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By Robert L. Slobod

In much of the work reported in the literature on long cores. true connate water value, probably have not been obtained because of insufficient flow of 011 to attain equilibrium. A -.satisfactory method for establishing connate water in long cores has been developed in which oil flow is maintained until no additiona1 water is displaced. INTRODUCTION Long cores have been used by sev-erals investigators in an effort to evaluate the efficiency of oil recovery for various producing schemes. The effects of many variables such as rate of displacement. pressure drop, volume of displacing medium, gas-oil ratio, inter-facial tension, and others have been investigated, and the merits of gas drive have been compared with water drive. In the older experiments no connate water was used. but in the more recent stndies the philosophy of the experiment calls for a core containing oil and connate water (irreducible water) as the starting point of the experiment. The method generally used to establish this condition in long cores involves dynamic' displacement wherein one or more phases are forced through the core. flow being maintained at a constant rate or at a constant pressure until a steady state is reached wherein there is no change of saturation with time. It is one purpose of this paper to point out that in much of the work reported in the literature true connate water values probably have not been obtained. The reason for this failure is pointed out. and a method for obtaining more reliable connate water values on long cores is presented. It is impossible at this time to completely evaluate the effect on the conclusions in the earlier papers resulting from the failure to obtain true connate water in the long cores, but some data are presented which indicate that serious errors may he present in many cases. MATERIALS AND APPARATUS Cores cut front outcrop sandstones (Strawn. Torpedo, and Elgin sandstones) with permeabilities of the order of 300 md were used. The major experiments were made with a core 18-in. long and 2-in. in diameter. Cores of the same diameter but only 12-in. long were used in a few tests? and in some work a core I-in. in diameter and 11-in. long was used. These materials were all somewhat bentonitic. 'To reduce the effect of such constituents, one of the cores (Torpedo No. 10) on which the most work was performed was acid extracted at the start of the experiment. Brine containing 50,000 ppm chloride and naphtha (Stoddard's Solvent) were used as the water and oil phases, respectively. The core was mounted in a rubber sleeve which forms the inner lining of a brass cylinder. In this arrangement2 the rubber sleeve is forced against the core by applying pressure to water in the annular space between the rubber sleeve and the brass cylinder wall. The core is therefore sealed in rubber so that all fluids introduced at the input end of the core flow through the core. With this equipment the core may be easily removed for inspection and analysis. Also, other cores may be introduced for study with no extra time for preparation such as is required when plastic mounting is used. When pressure or conductivity measurements are desired at intermediate points along tile length of the core, the brass cylinder comprising the outer jacket of the core holder is cut into section, of the desired length. Each section is then made up as an individual unit with its own rubber sleeve (see Fig. 1). The individual units are then butted up against a ring of plastic or other insulating material which carries an electrical contact for resistivity measurements and an opening which can be used for the measurements of fluid pressures. The individual units are forced tightly against the plastic ring separators and held in place with several tie rods. Inlet and outlet end butts of the same diameter as the core and several inches in length are provided to control the introduction and withdrawal of fluids and to complete the arrangement for sealing the core within the rubber sleeve. Fluid flow is maintained either by applying pressure to the liquid confined in a reservoir or by the use of a gear pump. The latter is preferable where continuous flow at a moderate rate over a long time interval is desired since a small volume of liquid can be readily recirculated using filters to prevent plugging of the core. EXPERIMENTAL The oven-dried core is weighed and is then completely saturated with brine

Jan 1, 1950

By A. W. McReynolds

E. OROWAN*—I observed the phenomenon of jerky yielding many years ago with zinc25 and cadmium single crystals. A significant point was that the jerks occurred not only when the stress was raised but also (sometimes, after a pause of many minutes during which no trace of creep was observable) at constant stress. The phenomenon may be closely linked with the inertia of the testing machine and of the specimen, although the inertia alone cannot account for it. If, during the test, the resistance of the material to plastic deformation suddenly diminishes while the applied force remains constant, a sudden deformation follows until the yield stress has risen, by strain hardening, to the level of the applied stress (= the value of the previous "upper yield point."). When this is reached, the rate of deformation has attained a maximum value because, up to this moment, the applied force was higher than the plastic resistance of the specimen, and the difference was used for accelerating the moving parts of machine and specimen. The kinetic energy accumulated is now transformed into plastic work by further deformation; that is. the deformation overshoots the point at which the plastic resistance equals the applied static force. When the kinetic energy has been used up, therefore, we are left with a specimen the yield stress of which is higher than the applied stress, and no further deformation can occur (apart from a little creep) until either the applied stress has been raised to the new yield stress level, or the yield stress has fallen by thermal recovery to the level of the applied stress. While this occurs, a new upper yield point can develop, for example, by precipitation.26

