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By P. Chiotti, E. R. Stevens

The electromotive force between pure magnesium and Mg-Zn alloys in a fused KC1-LiCl-MgC12 cell was measured over the temperature range 360° to 730°C and for alloy compositions of 0.052 to 0.635 atom fraction magnesium. The calculated activity coefficients of magnesium in the liquid alloys may he represented by the relation These data and the phase diagram were employed in calculating the standard free energy of formation for the compounds MgZn, MgZn2, and MgZn2, In the temperature range from 25° to 590°C the relation ZINC-rich magnesium alloys have been shown to be very effective in reducing various solute chlorides or oxides from fused salts such as KC1-LiC1 eutectic. Such reactions are of interest in the developinent of pyrometallurgical methods for reprocessing nuclear reactor fuels.' As the conceniration of the magnesium is increased beyond 5 to 10 wt pct the extent to which solutes, such as yttrium, lanthanum, cerium, and other rare earths, can be reduced or removed from the salt decreases. This effect is due to the resulting change in the activity of the solutes in the Zn-Mg alloy as well as the change in the activity of both the zinc and mag- nesium. The purpose of the present investigation was to determine the thermodynamic properties of the Zn-Mg system which, in addition to yielding information on the alloying behavior of these two elements, would permit a more quantitative understanding of the above reactions. Since this investigation was initiated several publications have appeared in the literature giving results on the thermodynamic properties for the liquid alloys of this system. 2-4 Kozuka, Moriyama, and Kushima3 measured the vapor pressure of zinc over four different alloy compositions by a carrier-gas technique. Eremenko and Tukashenko2 and Terpilowski4 measured the electromotive force between pure magnesium and various alloys in a fused salt cell. Earlier work has been summarized by Hultgren, Orr, Anderson, and Kelley.5 In the present investigation electromotive-force measurements were made on a cell of the type The temperature range covered for the lower-melting alloys was roughly 375° to 730°C. These data were employed in calculating the thermodynamic properties for the liquid alloys and in conjunction with the phase diagram,' reproduced in Fig. 1, were used in calculating the standard free energy of formation of the compounds MgZn, MgZn2, and Mg2 Zn11. The results obtained are compared with available data from the literature. MATERIALS AND EXPERIMENTAL PROCEDURES Materials employed were: Bunker Hill slab zinc, 99.99 pct pure; Ames Laboratory magnesium containing 13 ppm N, 195 ppm C, and trace amounts of calcium, copper, nickel, and silicon; reagent grade KC1, LiC1; and high-purity MgC12 obtained from Dow Chemical Co. The electrolyte consisting of KC1-LiCl eutectic (44.4 wt pct LiC1) to which was added 15 wt pct MgCl2, was dried in a quartz tube by heating to 340° C under vacuum for a period of 4 to 5 hr, and then passing HC1 through the salt as the temperature was slowly raised to above the melting point of the salt. After about 3 hr the HC1 was shut off and the system flushed with argon and then vacuum applied for 1 hr. The salt was finally siphoned through a sintered glass filter and cast into a Pyrex container which was sealed and

Jan 1, 1965

Procedures employing thiocyanate and dithiol complexes of molybdenum have been developed for the determination of the metal in the presence of large quantities of ferric iron. The procedures are developed for field application and it is possible to complete 200 analyses per day with laboratory accuracy. Use is made of sulphuric acid extraction and ascorbic acid reduction in the case of the thiocyanate procedure whilst the reducing system in the dithiol procedure is potassium iodide-sodium sulphite. Using a simple photometer the range of determination possible is 0-10~g for the thiocyanate procedure and 0-5 g for dithioI.INTRODUCTIONOf the many colorimetric procedures that have been developed for the determination of molybdenum only those using the thiocyanate or toluene-3, 4-dithiol complexes of the metal are sufficiently free from interference to be of use in geochemical prospecting. Rapid methods based on both these complexes 'have been developed at the. Broken Hill Division of The University of New South Wales as part of a general programme designed to improve geochemical procedures. Whilst speed rather than high accuracy is the important factor in prospecting, the aim of the programme is to develop procedures which will allow determination of 200· samples per man-day without loss of normal laboratory accuracy for the methods concerned.In most geochemical procedures visual estimation of a coloured complex is used in the determination of the quantity of metal present. At the high rate of sample determination of the improved methods this procedure places severe strain on the eyes. For this reason all methods are designed for determination by means of a simple filter photometer...

