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By E. B. Hunt

Paraffin deposition has been studied in the laboratory under conditions simulating deposition in well tubing. A theoretical analysis has been made of the cooling of the oil and the precipitation of paraffin from the oil as it flows up the well tubing and through surface flowlines. It is proposed that paraffin deposits are initiated by the precipitation of paraffin directly on or adjacent to the pipe wall and grow by diffusion of paraffin from solution to the deposit. This mechanism is consistent with laboratory and field observations, and has proved useful in the design and interpretation of laboratory paraffin-deposition tests. Tests have been made of the effect of plastic pipe coatings and chemical additives on paraffin deposition. INTRODUCTION Paraffin deposits which form in well tubing and surface flowlines interfere with production and must be removed. Over the years much progress has been made in developing and improving methods of removing these deposits after they form. Much less progress has been made in developing methods of preventing or inhibiting the formation of paraffin deposits. This is due, it is believed, to the lack of knowledge of the mechanism of paraffin deposition, the absence of satisfactory laboratory testing methods and the difficulties in evaluating the results of field tests of preventive treatments. The present investigation was undertaken to elucidate the mechanism of paraffin deposition and to develop suitable laboratory tests for studying the inhibition of paraffin deposition in well tubing and surface flowlines. Current theories on the mechanism of paraffin deposition have been evolved from field observations, from laboratory studies of various factors which might be involved in paraffin deposition, and from laboratory paraffin-deposition tests.1-9 Paraffin deposits have been formed in the laboratory by immersing a cold finger into a hot wax-oil solution and by flowing hot wax-oil solutions through cooled pipe or over cooled plates. These laboratory conditions differ in important features from field conditions, and the observed deposition behavior is not entirely field-like." Thus, there is reason to question the field applicability of the results of these tests. The present investigation was undertaken to determine how to perform and interpret laboratory paraffin-deposition tests to obtain information on the inhibition of deposition in the field. The paraffin problem in the broadest sense encompasses the formation of any predominantly organic deposit in well tubing, surface flowlines and other equipment in contact with crude oil or gas. The present investigation was limited to paraffin deposition involving the precipitation of paraffin wax from solution by cooling and its concentration in a deposit on a cooled surface. This probably excludes its applicability to those problems arising from asphaltic-base crudes, but not those arising from paraffin-or mixed-base crudes. This also excludes its applicability to emulsion and congealing oil problems which are often included as part of the paraffin problem. The phenomenon of cooling appears to be the controlling factor in paraffin deposition involving the precipitation of paraffin wax and its concentration in the deposit. Deposits of this type are usually found in the field only where cooling occurs. Early in this laboratory investigation, it was not found possible to form deposits under constant temperature conditions from a wax-oil slurry, either by steady flow through pipe or by gas-lift up a pipe. Thus, the investigation was limited to situations involving cooling. THEORY The relationships involved in establishing the temperature profiles in an oil stream as it flows up well tubing with a linear (geothermal) pipe-wall temperature distribution or through surface flowlines with essentially constant pipe-wall temperature are presented in the Appendix. The relationship between radial distance in the pipe and the rate of cooling of the oil is then combined with a relationship between cloud point and rate of cooling to develop the pattern of formation of a wax cloud in the oil. The following discussion of paraffin deposition under various laboratory and field conditions is based upon this development which is presented in the Appendix. PARAFFIN DEPOSITION IN SURFACE FLOWLINES The average temperature of the oil coming out of a well is somewhat higher than the ground temperature. Thus, the oil continues to cool on its trip through the surface flowline, and wax deposition can occur. The temperature distributions calculated from Eq. A-4 are given in Fig. 1. As can be seen, almost all the cooling occurs in the first 500 ft from the wellhead. In addition, the radial temperature gradient near the wall decreases rapidly with distance and becomes very small after a few hundred feet. Thus, growth of a paraffin deposit would be expected to decrease rapidly with distance from the wellhead and become negligible after a few hundred feet, since growth is dependent on concentration gradient. Wax precipitation and diffusion of wax to the already

E. D. Peters, Jr., Dorchester, Mass.: This paper of Mr. Keller's seems to me a step in a direction that has been very little exploited, and iff likely to lead to valuable practical re-

Jan 1, 1899

By G. R. Speich

The precipitation of the Feab and Fe,Ti Laves phases (MgZn, type, C14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been studied in the temperature range 500" to 800°C using hardness measurements, light and electron microscopy, and X-ray and electron diffraction. The Fe-Nb alloys contained 0.96, 1.67, and 3.80 pct Nb and the Fe-Ti alloys 3.5, 5.8, and 8.8 pct Ti. In both systems only the equilibrium Laves phase is formed, with nucleation occurring at grain boundaries, at dislocations, and in the matrix. No cellular precipitation or transition phases were observed. The precipitation of the Laves phase in a fine dispersion leads to significant hardening in both systems. The hardness of the aged alloys is proportional to the reciprocal of the square root of the interparticle spacing. The maximum solid solubility of titanium in a! iron is 9.0 pct Ti at 1280°C. THE precipitation of the FezNb and FezTi Laves phases (MgZn2 type, C 14) from Fe-Nb and Fe-Ti solid solutions, respectively, has been investigated as part of a continuing study of the mechanisms of precipitation from ferritic binary iron-base alloys. The iron-rich portions of the Fe-Nb and Fe-Ti phase diagrams are shown in Fig. l(a) and l(b). The Fe-Nb diagram is essentially that given by ansen' with the more recent work of Hume-Rothery and Gibson2 added. Goldschmidt3 indicates that the FezNb Laves phase has a solubility extending from 32 to 55 wt pct Nb. The Fe-Ti diagram is also essentially that reported by Hansen.l The recent results of Nishimura and kamei, Murakami, Kimura, and Nishimura,' indicate that the FezTi Laves phase has a solubility extending from 22.5 to 30.5 wt pct Ti. The L/6 + FezTi eutectic temperature of 1298°C indicated by Kornilov and oriskina' has been adopted. The addition of niobium or titanium to iron lowers the 6 — y transformation temperature and raises the y — a! transformation temperature. This results in a closed y field in the Fe-Ti system, but the lower solubility of niobium in a! (6) iron results in a eutec-toid, 6 — y + FezNb, at 1200°C, and a peritectoid, y + FezNb —-a, at 989°C in the Fe-Nb system. The maximum solubility of niobium is reported to be 4.5 wt pct in 6 iron,' 1.0 wt pct in y iron,7 and 1.8 wt pct in a iron.' Some results from the present work indicate that the maximum solubility in a! iron is actually less than 0.96 wt pct Nb. The maximum solubility of titanium in a! (6) iron is somewhat uncertain since the early work of To faute and Butting-haus indicated a value of 6.0 wt pct while later work of Kornilov and Boriskina6 yielded a value of 14.0 wt pct. The present work indicates that the maximum solubility is actually 9.0 wt pct. In both systems the phase in equilibrium with the iron-base solid solutions is a Laves phase (Mg znztype, C14), FezNb or FezTi. Both of these Laves phases have a wide range of Solubility. The precipitation-hardening behavior of Fe-Nb or Fe-Ti alloys has not been studied extensively. Genders and Harrison' reported that binary Fe-Nb alloys hardened upon aging. Peter and Fisher7 studied the mechanical properties of Fe-Nb and Fe-Ti alloys quenched from different phase fields.