Jan 1, 1950

By T. E. Leontis

Several publications1-7 during the past few years have demonstrated the markedly greater effect of cerium, as compared to all other alloying elements, in enhancing the strength and creep resistance of magnesium at elevated temperature either with or without the presence of other elements. In the work reported in Ref. 1-6, the cerium was added in the form of Mischmetal, which contains all the rare earth elements in essentially the same proportions as they occur in monazite sand, the principal ore of these metals. Mellor and Ridley7 have presented the creep characteristics at 200°C of magnesium alloys prepared both with pure cerium and with Mischmetal. Up to the present time, however, no comprehensive study of the effect of the various component elements of Mischmetal on the properties of sand-cast magnesium has been made. This hiatus in magnesium technology undoubtedly is associated with the difficulty in obtaining the rare earth metals separately. This investigation provides such a survey, the object of which was to determine which of the elements present in Mischmetal contributes the greatest effect in developing high strength and high resistance to creep at elevated temperatures. Toward this end the compositional variation of these properties has been determined as a function of temperature in the following alloy systems: 1. Magnesium-Mischmetal 2. Magnesium-cerium-free Misch- metal 3. Magnesium-didymiuin 4. Magnesium-praseodymium- lanthanum 5. Magnesium-cerium 6. Magnesium-lanthanum This designation, based on the names of the metals as furnished by the producer, is used throughout the paper in order to avoid the complicated system of listing all the elements present in the more complex alloys. The composition of the metals and the alloys is discussed in detail below. Preparation of Alloys ALLOYING INGREDIENTS The chemical composition of each of the six alloying ingredients used to prepare the alloys reported in this paper is given in Table 1. In each case, the percent total rare earths, percent cerium, percent neodymium, percent praseodymium, and percent thorium were determined in addition to the listed impurities. The percent lanthanum was determined by difference from the total rare earth content and consequently includes the other elements (samarium, terbium, yttrium, etc.) present in Mischmetal. These additional elements, however, seldom amount to more than 1 to 2 pet of the total rare earth content of Mischmetal. The iron content of the Mischmetal is considerably lower than that of the other metals. This grade of Mischmetal is now readily available. The metals are listed in the order of decreasing complexity. Elimination of the cerium from Mischmetal results in what the trade calls "Cerium-free Mischmetal." Carrying the separation a step further by eliminating the lantha-

Jan 1, 1950

By S. W. Ross

A. A. CENTER*—This paper reminds me of the beginning of the work of the Electrolytic Zinc Company of Australasia. Early work for this Company, as some of you may know, was done at the Bully Hill Plant in California. After working there for some time Herbert Gepp, now Sir Herbert, came to the Anaconda Co. plants in Montana where I met him. He spent some months there, in fact almost a year if I remember rightly. That was when we were breaking in the new electrolytic zinc plant at Great Falls, Montana. From there he went back to Australia and started in on the plant there. I believe they had an original plant of about 20 tons per day of cathode zinc. We heard from them for some time, until they were able to go along on their own, and they have done very well ever since as you have heard. Their practice, (the flow sheet, the leaching practice), has been quite different as reported in the paper and apparently they are still following that practice to some extent. While the earliest work on selective flotation was done down in Australia, the big companies there, strange to say, were far behind the American companies in taking it up; and it is only in comparatively recent years they have gone to the alkaline circuit and dropped out thereby more of their iron and lead. The zinc plant now is up to a capacity of 100,000 tons a year and I believe that may be notched up to about 105,000. T. H. WELDON*—I would like to ask