Jan 1, 1965

By I. L. Dillamore

I. L. Dillamore (University of Birmingham)—The different textures developed in various fcc metals have long awaited satisfactory explanation and it has now become clear that these differences are related to parallel differences in the deformation characteristics of the metals. Liu is correct, therefore, in seeking to account for the observed textures in terms of the flow mechanisms but I believe, for the reasons outlined below, that the particular interpretation of flow mechanisms proposed by Liu is open to substantial objections. By considering the forty-eight possible designations of the twelve octahedral slip systems found in fcc metals as distinct and separate deformation modes, Liu has fallen into the error of assuming that only positive glide dislocations associated with each system are present. In fact both positive and negative dislocations will be present and the only difference between for instance the systems B4 and B4' (in Liu's notation) is that under a stress of given sign the direction of motion of a dislocation is reversed on changing from B4 to B4'. For both orientations positive and negative dislocations will be present. In considering possible dislocation interactions it is, therefore, inadmissible to differentiate between R4 and R4' as Liu does. Liu considers those dislocation interactions which give the biggest reduction in energy to be the most favorable and neglects, on the grounds that they will form strong barriers to slip, interactions between dislocations with perpendicular Burgers vectors. Setting aside interactions between positive and negative dislocations of the same slip system, which must occur regardless of the combination of slip systems chosen, the biggest reduction in energy occurs for the Lomer-Cottrell interaction and it is Lomer-Cottrell barriers which are thought to provide the stronger dislocation obstacles. On the other hand the intersection of dislocations with perpendicular Burgers vectors is thought to be a low-energy process which contributes only a fairly small temperature-dependent part of the total work hardening. On this basis it seems doubtful whether the reduction in energy through possible dislocation interactions provides a reasonable criterion for choosing the operative slip systems. From the point of view of texture development it is unsatisfactory to ignore the slip rotations leading to an end position and to neglect to consider the stability of the chosen end point. It is also unsatisfactory to treat the two stress axes as interchangeable since, if the stress system is idealized as biaxial, one stress is compressive and the other is tensile. For the same reason the rotations of the two stress axes are not made compatible simply by assuming that the same slip directions are responsible for the rotations of the two stress axes. It is, in short, essential to treat the two stress axes as acting together on the same slip systems. Turning to the question of the difference between the copper-type and the brass-type texture, there now remains little doubt that the difference is attributable to differences in stacking-fault energy (y), as noted by Liu, but it is doubtful whether the temperature dependence of the texture in copper and in silver is due to increasing stacking-fault energy with increasing temperature. The results of Swann and Nutting42 cited by Liu were obtained in Cu-A1 alloys and the apparent increase in stacking-fault energy on raising the temperature may be influenced by short-range ordering. In pure metals such effects are absent and the only data available on the variation of y with temperature are those of Buhler et a1.43 for silver. They report a minimum at 200°C which does not fit the hypothesis put forward by Liu. It is much more likely that thermal activation of cross slip is important in determining which texture develops, as proposed by Dillamore and tors. These workers have proposed an explanation for the differences in observed texture among the fcc metals and the pole figures predicted consist of an orientation spread which is in better agreement with observation than the limited number of discrete orientations suggested by Liu. The theory of Dillamore and Roberts is also able to account for the differences between aluminum and copper which Liu still leaves unexplained. Y. C. Liu (author's veply)—The writer appreciates the interest of Dr. Dillamore, but must discuss some of his comments in order to avoid cross purposes. The phrase, "forty-eight slip systems," which appeared twice in the text—in the caption of Fig. 1 and the first paragraph in the Discussion—might unfortunately have led Dr. Dillamore to disagree

Jan 1, 1965

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By Edward E. Johnson

The Bureau of 'Mines publishes in its ?Minerals Yearbook? a series of indexes on the domestic minerals industry. Among these are the index of physical volume of mineral production, indexes of stocks, and indexes of average unit mine value and implicit unit value, This report describes the material coverage of these indexes and the methods used in their construction. Detailed descriptions are given for several other mineral-oriented indexes regularly published by other government agencies. These descriptions give the index user a better understanding of what each index purports to measure and aids him in selecting the most appropriate index for his purpose.