Jan 1, 1962

By H. E. Cook

The Ising model for the internal energy of a binary alloy has been used to obtain a general equation for the critical resolved shear stress of partially ordered crystals. The equation expresses the stress in terms of the Warren "alphas " and can be used to estimate the variation in strength with order without the assumption, present in the original formulation of this problem in terms of domain size, that order is complete within each domain and that the domains are of ungorm size and shape. In addition, it is the general equation, according to the Ising model, for strengthening by short-range order. Two applications of the equation are considered: One is an estimate of the variation in strength of CkAu with long-range order. The other is an estimate of the variation in strength of FeCo with quench temperature. Reasonable agreement is found with the variations reported in the literature. When the internal energy of an alloy crystal depends upon the distribution of solute, the strength of the crystal will also depend upon it because a portion of the applied stress for plastic deformation will be: where V is the volume of the crystal and E(E) is the energy change associated with the solute redistribution caused by the plastic strain, E. We expect T to equal zero for a crystal having a random arrangement of solute because the arrangement would remain random after plastic deformation. Likewise, we expect it to equal zero when the crystal is perfectly ordered because the motion of paired dislocations found in such crystals does not disrupt order. However, when short-range order exists or when long-range order is incomplete, plastic deformation will decrease the amount of order and additional work, proportional to the ordering energy, will be expended. Fisher' estimated T for crystals having short-range order by assuming an interaction energy between neighboring atoms and estimating the change in the number of unlike neighbors as a dislocation moved through the crystal. (His analysis was limited and several workers2"6 have since given more complete ones.) Fisher minimized the importance of a strengthening mechanism of this type for paired dislocations in a structure having long-range order. ~ottrell,' however, pointed out that T could be appreciable for ordered crystals having antiphase domains. He attributed the strengthening to the increase in surface energy of the domains as they were cut by paired dislocations. Ardley,' in his test of Cottrell's theory, found that r for Cu3Au crystals obeyed the equation: for 1 > t where 1 is the domain size, t is the domain wall thickness, and y is the surface energy of an antiphase boundary. His experiments represent the classic confirmation of the strengthening mechanism proposed by Cottrell. However, the assumptions involved in using Cottrell's theory are valid only for large domain size in CU~AU,~"~ i.e., when Eq. [2] reduces to: For small domains, ~linn~ has questioned Ardley's assumption that order was complete, and, indeed, Stoloff and ~avies" fpnd it incomplete until a size of approximately lOOA was reached. Even when the order within a domain is complete, it is not obvious how one determines the appropriate value for I in a structure where domains vary in size and are irregularly shaped. The purpose of this paper is to estimate T without restrictions upon the degree of order and domain shape. Our major assumption will be the use of a generalization of the model proposed by Bethe" (the Ising model) for the internal energy. This will in fact allow us to combine the theories for strengthening by short-range order and by antiphase domains into a single, general formalism. We will use the results to estimate the variation in strength of Cu3Au crystals with long-range order8 and the variation in flow stress of FeCo crystals with quench temperature.12'13 INTERNAL ENERGY For simplicity, we restrict our considerations to those binary solid solutions which can be described as an arrangement of atoms on a Bravais lattice. An atom site will be indexed by three numbers (PI, pz, p3) determined by the vector: from the origin fixed at atom (0, 0, 0) to the atom site where a', an, and a, are the lattice translation vectors. We write: For the energy of the crystal where pi(p) is the probability (either zero or one) of finding an atom of type i (i = 1, 2) at site (p), which is shorthand for (pl, pz, p3) and pj(p + r) is that for an atom of type j (j = 1, 2) at the site (p + r), which is shorthand for (pl + rl, The coupling parameter, resents the energy associated with the pair Pi(p), Pj(p + r). The crystal is assumed large enough so that surface effects can be neglected; therefore, trans-lational and inversion symmetry require the coupling parameters to obey the relations

Jan 1, 1969

By W. F. Kieschnick, C. C. Miller, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor' have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By C. C. Miller, W. F. Kieschnick, E. R. Brownscombe