Jan 1, 1950

By W. L. Finlay

Size effects in quenching steel are particularly prominent and well recognized because of the existence of a critical cooling rate separating nuclea-tion and growth transformations, as exemplified by the formation of pearl-ite, from the shear type of transformation characterizing the martensite reaction. The absence of a similar, sharply demarcating cooling rate is characteristic of precipitation hardening systems and size effects in these are correspondingly less prominent. This paper is concerned with a size effect in high-purity, precipitation-hardenable alloys which appears not to have been recognized previously. This effect is believed to result from the thermal fluctuations which inevitably occur in quenching a specimen of finite size into a cooling liquid rather than from the existence of a critical cooling rate. QUENCHING "ANOMALIES" The precipitation hardening literature contains many references to so-called anomalous quenching and aging results. By "anomalous", investigators usually meant that their alloys did not consistently harden on aging after quenching according to some anticipated pnttern: not infrequently virtually no age hardening occurred with compositions known to be precipitation-hardenable. Perhaps the most prominent series of anomalies was reported over a 15-year period by Gayler and coworkers on aluminum-copper.l,2,3,4 Working with silver-rich copper alloy, Cohen5 secured some very interesting Rockwell F hardness changes of from 1-5 Rockwell points between the first peak and valley. Fink and Smith borrowed one of Cohen's specimens and, following his heat treatment and quenching practice to the letter, secured6 very different results in which only one peak was obtained and in which the hardness level at the aging lime of Cohen's first peak was 20 Rockwell F points higher. Fink and Van Horn7 encountered serious deviations in age-hardening high purity aluminum-zinc alloys. They stated that "the discrepancies were larger than might be expected from possible experimental errors in the Brinell readings." Geisler, Barrett and Mehl8 likewise encountered anomalous hardening results in aluminum-silver alloys, securing quite different age-hardening curves from two identical specimens. They stated that "the treatments of these samples had been the same, so that the different behaviors could be attributed only to accidental variations in the quenching practice."

Jan 1, 1950

By S. S. Cole, H. Sigurdson

The melting points of mixtures of titanium dioxide and other titanates have been reported to a limited extent as binary systems and some results have been reported in conjunction with silicon dioxide. The limited data indicated that a low melting zone might exist in a ternary or quarternary system of CaO-MgO-TiO2-Al2O3, since the eutectics reported in the binary systems of MgO.TiO2-TiO2, Al2O3TiO2-TiO2 and CaO.TiO2-TiO2 were of about equivalent composition of TiO2. The importance of a low melting region with a high titanium oxide value in the developing of high titanium slags is fully appreciated by metallurgists. A comprehensive study was undertaken to establish basic information on low melting titanate mixtures. Compounds in the System CaO-MgO-TiO2 -Al2O3 Preparation of the titanates of CaO, MgO and Al2O3 confirmed reported data that the following compounds could be formed under oxidizing conditions in solid state reactions: CaO.TiO2, 2MgO.TiO2, MgO.TiO2, MgO-2TiO2 and Al2O3.TiO2. Under oxidizing conditions it was not possible to react MgO with TiO2 in mol ratios higher than 1:2 without having unreacted TiO2 in the product, nor was it possible to form calcium or aluminum titanates with a higher mol ratio of CaO and A12O3 to TiO2 than 1:1. By fusing mixtures of Al2O3-TiO2 and MgO-2TiO2 together a series of solid solution products were obtained, which showed an MgO-2TiO2 X ray diffraction pattern shifted to smaller inter-planar spacings. Range of Investigation Data in the literature1 indicated that these titanates had melting points which ranged from 1645 to 1860°C. Since the purpose of the study was primarily to provide useful data for smelting titaniferous ores, the work was restricted to the zone of the system which would include the crystalline phases present in the slags. The explored limits were bounded by CaO.-TiO2-MgO.TiO2-TiO2in the base plane. The system was extended to a fourth component Al2O3-TiO2 since many titaniferous ores contain appreciable amounts of A12O3. In the quarternary system CaO-TiO2-MgOTiO2-TiO2-Al2O3TiO2, a tetrahedron was used to represent graphically the components, with one component at each point of the tetrahedron. In the base plane, mixtures were pre- pared to represent fairly uniform changes of composition over the desired range expressed on a mol percent basis. Al2O3-TiO2 was brought into the system in increments of 10 mol pct up to 40 pct. Mixtures were then made up for each of the Al2O3-TiO2 planes. The ranges employed were then represented by five planes cutting the tetrahedron at 10 mol pct Al2O3-TiO2 intervals. Choice of Equipment Although it was necessary for all smelting work to be done in a strongly reducing atmosphere, it was decided that all melting point determinations should be done under oxidizing conditions. This decision was prompted by the fact that TiO2 reduced to lower oxides in a reducing atmosphere with consequent changes in melting points. The use of a micropyrometer and a platinum strip furnace for work of this type is adequately described in the literature.2 With modifications, equipment was selected which provided a fairly rapid method of determining melting points of refractory oxides. The final assembly, which was used, consisted of a platinum strip furnace and a Leeds and Northrup disappearing filament optical pyrometer attached to a special telescope which magnified the sample about 20 diam. The furnace assembly consisted of a platinum strip 0.005 X 0.3 X 2.2 in. mounted on brass posts on a refractory base. This was enclosed in a black steel shell which had a 2-in. opening at the top for purposes of sighting the telescope. The platinum strip was in series with two 0.04 ohm nichrome resistors connected to the secondary of a 2 kw transformer which supplied 17 volts. The current to the primary was varied

