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The following is an incomplete list of members and guests who called at Institute headquarters `during the period Aug. 10, 1918 to Sept. 10, 1918. Amil A. Anderson, Hill City, S. D. A. A. Holland. H. G. S: Anderson, Hurley, N. Al. Paul S. King, Wilmington, Del. Louis A. Barton, Capt., Engineers, U. S. A. Herbert G. Officer, Washington, D. C. K. Baumgarten, lst Lieut., U. S. R. A. B. Parsons. Charles W. Boise, Belgian Congo. Robert R. Pollock, San Francisco, Cal. Henry C. Carlisle, The Pas, Manitoba. Frank A. Smith, Edgewood, Md. J. Ross Corbin, Boyertown, Pa. Edward C. Thompson, Kennett, Cal. S. Le Fevre, Forest Glen, N. V. Malcolm M. Thompson, Morsemere, N. J. Harold P. Ford, Cleveland, 0. Lester C. Uren, Berkeley, Cal. William L. Hogg, Waynesboro, Va. Harold W. Aldrich has been appointed assistant general superintendent of the Inspiration Consolidated Copper Co. at Inspiration, Ariz. Capt. Percy E. Barbour, formerly with the New York State Troopers, has been granted a leave of absence from the Department for the period of the war, by the Governor, and has been appointed Captain in the Engineer Corps, U. S. A. He served on the Mexican border in the New York State National Guard. A. C. Barke, formerly with the United States Smelting, Refining and Mining Exploration Co., has accepted a position with the United States Fuel Co. at' Salt Lake City, Utah.

Jan 10, 1918

By W. L. McMorris, A. H. Brisse

IN the last several years the coal industry has intensified its effort to solve the growing problem of cleaning and recovering fine mesh coals. On one hand these has been increasing civic pressure for cleaner streams, and on the other hand there has been increasing production of fine mesh coal, resulting directly from adoption of the modern mining methods so essential to the economy of the coal mining industry. Cleaning fine coal with the same precision possible with coarser coals is a difficult task, and for coals finer than 200 mesh it has been impractical. Furthermore, the inclusion of —200 mesh material in the final product markedly increases costs of de-watering and thermal drying, which are necessary steps if coal is to meet market requirements. Consequently these extreme fines have generally been wasted. As a result, problems have been created in many districts because there has not been enough area for adequate settling basins. Wasting of coal in the -200 mesh slimes may account for a loss in washer yield equivalent to 2.0 to 2.5 pct of the raw coal input. With rising mining costs the value of such a loss is constantly increasing and a need for a better solution to the fines problem becomes more pressing every day. From an operating viewpoint, also, continuous removal of extreme fines from the washing plant circuit permits good water clarification practice, improving significantly the overall cleaning efficiency. The obvious desirability of recovering a commercially acceptable coal from washery slimes prompted U. S. Steel Corp. to investigate the merits of the Convertol process developed in Germany." Although this process has been used commercially in Europe for some time, little if any consideration has been given to its possible adoption in the U. S. until very recently. Fundamentals of the Convertol Process: In the Convertol process, droplets of dispersed oil are brought into intimate contact with the solids suspended in the coal slurry to be treated. This contact causes oil to displace the water on the surface of the coal by preferential wetting, or phase inversion, after which the coal particles are allowed to agglomerate in a manner permitting their re- moval from the slurry by centrifugal filtration. The clay and other particles of mineral matter suspended in the slurry do not have the affinity for oil the coal particles have. Consequently the oil treatment is preferential to coal to the extent that more than 95 pct of the oil used reports with the clean coal recovered. Figs. 1 through 3 will clarify the steps involved in the process. Fig. 1 shows the suspended material in the slurry to be treated, which is a thickened product containing 40 to 45 pct solids. Oil is now injected into the slurry under vigorous agitation to produce good oil to coal contact conditions, which result in preferential oiling of the coal particles. These coal particles are then permitted to agglomerate by gentle stirring in a conditioner to form flocs, as shown in Fig. 2. At this point in the process the agglomerated oiled coal can be washed and partially dewatered on a vibrating screen, as shown in Fig. 3. Finally, the washed flocculate can be further dewatered in a high-speed screen basket centrifuge or in a solid bowl centrifuge. Commercial Application of the Convertol Process in Germany: The original Convertol process was developed by Bergwerksverband zur Verwertung von Schutzrechten der Kohlentechnik, G.m.b.H., a German research organization controlled by the Coal Operators Assn. of the Ruhr Valley. The process as reduced to commercial practice in Germany' is shown in Fig. 4. In this process a thickened slurry (40 to 45 pct solids) mixed with a predetermined percentage of oil is fed from a surge tank to the phase inversion mill. After the phase inversion step, the slurry is usually discharged directly to a highspeed screen centrifuge. From 3 to 10 pct oil is used, depending on type of oil, size consist of coal to be recovered, and operating temperature. The top size of fine coal cleaned in Germany by the Convertol process is limited by the size of the openings in the centrifuge screen basket. Any mineral matter coarser than the basket opening, which is generally 60 to 80 mesh, must remain with the oiled coal. If the coal fines have been effectively cleaned down to about 80 mesh, the cleaning performance of the process is practically unaffected by the presence of coarse coal particles. However, since recovery of coal much coarser than 80 mesh is mow economical by conventional methods, it normally becomes more costly to allow substantial percentages of this coarse coal in Convertol process feed. Where the general plant layout does not permit effective cleaning of coal sizes down to 80 mesh or lower. there is some justification for a coarser Con-