Jan 1, 1965

By A. Yoshikawa, T. Sugeno

To detenmine the origin of the sharp fatigue limit in many ferrous metals, S-N curvces were determined in push-pull fatigue at 18.6 kc per sec at room temperature and - 67°C for various kinds of iron. These differed in carbon and nitrogen content and grain size (25 and 2500 grains per sq mm). Sharp knees appeared in the S-N curves of fine-grained specimens with high interstitial content at both temperatures. In coarse-gruined specimens, knees were not sharp .regardless of the interstitial content and the testing temperature. It is concluded from these results that the controlling factov for the appeavance of the sharp fatigue limit is not strain aging but grain size. It has already been mentioned that iron and some iron alloys show fatigue curves characterized by a more or less sharp knee and a fatigue limit.' Explanations of the origin of this characteristic behavior of fatigue in iron appear to fall into two broad classes. One is concerned with interstitial impurities through the aging or locking effect and the other is based on intrinsic plastic properties of iron. Levy and sinclair2 and Lipsit and Horne3 have suggested that the fatigue limit observed generally in iron and steel is due to interstitial solute aging during the course of fatigue. On the other hand, Thompson and wadsworthl have suggested that the fatigue limit may be analogous to the sharp yield point, in the sense that alternating stresses above the fatigue limit are necessary to break down the dislocation locking. However, there are some experimental results which cast doubt on the general validity of these suppositions.4-8 Ferro and Montalenti' have recently suggested that the typical form of the fatigue curve of iron seems to come from an intrinsic plastic characteristic of the iron structure. This suggestion is based on the experimental result that pure iron containing an insufficient amount of interstitial solute to alldw appreciable strain-aging effects still showed a fatigue limit at room temperature. Although systematic investigations on the effect of grain size are scarce, it is thought that this effect is important in relation to the sharp fatigue limit. In fact, sensible differences were observed by Oates and Wilson4 in fatigue behaviors of a low-carbon steel depending on grain size. Ideally, the fatigue limit will be defined as the upper limit of stress amplitudes at which the life is infinite. This ideal fatigue limit can never be determined because of the limited time available for experiments, and moreover scattered data points often leave the construction of S-N curves somewhat arbitrary. And, it is usually stated that a material has a fatigue limit when its statistical S-N curve becomes apparently parallel to the N axis with a more or less sharp knee. The meaning of the fatigue limit and the sharp knee will be discussed in detail in relation to the construction of S-N curves. The origin of this sharp knee was investigated by determining S-N curves of iron for various interstitial contents, testing temperatures, and grain sizes. EXPERTMENTAL PROCEDURE The material as received was a commercial-grade low-carbon steel in the form of 4-mm-diameter rods with the following composition in weight percent: C, 0.09; Si, 0.017; Mn, 0.43; P, 0.006; S, 0.012; Cu, 0.11. Five different groups of specimens were tested. The grain sizes and interstitial contents in each group are given in Table I. The specimens of group C-02 were decarburized by annealing for 100 hr at 700°C, followed by an additional 100 hr at 850°C in wet hydrogen. Specimens of groups N-2 and N-9 nitrided in a mixed atmosphere of ammonia and hydrogen after an initial treatment identical to group C-02. The specimens of group C-9 were prepared in a manner similar to those of group C-02, except heat treatment was carried out in a vacuum. After polishing their surface with emery paper, the specimens of all groups were given a final anneal for 30 min at 930°C and air-cooled in an evacuated quartz tube. For group C*-9 this

Jan 1, 1965

By Uusna S, Canning R. G, Goodheart B. A

The development of a process for removal of iron oxides from ilmenite is outlined whereby the Ti02 content of Western Australian ilmenites can be upgraded from 55 to approximately 90 per cent. In the first stage, the iron oxides are reduced with solid carbon (coal) to metallic iron. Experimental reductions were carried out in crucibles, a fluidized bed, and a small pilot plant rotary kiln. The reduced ilmenite was then agitated in aerated water, in the presenceof catalysts, so that the iron "rusted" away from the ilmenite grains and the precipitated iron oxide was easily separable by decantation.The influence of variables on the rates of reduction and oxidation are discussed. The oxidation rate was examined for both the physical oxygen transfer characteristics and electrochemically by reference to Pourbaix diagrams, in which redox potential is plotted against solution pH.The upgraded ilmenite is expected to be an attractive material for pigment manufacture, and the iron oxide has prospects of being a marketable by-product. The process may possibly be applied to other ores.INTRODUCTIONThere are extensive deposits of ilmenitic beach sands, Le. iron titanium oxides of the general formula FeTi03, 'occurring in the lower south-west portion of Western Australia, and although there has been considerable commercial development, local producers face keen competition on a freight-cost basis. Thus the removal of the unwanted iron oxide constituent would have the double advantage of reducing the freight differential and presenting a more attractivematerial to pigment manufacturers.

Jan 1, 1965

By J M. Anderson

The cable belt conveyor installation at Craigmont Mines Limited, Merritt, B.C., has the greatest one-stage vertical fall of any conveyor installed overland in Canada. Since the late summer of 1961, this conveyor has carried more than 5,000,000 tons of copper ore from open pit to concentrator site. When the conveyor is loaded, the drive motor acts as an induction generator, delivering power to an external circuit. This paper covers the selection, the operation, the performance statistics, and the installation and operating costs of this conveyor system. Introduction T HE Craigmont mine is located in the south-western interior region of the Province of British Columbia, approximately 240 miles northeast of Vancouver. A moderate climate, good roads, service by the Canadian Pacific Railroad, power from the British Columbia Hydro Authority, gas from the nearby main line of the Inland Natural Gas Company and close proximity to the village of Merritt provide a favourable location for this mining operation. The ore occurrences at Craigmont have a vertical extent of 1,500 feet,

