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By J. P. Doan, G. Ansel

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947

By G. Ansel, J. P. Doan

The important literature concerning zirconium in magnesium-base alloys is predominantly contained in patent references. Sauerwald, Eisenreich, and Holubl-4 discovered the profound grain-refining influence of small amounts of zirconium on cast magnesium and the attendant increases in strength and ductility. They extended their work to reveal that limited amounts of certain other elements, including zinc, could be added for further improvement in strength and hardness. British Patent 5111375 relates to the parent discoveries of Sauerwald, Eisenreich, and Holub. All of these references deal primarily with casting characteristics and properties in the cast state. Minor mention is made of desirable tensile strength, ductility, and toughness of wrought Mg-Zr alloys* modified by one or more additional elements. No extensive reference in the literature5. has been found to the particular characteristics of wrought blg-Zn-Zr alloys, with which the present paper is concerned. The work to be discussed represents essentially an extrusion study of the blg-Zn-Zr alloys and indicates that this system is highly interesting in the wrought state both academically and commercially. Accordingly, an important aim of this paper is to describe the hot-workability, tension and compression properties, metallography, and toughness of these alloys. Compositional variations are limited to the ranges 0 to 7 per cent Zn and 0 to I per cent Zr. Experimental Procedure Alloying and Casting Alloying ingredients were cell magnesium, commercial zinc (intermediate grade), and a chloride salt containing approximately 50 per cent ZrCl² and 50 per cent alkali chlorides. This salt is produced by Titanium Alloy Manufacturing Company. Melting, alloying, and pouring procedure essentially followed the crucible process as described by Nelson.6 The magnesium was melted using Dow No. 310 flux, and the temperature raised to 1350° to 1400°F for the alloying operations. After alloying of the zinc, the zirconium containing salt was added in small portions with vigorous stirring. This is an adaptation of the method described in British Patent 533264.7 The alloying efficiency of zirconium was approximately 30 per cent. During the alloying of zirconium, fluorspar was added in amount required as a flux-inspissating agent. Next the melt was refined with Dow No. 310 flux and held quietly for 15 min. Finally billets were cast in a book-type permanent mold

Jan 1, 1947

By George D. Dub

Owens Lake is at present a source of important nonmetallic minerals, sodium carbonate (soda ash, Na2CO3); sodium sesquicarbonate (trona, Na2CO3.NaHCO3.-2H2O) and borax, (Na2B4O7.10H2O). Owens Lake is a closed basin in the southern part of Inyo County, California, at the southern end of Owens Valley, east of the Sierra Nevada Mountains and west of the Coso and Inyo Mountains. Broadly considered, it is in the Great Basin area, but at no time was it a part of Lake Lahontan. Closed Basins Closed basins are phenomena of arid or semiarid regions where outflow is considerably less than inflow and where accordingly soluble salts concentrate in residual liquid. When inflowing waters originate in areas where the rocks are predominantly marine sediments, the residual basin liquid is primarily a chloride, brine; if the rocks are largely igneous, the residual brine tends to be alkaline containing carbonates, and sometimes borates as well. Since normally, both types of rocks occur in regions contiguous to closed basins, residual liquids do not often fit into the two broad divisions mentioned. No two residual brines are exactly alike, just as no two ore deposits are exactly alike. Even out of the same closed basin, it is possible to get widely different analyses of liquids since underground and surface flows, as well as local evaporation rates and other conditions might have a marked influence on residual-liquid compositions. At Searles Lake, The American Potash and Chemical Corporation is building a plant to process a lower-level brine which is considerably higher in sodium carbonate and borax, and lower in potassium chloride, than that company has processed for many years. F. W. Clarke1 has classified waters of closed basins as follows: I. Chloride type; largely sodium chloride (NaC1) and of oceanic type, such as Great Salt Lake. Related is -the Dead Sea, a bittern residue of magnesium, potassium and sodium chlorides. a. Sulphate type; largely sodium sulphate (Na2SO4) with considerable sodium chloride such as Sevier Lake, Utah; Laramie Lakes, Wyoming; Dale Lake, California. 3. Carbonate type; high in carbonates and fairly high in sulphates, such as Moses Lake, Eastern Washington; and the Nebraska Potash Lakes. 4. Carbonate—chloride type; lower in carbonates than type 3 and about equally rich in sulphates, such as Pyramid Lake, Nevada. 5. Sulphate—Carbonate type; quite high in sulphates and carbonates, such as Pelican Lake, Oregon. 6. Triple type; considerable quantities of carbonates, sulphates and chlorides

Jan 1, 1948

By George D. Dub

Owens Lake is at present a source of important nonmetallic minerals, sodium carbonate (soda ash, Na2CO3); sodium sesquicarbonate (trona, Na2CO3.NaHCO3.-2H2O) and borax, (Na2B4O7.10H2O). Owens Lake is a closed basin in the southern part of Inyo County, California, at the southern end of Owens Valley, east of the Sierra Nevada Mountains and west of the Coso and Inyo Mountains. Broadly considered, it is in the Great Basin area, but at no time was it a part of Lake Lahontan. Closed Basins Closed basins are phenomena of arid or semiarid regions where outflow is considerably less than inflow and where accordingly soluble salts concentrate in residual liquid. When inflowing waters originate in areas where the rocks are predominantly marine sediments, the residual basin liquid is primarily a chloride, brine; if the rocks are largely igneous, the residual brine tends to be alkaline containing carbonates, and sometimes borates as well. Since normally, both types of rocks occur in regions contiguous to closed basins, residual liquids do not often fit into the two broad divisions mentioned. No two residual brines are exactly alike, just as no two ore deposits are exactly alike. Even out of the same closed basin, it is possible to get widely different analyses of liquids since underground and surface flows, as well as local evaporation rates and other conditions might have a marked influence on residual-liquid compositions. At Searles Lake, The American Potash and Chemical Corporation is building a plant to process a lower-level brine which is considerably higher in sodium carbonate and borax, and lower in potassium chloride, than that company has processed for many years. F. W. Clarke1 has classified waters of closed basins as follows: I. Chloride type; largely sodium chloride (NaC1) and of oceanic type, such as Great Salt Lake. Related is -the Dead Sea, a bittern residue of magnesium, potassium and sodium chlorides. a. Sulphate type; largely sodium sulphate (Na2SO4) with considerable sodium chloride such as Sevier Lake, Utah; Laramie Lakes, Wyoming; Dale Lake, California. 3. Carbonate type; high in carbonates and fairly high in sulphates, such as Moses Lake, Eastern Washington; and the Nebraska Potash Lakes. 4. Carbonate—chloride type; lower in carbonates than type 3 and about equally rich in sulphates, such as Pyramid Lake, Nevada. 5. Sulphate—Carbonate type; quite high in sulphates and carbonates, such as Pelican Lake, Oregon. 6. Triple type; considerable quantities of carbonates, sulphates and chlorides