The possibility has been mentioned that large pressure gradients in a solution gas driven field caused by high production rates might lead to a reduction in the ultimate recovery obtainable compared to that which would be obtained by a very slow rate of production. In the present study the reservoir conditions accompanying a high rate of production and the corresponding ultimate recovery were compared with those obtained if the reservoir were produced at some marginal rate throughout its entire life. The method of calculation involved the application of fluid flow - material balance analysis to a series of successive steady state conditions in the reservoir. In the case studied very little difference in recovery was obtained at the abandonment pressure. An analysis of the basic factors involved indicates that the sane results would hold for considerable variation in properties of reservoir fluids, permeability of the formation or well spacing. Even if the reservoir has a water drive it appears that no harm will be done by- open flow production if the rate is cut back before any appreciable free gas is produced. However, any condition which leads to disproportionate withdrawal rates and which causes large pressure differences over large areas might result in substantial loss in ultimate recovery. INTRODUCTION When the pressure declines in a reservoir, gas is evolved from solution causing a shrinkage in the reservoir oil so that a stock tank barrel of oil with its residual dissolved gas occupies a smaller volume than originally. For a given reservoir oil saturation, therefore. stock tank oil content will be higher at the lower pressure. At the same time the evolved gas which remains in the reservoir reduces the reservoir oil saturation, and this would be expected perhaps to cause a reduction in stock tank oil content. However, around the well the shrinkage occurs so rapidly that stock tank oil may actually accumulate in this region in spite of the simultaneous reduction in reservoir oil saturation. If this accumulation should continue, spreading into a larger zone, the loss might be appreciable and because larger pressure gradients accompany higher rates the accumulation might possibly be large if wells are produced at too high a rate. It is the purpose of this paper to determine the effect of rate of flow on ultimate recovery by solution gas drive. The problem under consideration involves the unsteady state flow of oil in a closed radial system from which oil is produced by the evolution of gas as a finite drawdown is estalllished and the reservoir pressure declines. A somewhat similar unsteady state production problem dealing, however, with a linear system has been considered by Muskat and Meres, but these authors do not discuss the effects which rate may have on recovery. Other methods have been reported for estimaling recovery as a function of pressure decline when producing at an infinitesimal rate, and Muskat and Taylor' have shown the effect of fluid and reservoir characteristics on recovery under these conditions. Assuming steady state to exist, Babson has given a procedure for computing the decline in well productivity as the field is depleted, and Moyer has combined these methods to estimate abandonment conditions and the resulting ultimate recovery. These latter approaches to the problem either do not consider the effect of rate or assume steady state can be established. In detail this paper presents the behavior of the reservoir producing under unsteady state conditions and considers the effect of production rate during this unsteady state flow on the recovery attained. The analysis also shows that there will exist at abandonment a type of steady state, and on this basis a method has been clevelopetl for rapid calculation of abandonment conditions.

Jan 1, 1949

By Charles D. Walcott

Jan 1, 1901

By O. Mellgren, A. M. Gaudin, P. L. De Bruyn

The adsorption density of ethyl xanthate on pyrite was determined as a function of xanthate concentration. Surface preparation of the mineral appears to have asafunctionsome effect on the subsequent adsorption process, A monolayer of xanthate on the surface is exceeded only in presence of oxygen. The effect of OH- , HS- (and x and CN- S=)and on the amount of xanthate adsorbed was investigated. Competition between OH- and X- (xanthate) ions for specific adsorption sites is indicated over a wide pH range. IN the flotation of sulfide ores, xanthates are most commonly used to prepare the surface of the mineral to be floated so that attachment to air takes place. The quantity of agent required to make the mineral hydrophobic is usually very small, of the order of 0.1 to 0.25 lb per ton of mineral. Details of the mechanism of pyrite collection are for the most part unsettled. Adsorption of collector has long been believed to involve an ion exchange mechanism as demonstrated for galena' and for chalcocite.2 In the work on chal-cocite it was also demonstrated that a film of xanthate radicals unleachable in solvents that dissolve alkali xanthates, copper xanthate, or dixanthogen was formed at the surface of the mineral. The unleachable product increased with increasing addition of xanthate up to a maximum corresponding to an oriented monolayer of xanthate radicals. Pyrite is extremely floatable with xanthate if its surface is fresh.9 ut the floatability decreases rapidly as oxide coatings increase in abundance. Pyrite shows zero contact angle when in contact with ethyl xanthate solution at pH higher than about 10.5;4 at neutrality, a contact angle of 60" is obtained at a reagent concentration of 25 mg per liter. Alkali sulfides and cyanides are pyrite depressants. In this study of pyrite collection the writers have sought to relate measured xanthate adsorption to the method used in preparing pyrite, to the presence or absence of oxygen, to concentration of hydroxyl, hydrosulfide, sulfide, and cyanide ions. The principal experimental tool has been radioanalysis," " using xanthatcx marked with sulfur 35. Experimental Materials Pyrite: Unlike most sulfides, pyrite is a poly-sulfide. The structure given by Bragg7 resembles that of sodium chloride, the iron atoms corresponding to the position of sodium and pairs of sulfur atoms corresponding to the position of chlorine. The edge of the unit cell in pyrite is 5.40 A and in halite 5.63 A. The S-S distance in pyrite is 2.10 A; the Fe-S distance, 3.50 A: and the Fe-Fe distance, 3.82 A. Natural pyrite from Park City, Utah, was used in this investigation. Pyrite 1 was obtained by hand picking pure crystals. Pyrite 2 and Pyrite 3 were obtained from finer textured crystalline material containing inclusions of silicates. The same cleaning technique was utilized for the preparation of Pyrite 2 and Pyrite 3, whereas a different cleaning technique was used for Pyrite 1. Pyrite 1 was prepared as follows: The crystals were ground in a porcelain ball mill and the 200/400 mesh fraction was separated by wet screening with distilled water, followed by washing for 1 hr with deoxygenated distilled water acidified with sulfuric acid to pH 1.5. The acid was removed by rinsing with deoxygenated distilled water on a filter until a pH of 6.0 was reached in the effluent. This filtration was carried out under nitrogen. The sample was then dried in a desiccator under nitrogen. The period of time for which this pyrite sample was in contact with water containing oxygen was about 4 hr. The specific surface as determined by the BET gas adsorption method was 582 cm2 per g. Final material assayed 53.12 pct sulfur and 46.5 pct iron (theoretical, for FeS,: S, 53.45 pct; Fe, 46.55 pct). After crushing, Pyrite 2 and Pyrite 3 were washed with 1 M HCl. rinsed, and fed to a laboratory shakinq table to remove the small amount of silicates. The concentrate obtained was ground in a laboratory steel ball mill. The 200/400 mesh fraction was separated by classification in a Richards hindered settling tube. This fraction was then given a final wash with 0.1 M HCl and deoxygenated water was filtered through the sample. The final effluent showed a conductivity equivalent to that of a solution having a salt concentration of 0.3 ppm. Aqueous hydrogen sulfide solution was then added to the sampln (about 100 ml saturated H,S solution to about 1000 g pyrite under a few hundred milliliters of water) which was stored wet under nitrogen. The sample stored in this manner showed no indication of formation of iron oxides, whereas iron oxides appeared