Jan 1, 1959

By V. Koump, T. F. Perzak, R. H. Tien

A series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts Mere measured during essentially one-dimensional freezing of Al-Cu alloys. The dimensions of the ingots were 3 by 5 by 6 in. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experitments. For each alloy the rate of heat removal was varied to give a total jreezing time in the range 3 to 30 min. The results of these measurements cowlpared favorably with the theoretical model of freezing of binary alloys with time-dependent surface temperature. IN engineering analysis of solidification of commercia1 steels and nonferrous alloys it is a common practice to assume that an alloy freezes by propagation of an isothermal solidification front, i.e., essentially as a pure metal. In two recent theoretical investigations'j2 the present authors explored the possibility of a more realistic approach to the problem of solidification of alloys. In the proposed model the freezing of an alloy is assumed to take place by propagation of two isothermal fronts, i.e., the liquidus front and the solidus (or eutectic) front. The region between the two fronts contains both liquid and solid and is referred to as the solid-liquid region. The width and the solid content of the solid-liquid region vary with alloy type, solute concentration, and cooling rate. For a given alloy system, initial concentration of solute, and the mode of heat removal, the proposed model yields the temperature distribution within the solid skin, temperature, solid fraction, and concentration distributions with the solid-liquid region, and the rates of propagation of the liquidus and the solidus fronts. This model is obviously of considerable practical importance in engineering analysis of solidification processes, since it gives a more realistic estimate of skin strength during solidification and a better estimate of the total freezing time. Before the new model can be used with confidence, however, it is necessary to test this model experimentally. The experimental testing of the proposed model is a relatively simple matter since the effects to be measured are large and a relatively simple experiment will suffice. The theoretical model predicts, for example, that during freezing of an alloy containing substitutional type solute (negligible diffusion in the solid during freezing) the solid-liquid region occupies an appreciable portion of the ingot, even at low concentration of solute.' Another prediction of the theo- V. KOUMP, formerly with U. S. Steel Corp., is now with Research and Development Center, Systems and Process Division, Westinghouse Electric Corp., Pittsburgh, Pa. R. H. TlEN is Senior Scientist, Fundamental Research Laboratory, U. S. Steel Corp., Research Center, Monroe ville, Pa. T. F. PERZAK, formerly with U.S. Steel Corp., is now with Fiber Industries, Greenville, S. C. Manuscript submitted March 6, 1968. IMD retical model, easily verifiable by experiment, is that the rate of propagation of the solidus (or eutectic) front increases as the solidus front approaches the center of the slab. This prediction is contrary to well-known behavior of the solidification front during freezing of pure metals, where the rate of propagation of the solidification front decreases with time and freezing is completed at the lowest rate. A rather severe test of the proposed model is provided by comparison of theoretical predictions and experimental measurements of the effects of cooling rate and composition on the rates of propagation of the liquidus and the eutectic fronts. In order to test the soundness of the formulation and the method of solution of the problem of solidification of alloys a series of experiments were carried out in which the rates of propagation of the liquidus and the eutectic fronts were measured during essentially one-dimensional solidification of A1-Cu alloys. The A1-Cu system was chosen strictly as a matter of convenience. Three different alloys containing 0.1, 4.5, and 17 pct Cu were used in these experiments. For each alloy the rate of heat removal was varied to give the total freezing time in the range 3 to 30 min. The results of these measurements are compared with the predictions of the theoretical model of solidification of binary alloys, with time-dependent surface temperature.' Before the experiments described in this paper were undertaken, a serious attempt was made to utilize the measurements of previous investigators to test the theoretical model. In the course of this preliminary study a careful review was made of experiments of Pellini and coworkers3 and Doherty and Melf~rd.~ The measurements in Pellini's work were carried out using a steel containing at least four major components. Evaluation of the solid fraction-temperature relation for this steel (required in the theoretical model) is difficult and uncertain. Doherty and Melford, on the other hand, measured the solid fraction-temperature relation experimentally, but did not give sufficient data to explore the effects of composition and the cooling rates on solidification. Hence it was not possible to utilize these measurements to test our theoretical model. EXPERIMENTAL METHOD The experimental technique used in this investigation differs somewhat from the more conventional techniques employed in solidification studies. This technique was developed primarily to eliminate con-vective mixing in the molten metal caused by pouring of molten metal into the mold. In our experiments A1-Cu alloys were melted directly in the mold. The mold assembly used in solidification experiments is shown in Fig. 1. The mold was fabricated from *-in. stainless-steel sheet. The dimensions of

Jan 1, 1969

By R. S. French

The purpose of this paper is to present data that have been obtained during the past two years concerning the effects of prior cold-work and temperature and time of anneal upon the recrystallization and grain growth of 70-30 cartridge brass. It was desirable to study certain of these phases so that an accurate picture of the principles of the subject could be shown. The work is not intended to provide explicit annealing data, but to provide material examples that may help to clarify analogous problems concerning this alloy. Specifications often set limitations upon the grain size of annealed materials because of the importance of grain size upon subsequent manufacturing operations. It was, therefore, worth while to study the variables that affect the recrystallized grain size of this material. C. H. Mathewson and A. Phillips,l W. R, Webster,2 and others have presented annealing characteristic curves of this alloy. A recent typical curve presented by R. S. Pratt3 is shown in Fig. I. The tensile properties and grain sizes are shown as functions of the annealing temperature. Such curves serve as a useful guide in determining the physical properties of annealed material, but as they are made generally under carefully controlled laboratory conditions they do not indicate the performance of metal annealed in a mill muffle, where such conditions as amounts of metal, heating time and temperature may differ. Study of the effect of time and temperature upon grain growth and subscquent recrystallization was made with a coil of metal having the following analysis: 70.04 per cent copper; 0.007 lead; 0.007 iron; 0.00 tin; 0.00 silicon; 0.001 nickel; 0.000 phosphorus; balance zinc. The sample coil was obtained from metal that had been rerolled from hot-rolled mill stock, and was received at 0.228-in. gauge, soft, with a grain size of 0.125 mm. This material was then rolled 43.5 per cent to 0.129-in. gauge and annealed to a 0.053-mm. grain size. In this condition, samples were cut and used in all of the experimental work reported in this paper. Time The first study was of crystal growth at a constant temperature over a moderate length of time. Material was cut from the stock coil at 0.129-in. size and rolled 75 per , cent hard to 0.032-in. gauge. From this piece small samples were cut M by 2 in., suitable for grain-size determina.tions. Twelve samples were placed in an electric furnace uniformly across the width, approximately an inch from the floor. A thermocouple was wired to the center sample, so that the approximate metal temperature could be followed. At various