Jan 1, 1948

By C. S. Samis, J. C. Mitchell

Sodion activity data have been obtained for the Na-A1 system for sodium concentrations in aluminum between NN, = 25 . 10-and 300 x 10'. This concentration intert-a2 encompasses those sodium concentrations nor1)zally encountered in aluminum reduction cell operation. The sodium activity data were measured by a two-phase equilibration of sodium between a lead and an aluminam rich phase. The Na-Pb system was emplojed as a reference for the determination of the actiz7itj 0.f sodium. The activity of sodiin in aluminuwz exhibits large positi2.e deviations frorn ideality and a strong dependence, on concentration below NN, = 100 x 1K6. The inteated data indicate that the activity of aluminium is equal to its mole fraction over the range of miscibility of the Na-A1 sgstem. The data on the Na-A1 binary have been combined with experimental data on the cryolite-A1 system at 1025°C to obtain the activities of Na F and AlF, in liquid cryolite oz2er the cornposition 1-ange encountered in aluminum cell operation. The results are in agreement with activities calculated from the NaF-AlF, phase diagram. ALUMINUM is produced commercially by the electrolytic reduction of aluminum oxide dissolved in molten cryolite. There is considerable controversy over the actual mechanism of the discharge processes, but sodium potentials in the systems appear to play an important role in the reduction mechanism. The metal-salt reaction involving NaF and aluminum to produce A1F3 and sodium is responsible for the presence of sodium in the aluminum metal phase. Additional sodium may be produced from the simultaneous deposition of sodium and aluminum at the cathode as a result of a cathodic overvoltage. runert' has suggested that sodium gas at atmospheric pressure would be the result of reaction between cryolite and aluminum at 1000°C. Subsequent investigations have shown that production of sodium at atmospheric pressure does not occur. These later investigations can be conveniently separated into two categories. The first involves sodium, aluminum, and cryolite, in which the sodium activity was measured. The second includes a lead phase for sodium activity measurement. Jander and errmann,' studied the reaction: at 1090°C in alumina crucibles under an atmosphere of dry, oxygen-free nitrogen. The equilibrium constant for the reaction was expressed in terms of concentration. Their results in Fig. 1 show an increase in sodium content of the aluminum with increasing NaF/A1F3 weight ratio. Pearson and waddington3 performed similar experiments at 1000°C. Their results are included in Fig. 1. Dewing and ollinshead have measured the sodium content of aluminum as a function of the NF/AF, ratio at 1025"C, Fig. 1, and ewin' measured the sodium content of the aluminum in a system involving the solid reactants NaF, cryolite, and liquid aluminum. This reaction is different from those discussed above. Two solid phases, NaF and Na3A1F6, and a liquid aluminum phase were present. The sodium concentration in the aluminum was determined by the temperature. Dewing's measurements covered the temperature range 679" to 896°C. Omo, Matsushima, and 1t02" investigated the equilibrium 6NaF ential thermal analysis. Stokes and Frank6 determined sodium activities by

Jan 1, 1970

By C. E. Lesher

Low-TEMPERATURE carbonization needs no introduction to the literature on coal. This paper will attempt no review of that literature; it tells the story of the commercial development of one of the processes for carbonizing coal at so-called low temperatures, dealing with the technology and economics of the process rather than with the design of equipment. The process used is that covered by the patents of C. B. Wisner, with improvements and changes made by the Pittsburgh Coal Carbonization Co. The important and novel feature of the process is the phenomenon of making the product in ball form (Fig. 1). Melting coal dust into smokeless solid fuel in an apparatus as simple as a revolving cylinder of ordinary mild steel has been proved to be practical. Furthermore, it has been found that the process has a wide application, for by applying a knowledge of why and how this balling action is accomplished, the apparatus can be designed and adapted to treat any coal that has a certain minimum agglutinating property. The operating plant is 20 miles west of Pittsburgh, adjacent to the Champion preparation plant of the Pittsburgh Coal Co. The coal used is cleaned minus 3/8 -in- or finer sizes. The products are low-tem-perature coke, tar and tar products. Present capacity is 7000 tons per month of low-temperature coke and 140,000 gal, of tar. There is no surplus gas for sale, and none of the light oils are stripped from the gas. The coke is marketed in two sizes, 1 to 2 in. and 1 to 6 in., through retail coal dealers for domestic con-sumption in hand-fired furnaces, and for fireplace fuel. The smaller size is bagged by dealers. Crude tar and many distillates and road tars are sold.