Jan 1, 1965

By Richard H. Rein, John Chipman

The activity of SiO2, in the entire liquid system SiO2-CaO-Mg0-A12O3 at 1600°C is calculated from the distribution of silicon between these slags and Fe-Si-C alloys saturated with either graphite or silicon carbide, the activity coefficient of silicon in these alloys, and the requisite thermodynamic data. The activities of the other components in the ternary systems SiO2-CaO-A12O3, SiO2-MgO-CaO, SiO2-MgO -A12O3 are computed from these data by the IrON blast-furnace slags can be regarded as consisting of the four major oxide components, SO2, CaO, MgO, and A12O3 along with minor proportions of other oxides and of sulfur. The purpose of this study is to measure the activity of silica in the liquid solutions of these four oxides at iron-making Gibbs-Duhem equation with the aid of the known free energies of several of the interoxide compounds and the accepted phase diagrams. Based on these activities, new data are Presented for the free energy of formation of a number of the interoxide compounds. The free energy of mixing the liquid metasilicates of CaO and MgO shows slight positive deviations from the ideal. temperatures and to obtain activities of the other components by application of the Gibbs-Duhem equation and the properties of several interoxide compounds. Recent investigations on the activity of silica in the SiO2-CaO-A12O3 system1-3 and recogntion of a serious error in older data for the free energy of formation of SiO2 (Ref. 4) have succeeded in bringing a fair degree of concordance into the results of different investigators. In the present study, the activity of silica is obtained from the silicon-distribution experiments described in a previous paper,' the revised activity coefficient of silicon

Jan 1, 1965

By W. C. Browning

The influence of the hydroxyl factor is more damaging to formations penetrated and causes greater consumption of drilling mud additives than previously realized. This hydroxyl effect on clays is essentially independent of the cations present in the drilling fluid and thus differs from the base exchange reactions that have preoccupied mud chemistry with sodium and calcium bentonite concepts for nearly two decades. The new organic polyelectrolyte-con-ditioned muds haw made it possible to use materials other than sodium hydroxide to maintain the alkalinity of such muds. The properties of silicates, as indicated by their dissociation characteristics and buffering action, are such that they can control he pH and alkalinity of drilling muds at the desired level and, at the same time, minimize undesirable hydroxyl effects associated with sodium hydroxide. This use of silicate compounds is different and distinct from prior applications of silicates as deflocculants or shale preservers. Laboratory and field data presented in this report show that silicate compositions can be utilized to adjust the alkalinity of drilling muds and, at the same time, minimize hydmxyl-promoted clay cleavage. INTRODUCTION Studies for improving the efficiency of rotary drilling techniques must consider the chemistry of drilling fluids and of the formations being penetrated. The chemical aspects of drilling must be studied in conjunction with and in relation to the mechanical factors if, for example, penetration rates are to be optimized. Drilling fluid technology has been largely influenced by chemical reactions of the montmorillonite (bentonite) clay minerals. Most of the literature of mud chemistry concerns the properties of bentonite. Clays of the kaolin or illite type, which are nonswelling, are not generally regarded as sources of drilling mud problems. If these nonswelling shale clays are considered, they are commonly regarded as inert solids. Particularly noteworthy is the fact that the relation of surface and colloid chemistry to massive shale bodies has received only scant attention from drilling technologists. Clay studies reported in the drilling mud literature have dealt, for the most part, with the properties of clays in a finely divided state, and often in very dilute suspensions. Yet frequently during drilling, shale problems not related to the rheology of clay suspensions develop in massive non-bentonitic shale sections of zero or near zero permeability. This paper is concerned with surface chemical reactions that can influence the behavior of these non-bentonite clay masses in such a manner as to adversely affect drilling operations. Browning and Perricone1,2 have pointed out that some of the most troublesome shales to drill, such as the Atoka, contain no montmorillonites. They also pointed out that mud problems can frequently be mitigated by reduction of clay cleavage achieved by using drilling fluids with a minimum of available hydroxyl ions. If pronounced clay cleavage occurs during drilling, the borehole may soften, increasing the possibility of sloughing. In addition, the resulting increased incorporation of high-surface-area clay solids into the mud system can reduce penetration rates and necessitate greater chemical treatment. This increase of shale, of colloidal or near-colloidal dimensions, into the drilling mud is due to clay aggregate cleavage and not to base exchange or swelling reactions, such as occur with bentonites. Searle and Grimshaw3 point out the difference between cleavage or slaking reactions of nonswelling clays (such as illite and kaolinite) and the swelling of bentonite. They further state that the speed of slaking is increased in alkaline water. Eitel1 cites Salmang and Becker, who recognized that clay surface reactions impart plasticity and workability to clay masses. Their results clearly show that all liquids which contain hydroxyl groups in their molecules favor the workability of clays. The ancient technique of aging clays in the moist condition to increase their "workability" is evidence that these clay cleavage phenomena are of considerable importance. The same hydration cleavage that occurs during the aging of nonswelling clays for ceramic use also acts to break up cuttings and soften the borehole during drilling operations. The mechanism of cleavage of the crystalline aggregates of illitic, kaolinitic and other nonswelling clays; and the chemical means of controlling this cleavage are therefore of considerable significance to the drilling mud chemistry. Inasmuch as there is little reference in the drilling mud literature to the cleavage reactions of nonswelling clays, the structure of these clays and certain properties that relate to the mechanism of clay cleavage will be reviewed briefly. STRUCTURE OF NONSWELLING CLAYS Clays such as kaolinite, illite and montmorillonite are compmed of alternate layers of (1) silicon-oxygen tetra-

