admitted over the melt before it was

Jan 1, 1962