Jan 1, 1940

By F. Keller, A. H. Geisler

Some of the important changes that take place in the structure of aluminum alloys are largely submicroscopic in character. This is especially true of the changes that accompany age-hardening and recrystallization. Although improved metallographic practices have been helpful in indicating some of these changes indirectly, results are limited by the resolving power of optical microscope lenses. The electron microscope, however, provides a new and important means for investigating the fine structure of metals in a range not possible heretofore. It is anticipated that this microscope will yield new and useful information to metallurgists when suitable techniques are developed to utilize its very high resolving power. Several unique methods have been devised to permit the examination of the structure of opaque samples by the electron microscope. These are all based on the principle of producing a very thin film that represents the prepared surface of the opaque metal sample, which can be examined in the transmission microscope; however, the available methods fall into three categories, depending on the manner in which the film is obtained. With the oxide-film method developed by Mahl3-17 a very thin surface layer of the metallographic sample is converted into oxide by a thermal, chemical or anodic treatment. After removal from the metal sample by one of the special techniques described by Evans,19 this oxide film is examined in the electron microscope, and is found to portray the structure of the original metal surface. Films formed on aluminum,8,17 nickel,7 iron 3,8,9 and a nickel-beryllium alloy" by heating; films formed on iron 8.9 by chemical action; and films formed on aluminum3-16 by anodic oxidation, have been examined. The other two are more recent methods developed principally in this country; they consist in making the thin film in the form of a mold or replica of the surface contour of an etched sample. With the negative replica method the thin film is made directly on the sample; with the positive replica method it is made on a negative reproduction of the sample. With both methods, variations in the contour of the metal sample, caused mainly by etching, produce variations in the thickness of the surface replica. Because of the direct dependence of the amount of scattering of the illuminating electrons upon the thickness of the film penetrated, only the variations in thickness of the replica are responsible for tones in the electron image. Negative replicas are made by forming a thin film of some suitable material directly on the polished and etched metal sample, and derive their name from the fact that after removal from the sample they have the high and low points in the sample reversed, as shown in Fig. I. Nega-

Jan 1, 1944

By Matsubara, A.

THE problem of the equilibrium between iron, carbon, and oxygen was first carefully investigated by E. Baur and A. Glaessner,1 who determined the equilibrium conditions of the two reactions Fe304 + CO ? 3FeO + C02 (1) FeO + CO ? Fe + C02 (2) within the range of temperature of 350 to 900° C. The next series of investigations was made by R. Schenck and his co-workers,2 who sought to check the results of Baur and Glaessner's work within the range of 550° to 700° C. and to elucidate the conditions of formation of iron carbide. The equilibrium conditions at the higher temperatures, however, are generally understood to be much more complicated, owing chiefly to the formation of solid solutions between iron, its oxides, and carbide; nevertheless their determination is of much more practical importance than those at the lower temperatures. It is well known that each of the reactions is reversible; equilibrium is established when the partial pressure of oxygen in the gaseous phase has become equal to the dissociation pressure of magnetic oxide in equation 1 and that of ferrous oxide in equation 2. These equilibria are subsequently designated by "the Fe304-FeO equilibrium" and "the FeO-Fe equilibrium," respectively. As the Fe304-FeO equilibrium has three phases with three components, it must be bivariant. But the reaction involves no pressure change in the gaseous phase, hence the final composition of the latter is practically unaffected by pressure. To know, the equilibrium conditions, the compositions of the gaseous phase at different temperatures must be determined. At the higher temperature, however, iron and its oxides dissolve one another in various proportions forming solid solutions; in many cases the content of oxygen in the solid phase becomes a new independent variable.