Jan 1, 1965

By William V. Kotlensky

PYROLYTIC graphite may be represented by a stack of overlapping, wrinkled sheets with the graphite basal planes more or less parallel to the deposition surface. Previous work1" has described two stages in the deformation above 2600°C produced by applying a stress parallel to the deposition surface. The first stage occurs at deformations less than about 15 pct and involves dewrinkling accompanied by basal-plane slip and basal-plane reorientation. The basal planes are not perfectly

Jan 1, 1965

By Rudecindo S. Silo

[The principal characteristics of the process is that when applied in medium or in great degree it only needs unelaborated raw materials such as sodium chloride and calcium carbonate, or of medium elaboration, as sulphur which is found in large quantity in the North of Chili; however, the may be also applied to small copper plants provided that low cost sulphuric acid is available as a substitute for sulphur, that is, in. those plats of small capacity where large additional installations are not needed for the regeneration of the leaching solution. The method itself comprises 6 stages, namely: crushing, leaching, washing; of solutions, precipitation, regeneration of the leaching solution and fusion.]

Jan 1, 1965

By R. Steinitz, L. Seigle, R. Resnick

THE rates of growth of the carbide phases MC and M2C in the Ta-C and Cb-C systems have been measured at various temperatures and the results used to estimate the rate of carbon diffusion within the inter metallic phases. Sheets of high-purity tantalum (50 ppm Cb, <25 ppm Ti, 10 ppm Fe, 5 ppm Cr, <50 ppm Mo, W, and all other metals, 15-75 ppm O2, 10-30 ppm N2, and 10-30 ppm C) approximately 1/4 by 1/2 by 0.020 in. were heated to temperatures between 1800" and 2700°C in a carbon resistor furnace under an atmosphere of argon plus sufficient methane to maintain an excess of carbon at the sample surface. The thicknesses of the carbide layers, illustrated in Fig. 1, were measured with a filar micrometer and plotted logarithmically as a function of time. Fig. 2 is a typical plot for the TaC phase. The points may be represented within experimental error by lines with slope equal to 1/2; therefore the growth of the layers may be described by the usual expression X = kt1/2, where X is the layer thickness, t is the time, and k is a temperature-dependent constant. From these data and compositions at the phase boundaries, it is possible to estimate values for the diffusion coefficients of carbon in each phase, assuming that layer growth occurs by carbon diffusion alone, and that the dif-fusivity is not a function of composition within each

Jan 1, 1965

By I. R. Kramer

I. R. Kramer (Martin Co.)—In a recent paper Nakada and Chalmers24 reported some observations of effects of surface conditions on the stress-strain curves of aluminum and gold single crystals. It is of interest to compare these observations with the results published previously in this journal and to comment on their general conclusions. In brief, Nakada and Chalmers concluded that the removal of the surface layer of a prestrained specimen lowered the stress-strain curve for aluminum but not that for gold. Further, they concluded that the surface work hardening of aluminum is confined to a depth not more than l0-3 cm. In our results25 published previously, it was pointed out that when prestrained specimens of aluminum and gold were polished to reduce the thickness upon reloading the initial flow stress decreased markedly. Further if a sufficient amount of metal was removed, the yield point failed to appear. With continued application of the load the stress-strain curve became coincident with that of the virgin crystal. We have found this behavior in some 100 determinations to hold consistently for gold, aluminum, and copper in both single and poly-crystalline specimens. The amount of strain required before the curves coincided depends upon the amount of metal removed but it is usually less than 0.01. This type of behavior is the same as that reported for metarecovery by other investigators.29 For aluminum specimens which have been prestrained and then heated to temperatures above 50°C we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen. With respect to Ref. 24 the curves for aluminum are always below that of the virgin curves, while those for gold become coincident. This observation indicates at least for aluminum that the specimens must have been heated to a temperature high enough to cause recovery by an alteration of the internal dislocations. In addition, a recovery would be expected because of the removal of the surface work-hardened layer. Nakada27 had reported that, with his particular apparatus in which a perchloric acid polishing solution was used, the temperature of the specimen increased 65°C. The curves presented in Ref. 24 for gold do not permit one to detect the initial flow stress upon reloading after the surface-removal treatment. In fact, contrary to the method used by Nakada and Chalmers, the change in the stress-strain curve produced by a surface-removal treatment cannot be described in terms of a decrease in stress at strains much higher than that at the initial flow stress because of the coincidence of the curves at the higher strain values. With regard to the depth of the work-hardened surface layer, our data show for aluminum single crystals (7.5 by 0.3 by 0.3 cm) that the initial flow stress remained constant after 12 x 10-3 cm had been removed from the thickness. This depth was independent of the prior strain. For gold crystals this depth is somewhere between 10 x 10-3 and 20 x 10-3 cm. Y. Nakada (author&apos;s reply)— Kramer states,28 "for aluminum specimens which have been prestrained and then heated to temperatures above 50°C, we have consistently found that the stress-strain curve was typical of the orthorecovery28 type. In this case the stress-strain curve always lies below that of the virgin specimen." However, Cherian et a1.26 discovered that aluminum polycrystals annealed at 32" and 100°C showed the metarecovery behavior. They showed that the orthorecovery behavior did not appear until the crystals were annealed at 150°C. Kramer suggests28 that the drop in the flow stress of aluminum crystals after the surface removal by electropolishing24 may be due to the recovery caused by the temperature rise which may occur during the electropolishing.27 However, as indirectly stated in Ref. 24, the current density used in these electro -polishing experiments was 0.15 amp per sq cm. According to ref. 27, this current density should cause a temperature rise of only 40°C. This may cause the metarecovery but not the orthorecovery. Furthermore, as stated explicitly in Ref. 24, the surface removal was accomplished by chemical etching as well as by electropolishing. The results were the same for both electropolishing and etching. During the etching, the specimen temperature did not rise above 35°C. Some aluminum crystals were placed in water at 35° C for 30 min. These crystals did not show the decrease in flow stress. Therefore, it is quite clear that the flow-stress drop after the surface removal is not caused by a high-temperature recovery. However, as Kramer points out,28 it is quite possible that the internal dislocation structure may have been altered because of the removal of the highly work-hardened surface layer. However, how much this rearrangement contributes toward the flow-stress decrease is not known at present.