Jan 1, 1957

By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,' Morozov and Novokharski,' and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By R. T. DeHoff

Saltykov's meihod for the determination of the size distribution of spherical particles from measurements made on random plane sections is extended to particle shapes which are not equiaxed. The analysis permits the deterrrzination of the size distribution of aggregates of ellipsoidol particles provided all particles have tlze same shape. V ARIOUS solutions to the problem of the determination of the size distribution of spherical particles from measurements made on random plane sections have appeared in the literature since the original solution was first published by Scheill in 1934. Solutions have been offered utilizing measurements of the diameter1y2 or area3'4 of circular sections that result when a test plane is passed through an aggregate of spherical particles, and the length of intercept5y6 that results when a test line is passed through the aggregate. To the best of the knowledge of the author, no method has been proposed which permits the determination of the size distribution of particles that are not equiaxed. The purpose of this paper is to develop a method which permits the determination of the size distribution for a specific class of particle shapes which cover awide range of axial ratios; namely, ellipsoids of revolution. In the interests of simplicity, it is necessary to limit consideration to aggregates of particles which are all similar in shape; that is, the ellipses which, by rotation about one of their axes, generate the particles, all have the same axial ratio. The size distribution, which is to be determined by the analysis, is arbitrary. It is also assumed that the section, or sections, upon which the measurements are made represent the average of all possible sections through the structure. This ideal condition can be approached as nearly as may be desired by observing a sufficient area of sections taken at random positions in a randomly oriented aggregate, and in random positions and orientations in an aggregate that has one or more axes of orientation. SIZE DISTRIBUTION FOR PROLATE ELLIPSOIDS Consider an aggregate of cigar shaped, geometrically similar particles (prolate ellipsoids), dispersed in an opaque matrix. Let the size of each particle be specified by the length of its minor axis, By Fig. 1, and the shape, q, be defined by the ratio of its minor to its major axis, B/A. Let the index, j, refer to dimensions of ellipsoids in a particular size class, and the index, i, to dimensions of an ellipse resulting from the intersection of a test plane and a particle. The size of such a section is specified by the length of its minor axis, b. Let the particles be arbitrarily divided into k size classes, and let the increment of size between each class be A, where A = &,$, B,,,being the minor axis of the ellipsoids in the largest size class. Since all sections are represented on the test plane, the minor axis of the largest of the sections observed, results from the intersection of the test plane with an ellipsoid in the largest size class at its center, and is therefore equal to Bmax Thus the increment, A = The final result will consist of the k numbers which represent the number of particles in each size class per unit volume of aggregate:

Jan 1, 1962

By J. Gurland

The effects of variations of carbon content on the constitution and properties of sintered WC-Co alloys were studied. The grain growth of tungsten carbide during sintering was measured and it was shown that it takes place mainly by solution and reprecipitation of the carbide in and from the binder at the sintering temperature. It was found that the decomposition of W3C03C by carburization during sintering is responsible for the formation of very large grains. THE properties of sintered WC-Co alloys are critically dependent upon their final composition and structure. Slight changes of cobalt and carbon contents and small variations of grain size result in marked changes of mechanical properties and performance of products. Previous investigators have studied the microstructure as a function of composition' and have dealt with the influence of cobalt upon properties.' The present work is concerned with the effect of carbon content upon constitution, microstructure, and grain growth during sintering, as well as upon the physical properties of sintered compacts. Phase Boundaries at the Sintering Temperature The WC-Co section through the ternary diagram W-Co-C has been studied by Wyman and Kelley,' Takeda,V andford and Trent," and Rautala and Norton." Two phases, namely WC and a cobalt-rich solid solution (P), appear in the sintered structure if the carbon composition corresponds very nearly to the theoretical carbon content of WC (6.12 pct C). But small deviations from the ideal carbon content will bring about the occurrence of either graphite or the double carbide W,Co3C (7) . The 7 phase was long believed to be metastable, this conclusion being based mainly on the work of Takeda. More recent studies have shown that it is a stable phase of the ternary system,"5 but the actual phase boundaries have not been established and there has been some discussion as to whether or not the 7 phase occurs at some stage of sintering in the fully carburized alloys." In view of this uncertainty it was thought advisable to undertake an investigation of the phases present during the sintering of WC-Co alloys. Commercially available tungsten, cobalt, and carbon powders were used in the present study. A typical analysis of impurities in a sintered compact is reported in Table I. The desired carbon compositions were attained by varying the amount of carbon added to the tungsten during carburization and controlling the composition during sintering by packing the compacts into beds of mixed alundum-carbon powders of suitably selected ratios. The alloys were sintered in a hydrogen tube furnace at 1400°C, then brought to equilibrium at the temperature under investigation and quenched in water. The high temperature phases were identified by metallographic and X-ray diffraction techniques. The samples were etched with a 10 pct solution of alkaline potassium ferricyanide. The phase boundaries, established by metallo-graphic examination, are shown in Fig. 1, which is a vertical section through the ternary diagram at 16 pct Co. The temperatures of the invariant planes, at 1298" and 1357°C were established by Rautala and Norton. The vertical section shows that the three-phase field, WC + 7 + L, extends into the two-phase field, WC + L, but does not include the stoichiometric composition of WC. In practice this means that the 7