Jan 1, 1944

By R. S. French

The purpose of this paper is to present data that have been obtained during the past two years concerning the effects of prior cold-work and temperature and time of anneal upon the recrystallization and grain growth of 70-30 cartridge brass. It was desirable to study certain of these phases so that an accurate picture of the principles of the subject could be shown. The work is not intended to provide explicit annealing data, but to provide material examples that may help to clarify analogous problems concerning this alloy. Specifications often set limitations upon the grain size of annealed materials because of the importance of grain size upon subsequent manufacturing operations. It was, therefore, worth while to study the variables that affect the recrystallized grain size of this material. C. H. Mathewson and A. Phillips,l W. R, Webster,2 and others have presented annealing characteristic curves of this alloy. A recent typical curve presented by R. S. Pratt3 is shown in Fig. I. The tensile properties and grain sizes are shown as functions of the annealing temperature. Such curves serve as a useful guide in determining the physical properties of annealed material, but as they are made generally under carefully controlled laboratory conditions they do not indicate the performance of metal annealed in a mill muffle, where such conditions as amounts of metal, heating time and temperature may differ. Study of the effect of time and temperature upon grain growth and subscquent recrystallization was made with a coil of metal having the following analysis: 70.04 per cent copper; 0.007 lead; 0.007 iron; 0.00 tin; 0.00 silicon; 0.001 nickel; 0.000 phosphorus; balance zinc. The sample coil was obtained from metal that had been rerolled from hot-rolled mill stock, and was received at 0.228-in. gauge, soft, with a grain size of 0.125 mm. This material was then rolled 43.5 per cent to 0.129-in. gauge and annealed to a 0.053-mm. grain size. In this condition, samples were cut and used in all of the experimental work reported in this paper. Time The first study was of crystal growth at a constant temperature over a moderate length of time. Material was cut from the stock coil at 0.129-in. size and rolled 75 per , cent hard to 0.032-in. gauge. From this piece small samples were cut M by 2 in., suitable for grain-size determina.tions. Twelve samples were placed in an electric furnace uniformly across the width, approximately an inch from the floor. A thermocouple was wired to the center sample, so that the approximate metal temperature could be followed. At various

Jan 1, 1944

By A. Goldberg, T. E. Tietz, J. E. Dorn

Introduction The concept that the flow stress for plastic deformation of metals in the work hardening range is a function of the instantaneous values of the strain, strain rate and test temperature was promulgated by Ludwick' many years ago. This thought has been more or less a guiding principle throughout the immediate period of development and growth of mechanical metallurgy. It has been tacitly assumed or knowingly applied to many investigations on the plastic behavior of metals. Spurred by the theoretical interest and practical importance of the plastic behavior of metals, many investigators have attempted to determine empirical, semi-empirical, and theoretical equations2-l8 relating the flow stress with the strain, strain rate, and temperature. Although the applications of such equations have been extensive, the experimental verification of the existence of a mechanical equation of state is weak. Furthermore, some of the available evidence on plastic flow appears to suggest that no simple functional relation between stress, strain-rate, strain and temperature can exist. The mechanical equation of state demands that Where a = true stress = loadlinstantaneous area e = true strain _ Instantaneous gauge length ~ initial gauge length i = true strain rate T = temperature This formulation implies that da is an exact differential. Therefore the flow stress (a) is a function of the instantaneous values of the strain (c) the strain rate (i) and the temperature (T), independent of the previous mechanical or thermal history. Having reached a certain strain, strain rate, and temperature, by any path whatsoever, a definite and fixed value of the flow stress should be obtained. One check on the validity of the mechanical equation of state is easily obtained. Consider the following three tests on the stress-strain curve at constant temperature: A. Strain at rate :I B. Strain at rate it C. Strain at rate 11 to el and continue test at &. A graphical representation of possible results of such tests are shown in Fig I. If, for strains greater than el, test (C) data coincide exactly with the data from test (B), as shown in Fig ra, a limited verification of the mechanical equation of state is obtained for the range of strain rates from il to iz. But if the data from test (C) differ from those of (g) beyond strain t\ where the strain rate is changed from il to k2, the mechanical equation of state is not

Jan 1, 1949

By C. F. Jenkins, G. V. Smith

Serrated plastic flow in stable austenitic alloys based on Fe/Ni has been shown to be related to the presence of carbon and/or chromium in the systems. Strength peaks and plateaus in the serrated-flow temperature region for a commercial alloy correlate with an increased dislocation content, arising, presumably, from enhanced multiplication as a result of a strong interaction between dislocations and solute atoms. The data generally support a mechanism controlled by migration of vacancies, with the energy for vacancy motion being modified by the presence of chromium. Chromium atom -dislocation interaction is responsible for effects above 500°C, whereas the defect interacting with dislocations between 200" and 500°C is suggested to be a carbon-vacancy Pair. ThE phenomenon of jerky flow, serrated flow, or the Portevin-le Chatelier (P-C) effect in austenitic stainless steels is usually attributed to substitutional at1,2 mospheres1,2 or to precipitates&apos;-4 which form at dislocations during plastic deformation. On the other hand, evidence exists which supports a direct inter-stitial-dislocation interaction mechanism for serrated flow in fcc Ni-C,5,6 Ni-H7-9 and in nickel-austenites containing carbon." The present work consists in a study of serrated plastic flow in stable austenitic al-loys. The effects of carbon and of chromium were investigated separately, and a commercial stainless steel with different levels of interstitial impurity concentration was studied in an attempt to delineate the combined effects of the alloying elements. EXPERIMENTAL TECHNIQUES a) Materials and Fabrication. A commercial AISI 330 stainless steel and several specially prepared aus-tenitic alloys have been studied. The experimental alloys were prepared by arc melting the constituents under purified argon. Analyses of the materials are given in Table I. The commercial alloy was obtained as 5/8 in. bar stock and rolled to 0.092 in. sq, with several intermediate anneals. At this stage some of the material was annealed in Pd-purified hydrogen at 1100°C to establish different levels of interstitial content. All other heat treatments were in vacuum (10-5 torr). The "pure" alloy ingots were swaged to 0.120-in. rod and annealed in Pd-purified hydrogen at 1100°C. The analyses for these conditions are also contained in Table I. Following the above treatment, the final wire sizes Table I. Chemical Analyses of Test Materials Hrin Hydrogen at Cr, Ni, Alloy 1lOO°C wt pct wt pct C, ppm* N, ppm* Type 330 As-received 14.78 33.25 430 300 Type 330 64 14.78 33.25 40 50 Type 330 200 14.78 33.25 27 21 Fe/35 Ni 72 - 35.10 <10 62 Fe/35 Ni 200 35.10 <I0 44 Fe/35 Nil15 Cr 72 14.95 34.94 <I0 61 Fe/35 Ni/15Cr 200 14.95 34.94 <10 45 Fe/35 Ni/C $ 35.OM 380 *Sensitivity: N t 5 ppm Ct10ppm. f Nominal Ni content. % A master NiC alloy was used in preparation of this material; courtesy of D.E. Sonon. were obtained by either swaging or cold drawing. The test results did not vary with these techniques. b) Specimen Preparation. Two sizes of specimen and two gripping systems were used. i) 0.070-in. wire with a chemically milled gage section: 0.75 in. long, 0.060 in. in diam. These were fastened into grips containing tapped grooves. ii) 0.050 in. wire, gage length 1.5 in. Ball bearings were welded to the ends of the wires and the gage length was taken to include all material between the welds. Socket-type grips were used with these specimens. With specimens of type ii), joining was performed in a specially constructed brass jig, under argon, and automatic timing was utilized in the procedure. No adverse effects of welding were noted. Specimens were encapsulated and solution treated for 1 hr at temperatures selected to produce the same average grain size, -50 µ. Annealing twin boundaries as well as normal crystal boundaries were counted. The temperatures used are listed in Table 11. Table 11. Specimen Size. Temperature of Heat Treatment and Resulting Grain Diameters for Test Materials Recrystallization Resulting Material Condition Temperature Grain Sue AISI 330 Not H purified 0.070 120O°C 45 to 55µ in, wire AlSl 330 H , pure, 0.070 in. 1150°C 45to55µ wire Fc/35Nil15Cr Pure, 0.070 in. wire 1000°C 45tossp Fe/Ni Pure. 0.070 in. wire 775°C 45 to 55µ Fe/Ni/C Pure, 0.050 in. wire 850°C 10 to 20p AlSl 330 Not purified, 0.050 1150CC 45to55p in. wire AlSl 330 ti, pure, 0.050 in. 1150°C 45to55p wire