Jan 1, 1965

By Nicholas J. Grant, Robert H. Kane, Bill C. Geissen

The platinum-rich section of the Ta-Pt Phase diagram was worked out by metallographic and X-ray techniques, using twenty alloys; solidus temperatures and solid solubilities were determined. Besides s phase, four intermediate stoi-chiometric phases were found: TaPt (high-temperatzrre phase, structure unknown); TaPt2 (ortho-rhomhic, new type); a TaPt3 (orthorhombic, TiCu3 type); ß TaPf3 (monoclinic, new type). TaPt2 and TaPt3 melt congmentlv; two eutectic, two beritec-tic, and one eutectoid reactions occur in the inuestigated range. THE Ta-Pt system was examined as part of a study of the phase diagrams and the intermediate phases of niobium and tantalum with Group VIII transition metals. Since the main scope of this work was the relation among the ordered close-packed phases occurring in the concentration range from AB to AB3 (A = Nb, Ta; B = Pd, Pt, and so forth), only the platinum-rich side of the diagram was worked out thoroughly, while spot checks were made to determine the approximate outline of the tantalum-rich portion. The system has not been thoroughly treated in the literature; Greenfield and Beck1 in their survey of refractory metal intermediate phases found a o phase between -18 and 37 at. pct Pt which coexists at higher platinum concentrations with an unidentified intermediate phase. Browning2 worked on the range between 55 and 100 at. pct Pt; however, this preliminary study did not cover temperatures >1500°C, and included no conclusive crystallo-graphic data. More recently, a study of the platinum-rich section of the Ta-Pt system has been carried out by Ray,3 while Hartley, Parsons, and steedly4 have studied the tantalum-rich section. The crystal structures of TaPt2, a TaPt3, ß TaPt3, and others have been reported in abstracted form by Giessen and Grant.5 EXPERIMENTAL METHODS The methods of alloy preparation and processing and of the metallographic and X-ray procedures follow very closely those described by Ritter, Giessen, and rant&apos; for other refractory metal-noble metal systems, and will not be repeated except where significant differences exist. Starting materials were: tantalum rod of 99.95 pct purity, supplied by National Research Corp., and platinum sponge 99.9 pct, supplied by The International Nickel Co. An oxygen analysis of the tantalum rod showed 30 ppm O; other impurities were C, N, Si, Nb, Mo, none of these exceeding 50 ppm, and 100 ppm W. Homogeneous buttons were readily prepared as follows: ingots of 5 g were weighed and arc-melted under welding grade argon, followed by two remelts after inverting the button. Between 40 and 100 at. pct Pt, weight losses during the first melt rarely exceeded 0.1 pct, in which case the alloy was rejected, and were nil on subsequent remelts. Since the vapor pressure of platinum far exceeds that of tantalum, the small evaporation loss could be assumed to consist of platinum; therefore, a corresponding amount of platinum was added on the second melt. Since it was confirmed on pure tantalum samples that no weight gain through oxygen or impurity pickup occurs (see Ref. 71, it could be assumed that the uncertainty in the composition did not exceed ±0.1 at. pct for the range 40 to 100 at. pct Pt. For the four control melts from 0 to 40 at. pct Pt, an error of ±0.5 at. pct was calculated. Microscopic examination of the whole buttons after melting showed no inhomogeneity other than local coring. This was eliminated by a homogenization heat treatment. A total of twenty-three alloys were prepared. Heat treatments were carried out in a tantalum