Jan 1, 1955

By Blamey Stevens

(San Francisco Meeting, October, 1911.) IN this paper, which is a logical extension of my paper, The Laws of Intrusion, 1 the various pressures of emanation and their mechanical causes and effects on the large scale of nature are determined, .and a classification of emanations is deduced therefrom. The Subterranean Sea. The subterranean sea is here defined as the intercommunicating water contained in the trains of pores and fissures of the rocks down to great depths. Whether the actual amount of water constituting this subterranean sea be large or small, does not enter into the present argument, since the static pressure of this water at any particular depth is not a function of the quantity : it involves only the depth and the density of the water. Densities. The total pressure at depths down to 10 or 15 miles is made up of the rock-stresses investigated in my previous papers, and the pressure of the subterranean sea. The latter component must evidently be equal to the weight of a solid column of the overlying water of unit sectional area. As water expands with heat, it should really be necessary to sum the density at every level. A knowledge of the densities of water under a variety of conditions is therefore needed, but does not seem ever to have been ascertained for such combined pressures and temperatures as we have to consider. The specific gravity of water at 28° C. for various pressures up to 400 atmospheres, has been determined by Barus,2 who

Apr 1, 1912

By AIME AIME

AWRDED jointly by the four AW Founder Engineering Societies the John Fritz Medal is generally regarded as the most signal honor that American engineers can confer on a fellow engineer. The roll of 34 recipients contains the names of Lord Kelvin, George Westinghouse, Alexander Graham Bell, Thomas. A. Edison, George W. Goethals, Guglielmo Marconi, and Michael I. Pupin; and among members of the A.I.M.E. now living, Sir Robert A. Hadfield, Herbert Hoover, and Daniel C. Jackling. On the evening of March 1 7 the name of Paul Dyer Merica was formally added to this list of illustrious engineers when the medal was presented to him at a dinner at the Metropolitan Club in New York. The citation read. For important contributions to the development of alloys for industrial uses. Arrangements for the dinner were made by the following committee representing the four Founder Societies: R. C. Allen, George S. Davison, A. A. Potter, and J. B. Whitehead.

Jan 1, 1938

By Charles E. Lundin

Pressure-temperature-composition data were obtainedfor the Er-H system. Measurements werecar-ried out in the temperature range of 473° to 1223°K, the composition range of erbium to ErH,, and the pressure range of 10-5 to 760 Torr. Solubility relationships were established from these data throughout the system. Three solid-solution phases were delineated: metal solid solution, dihydride phase, and trihydride phase. The trihydride Phase decomposes at about 656°K and 1 atm pressure. The dihydride phase is stable to about 1023°K, but becomes more deficient in hydrogen above this temperature. The equilibrium decomposition pressure-temperature relationships in the two-phase regions, erbium solid solution plus dihydride and dihydride plus trihydride, were deter- The differential heats of reaction in these two regions are AH = - 52.6 * 0.3 and - 19.8 i 0.2 kcal per mole of Hz, respectively. The differential entropies of reaction are AS = - 35.2 * 0.3 and - 30.1 * 0.4 cal per mole HZ.deg, respectively. Relative partial molal and integral thermodynamic quuntities were calculated in the system to the dihydride phase. RARE earth metal-hydrogen systems have been the subject of general survey,1"4 and all have been found to form hydride phases. The heavy rare earths, of which erbium is a member, form dihydride and trihydride phases with different crystal structures, whereas the light rare earths form only a single-phase dihydride which expands without structure change, as hydrogen is added, to the trihydride composition. These materials are of interest primarily because of their theoretical properties, such as bonding, defect structure, and thermodynamic and electronic characteristics. Erbium has been studied in several previous investigations.5, 6 It was deemed desirable to more thoroughly and accurately define the system, both for the phase equilibria and the thermodynamic properties. I) EXPERIMENTAL PROCEDURE A Sieverts&apos; apparatus was employed to conduct the experimental measurements. Briefly, it consisted of a source of pure hydrogen, a precision gas-measuring buret, a heated reaction chamber, a mercury manometer, and two McLeod gages (a CVC, GM 100A and CVC, GM 110). Pure hydrogen was obtained by passing hydrogen through a heated Pd-Ag thimble. The hydrogen was analyzed and found to have only a trace of oxygen and nitrogen. A 100-ml precision gas buret graduated to 0.1-ml divisions was used to measure and admit hydrogen to the reaction chamber. The reaction unit consisted of a quartz tube surrounded by a nichrome-wound furnace. The furnace temperature was controlled by a recorder-controller to ±1°K. An independent measurement of the sample temperature in the quartz tube was made by means of a chromel-alumel thermocouple situated outside, but adjacent to, the quartz tube near the specimen. Pressure in the manometer range was measured to ±0.5 Torr and in the McLeod range (10-4 to 10 Torr) to ±3 pct. The hydrogen compositions in erbium were calculated in terms of hydrogen-to-erbium atomic ratio. These compositions were estimated to be ±0.01 H/Er. The erbium metal was obtained from the Lunex Co. in the form of sponge. The metal was nuclear grade with a purity of 99.9 pct +. The oxygen content was reported to be 340 ppm and the nitrogen not detectable. Metallographically the structure was almost free of second phase (<1 vol pct). A quantity of sponge was arc-melted for use as charge material. The solid material was compared with the sponge in the pressure-temperature-composition relationships. They were found to be identical. Therefore, sponge material was used henceforth, so that equilibrium could be attained more rapidly. The specimen size was about 0.2 grain for each loading of the reaction chamber. The procedure employed to obtain the pressure-temperature-composition data was to develop experimentally a family of isothermal curves of composition vs pressure. First, a specimen of erbium was wrapped in a tungsten foil capsule to prevent contact with the quartz tube. After loading the specimen, the system was evacuated to less than l0-6 Torr, flushed several times with high-purity hydrogen, and evacuated again ready for the start of the experiment. The furnace was then brought to the desired temperature. A measured amount of hydrogen was admitted into the chamber. Equilibrium was allowed to be attained, the pressure read, and the process then repeated many times until 1 atm of gas pressure was finally reached. Other isotherms were then developed in the same manner. The partial pressure plateaus were determined by another manner. In the solid solution-dihydride region a composition of approximately 1.0 H/Er was selected on the plateau. The temperature was varied throughout the range of interest. At each temperature level, equilibrium was achieved, the pressure read, and the next temperature attained. The temperature was cycled both up and down. In the dihydride-trihy-dride region, the plateaus were determined in the 473" to 651°K range only by heating to the desired temperature and not by both heating and cooling. The data were much more reproducible in this manner. Equilibrium required long periods of time. Specimens were initially hydrided to 2.8 H/Er, so that at the higher