Jan 1, 1970

By Rodney P. Smith

The diffusivity of carbon (0.1 wt pct C) in Fe-Nz alloys (0 to 100 pct Ni) has been determined for the temperature range 860° to 1100°C. As a function of nickel content, the diffusivity has a maximum near 60 pct Ni (the maximum diffusivity being about 1.3 times that in the absence of nickel); the activation energy has a maximum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The difference between the minimum activation energy and that in iron is about 3000 cal pev g-atom; Do has a minimum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The results cannot be rationalized by an approximate thermodynamic treatment. THE diffusivity of carbon has been determined in a number of iron alloys over a limited concentration range. It seemed desirable to investigate a system which allows an extended range of alloy composition within a single-phase region. The Fe-Ni system is ideal in this respect, in that all alloys from 100 pct Fe to 100 pct Ni are fee in a convenient temperature range.&apos; The carbon diffusivity was determined by a decar-burization method. The experimental procedure was identical with that used to determine the diffusivity of carbon in y Fe-Co alloys.2 The experimental data are given in Table I. A small correction (order of a few percent) has been made to the measured carbon loss to correct for the carbon lost from the ends of the cylinders.&apos; Since the diffusivity of carbon varies with carbon content the measured diffusivity is an average value for a carbon content between zero (surface) and that at the center of the sample at the end of the decarburization periods. In making the correction in D to 0.1 wt pct C it is assumed that the measured D corresponds to the arithmetical mean of the carbon content at the surface and at the center of the sample at the end of the decarburization period.3 Since this correction is small (<4 pct in D) and since for our decarburization times the changes in carbon content at the center of the sample was small the mean carbon content could have been taken as half the initial value. It is further assumed that the change in D with carbon content for the alloys is the same as that for the diffusion of carbon in iron. From the data of Wells, Batz, and Mehl4 and of smith5 the correction of D from the mean carbon content to 0.1 wt pct C is 0.3 (0.1 - mean wt pct C). The results for iron are given in Ref. 2. Within the experimental error log Do.l%C for each alloy is a linear function of 1/T; the constants for the equation determined by the method of least squares are given in Table I. The deviations of the experimental points from the least-squares line are of the order of 2 pct in D. A comparison of our results for the diffusivity of carbon in nickel with those of other investigations is shown in Fig. 1. The lower curve in Fig. 1 is a linear extrapolation of values calculated* from the equation of Diamond6 for the relaxation time (temperature range 100° to 500°C). The results indicate a small increase in the activation energy over the temperature range 100° to 1400°C; however, it is difficult to say whether the change in Q is real or experimental error. Certainly the change in Q is less than the variation of 5 kcal per g-atom in the diffusivity of carbon in a iron.6 The experimental data for all the alloys are plotted in Fig. 2. As a function of nickel content the diffusivity has a maximum near 60 wt pct Ni at all temperatures investigated and possibly a minimum between 80 and 90 wt pct Ni for temperatures below 1000°C. The activation energy, Q, and log Do are plotted as a function of the nickel content in Fig. 3. Due to the limited temperature range of our experiments neither Q nor Do can be determined precisely; the activation energies appear to be consistent to ±0.3 kcal per g-atom; however the deviation from the absolute values may be considerably larger, see Table II. The Do values probably have little significance. The solid line for Do in Fig. 3 represents the values required to reproduce the experimental values for D when Q has values represented by the upper solid line The diffusivity of carbon may be expressed in terms of the mobility B22, the activity coefficient r2,

Jan 1, 1967

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.&apos; These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that &apos;relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By H. K. Livingston