Jan 2, 1921

By H. I. Aaronson, H. A. Domian, G. M. Pound

The thernodyna,nics of I the Proeutectoid ferrite re-action ha1.e been investigated on the bases of three diifevent descviptions of the statistical thernzodynamics of interstitzal solid solutions. Especially at low ternperatures, substantial dijeretzces are found in the valltes of the extrapolated y/y + a and cr/a + y equilibriurn curls, and in the To- co7nposilion metastable eqliilibriunz curl-es thus co,npited. Although neither actiztity nor phase-diagram date are able to distingrish udeqiutely among the various descviptions, the statustics of Lacher, Fouller, and Guggenheinz provide the ?nost conplete epresentation az3ailable of the single carbon-ctrbon interaction energy (w) nzodel of an intevstitiril solid solution, and the relationships deduced frojrl then2 are accordingly pre.ferred. The findings tlzut w in austenite 'aries significu?ztly uith tenpevntrue and that phase-diagawr data arc not accurately con?palible usith eqcrctions deduced on the basis of actility infoation indicate, hou'e13er, that a wzore cornplex nlodel of the uustenite , und pvobably of the .feyrite, solirl solutions will have to forn the basis of f4tuve statistical t1.eat1nents. Some suggestions for such a ruodel arc advanced. Althoug11 w represents a vepltlsio energy in austozite, it was found to corvcsporzd in ferrite to a binding energy, in qualitatit.e accord zc,itlz the internal-friclion results of Keefer and wert. ThE transformation of austenite to proeutectoid fer-rite is becoming recognized as an exceptionally useful vehicle for quantitative studies of the kinetics of phase transformations.'" Reasons for this popularity include well-characterized microstructures which develop on a convenient scale with acceptable kinetics within a considerable temperature-composition region, the absence of great sensitivity to common impurities, and, especially. the availability of a unique wealth of the ancillary information indispensable for the quantitative interpretation of kinetic measurements, including phase diagram,3 crystallographies diffusivity,5 inter-facial energy,=17 elastiit," specific vlume, ''' and ativity'-' data. Development of considerable amounts of additional thermodynamic information from activity data is of particular importance with respect to kinetic studies, since much of this information is needed in temperature-composition regions not directly accessible to presently available techniques for the measurement of equilibrium properties. A generally useful approach to the thermodynamics of solid solutions, which is of especial value in this situation, is based upon the formulation of the free energy of such solutions as a function of temperature and composition. The free energy of solid solutions has been resolved into many components. Particularly in the case of interstitial solutions, with which we shall be concerned in the present study, however, only the positional entropy component has been intensively studied. The other components are conventionally taken into account by fitting equations for the activity of the interstitial species or the temperature-composition path of phase boundaries, derived principally from positional entropy considerations, to experimental information on these quantities through adjustment of one or more constants in the equations. A number of studies of the thermodynamics of interstitial solid solutions have been made primarily on this basis,'"25 but only Kaufman, Radcliffe, and cohenZ2 (hereafter KRC) and ener''% ave applied the results of such studies to develop relationships for the thermodynamic quantities of interest in the austenite —- proeutectoid ferrite transformation. KRC made use of a model developed by cheil'' (on the basis of a previous study by ohansson'), and subsequently rede-rived correctly by Speiser and retnak,' in which a carbon atom is considered to inhibit occupancy of a certain number of its nearest-neighboring interstitial sites. schei120 determined the number of sites in austenite thus excluded by matching calculated and experimentally measured curves for the variation of carbon activity with the mole fraction of carbon. zener17 used a different approach. He assumed that the positional entropy of carbon is ideal both in austenite and in ferrite (i.e., no excluded interstitial sites), and included all other contributions of carbon in a temperature-independent "free-energy change" accompanying the transfer of 1 mole of carbon between the two phases. This quantity was determined by "pinning" an equation derived for the boundaries of the a + y region to experimental data on the compositions of these boundaries at a single temperature. In the present investigation, three different approaches to the thermodynamics of the proeutectoid ferrite reaction are examined comparatively: I) the method of Zener; 2) the model employed by KRC and predecessors; and 3) the more detailed statistical thermodynamic treatment of the same model developed by acher and Fowler and uenheim, ' in which the problem of overlapping regions of influence of individual interstitial atoms is resolved. In order to make these comparisons, it is necessary to undertake an extension of one aspect of Zener's method; since the Lacher- Fowler -Guggenheim (LFG) treatment has not been previously used in the present context, the necessary thermodynamic "superstructure" for this treatment will be developed in parallel

Jan 1, 1967

By Joseph E. Pogue

FOR a number of years the petroleum department of The Chase National Bank has been making a continuing study of the financial aspects of thirty oil companies. (See Pogue and Coqueron, "Financial Analysis of Thirty Oil Companies," pamphlet, The Chase National Bank, November 1945, for data covering eleven years, 1934-1944, and the list of the companies making up the group. See also "Capital Employed in the Petroleum Industry," by the same authors, M&M, November 1944.1 This group represents a large sample of theAmerican petroleum industry, covering about two thirds of the business. Certain aspects of this study concern the capital employed in crude oil production, the main features of which arc presented in this paper.

Jan 1, 1946

By P. Datta, L. L. Handy

For a wetting phase displacing a nonwetting phase from a porous medium the distribution of the residual fluid may depend on displacement conditions. Although this subject has been debated in the literature, only a few experiments have been cited to support the various conclusions. Experimental results presented in this paper show that fluid distributions are dependent on imbibition pmcedures. Results agree qualitatively with predictions from the pore doublet model. If the rate of water imbibition is restricted, the nonwetting phase is trapped preferentially in .the larger pores as expected. But if the rate of water imbibition is unrestricted, trapping occurs somewhat more in the smaller pores. These conclusions were deduced primarily from relative permeability measurements. INTRODUCTION Relative permeabilities are known to depend on the saturation history of the porous medium. For either continuously increasing or continuously decreasing wetting phase saturations, however, they have normally been assumed to be single-valued functions of saturation. Severat investigators have compared relative permeabilities measured by different methods and have reported acceptable agreement.1-5 Studies of simple models of the displacement process suggest that the distribution of residual fluids can be influenced by the displacement method. If this is so, relative permeabilities also should depend on the method of displacement. These predictions have not been supported by experimental data. The object of this paper is to investigate experimentally some of the predictions of these model studies. The particular question of importance is whether steady-state and unsteady-state methods should be expected to give the same values of relative permeability. Much of the reported data showing agreement between steady-state and unsteady-state methods have been obtained on un consolidated sand. Johnson, Bossler and Naumann, however, compared steady-state and unsteady-state results for Weiler sandstone and found no significant differences.5 Levine made a detailed study of pressure and saturation distributions for a laboratory waterflood in a consolidated system but made no attempt to calculate performance from steady-state relative permeability data Bail and Marsden in a somewhat similar set of experiments did attempt a comparison of observations with predictions but the results were inconclusive.7 Excluding gravity, two forces affect the distribution of wetting and nonwetting phases during an unsteady-state, immiscible displacement: viscous and capillary forces. If relative permeabilities are indeed the same when measured by steady- or unsteady-state methods, the fluid distributions at the same fluid saturations must be similar for both methods. Furthermore, the implication is that the relation between capillary and viscous forces is the same for both methods insofar as the effect on microscopic fluid distributions is concerned. Unsteady-state displacements are normally run at high rates to maximize the ratio of the viscous to capillary forces. The objective is to reduce the effect of capillary forces on macroscopic fluid distributions. For floods in which the phase which wets the porous medium displaces the nonwetting phase, capillary forces compete with viscous forces in determining fluid distributions.8 The residual nonwetting phase is discontinuous. Competitive aspects of viscous and capillary forces and the resulting effect on water-oil distribution in porous media have been illustrated in an elementary way using a pore doublet model. This model and predictions from it have been discussed at considerable length by Rose and Witherspoon, Rose and Cleary and by Moore and Slobod.9-13 Rose and Witherspoon show that so long as water invades the model at a rate equal to or greater than the free imbibition rate, the water will move through the larger capillary of a doublet first and trap oil in the smaller capillary. On the other hand, if a negative pressure is applied to the water