Jan 1, 1965

By J. J. Cosgrove, J. E. Warren

A general model which approximates the effect of cross- flow has been developed to give a practical method for predicting the waterflood behavior of a stratified reservoir. The model is based on a modification of Dietz&apos;s theory and allows for variations in both the permeability and hydrocarbon pore volume. In the particular cases considered, it is assumed that the permeability can be characterized by a log-normal distribution and the hydrocarbon pore volume by a normal distribution. A simple graphical method which enables the practicing engineer to predict the behavior of a stratified system is presented The results obtained by the proposed method are compared with those obtained by the Dykstra-Parsons method. As a result of this study the following conclusions have been drawn: (1) The effect of cross-flow in a stratified system can be appreciable, particularly at very favorable or very unfavorable mobility ratios; (2) Under normal conditions, the effect of variations in the hydrocarbon pore volume can be neglected; and (3) The failure to use all of the available permeability data can lead to large errors in the prediction of the behavior of a stratified reservoir. INTRODUCTION Various methodshavebeenproposedto characterize and to predict the waterflood behavior of a stratified reservoir. Most of the methods assume that the reservoir is composed of discrete homogeneous continuous layers. With this model, the degree of stratification can be measured by several parameters based on core-analysis data. Among these are the Lorenz coefficient1 and the variation of a log-normal permeability distribution? The behavior of stratified systems is usually predicted by the Stiles, Dykstra-Parsons method or some modification of these. In both of these methods the reservoir is divided into discrete homogeneous layers with no cross-flow between layers. In the Stiles method the mobility ratio is assumed to be equal to unity while in the Dykstra-Parsons method it is allowed to take on any value. Other predictive methods have been proposed; method allows for cross-flow between the beds and a method by Schmalz and Rahme6 correlate.s the recovery directly with the Lorenz coefficient. In this new approach, which is essentially a continuous analog of Hiatt&apos;s method, the effects of both mobility ratio and cross-flow between the beds have been included. It is assumed that the permeability can be represented by a log-normal distribution and the hydrocarbon pore volume or porosity by a normal distribution. These types of distributions have been observed by several authors, 1,2,4 and most field data seem to confirm their observations; e.g., if these distributions are assumed and there is a 1:l correspondence between porosity and permeability samples, the commonly encountered linear relationship between porosity and the log of permeability is obtained. Since, in many field cases the permeability and poro sity data are truncated or cut-off at predetermined upper and/or lower values, the effect of discarding part of the data was investigated with the proposed method. A better technique for truncating the data is suggested. THEORY In the derivation of the method to be described in this paper the following assumptions are made: 1. Capillary forces are negligible per se; their effects are only manifest in the relative permeability curves. 2. The fluids are immiscible, incompressible and homogeneous. 3. The reservoir is horizontal and uniformly thick; it is initially liquid saturated i.e., connate water and oil. 4. The reservoir is composed of discrete layers, each having its own permeability, porosity and connate water saturation; each layer is homogeneous,

Jan 1, 1965

By A. G. Crocker

The positions of twin reflections in electron-dijjcraction patterns obtained from thin metal foils may he calculated for any twin in any crystal structure by means of an elementary application of vector algebra, General equations for the four classical orientation relationships are presented using the superscript and subscript notation of the tensor calculus, which is briefly described. As an example of the application of these expressions, the case of twinned rhomhohedral crystals, and hence as a special cased twinned cubic crystals, is examined. CONSIDERABLE interest has recently been shown in the interpretation of electron-diffraction patterns obtained from twinned regions of thin metal foils. In the present paper, it is shown that the necessary information may be obtained directly for all twins in any crystal structure by means of a very elementary application of vector algebra. The equations involved are most conveniently presented by making use of the very powerful superscript and subscript notation of the tensor calculus. The use of this notation will first be described and then applied to the problem of calculating diffraction patterns for any twinned crystal. Finally, as an example of the application of the method, the specific case of twinned rhombohedra1 crystals will be considered.

Jan 1, 1965

By Charles W. Merrill

The U.S. Treasury stocks of silver have been reduced at such a rapid rate to meet industrial and coinage requirements that they face exhaustion in 3 or 4 years. Alleviation of the silver problem will require increasing supply or reducing demand. This paper examines possible long-range resource development and research programs and improved secondary recovery. The possible reduction or elimination of silver in coinage and development and introduction of substitutes in the arts and industry are also discussed.