A technique has been developed which makes it possible to determine the spreading pressure of liquids and solids, for simple systems. Data for surface tensions, interfacial tensions, spreading pressures, and contact angles for water, heptane, and silica are tabulated.&apos; These results can be applied to the evaluation of capillary rise and displacement pressure in a petroleum reservoir. Appropriate equations are presented and the application of these equations is discussed. The presence of surface-active components affects both capillary rise and displacement pressure and also seems to influence the rate of fluid flow. The purpose of this paper is to supplement and bring up to date the last article on the subject of the surface chemistry of petroleum reservoirs, that of Garrison in the 1935 Oil and Gas Journa1.1 A discussion of the "adhesion tension" concept used by Garrison has been presented in another publication,2 together with the reasons for the recommendation that the term "adhesion tension" be abandoned. In view of the fact that some of the data used by Garrison have been superseded by more recent work, it seemed advisable to call attention to this fact and present the more important data currently believed to be correct. In the earlier paper, Garrison set up the equations that &apos;relate solid-oil and solid-water interfacial tensions to each other, and applied data from Bartell and Miller3 to these equations. However the adhesion tension measurements made by Bartell and Miller involved a confusion of symbols, so that they did not actually measure the spreading pressure, ?s — ?sf.2 The spreading pressure is a convenient method of indicating the amount by which the surface energy of a solid surface is lowered on immersion in a liquid or vapor. Since the initial value of the free surface energy is represented by the symbol ?s and the final value is ?sF, the spreading pressure is ?s — ?SF. A technique has now been developed4 that makes possible the determination of ?s — ?sF for simple systems. This method would be very difficult to carry out with a multicomponent system such as exists in the petroleum reservoir. However, already results have been obtained for ?s — ?sF for water and heptane in contact with silica and graphite. These values will be of the same order of magnitude as those in the petroleum reservoir. Accordingly, it is possible for the first time to discuss the surface-energy relations of the petroleum reservoir on a semi-quantitative basis. Preliminary Generalizations A petroleum reservoir may contain the following four phases: gas, hydrocarbon liquid, aqueous liquid, and solid. The three fluid phases are dispersed through the solid reservoir rock. If gravity were the only force acting, it is obvious that the

Jan 1, 1943

By Y. Kondo, A. M. Gaudin

A combined method for sizing in the sub-micron range was developed using centrifugation and gamma emission. Its essential features are: 1) Centrifugation of suspended mineral in water carried out at 4°C where water has its maximal density and zero temperature gradient of density 2) Gamma activition of the sample suspension induced by irradiating it in a nuclear reactor prior to centrifugation 3) Measurement of the activity of a beam of suspension as it is sedimenting in the centrifuge, using a scintillation counter provided with a discriminator. Albite, the sodium feldspar, was used as feed to the comminution step, and the induced gamma activity of Na24 was measured. Dissolved sodium ion caused a a non-settling activity in the measurement. Other "noise" is due to scattered gamma radiation from albite particles in the centrifuge outside of the line of sight. These two activities were obtained sep arately and subtracted from the total activity counted. The relative solid concentration in the suspension under the collimating slit is proportional to this net activity. The cumulative weight per cent of undersize particles was calculated and plotted against size on logarithmic scales. The relationship was found to be linear down to about 30 mµ. The specific surfaces calculated from particle size distribution agree with those measured by krypton gas adsorption. The measurement of particle size distribution of comminution products has been of interest in clarifying the mechanism of the process. The Gaudin-Schuhmann equation1,2 relates the cumulative percentage undersize, y, to relative particle size x/k. The particle size, x, and the size modulus, k, together with the distribution modulus, m, characterize the particle size distribution, m is the slope of a plot of log (y) against log (x/k). This equation has been verified for ground particles down to 1 micron in size.3&apos;4 For particle sizes smaller than a few microns, the precision and facility of sedimentation and microscope techniques become questionable. Use of a centrifuge which shortens settling time from weeks to hours is attractive. Many centrifugal methods have been proposed; however, determination of the solid concentration of the suspension at a reference level as a function of time is difficult, and sampling the suspension is likely to introduce errors. Measurement of particle size distribution by X-ray absorption in gravitational5 and in centrifugal6 sedimentation have also been tried. In these methods, the absorption coefficient for the solid is independent of size, since the wave lengths of the X-rays and gamma-rays are orders of magnitude smaller than the particles. Radiometric techniques7 in size distribution measurement have been developed within the last several years. They offer advantages over usual gravimetric and optical methods. PRINCIPLE OF METHOD The combined method of centrifugation and gamma emission for sizing in submicron range described in the present paper has the following essential features. 1) Centrifugation is carried out at 4 ± 0.1°C. Convection currents in the water phase due to density changes caused by temperature variation may disturb completely the settling system. To avoid this difficulty, the unique property of water having zero temperature gradient of density at 4°C is used. 2) Prior to size measurement the sample suspension is irradiated in a nuclear reactor and gamma activity induced. The gamma activity of the particles sedi-mented radially is measured by a scintillation counter provided with a discriminator. By this method, interruption of centrifugation by withdrawing samples is avoided and the counting rate at any time represents the solid concentration in the suspension at the level of the collimating slit of the centrifuge at the particular time at which the measurement is made. 3) By proper selection of the feed material and of the comminution device, gamma activities of foreign

Jan 1, 1964

By M. P. Tixier, M. Gondouin, G. L. Simard

In the quantitative interpretation of the SP logs, the electrochemical component is generally taken equal to — K log Rm /Rw where K has the theoretical value corresponding to solutions of pure sodium chloride. This method may be misleading when relatively large quantities of salts other than NaCl are present in form-rrtion waters—as is generally the case for low salinities —or in gyp-base muds. In such cases recourse is made in the field to changing the K value or to adding a correction term to the equation on the basis of local experience. An investigation has been made in the laboratory of the influence of HCO3, SO4=, Ca++, and Mg++ on the amplitude of the SP deflection, which included in par-ricular determinations of the activity coefficients of Ca++ and Mg++. The theory, the experimental techniques and a tentative method for applying the results are described. So far, applications to actual field cases where chemical analyses of waters were available have provided an excellent confirmation of the proposed method. The case of the SP in very salty brines is also considered and it is shown that the use of activity data for sodium gives satisfactory results. HISTORICAL In early times of electrical logging, the SP curve was used exclusively as a tool for the location of permeable beds and the definition of their boundaries. Later, with the introduction of methods of quantitative analysis, attention was called to the possibility of deriving from the SP log some information on the formation water resistivity, which constitutes one essential element for the computation of water saturation from log data. The first laboratory experiments&apos; in 1932 had shown that, as a result of electrochemical phenomena arising at the contact of the niud and the formation, the amplitude of the deflection of the SP curve was, at least partly, a function of the salt concentration of interstitial water and accordingly of its resistivity. It was indicated that the amplitude of the electrochemical component of the SP should be equal to K log R1/R2, R1 and R2 being the resistivities of the mud and of the formation water respectively. However, the exact value of the K coefficient was not determined at that time because the surface clay used for a laboratory model was far from an ideal shale membrane. Consequently, the way was not yet open towards quantitative interpretation. In the early forties, Tixier reported2, on the basis of field log observations, the following equation for the case of NaCl solutions, SP = -71 log f1c1/f2c2, c1 and c2 being the concentrations and f1, f2 the mean activity coefficients. The local variations observed in the empirical values of K, chiefly in the Rocky Mountains, led him to advance the opinion that, besides the relative amounts, the nature of the salts present in the solutions had a bearing on the magnitude of the SP. At about the same time Mounce and Rust- ad published laboratory results which emphasized the part played by the shale in the generation of the SP. On the basis of laboratory tests and theoretical considerations, Wyllie in 1948&apos; published the following equation of the electrochemical SP for the case of NaCl solutions, SP= - 71 log (a1)m/(a2)m