Jan 1, 1950

By C. W. Sherman, N. J. Grant

The correlation of the high temperature chemical properties of slag-metal systems with some easily measured property of either slag or metal at room temperature has been the goal of both process metallurgists and melting operators for many years. There are several rapid methods for estimating various constituents in steel in addition to the conventional chemical methods which are quite fast, but these do not reveal the nature of the slag as a refining agent, which is of primary interest to the steelmaker. Furthermore, there are several methods for examining slag, the three principal ones being slag pancake, petrographic examination, and the previously mentioned chemical analysis. The main objection to the last two is the lime required to make a satisfactory estimate of the mineralogical or chemical components. The objection to the first is the inadequacy of the information obtained. A new technique has been developed by Philbrook, Jolly and Henry1 whereby the properties of slags are evaluated from an aqueous solution leached from a finely divided sample of slag. It is known that the pH or hydrogen ion concentration (of saturated solutions that have dissolved certain basic oxides, notably calcium oxide) will indicate a pronounced basicity. Philbrook, Jolly and Henry devised the pH measurement technique in order to supply open hearth operators with a fast, reasonably accurate method of estimating slag basicity. They offered the method as an empirical observation and made no claims as to its theoretical justification. The results were presented as an experi-metally observed relationship which applied over an important range of basic open hearth slags. They found that, in plotting the measured pH against the basicity, the best relationship existed between the pH and the log of the simple V ratio, CaO/SiO2. Extensive investigation also showed that there were several variables in the experimental technique that influenced the results and necessitated following a standard procedure to obtain reproducible pH readings. These variables were: 1. Particle size of the slag powder used. 2. Weight of sample used per given volume of water. 3. Time of shaking and standing allowed before the pH was measured. 4. Exclusion of free access of atmospheric carbon dioxide to the suspension. 5. Temperature of the extract at the time the pH was measured. In subsequent investigations of the pH method by Tenenbaum and Brown2 and by Smith, Monaghan and Hay3 the general conclusions of Philbrook's work were reaffirmed. It was the object of the present investigation to extend the technique to a point where it could be used to evaluate slags of all types. Experimental Results PARTICLE SIZK OF SLAG POWDER A large sample of commercial blast furnace slag of intermediate basicity (V-ratio 1.15) was selected for the study. The slag had been put through a jaw crusher until all of it passed through a 20 mesh screen. Five fractions of this crushed material were separated, -20 to +40, -40 to +60, -60 to +100, -100 to +200, and -200 mesh. A representative sample of 0.5 g was removed from each fraction and the pH determined using the method of Philbrook. Check pH analyses on the sample fractions varied due to the different amounts of shaking. To eliminate this variable, a mechanical shaker was employed. In order to know the exact time of contact between the slag and water, it was found necessary to filter the extract at the end of the shaking period. Using the mechanical shaker and a filtering apparatus, similar runs were made on the five fractions for contact times of 5, 10, 20, and 40 min. Random checks gave reproducible results within 0.02 pH. The data are plotted in Fig 1. It can be seen from the plot that each slag fraction is hydrolyzed to an extent that is roughly proportional to the surface area exposed to the water. The (—100 to +200) mesh material changed very little in pH after 10 min. shaking time. The curves are symmetrical and lie in proper relation to one another. The —200 mesh curve appears to be somewhat flatter than the others, but this can be attributed to the portion of very fine material that is not present in the other fractions. The closeness of the (-100 to +200) mesh curve to the —200 mesh curve and the fact that a —100 mesh sample would contain amounts of slag down to 1 or 2 microns in diam were considered sufficient reasons for selecting a —100 mesh sample as representative of the whole sample of slag for the purposes of this investigation.