Jan 1, 1969

By H. T. Shore, J. M. Schultz

A number of experimental rnethods—X-ray powder diffractometry, Laue photography, X-ray small-angle scattering, and transmission electron microscopy and dijfraction—have been utilized to examine the morphology associated with precipitation from the terminal, g, solid solution of a Zn-1 pct Cu alloy. A significant age hardening was observed in a 1 pct Cu alloy. X-ray and electron diffraction results showed that the structural inhomogeneities associated with the hardening were isotructural with the matrix. The average size and shape of the inhomogeneities were deduced from the electron microscopy and X-ray small-angle scattering. The preprecipitates are hexagonal platelets some 300? in diam. and some twelve unit cells thick. The orientation of the platelets was deduced from Laue photographs and electron diffraction. The platelet plane is (0001). When a large amount of pre-precipitation is present in a localized volume the new lattice is often disoriented by a rotation about (0001) of of the matrix. WhILE dilute Zn-Cu alloys have been commercially important for some 50 years, relatively very little is known metallographically about this material. The "Zilloys", zinc with about 1 wt pct Cu and sometimes a small addition of magnesium, are used to produce rolled zinc which is harder and stronger than that produced by other rollable zinc alloys.&apos; According to the phase diagrams of the zinc-rich side of the Cu-Zn system, such dilute Zn-Cu alloys should age-harden;2-5 the solubility of copper in zinc, g-phase, at 424°C is 2.68 pct, while at 0°C it is only to 0.3 pct. However, the published literature on the aging of this system appears to be limited to a documentation of the contraction of 1, 2, and 3 pct Cu alloys aging at 95°c,6 and an attempt to measure changes in lattice parameters during aging.&apos; In the latter work, no lattice parameter changes were detected, although a broadening of the highest-angle lines was detected and considerable diffuse scattering was observed. Micro-structural investigations have been limited to the latest stage of aging, wherein Widmanstatten precipitates are formed.3,47 These alloys are of interest for still another reason. The two most zinc-rich phases in the Cu-Zn system, 77 and E, are both hcp. Moreover, the change in a, between 17 and t for a 1 wt pct Cu alloy is onlv 3.64 -,~ct: the change in Co is 12.0 ict. It would be anticipated that precipitation in such a material might occur through metastable phases or G.P. zones with epitaxy along mutual 0001 planes. The goals of the present work are aimed at partially filling the void of knowledge concerning the early stages of precipitation from the g phase. In particular, we have attempted to document the magnitude of the age hardening of this system and to determine the size, shape, and orientation within the matrix of the elements of precipitation in an early stage of condensation. EXPERIMENTAL A) Specimen Preparation. Specimens were prepared In two somewhat different ways, one method being used for X-ray Laue and diffractometer measurements, optical microscopy, and Rockwell hardness measurements and the other used for electron microscopy and X-ray small-angle scattering. In the first case zinc and copper in the proper proportions to yield a 1 wt pct Cu alloy were melted together in a closed graphite crucible. Castings so made were free of apparent segregation or oxidation. The castings were then solution-annealed at 400°C for several days and then quenched in water to room temperature. Filings of portions of the specimens were made for use as X-ray powder diffractometry specimens. The electron microscope material was made as follows. Castings were made under vacuum with copper powder placed inside a hollow zinc cylinder to insure good contact of the materials. These 1 wt pct Cu pieces were then rolled to 0.1 mm with an intermediate anneal in vacuo. The rolled sheets so formed were then annealed for about 6 hr at 225°C. Finally the specimens were electropolished slowly until thin enough for transmission electron microscopy. The polishing is discussed in greater detail in the Results section. B) Measurements. X-ray measurements of three types were performed. A G.E. XRD-5 diffractometer was used to examine powders of the alloy for identification of second-phase material. A Kratky small-angle camera, also operating from a G.E. tube, was used to investigate the sizes of small precipitate particles. In both cases, nickel-filtered copper radiation was utilized. Finally, individual grains of the large-grained castings were examined in the back-reflection Laue geometry. Electron microscope studies were carried out with a J.E.O.L. Model 6A instrument. RESULTS A) Hardness Measurements. Hardness measurements performed at room temperature on the large-grained polycrystalline specimens showed a hardening which was essentially complete in 3 hr. Fig. 1 shows a typical plot of hardness vs aging time. The relative magnitude of the ultimate hardening varied from run to run between 150 and 200 pct of the value for the material immediately after quenching from the solution anneal. Most probably the variations reflect small changes in the time taken to remove the specimen from the vacuum furnace after the solution anneal.