Jan 1, 1958

By R. W. Armstrong, P. C. Jindal

WE should like to point out that Hu and cline.1 in their study of the recrystallization of titanium, have obtained data which appear very important for accurately determining the dependence of hardness on grain size for this material. It has been proposed2,3 that the macrohardness. H. of a poly crystalline material should depend on its average grain diameter, l. in accordance with the relationship: H =H0 + kHl-1/2 [1] where Ho and kH are experimental constants. This relationship follows from the hardness dependence on yield stress or flow stress4 and. thence. the Hall-Petch stress-grain size relations.5&apos;6 Fig. 1 shows the Diamond Pyramid Hardness. Dph. values vs the reciprocal square root of the average diameter of the recrystallized grains, taken from the titanium data reported by Hu and Cline. The data in this figure give a linear relationship for the hardness over a wider range of grain diameters than anyone has previously measured. The data are not linear, for example. on an I-1 or l-1/3 scale. At the very large grain sizes the data are in reasonable agreement with measurements earlier reported by Holden, Ogden, and Jaffee.7 For the grain sizes smaller than 1 µ, which correspond in Fig. 1 to hardness values greater than 150, the material was reported as not being completely recrystallized and, therefore, these data appear less meaningful as far as the hardness dependence on grain size is concerned. However. it has been suggested by other investigators that deformed materials exhibit strengthening due to an effective grain size refinement even in the unrecrys-tallized condition.8-10 Also. Hu and Cline have shown that a change in texture occurs for titanium during the recrystallization process and. especially. following it. The influence of this texture change on the hardness-grain size relation would be expected to be less than that reflected in the unidirectional stress-strain behavior, even for an hcp material. because of the actual combined stress system which applies for the hardness test. For, at least, certain combined stresses, average values of the orientation factors should still occur in the stress-grain size analysis of a material exhibiting a preferred orientation.&apos; We previously suggested3 that the experimental constants. H0 and kH. from the Meyer hardness-grain size relation should be correlated with the Hall-Petch constants, uoy and ky.5,6 Our recent study" of the Hall-Petch relation and the hardness-grain size results which obtain for a number of polycrystalline materials shows that: The inequality [2] is explained by noting that the hardness should be correlated. perhaps, with the flow stress at some value of strain, as suggested by Dugdale,12 and. also, that the influence of strain on the Hall-Petch relation is to increase uo and not change k very much." Normally. Dph values and Brinell hardness values are nearly equivalent to each other and to the Meyer hardness number. For the case of titanium, then. the inequality [2] may be evaluated using the experimental values of ao = 8.0 kg per sq mm and ky = 1.3 kg per mm3/2 obtained from the experiment of Guard.6,13 Thus, (Ho/uo) = 12 and (kH/k3) = 1.3. This research has been supported at the University of Maryland through the Center of Materials Research by the Advanced Research Projects Agency of the U.S. Government.

Jan 1, 1969

By M. L. Holzworth, Joseph C. Kremer, Paul A. Beck, L. J. Demer

FOR alloys which are in practice heat treated to obtain increased strength, such as steels, duralumin, copper-beryllium, and others, the treatment usually involves heating to a relatively high temperature. At such temperatures the grain size of the product is largely determined by grain growth. Even in metals and alloys annealed merely to relieve work hardening, recrystallization is generally followed by a certain amount of grain growth. Thus, effective grain size control, which is often of great practical importance in manufacturing processes, depends on the grain growth behavior of the material used. Despite its importance, grain growth has been the subject of few investigations of a fundamental nature. The term "grain growth" has been used to designate a group of related, but distinctly different, phenomena. The two most important and best known of this group are illustrated by the following example. Curve a in Fig r shows the increase of the average grain size of a copper-beryllium alloy, containing 2 pct Be and 0.15 pct Co, with increasing annealing temperature. The time of annealing was 2 hrs. The grain size was quite uniform in all specimens. The results of a similar experiment with an alloy containing 2 pct Be and 0.31 pct Co are shown by curve b. It is seen that for any annealing temperature below T. the grain size was smaller than in the previous case. Grain growth became slower with the higher Co content. This "inhibiting" effect of the higher Co addition was associated with the appearance in the microstructure of fine, light blue particles of the CoBe phase. Up to temperature T. the structure of the inhibited alloy (curve b) was just as uniform as the structures represented by curve a. However, after annealing at T, or at higher temperatures, the inhibited alloy showed some extremely large grains (much larger than the grain sizes developed by the uninhibited alloy with low Co content) mixed with the small grains according to curve b. The presence of these mixed or "duplex" structures is indicated in Fig 11 by the vertical lines branching off curve b. The type of grain growth occurring in uninhibited Cu-Be alloys (curve a) has has been most frequently and best investigated in brass. This type has been designated as "normal grain growth," while the grain growth phenomena occurring in inhibited materials were, at times, referred to as "abnormal grain growth." However, since the latter term has been applied occasionally to the phenomenon of critical recrystallization, which also results in large grains although by an entirely different mechanism, in the present paper a different nomenclature has been adopted in order to avoid confusion. Typical of the grain growth in uninhibited metals and alloys is the continuous