Jan 1, 1967

By E. Amott

A test is described in which the wellubility of porous rock is measured as a function of the displacement properties of the rock-water-oil system. Four displacemet operations are carried out: (I) sponlaneous displaceti?ent of water by oil, (2) forced displacement of water by oil oil in the same system using a centrifuging procetllrre, (3) spontaneous displacement of oil by water. and (4) forced displacment of oil by water. Ratios of the spontaneous displacement volumes to the total displucenlent volumes are used as wettability indicates. Cores having clean mineral surfaces (strongly preferentially water-wet) show displacement-by-waler ratios approaching 1.00 and displacement-by-oil ratios of zero. Cores which ([re. strongly preferentinlly oil-wet give the reverse resu1ts. Neutral wellability cores show zero values for both ratios Fresh cores from different oil reservoirs have shown wettabiltties in tlris te.st covering rrlti~ost 111e conlplrtt, range of thr: te.st. Notvever, nlo.s/ of tlle fresh California cores tested were slightly prcfere111icrlly wclter-\vet. The chrrnge.~ in coro u ('liabilities, as indicated hy this te.st, r~.sril/ing from various CO~P hanrlling procedures tt,ere oh.served. In sonie ca.sc,s /Ire ~,cttahilitio.c. of fresh cores were changell by drxi:~g or 11y e.x/rclct ing with iolcreiii~ or. dioxunc~; in o/h~r cases they were 1101 changed. Co~ltrrc/ of cort,.s ~.ith filtrc~t~c. from water-base rlrilling rilrrrls crlrc.sed littlc change in we/ /ahility ivhile contnct with filtrates frorii oil-hus~ ri1rlcl.s tlecrrascrl the prefcrerlcc, of the, cores for )I.NI Usitig thi,s test to ri.crl~lute n~r~ttubili~y, N .vt~ldy was iilarle of /lie correlmtio~i of wettability with wa/erfloocl nil recovery for orttcrop Ohio sand.stone and for Al~ln-tlunl. Resul/.v indicate thml no single correlatioti between these factors applies to different porous rock syste~n. It is thought that diflerences in pore gen~netry resrrlt in diflrrerrce.~ in this correlurio~z. INTRODUCTTON Most investigators who have reported on the wettahility of porous rock have described such rock as prcferentially water-wet or preferentially oil-wet. In some cases a third classification, neutral wettability. has been used. The efficiency of water floods in each of these wettability groups has been described in numerous publications. Several methods for characterizing porous rock wet tability more precisely have been reported,' " but it appears that because of one weakness or another. none of these has been generally accepted. Early in our studies in this field, it was found that the displacement efficiency of oil by water in a particular porous rock having a strong preference for water was quite different from that in a similar rock having only a moderate preference for water. Thus, there appeared to be a need for a practical, reasonably precise wet tability test. one which could classify porous rocks into 10 to 20 different groups rather than the two or three broad groups listed above. The test developed to meet this need is described in this paper. Also, changes in wettability, as indicated hy this test, resulting from various core handling procedures are discussed. Finally, data showing the corrclation of wettability with waterflood oil recovery for two different types of cores are presented and discussed. Some confusion has resulted from the failure of certain writers to define clearly some of the wettability terms they have used. Accordingly, the following commcnts concerning definitions are offered. The wc t ta-hility of a solid surface is the relative preference of that surface to be covered by one of the fluids under consideration. It is felt that this is the generally accepted definition. The fluids being considered must bc specified (or understood) before the term wettability has any significance. In the work reported here these fluids are water (3 per cent brine) and oil (kerosene). The term preferential wettability is sometimes used, but we think that the word preferential is redundant here and should not be used. Tn line with the definitions of Jennings', a preferentially oil-wet solid surface is regarded as a surface which will show an oil advancing contact angle less than 90" (measured through the oil) in the water-oil-solid system. Oil will spontaneously displace water, if both are at the same pressure, from such a surface. A preferentially water-wet surface is analogous. This is consistent with the wettability definition above. As Jennings has said, frequently the term oil-wet is used to mean the same thing as preferentially oil-wet. However, oil-wet also has been used occasionally referring to an oil-covered surface when the availability of water was limited. To avoid confusion from this source, we do not use the terms oil-wet and water-wet. DESCRIPTION OF WETTABTLITY TEST The following points were considered desirable in a wettability test for our purpose. 1. The test should be a displacement test resembling