Jan 1, 1965

By W. F. Rogers, J. A. Stewart, P. J. Kalish, E. O. Bennett

Detailed descriptions are given of materials, apparatus and the experimental procedure used to study the effect of bacteria on sandstone permeability. The factors affecting permeability during injection of bacterial suspensions which have been investigated are: (I) concentration of bacteria; (2) core permeability and median pore size; (3) species of bacteria, mode of aggregation and relative size; (4) injection rate or pressure differential; (5) mean pressure; and (6) depth of penetration of bacteria. The investigation demonstrated that bacteria cannot reduce core pertneability to zero and that their effect on permeability is subject to definite limitations. Remedial or permeability restoration studies also were made. Acidization in combination with reverse flow war found to be an effective method for restoring permeability In cores partially plugged with bacteria. The relationship between the bacterial quantities in the laboratory tests and those found in field operations is discussed. The linear laboratory flow data have been translated into terms of field radial systems; these data indicate the most practical methods of maintaining injection rates in the presence of bacteria are to increase injection pressures or hydraulically fracture the formation. INTRODUCTION It has long been known that various bacteria flourish in the above-ground components of oil field water-injection systems. The presence of these bacteria has led to the suspicion that they might enter into the causes for reduction of injection well permeability, but only recently has an attempt been made to describe the effects quantitatively.1 Biocides are used in many cases without a firm knowledge as to whether the bacteria are killed, or if they are, whether the dead cells affect formation permeability. This project was undertaken as part of a study to determine the effect of bacteria, residual oil and precipitated solids such as iron sulfide or calcium carbonate on the permeability of sandstones and to learn whether any of these materials adversely affect brine injectivity in secondary recovery or disposal operations. This report deals with that portion relating to the effect of bacteria. MATERIALS CORES Three different permeability ranges of Berea sandstone cores were used in the study. The range of initial, absolute brine permeabilities kj were: high — 278 to 400 md: medium—130 to 162 md; and low—17.7 to 48.3 md. The permeability data for the cores used in the tests are included in Table 1. All cores were cut to a nominal 1 in. diameter. Following air permeability determinations, they were molded with an epoxy resin in 1.5 in. ID aluminum sleeves. The sleeves had drilled and tapped holes for intermediate pressure connections along the length of the cores. After molding, the high- and medium-permeability cores were trimmed to 4 in. in length and the low-permeability cores to 2 in. These lengths resulted in pore volumes of approximately 10.9, 10.4 and 4.4 ml, respectively, for the high-, medium- and low-permeability cores. Pressure-transmitting channels were drilled through the plastic into the core proper, using the sleeve holes as drill guides. Width and depth of channel penetration into the core proper were approximately 0.03 in. and 0.05 in., respectively. Three pressure taps were used with all cores; for the high- and medium-permeability cores the taps were spaced 1 in. apart; for the low-permeability cores the taps were spaced 0.4, 0.8 and 1.2 in. from the inlet end. Pore size distributions were calculated from restored-state capillary pressure curves for representative cores in each of the three permeability ranges. In each case the pore size range with the greatest percentage of the pore space included the very small pores up to 0.5 micron in radius. The median pore radii were in the 5.5 to 6 micron range for the high-permeability cores; in the 4.5 to 5 micron range for the medium-permeability cores; and in the 3.5 to 4 micron range for the low-permeability cores.

Jan 1, 1965

By P. W. Davies, B. Wilshire

PREVIOUS investigations on the effect of stress changes on the high-temperature creep and fracture behavior of metals have been confined mainly to the testing of complex alloys.172 Most of these alloys are structurally unstable during creep because of such effects as recrystallization, overaging, and so forth, so that the results are of limited application. The only pure metals on which observations have been made appear to be lead3,4 and aluminum5 tested under conditions which allow rapid recovery to take place. The present work describes the effect of a single stress change on the creep and fracture properties of a metal in which recovery is very slow. A Ni 0.1 at. pct Pd alloy was used so that grain growth and recrystallization did not occur during creep testing. Specimens of this material were heat-treated to give a uniform grain size of 10 grains per mm. Creep tests were carried out at 500°C using Denison T.47 machines; details of the creep-testing procedure have been given elsewhere.&apos; All specimens were tested at a constant initial stress of 5 tpsi which gives, in an uninterrupted test, a minimum creep rate of ~10-3 pct per rnin and a life of -7000 min. Specimens were loaded under these standard conditions and after 1500 min, when secondary creep was well-established, the stress was changed to either 8, 7, 6, 4, 2, or 0 tpsi for a period of 180 min. After this time the original load was reapplied and the tests continued to fracture. The results are shown in Fig. 1. No detectable creep occurred during the period of reduced load, even at 4 tpsi, and on reverting to 5 tpsi the creep rate returned to its original value immediately. Increasing the stress to 8, 7, or 6 tpsi resulted in an instantaneous extension followed by a period of transient creep leading to a new steady creep rate. On returning from these higher stresses, the resulting creep rate at 5 tpsi was very low compared with the original value. Furthermore, the higher the stress during the stress change, the lower was the final creep rate. It is significant that the rupture life is comparatively unaffected by any of these stress changes.

Jan 1, 1965