Jan 1, 1947

By I. J. Demer, M. L. Holzworth, J. C. Kremer, P. A. Beck

For alloys which are in practice heat treated to obtain increased strength, such as steels, duralumin, copper-beryllium, and others, the treatment usually involves heating to a relatively high temperature. At such temperatures the grain size of the product is largely determined by grain growth. Even in metals and alloys annealed merely to relieve work hardening, recrystal-lization is generally followed by a certain amount of grain growth. Thus, effective grain size control, which is often of great practical importance in manufacturing processes, depends on the grain growth behavior of the material used. Despite its importance, grain growth has been the subject of few investigations of a fundamental nature. The term "grain growth" has been used to designate a group of related, but distinctly different, phenomena. The two most important and best known of this group are illustrated by the following example. Curve a in Fig I shows the increase of the average grain size of a copper-beryllium alloy, containing 2 pct Be and 0.15 pct Co, with increasing annealing temperature. The time of annealing was 2 hr. The grain size was quite uniform in all specimens. The results of a similar experiment with an alloy containing 2 pct Be and 0.31 pct Co are shown by curve b It is seen that for any annealing temperature below T, the grain size was smaller than. in the previous case. Grain growth became slower with the higher Co content. This "inhibiting" effect of the higher Co addition was associated with the appearance in the microstructure of fine, light blue particles of the CoBe phase. Up to temperature T, the structure of the inhibited alloy (curve b) was just as uniform as the structures represented by curve a. However, after annealing at T or at higher temperatures, the inhibited alloy showed some extremely large grains (much larger than the grain sizes developed by the uninhibited alloy with low Co content) mixed with the small grains according to curve b. The presence of these mixed or "duplex" structures is indicated in Fig I by the vertical lines branching off curve b. The type of grain growth occurring in uninhibited Cu-Be alloys (curve a) has been most frequently and best investigated in brass. This type has been designated as "normal grain growth,&apos;&apos; while the grain growth phenomena occurring in inhibited materials were, at times, referred to as "abnormal grain growth." However, since the latter term has been applied occasionally to the phenomenon of critical recrystallization, which also results in large grains although by an entirely different mechanism, in the present paper a different nomenclature has been adopted in order to avoid confusion. Typical of the grain growth in uninhibited metals and alloys is the continuous

Jan 1, 1949

By H. H. Einstein

Swelling ground is one of the most feared problems in tunneling. Although usually not causing sudden failures during construction, the very large and longlasting deformations give contractors and designers the impression of facing an inevitable phenomenon against which there is no technical defense. Examples are concrete liners up to 1 m (3 ft) thickness that have been cracked or crushed, tunnel inverts that are heaving at 0.1 m (0.3 ft) per week during construction and continue to heave during decades. This paper summarizes essential components of design construction procedures where tunnels in swelling rock can be built to perform satisfactorily. It is important to point out that design and construction cannot and should not be separated. The way the tunnel will be built has to be an integral part of the design. Swelling can be defined as time dependent volume increase and is distinguished from squeezing, another time dependent phenomenon occurring in tunneling. Squeezing involves exceeding the shearing resistance while swelling usually does not. Swelling of rock masses can occur as swelling of the intact rock, swelling of wall rock, of gouge and of filler in the discontinuities of a rock mass, and as a combination of the above. Swelling mechanisms have been discussed elsewhere (ISRM 1983).

Jan 1, 1984

By C. E. Kemp, A. B. Dyes

Results of a field research project on the thermal recovery of oil by movement of a combustion front are presented. This field test was conducted in the South Belridge field, This The war paitern was a Southsing1e 2.5-acre five-spot pattern in the 700-ft deep Tulare sand. Results of this project indicate the technical feasibility of producing high viscosity, low-grallity crude oils by thermal means. It was demonstrated that heavy oils could be moved rapidly over considerable distances by thermal drive, and that high percentage recoveries of oil could be effected. The bulk of the oil recovery came after arrival of the burning front at a production well. However, rapid corrosion and high-temperature failure of conventional pipe and equipment both below and above surface occurred. Stainless steels gave more satisfectory performance under these conditions than did conventional steels. Oxygen was seldom observed in gas from wells ahead of the burning front, and it appears that the front was continuous throughout the life of the experiment. INTRODUCTION During late 1953 and early 1954, industry-wide attention was focused on the thermal recovery of oil by movement of a combustion front through an oil zone. Two separate Oklahoma field tests were described in publications by Kuhn and Koch, and Grant and Szasz. To obtain basic information needed for making engineering and economic appraisals of commercial recovery of heavy oil by this thermal recovery method, a new field research projecta3,4 was started May 31, 1955. Twelve oil companies contributed to this project with General Petroleum Corp. as operator. Since combustion recovery experiments* with heavy oils in other areas had been conducted in small patterns,"&apos; an important purpose of this test was to determine whether the process could be operated in a pattern of near-commercial well spacing. The south Belridge field, located 30 miles north of Taft, Calif., was chosen because its oil sands are similar to many heavy oil sands which typically have low primary recovery and leave a large amount of oil in place. such fields are not particularly suited for common secondary recovery methods. DESCRIPTION OF TEST SITE The test interval was a Tulare sand at a depth of about 700 ft. Nine test wells were drilled, cored and completed from Oct., 1955, through Jan., 1956. The initial pattern shown on the map, Fig. 1, consisted of an injection well (II)&apos;, four producing wells (1P-4P), and four observation wells (IT-4T). An old well (81) was also recompleted for use as an observation well. The area enclosed by the original four production wells was 2.5 acres; the distance from the injection well to each production well was 233 ft. During the combustion period, Well 5P was drilled to replace Well 2P, and Well 6P was drilled to replace Well 3P. The new wells were 25 ft beyond the old production wells along a diagonal from the injection well, and resulted in an increase in pattern area to 2.75 acres. Isopachs are shown in Fig. 1. The average thickness of the oil sand in the test pattern was 30 ft. Fig. 2 presents two cross sections through the test pattern. Oil sand is represented by white and claystone by gray. The dashed lines indicate layers of conglomerate grading to claystone. The sand thickness was fairly uniform throughout the test pattern except in the 1P area. The sand body dips gently from the northwest to southeast, about 3 degrees from horizontal. The sand is unconsoli-dated, and grades from very fine material to pebbles as large as 2 in. in diameter. Table 1 presents the average initial properties of the formation. The in-place porosity of 37 per cent was estimated from the porosity of coke-consolidated cores taken after combustion. Original core analyses data were adjusted to 37 per cent, giving pore volume saturations of 60 per cent oil, 37 per cent water, and 3 per