By D. G. Russell

A simple method has been developed with which flowing bottom-hole pressure data from two-rate flow tests in oil or gas wells can be analyzed to estimate the formation permeability, skin factor and average reservoir pressure. The required pressure data are obtained by observation of the transient bottom-hole pressure behavior after the stabilized producing rate of the well is changed to another, higher or lower, rate. The new method yields the same information as a conventional pressure buildup analysis, but eliminates the need for closing in the well. The analysis of a two-rate flow test is of the same degree of difficulty and requires about the same engineering time for application as a conventional pressure buildup analysrs. The extended closed-in periods experienced with conventional buildups because of long, low-rate afterproduc-tion periods are eliminated by fIow tests. Other anomalous pressure buildup effects, such as "humping" due to weli-bore phase segregation, can be successfully eliminated with the new method. Generally, flow tests of about 24 hours' duration run with conventional pressure measurement equipment are sufficient for interpretation purposes. Field testing of the two-rate flow test method has established that it is a reliable and economical method which can be used in many instances to complement or even replace conventional pressure buildup methods. INTRODUCTION The principal method for estimating formation permeability and well damage, or skin factor, in a producing oil or gas well is the analysis of shut-in bottom-hole pressure buildup data.' This familiar method has been used quite successfully by reservoir engineers for many years. It is based on the solution of the radial flow equation for constant rate conditions, and requires that the well be closed in for a sufficient period of time to obtain a clearly defined linear portion on the plot of observed t + ?t bottomhole pressure vs log t + ?/?t(where At is shut-in A? time, and t is producing time to the instant of shut-in). From the slope of the plot and other normally obtainable data, the permeability, skin factor, and reservoir pressure at infinite shut-in time (if the reservoir were infinite) can be estimated. Over the years several drawbacks have become apparent in the use of conventional shut-in pressure buildups for determining permeability and skin factor. The conventional pressure buildup interpretation theory assumes that a well is closed in at the sand face and that no production into the well occurs after shut-in. In practice, of course, the well is closed in at the surface, and inflow into the well continues until the well fills sufficiently to transmit the effect of closing in to the formation. This adjustment period is commonly referred to as the "after-production" portion of the pressure buildup. In the tight reservoirs, long, low-rate after-production periods frequently occur, and the well must be shut in for several days or, in some instances, even weeks to obtain an interpretable buildup curve.' Obviously, such long shut-in times can cause loss in current income, both from reduced oil production and from the fact that personnel and pressure measurement equipment are occupied with a single well for too long a time. In other cases, even long shut-in periods do not seem to be of much aid in obtaining an interpretable buildup." If there is considerable phase redistribution (liquid fallout or bubble rise) after a well is shut in, then curves with no interpretable portion are often obtained during the buildup. In addition to instances in which wellbore effects cause trouble, there are also cases in which the major objection to use of the closed-in pressure buildup is simply the fact that the well must be shut in. When there is no proration and when the well has limited producing capacity. closing in the well means loss of income. From the foregoing discussion it is apparent that it ib desirable to have an alternative method of obtaining the same information as that derived from a conventional buildup without the need of closing in the well. One possible solution which has been offered for this problem is the use of a bottom-hole shut-in tool' which isolates the major portion of the flow string from the formation face during the buildup. In this paper an alternative method which is frequently successful in avoiding wellbore effects and which does not require the use of special equipment is presented. A new, simple method has been developed with which the flowing bottom-hole pressure data from flow tests in oil or gas wells can be used to estimate permeability, skin factor and the average reservoir pressure. The required pressure data are obtained by observation of the transient bottom-hole pressure behavior after the stabilized production rate of the well is changed to another, higher or lower rate. The need for closing in the well is eliminated, and pressure measurement periods of only 18 to 24 hours arc usually sufficient, even in tight reservoirs. Thus, the new

By B. H. Caudle, L. G. Davies, I. H. Silberberg

This paper presents a method of predicting the recovery and performance of a five-spot steam injection project, in which a realistic approach to pattern sweepout efficiencies is made. Published methods for radial systems were modified for the five-spot pattern by approximating the stream lines with straight lines radiating from the injection well and then converging to the producing well. In each radial segment, the position of the steam front and the temperature profile ahead of the steam front were determined by heat balance equations, which included an estimation of heat losses to surrounding formations. The location of the saturations behind the cold water front was determined from a Buckley-Leverett solution to the material balance equation. Results from this program show steamflood recovery in a five-spot pattern to be considerably less than that predicted for true linear or radial flow systems. For a specific reservoir containing 900-cp oil, a steamflood in a purely radial flow system was predicted to recover more than 75 percent of the original oil in place when 2 PV of water had been injected as steam. A five-spot steamflood with otherwise identical properties was predicted to recover 10 percent of the original oil in place when 0.15 PV of water had been injected as steam and to recover almost no oil thereafter. A cold water five-spot flood in this system was predicted to recover approximately W percent of the oil in place with I PV of water injected. For a five-spot pattern in an example reservoir with 10-cp oil, steam injection similarly showed lower ultimate recovery than water injection but no improvement in recovery rule. Introduction The thermal recovery method considered in this study is steam injection in a five-spot pattern. Pattern steam injection has been given little attention in the past, possibly because of some rather obvious disadvantages. Unless steam temperature is maintained throughout the entire swept area, the process will revert to simple waterflood with all heat being lost prior to reaching the oil bank. Also, the oil viscosity reduction takes place near the steam front and not around the producing wellbore, so that low producing rates must still be endured. This is the reason for the success of the steam stimulation, or cyclic injection, in which the fluids are produced from the same well used for injection. On the other hand, steamflooding can offer some advantages. Oil displacement is by four methods: (1) mechanical displacement by the condensed water, (2) viscosity reduction of the crude oil, (3) swelling of the crude oil, and (4) distillation of the crude oil in the steam zone. Although dependent upon the crude, laboratory experiments have shown displacements up to 80 percent by steamflooding. In addition, steam is a good heat transport medium, since it is cheap and has a high heat content. Previous Investigations Previous publications have reported methods for predicting recovery in a steamflood for linear and radial systems. Since no pattern sweep efficiency is taken into consideration, the recovery even from a radial system must be greater than from more realistic geometries such as the very common five-spot patterns. Probably the broadest coverage is given by Willman who reported experimental results and offered a method of predicting recovery for a radial flow system. They concluded that both hot water and steam injection recover more oil than an ordinary waterflood, and that steam injection could yield recoveries "as much as 100 percent greater than by water flood." They also concluded that both the heat requirements for a reservoir and the residual oil remaining in the reservoir after steam injection were independent of the amount of oil originally in place, that short exploitation times were desirable, and that a high percentage of net sand in the reservoir with a high initial oil saturation was desirable. The method assumes that the flood occurs in three concentric cylindrical zones: (1) an inner steam zone, (2) a central hot water zone, and (3) an outer cold waterflood zone. Displacement in the steam zone is based on laboratory-determined residual oil saturations while the hot water and cold water zones use the conventional Buckley-Leverett equations. Although the results shown by Willman et al. are for a radial system flowing out from the well to an assumed external circular boundary, their equations did