Jan 1, 1969

By W. R. Hibbard

It has been proposed1 on the basis of slip and flow that the ideal deformation texture of drawn wire for face-centered cubic metals is a (111) direction parallel to the wire axis. Under these considerations, an intermediate [loo] texture is permissible but should eventually change to the stable [Ill] orientation. This theory does not explain why copper and its alloys containing up to about 30 pct nickel, 5 pct zinc and 1 pct aluminum were found to have a double [Ill], [100] texture, while alloys with at least 8 pct zinc and 2 pct aluminum developed essentially a single [Ill] texture.1,2 It does suggest, however, that the [loo] component of the former alloys should disappear with additional deformation.3 Some evidence exists to support this suggestion. Howald4 reported that annealed copper wire previously drawn 93.8 pct and 98.5 pct developed a single [Ill] texture. Since, in wire, the drawn and annealed textures are similar, these wires probably had a single [Ill] deformation texture before annealing. In addition, although cold rolled polycrystalline copper and 80-20 brass were found to form different types of pole figures,5,6 single crystals of these metals when rolled from the stable (110) [112] orientation were found to produce essentially the same polo figure.7.8 It may be, therefore, that while the addition of solute elements changes the path by which the final texture is obtained, the final texture is not changed. Experimental Results The wires remaining from the previous investigation1 already drawn about 50 pct reduction in diameter were further drawn to 86 pct and then to 96.4 pct total reduction in diameter. The textures were determined after these stages by transmission X ray photograms taken with a copper K-alpha beam rotated 0 degrees toward the wire axis. It was found that the ratio of the [111].] and [100] intensities of the double texture in copper and its alloys containing 0.94 pct aluminum, 30.70 pct nickel, 2.61 pct zinc and 4.99 pct zinc increased from about 3:l for the 50 pct reduction to about 9:l for the 86 pct reduction. After 96.4 pct reduction, these wires exhibited essentially a single [lll] texture. Summary Thus, the drawn wire deformation texture of copper and its alpha solid solution alloys containing aluminum, nickel or zinc is essentially a single [Ill] texture as predicted by theoretical considerations of slip and flow.&apos; For copper and its alloys containing up to about 1 pct aluminum, 5 pct zinc and at least 30 pct nickel, an intermediate [loo] component is found after about 50 pct reduction in diameter, but disappears after about 95 pct reduction in diameter. For alpha solid solution alloys containing at least about 2 pct aluminum and 8 pct zinc the single [Ill] texture is developed considerably more easily and is found after about 50 pct reduction in diameter. No explanation of this compositional effect is apparent. Similar work is contemplated for cold rolled and cold compressed alloys. References 1. w. R. Hibbard, Jr. and M. K. Yen: Trans. AIME 175, 126. Metals Tech., Feb. 1948, TP 2334. 2. W. R. Hibbard, Jr. and D. E. Trout, 11: Trans. AIME 185, 620. Jnl. of Melals, Sept. 1949, TN 18. 3. W. R. Hibbard. Jr.: Disc. of R. M. Brick&apos;s paper on Deformation Textures, ASM Symp. on Cold Working of Metals, Oct. 1948. 4. T. S. Howald: Disc. of Ref. 1. Trans. AIME, 175, 126. Melals Tech. Aug. 1948, TP 2449. 5. R. M. Brick, D. L. Martin and R. P. Angier: Trans. ASM (1943) 31, 675. 6. 0. Dahl and F. Pawlek: Zlsch. Melall. (1936) 28, 266. 7. C. S. Barrett and F. W. Steadman: Trans. AIME (1942) 147, 57. 8. J. E. Burke and C. S. Barrett: Trans. AIME 175, 106. Melals Tech., Feb. 1948. TP 2327.

Jan 1, 1950

By Evan Evans

IT is appropriate to evaluate 1947 in review as a year of a peacetime record production of about 676,000,000 tons of coal (anthracite and bituminous), closely approaching the extraordinary wartime output in 1944. Considering the general price-wage inflation, it is in point to note that the coal industry sustained the highest wages paid to workers in any major industry, but that coal prices at wholesale levels have risen much less percentage wise than the average for all commodities. The sellers&apos; market continues to prevail. In addition to serving our own country&apos;s enormous needs, our coal industry is exporting extraordinary tonnages overseas. This unusual export demand is likely to continue for a while. Moreover, the demand in Europe for American coal mining machinery is a real tribute to the management efficiency of our modern mechanized coal industry. Competitively, the petroleum industry is concerned over its long-term supply, and already a synthetic fuels industry is being publicly advocated. In due time coal and lignite are bound to be

Jan 1, 1948

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a&apos; phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a&apos; platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a&apos; phase in titanium binary alloys.&apos; In the Ti-Mo system,&apos; two modes of a&apos; decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a&apos;, and the other involves diffusion across the a&apos;-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a&apos; along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a&apos; phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a&apos; over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a&apos; structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a&apos; are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a&apos; peaks broadened during the initial stages of tem-