By J. M. Sands

THE state of Kansas had a daily average crude-oil production of about 87,000 bbl. at the beginning of the year. This showed a steady but consistent decline during the 12 months, so that the daily average production at the end of the year was slightly over 68,000 barrels. GREENWOOD COUNTY THE most active development in Kansas during the year was in Greenwood County, in a line from near Sallyards in T 25-R 9 to east of Madison in T 22-R 11. The main part of this development has been in a succession of pools beginning at the south with the Polhamus pool in 34-24-9 and 3 and 4-25-9; Thrall pool in 28, 29, 32 and 33-23-10; Burkett pool in 13, 23, 24 and 26-23-10; Seeley and Wick pool in 22, 27, 28,. 32 and 33-22-11 and 5, 6, 7, and 8-23-11; Frohm pool in 11, 14 and 15-22-11; Madison pool in 31 and 32-21-12 and 6, 22, 12 and 1-22-11. Some of these pools have two or more sands, locally called Bartlesville and Burgess Sands. They range in depth from 1850 ft. near Madison to 2450 ft. near Sallyards, the general dip being to&apos; the west. The thickness of these sands run from 20 to 100 ft., the initial production of the wells being 50 to 1000 bbl of 40-gravity oil or better.

Jan 3, 1924

By W. H. Smith

IN connection with some recent work on the effect of impurities on the ductility of chromium, it appeared desirable to know the solid solubility of carbon in chromium. A literature survey indicated that this information was not available. Although considerable work has been done on the Cr-C phase diagram,&apos;.&apos; previous investigators have been more concerned with the structure and phase boundaries of the carbide phases than with the terminal solid solution. The phase diagram shown in Fig. 1 is taken from the work of Bloom and Grant&apos; and represents the most recent determination. As indicated by the dashed line, the a solid-solubility limit was not determined. Experimental Procedure Alloys of chromium were prepared from hydrogen-treated and vacuum-degassed electrolytic chromium plus spectrographic grade carbon. The oxygen and nitrogen content of the alloys was <0.002 pct. After melting, analysis of the alloys showed them to contain 0.02, 0.08, 0.15, and 0.55 pct C. Pieces of the alloys were heated in a protective atmosphere to various temperatures and then quenched after holding for a time sufficient to insure equilibrium. Microscopic examination of the as-quenched alloys for the presence of a second phase was used as a measure of the solubility limit. The heats were made in a multiple hearth arc-furnace using a zirconium-gettered static argon atmosphere. A zirconium melt was made before each Cr-C heat. Triple melting was used to insure ingot homogeneity as shown by microscopic examination. The alloys were prepared by adding portions of a 4.5 pct C-Cr master alloy to high purity chromium. The carbon contents listed previously were those obtained by analysis. The nitrogen and oxygen contents after arc melting were both <0.002 pct. Sections 1/8X1/4X1/2 in. were cut from the 100-g ingots and a hole drilled in one end in order to suspend the sample from a molybdenum wire. After the surface was carefully cleaned, a sample of each melt was hung in a mullite tube heated externally by a platinum resistance furnace connected to a vacuum system. The lower portion of the mullite tube was sealed to Pyrex and closed off several inches below the furnace. This was filled with sili-cone oil kept cold by circulating cold water around the outside of the Pyrex. Quenching into the oil bath was achieved by melting a fuse wire supporting the sample. It required about 4 sec for the sample to cool from 1400" to 600°C. This severity of quench was considered satisfactory to freeze-in the high temperature equilibrium. For tests made at temperatures of 900" to 1200°C, heating was done in vacuum; for tests above 1200°C, an argon atmosphere was used. The holding time employed ranged from 12 hr at 900°C to 6 hr at 1400°C. Experiments were performed at temperatures of 900°, 1000°, 1100°, 1200°, 1300°, and 1400°C. Microscopic examination for evidence of a second phase was done at X1500. Experimental Result The microstructures of a 0.08 pct C-Cr alloy as-cast and after quenching from 1300°C are shown in Figs. 2 and 3. A 0.15 pct C-Cr alloy quenched from 1300°C is shown in Fig. 4. The data obtained from the quenching experiments is shown graphically in Fig. 5. If the Van&apos;t Hoff equation is obeyed, a plot on a logarithmic scale of the mol fraction of solute vs the reciprocal of the absolute temperature should give a straight line. For dilute solutions the weight percentage can be substituted for the mol fraction without introducing any appreciable error. The Van&apos;t Hoff equation can then be written as where H is the heat of solution in calories per mol. The slope of the straight line on the log pct C vs 1/T plot gives the value of AH. Assuming that the Van&apos;t Hoff equation is obeyed, which is probably justified for the dilute solution of carbon in chromium, the heavy straight line shown on Fig. 5 represents the best fit of the data. This line was obtained as follows. On Fig. 5 the results of the microscopic examination of all alloys following quenching were plotted and designated as to whether one or two phases were seen. Below 1100°C all alloys showed a second phase on quenching. The heavy vertical lines shown in Fig. 5 therefore represent the possible range of the ter-

Jan 1, 1958

By E. A. Devuyst, M. A. Mosoiu, V. A. Ettel

Nickelic hydroxide is an important metallurgical reagent used for precipitating cobalt from nickel sulfate solutions. Existing methods of preparation of nickelic hydroxide involve electrolytic oxidation of Ni(OH)2 or the use of strong oxidizing agents such as chlorine, ozone and persulfate. Although the oxidizing properties of the SO2 + O2 system have been known for some time, e.g., detection of SO2 and oxidation on iron in acidic solution, the application of this system for the preparation of nickelic hydroxide as a process was not considered in the past. The present paper describes a new method for chemical preparation of nickelic hydroxide which has been developed in INCO laboratories. The technique consists of reacting nickelous hydroxide suspensions with a slurry of calcium sulfite in the presence of air or oxygen. The main advantage of the process is the cost of reagents and an absence of soluble by-products (e.g., C1-). The chemistry of this process is unusual since the redox potential obtained during the reaction exceeds that of the oxygen electrode. Therefore, the effect of CaS03 is not just a catalytic acceleration of the reaction NI(OH)~ + 02. The so3= must be involved in the stoichiometry of the overall reaction producing in the initla1 phase some strongly oxidizing intermediate species.

Jan 1, 1981