Jan 1, 1969

By F. H. Wilson, M. L. Kronberg

The low temperature recrystalliza-tion of very heavily rolled copper produces a fine grained structure with a high degree of preferred orientation. Additional heating to within a few hundred degrees of the melting point may induce an abrupt and pronounced increase in the grain size, with the resulting crystals having new orientations. This behavior at high temperatures is commonly termed "secondary recrystallization." Several investigations have dealt with the phenomenon arid have served to bare many features of the beha~ior.1-4 In general,observations have been made on the sizes and shapes of the grains, and data have been presented showing the existence of an induction period in isothermal experiments. Although it has been well established that the orientation before the change is statistically (100) 10011, the so-called "cubically aligned" texture, there is no such agreement on the orientation after the change. For example, Dahl and Pawlek1 describe it as being equivalent to an approximately 30" rotation about the [l00] axis of the ideal cubic texture which is parallel to the rolling direction, the resulting orientation being near (210)[001]; and Cook and Richards2 find an orientation of approximately (110)[L12]. Since the completion of most of the work to be reported in this paper, Rowles and Boas3 have published their ver] illuminating paper on "secondary recrystallization," in which they present convincing evidence for a third orientation and show that their esperiments give no evidence for either of the other two orientations. The orientation is described as equivalent to an approximately 30° rotation about a [ 111] pole of the ideal cubic orientation. The existence of a variety of reported orientations is not unique for copper, for a similar state of affairs exists for other systems that have been studied— aluminum, nickel, nickel-iron alloys, and others. It seems therefore that the existence of this variety does not necessarily constitute a contradiction, but rather indicates that different experimental conditions yield different results. The fundamental nature of the phenomenon has not been elucidated. However, it has been generally recognized that the large grains could be the end product of growth of a few select grains already existing in the sample in minor amounts—too small to allow detection—or that entirely new ones could be formed by a process of nu-cleation and growth. Existing experimental evidence does not distinguish between these two most apparent possibilities. Nevertheless, the former has been more generally favored largely because our current understanding of the state of an annealed metal has not made it seem reasonable to expect a nucleation event to occur at temperatures above those required for the primary recrystallization. Observations on the Preparation and Heating of Twin-bearing Cubically Aligned Copper The starting material used throughout. the investigation was a bar of OFHC copper, forged and annealed at 950°C. Visual inspection showed the grain size to be around 0.5 mm, and did not disclose any preferred orientation. A chemical analysis showed the following composition: Cu + Ag— 99.99 Pct S — 0.005 pct 0 — <0.005 pct For the preparation of cubically aligned copper, ¾ in. thick slabs were cut from the bar, heavily pickled in concentrated HNO3 and cold rolled to sheets about 0.012 in. thick. The reduction in thickness was approximately 98.5 pct. Standardized annealing techniques were followed. Samples to be heated were lightly dusted with alumina in order to prevent sticking and then sandwiched between 1/16 in. copper plates. The resulting sandwich was heavily wrapped with copper sheet, and then annealed in air. The protection was such that only very thin films of oxide were formed. That the associated light oxidation of the samples had no specific effect on the recrystallization behavior was shown by the similar results that could be obtained on annealing in highly purified and dried hydrogen. Two methods were used in bringing samples to temperature: (1) by placing the package directly in the furnace at temperature and (2) by placing the package in the furnace at room temperature, and then slowly increasing the temperature. The corresponding heating rates are illustrated in Fig 1, and will be referred to as "rapid" and "slow," respectively. Unless specified otherwise, all anneals will be of the former type. Metallographic examination was made on samples prepared by electrolytic polishing and etching as described in the Metals Handhook.* STRUCTURES FOUND BEFORE "SECONDARY RECRYSTALLIZATION" OCCURS Annealing the rolled material for 1 hr at 400°C produced a heavily twinned, cubically aligned structure, the grain size being of the order of 0.03

Jan 1, 1950

By M. G. Corson

THE iron-silicon alloy series has always been one of the most puzzling among the binary alloys. Examining the well known mechanical properties of the iron-rich alloys only we meet the following situation: The ultimate strength and yield point of alloys worked and annealed under the usual conditions represent nearly a straight line function of the silicon content up to 4.5 per cent. silicon (Fig. 1). Starting at the ultimate strength of 35,000 lb. and at a yield-point of 16,000 lb. for pure electrolytic iron, one reaches a -maximum strength of 93,000 lb. and a maximum yield point of 74,000 lb. at 4.5 per cent. silicon. This corresponds to an increase in ultimate strength by 13,000 lb. per each per cent. of silicon added and nearly the same rate applies to the yield point. The data mentioned are taken from the investigation by T. D. Yensen,1 and while they do not exactly corroborate the results obtained by earlier investigators, they seem to be the most correct. Plastic properties of the alloys are controlled by a much more complicated relationship. Up to 2.5 per cent. Si, the elongation stays close to 50 per cent. (in 2 in.) and the area reduction amounts to 85 per cent., a situation that forms the usual feature of all alloys representing strictly solid solutions. The plasticity of the latter is always nearly equal to that of their base metal. Beyond 2.5 per cent. silicon, the situation becomes much more complicated Yensen observed an enormous drop in elongation and area reduction at about 2.65 per. cent. silicon, where the first hardly reaches 10 per cent. and the second is still lower; he found, however, a considerable recovery in plasticity at about 2.8 per cent. Si and up to. 4.5 per cent. Si it is represented by 20 per cent. for the elongation and 30 per cent. for area reduction.