Jan 1, 1965

By N. J. Grant, A. W. Mullendore

Three aluminum alloys of 0.94, 1.92, and 5.10 pct Mg, prepared from very high purity metals, were tested at 500°, 700°, and 900°F in creep rupture. The degree of strengthening through solid-solu-tion alloying and the effects on the deformation characteristics and fracture were examined. The ductility of the alloys as a function of stress and temperature was closely followed. STUDIES of the creep process in pure metals in recent years have done much to expand the understanding of the fundamental deformation and recovery processes that contribute to overall creep behavior. In order that this knowledge may be applied to commercial alloys, it is necessary to know the principles governing the effect of alloying on the mechanisms of creep. A limited amount of work has been performed in this field, but few investigators have attempted to follow the changes in particular creep mechanisms with alloying. Recently, studies of the effects of solid-solution alloying on the plastic properties of aluminum have been conducted by Dorn, Pietrokowsky, and Tietz,1 Sherby, Anderson, and Dorn,2 and Sherby and Dorn.3 This paper presents the results of an investigation of the effect of solid-solution alloying of high purity aluminum with magnesium on the creep-rupture properties, and correlates these observations with changes in the creep mechanisms. This work is thus an extension of the creep-rupture observations of Servi and Grant4,5 and the deformation studies of Chang and Grant.6,7 Experimental Procedure Three alloys of aluminum containing approximately 1, 2, and 5 pct Mg were tested. These alloying additions are all within the solid-solubility limit at the testing temperatures.&apos; The analysis of the materials is presented in Table I. The tests fall into two categories: l—creep-rup-ture tests at 500°, 700°, and 900°F, and 2—structure study tests performed primarily at 700°F. Speci-mens of 0.160 in. diameter with milled flats for metallographic observations" &apos; were utilized for the structure studies. All specimens were annealed in one step to give the desired grain size for the tests. Table II presents the annealing data and final grain sizes. The specimens were polished electrolytically before testing with Jacquet solution (2/3 acetic anhydride, 1/3 perchloric acid) at 25" to 30°C, and 15 to 20 v. Creep-rupture testing was performed under constant load with the apparatus previously described." Results and Discussion Creep-Rupture Properties: The log-log plots of creep-rupture data are presented in Figs. 1 and 2. For these very pure single-phase alloys, the minimum creep rate and the rupture life both exhibit straight-line dependence on stress in this method of plotting as they have for commercial alloys0,10 and for pure aluminum." Curve breaks, based on the use of straight-line segments, at 500°F have been found by metallographic study to correspond to a transition from low to high temperature behavior and so represent zones of equicohesion. Specimens on the high creep-rate side of the break showed normal granular deformation processes whereas those on the low creep-rate side showed rapidly increasing grain-boundary sliding and migration with extensive evidence of intercrystalline cracking at 500°F. Two micrographs of the 0.94 pct Mg alloy, Fig. 3, show the increased participation of the grain boundary in the deformation process at 500°F with decreasing stress. In Fig. 3a is shown the structure of a specimen which exhibits little deformation along the grain boundaries and failed transgranularly; in Fig. 3b is shown the increased deformation along the grain boundaries at a lower stress for a specimen which showed appreciable intercrystalline cracking. The severity of intercrystalline cracking increased with increasing magnesium content at 500°F. Intercrystalline cracking disappeared in most of the specimens at 700°F and persisted only in the 5 pct Mg alloy at high creep rates. At 900°F all of the specimens deformed with extensive grain-boundary participation, including extensive grain-boundary migration. None of the alloys at 900°F showed intercrystalline cracking.

Jan 1, 1955

By T. Watanabe, S. Karashima, H. Oikawa

Creep tests of a! iron and its solid-solution Fe-Mo, Fe-Co, and Fe-Si alloys with bcc structure were conducted under constant stresses in ferromagnetic and paramagnetic temperature regions above 0.5T,(T, is the absolute melting temperature). It was found their high-temperature creep behavior changed in the vicinity of the magnetic transformation temperature, that is Curie temperature, TC. In the ferromagnetic region below the steady-state creep rates were lower than those expected from the extrapolation of the data in the paramagnetic region, the amount of decrease being affected by solute addition. Also, activation energies for steady-state creep were different in the two temperature regions. The observed changes were concluded to be due to the effect of ferromagnetism on diffusion. It is well-known that plastic deformation of metals and alloys in the temperature region where mobility of atoms becomes high enough is controlled by atomic diffusion." Many experimental results394 on fcc and hcp materials have been reported to confirm this view. In bcc metals and alloys, not much basic investigation of creep deformation has been performed. In particular, experimental work on iron5-&apos; and its alloys, covering a quite wide temperature range is extremely scarce. On the other hand, the effect of ferromagnetism on diffusion has recently been demonstrated in a iron and its alloys;&apos; it has been made clear that diffusion rates in ferromagnetic temperatur~e region are significantly lower than those expected from diffusion measurement in the paramagnetic region. Therefore, it is concluded that the magnetic effect influences the high-temperature creep behavior in a! iron and in its alloys. The present authors have conducted creep experiments on a iron and its solid-solution alloys over a very wide temperature range, and have demonstrated the magnetic effect. A part of the result has already been reported elsewhere.26 In this paper, the experimental results will be described in detail. While the manuscript was in preparation, a similar magnetic effect on creep deformation of a iron was reported by Ishida . Though their experiments covered an extremely wide temperature range, the creep stresses varied from several thousand psi to several ten thousand psi with decreasing temperature. Consequently, it may be said that there remain some questions concerning their results. I) EXPERIMENTAL PROCEDURE The materials used in the experiments were pure iron and its alloys; they were prepared by vacuum melting (10"" mm Hg) electrolytic iron (99.9 pct), molybdenum powder (99.9 pct), ultrapure silicon, and cobalt pellet (99.5 pct) in alumina crucibles. The ingots were hot-forged to plates 10 mm thick and 50 mm wide, and then were hot-rolled at about 700°C into sheets 1 mm thick. Creep specimens, 5 mm in width and 15 mm in gage length, were machined from the sheets. They were annealed at temperatures which were well above their respective recrystallization temperatures. The chemical compositions of the metal and alloys are shown in Table I together with their heat treatments. High-temperature creep tests by the use of a lever-type creep testing machine were carried out in argon atmosphere under constant tensile stress. In order to keep &eep stress constant within about *0.5 pct, stress change due to specimen elongation was compensated by tensile force of a stainless-steel bellows which was inserted between the loading lever and lower specimen grip with the assumptions of a linear relationship between change in cross section and strain and uniform strain along the section. Beyond the limit of compensation by the bellows, small amounts of load were removed after appropriate strains. The testing temperatures were maintained to within i2"C of the reported values. Creep deformation was auto-graphically recorded at the upper (moving) specimen grip using a linear differential transformer which was held by a stainless-steel rod mechanically connected to the lower specimen grip. It was also directly measured with a dial-gage reading to -& mm. 11) EXPERIMENTAL RESULTS AND DISCUSSION 1) Creep Curves of a Iron and Its Alloys. Creep curves of a! iron, Fe-Si, Fe-Co, and Fe-Mo (<2 at. pct Mo) alloys usually consisted of three stages, that is transient (primary), steady-state (secondary), and accelerating (tertiary) stages. An example is illustrated in Fig. 1 for a! iron. However, in Fe-Mo alloys with more than 2 at. pct Mo, an inverse transient creepZ8 was observed as indicated in Fig. 2. The inverse behavior, which varied with the amount of molybdenum, may be due to the substructure* in the annealed specimen as was sug-

Jan 1, 1969