Jan 1, 1928

THE Institute Committee on Industrial Relations, of which Robert Linton is chairman, held a meeting on Feb. 21, listed as one of the technical sessions of the annual meeting, at which reports of the sub-committees were presented. Following are abstracts of these reports. The Institute can furnish mimeo-graphed copies of the complete reports on Safety, Employment, Illness, Mental Factors, and Cripples in Industry. The supply of the other reports has been exhausted. A paper by George F. Kunz, which was presented at the same meeting, is printed here in full.

Jan 6, 1922

By S. D. Strauss

The marketing of nonferrous metals and of the ores and concentrates from which these metals are recovered is a fascinating trade, international in character, sensitive to every change in the economic tide, and complex in its organization. Each individual metal has its own marketing mechanism; no two are exactly alike. The differences sometimes are a matter of tradition rather than of necessity, but usually they have developed because of the very nature of the problems of producing or consuming the individual metal. This description, because of limitations of space, can do no more than indicate the major aspects of the trade and touch lightly on the marketing structure of each metal. The dictionary states that a market is a "meeting of people for selling and buying." In the case of nonferrous metals this meeting may occur on a half-dozen different occasions between the time the ore has been first mined and the time the refined metal is available for use by industry; or it may not occur at all until after the metal itself has been rolled, drawn, stamped, cast, or forged into a useful semifabricated shape. To illustrate: A Chilean miner may sell his small ore production to a custom mill, which produces concentrates that are sold to an ore dealer, who finances the shipments of the concentrates to a United States custom smelter, which buys these&apos; concentrates for conversion into blister, which is subsequently refined into electrolytic copper and sold. Conversely, much of the production of aluminum is in the hands of integrated concerns that mine bauxite, convert bauxite to alumina, smelt the alumina to produce aluminum, and then fabricate the aluminum into semifinished or even finished products before title to the material changes hands for the first time. Some nonferrous ores are not converted into metal at all but are sold by the miners or dealers directly b the ultimate consumers. A good example would be chrome ores used by the chemical industry. And of course a substantial part of the commerce in nonferrous metals is in scrap, which is the reconversion into useful form of metals that have long since been mined and smelted. Thus, one-third of all the lead used in the United

Jan 1, 1959

By Owen Thornton

Recently equations have been presented by Rose and Bruce&apos; and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"&apos; multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately&apos;: — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949

By Owen Thornton

Recently equations have been presented by Rose and Bruce&apos; and by Rose², showing how the relative permeability of a reservoir rock may be determined from the capillary character of the rock. In particular, equations were developed to show the relationship between capillary pressure and the effective permeability to the wetting phase in a poly-phase flow system. The equations are as follows (nomenclature the same as in the Rose and Bruce paper) Rose and Bruce assume that the average length of path (L,), which the wetting fluid follows in flowing through a porous media is independent of the saturation to the wetting phase, so that 1 is a constant dependent only on the k rock, and the permeability to the wetting phase is a function of the saturation and of the capillnry pressure: In measuring the flow of ekctric current through partially saturated core samples, it has been observed that the electrical resistance usually is not a simple linear function of saturation. This fact indicates that the average length of path in the flow of electric current is not independent of saturation, but rather that the tortuosity of the path depends upon the average saturation to the conducting fluid as well as upon the characteristics of the rock. itself. Inasmuch as the flow of fluid and the flow of electric current in many respects are analogous, it may be indicated further that the length of path for fluid also may not be independent of saturation. The following relationship can be derived to express the resistance to flow of electric current through a core sample partially saturated with conductive wetting phase, the non-wetting phase being non-conductive: where L is the average length of path followed by the current in flowing through a length L of partially saturated core, where L is the length of current path when the core is fully saturated, and where Rs and R, are the specific resistivities of the partially saturated and saturated core sample, respectively. It will be noted that R., the specific resistivity of the core sample when S, = 1.0, is equal to the "formation resistivity factor"&apos; multiplied by the specific resistivity of the saturating fluid. If it be assumed that the average lengths of path for fluid flow and for the flow of electric current are the same, then equation (5) may be combined with equations (l), (2) and (3) to give the following relationship: The above equation suggests including a correction for tortuosity when calculating the relative permeability of a reservoir rock to a wetting phase. The correction factor may be obtained from the resistivity-saturation relationship. For instance, the following calcu- lations are obtained for the unconsoli-dated sands described by Leverett Kw Kw Sw R°/Rs Pt/Pc¹ (Calc.) (Obs.) 0.30 0.08 0.88 0.02 0.0 0.40 0.16 0.94 0.06 0.04 0.50 0.27 0.97 0.14 0.11 0.60 0.40 0.98 0.26 0.21 0.70 0.53 0.98 0.39 0.35 0.80 0.68 0.99 0.57 0.54 0.90 0.84 0.99 0.77 0.76 1.00 1.00 1.00 1.00 1.00 It will be noted that the agreement between the calculated points and the observed data is rather good. Further investigation of the above method for obtaining relative permeabilities may be merited. For many sands within specified ranges of saturations the following relationship has been found to hold approximately&apos;: — =SW"......(7) Rs The exponent n in the above equation has been found to equal two for many sands so that equation (6) reduces to the following: The writer acknowledges the permission of The Texas Co. to submit this note for publication. 1. Walter Rose and W. A. Bruce—Jnl. of Pet. Tech., Vol. 1, No. 5, p. 127 (1949). 2. Walter Rose—Jnl. of Petr. Tech., Vol. 1, No. 5, p. 111 (1949). 3. G. E. Archie— -Trans. AIME, 146, 54 (1942). 4. M. C. Leverett— Trans. AIME, 142, 152 (1941). 5. M. C. Leverett—Trans. AIME, 132, 149 (1939).

Jan 1, 1949