Jan 1, 1950

By J. B. Hess, C. S. Barrett

Single crystal rods of cadmium collapse under uniaxial compression into peculiar kinks if the (0001) glide plane is nearly parallel to the axis of compression. In his report first describing this behavior, Orowan1 proposed that these "kink bands" do not develop entirely by ordinary gliding and twinning but by a special mechanism in which glide lamellae of uniform thickness snap abruptly to a tilted position that permits lattice continuity across the glide planes. He concluded that a portion of each boundary of a kink band consists of a plane (non-crystallo-graphic) which bisects the angle between the glide planes on the two sides of it, and along which the bending and the dislocations are concentrated. The data presented by Orowan seemed to us to be insuffcient to conclude that a wholly new mechanism of deformation was responsible for the kinks. Therefore, we have investigated zinc, which is hexagonal close-packed and has an axial ratio near to cadmium, to see whether similar bands are produced, and whether the ordinary mechanisms of glide, bend-gliding, twinning, and the formation of deformation bands can account for its mode of deformation. We find that kinks form profusely in zinc as shown in Fig 1. The structure of these kinks, reported below, seems to require no new mechanism for their explanation, but indicates that kink bands are a special form of deformation bands and develop gradually, solely from basal glide. A theory covering the formation and structure of the bands is presented in detail because it is seldom possible to study deformation bands under such simple conditions, yet many principles applying to these kinks should also apply to deformation bands in general. Experimental Procedures Single crystal rods of 2-3 mm diam and 10-15 cm length were grown by the Brideman technique from swaged wire of Horsehead Special zinc in un-coated pyrex tubes. Orientations of the rods were determined with an optical goniometer after cleaving the rods at liquid air temperature. Crystals of desired orientations were then selected and used as "seeds" to grow additional crystals approximately 4 ft in length from which all specimens were cut. The wires were compressed in two ways: in a simple hydraulic handpress —a "soft" machine—and in a Riehle hydraulic testing machine modified to produce very "stiff" action by the simple expedient of inserting lengths of steel bars at the sides of the zinc crystals between the compression plates. For metallographic examination, the specimens were mounted in sealing wax. Hand polishing was employed, with no grits coarser than No. 1 paper; following the abrasives about 0.025 in. was removed by an etch-polishing reagent.* Final etching to reveal ori-

Jan 1, 1950

By Morris Muskat

A theory is presented for calculating the performance history of complete water-drive systems producing from idealized stratified formations. The general equations are applied to systems where the permeability stratification is either of the exponential or linear type. Calculations were carried through for different degrees of permeability stratification, but with special emphasis on the effect of the mobility ratio between the produced oil and the invading water on the resultant performance. These results are also expressed graphically as curves for the initial water breakthrough recovery, for the different degrees of stratification, as a function of the mobility ratio, and of the composition of the produced fluid stream as a function of the cumulative oil recovery. For several typical cases the latter has also been plotted as a function of the cumulative oil and water throughflow. The general result is that when the mobility of the oil is lower than that of the invading water the channelling tendency resulting from the permeability stratification becomes aggravated as the higher permeability zones become flooded out. Situations of this type would obtain when producing low gravity or highly viscous oils. Conversely, if the mobility of the oil is high compared to that of the invading water, the flooding of the high permeability zones will lead to a retarding and choking effect, and the gross bypassing phenomena will be partially suppressed. These conditions would correspond to those of flooding high gravity or low viscosity oils. A discussion is given of the various basic assumptions made in the analysis, including that of ignoring the stripping phase of the production history as implied by relative permeability concepts. INTRODUCTION The physical ultimate recoveries from oil reservoirs are basically determined and limited by the physical oil displacement processes associated with the reservoir producing mechanism. In practice, however, the economic ultimate recoveries are further limited by the mobility of the reservoir fluids and the uniformity and continuity of the producing formation. In fact, it is the differential depletion between the component parts of the composite reservoir which ultimately determines the total recovery at the time of field abandonment. While this observation applies to both the solution gas drive and gravity drainage mechanisms, in which use is made only of the energy contained within the original oil-bearing reservoir, it is of even more paramount importance under operations wherein the energy associated with extraneous fluids provides the ultimate oil expulsion mechanism. Whether the invading fluid is the water from an edgewater drive, water injected for pressure maintenance, gas injected for pressure maintenance, or gas returned to the formation in a cycling program, it is often the continuity and uniformity of the producing section which will control the economic efficiency of the operations. The importance of the problem of reservoir non-uniformity does not, of course, lessen its complexity or the difficulties of its solution. In fact, these are inherently such that the concept of a "general" solution is virtually meaningless. About all that can be reasonably hoped for is the analysis of specific and well-defined types of non-uniformity which may give some degree of approximation to actual reservoir conditions. Since variations in the nature of the reservoir which depend only on the position along the streamlines will not lead directly to major differential depletion development within the reservoir, the types of non-uniformity considered thus far have involved stratification assumptions. That is, the producing section has been replaced by a multi-layer "sandwich," each uniform areally, and differing from the others only in its basic physical constants as to thickness, porosity and permeability. The fluid motion in the composite system is thus approximated by a parallel superposition of the independent fluid movements in the individual strata. For the specific application to cycling operations the theory of the effect of permeability stratification has been developed for both discontinuous' and continuous types of permeability stratification. Among the latter, treatments have been given of systems in which permeability distributions are governed by exponential, linear' or probability3 functions. In all these studies complete dynamical equivalence was assumed between the injected dry gas and the displaced wet gas. The overall effective permeability of each stratum was therefore considered as constant and independent of the degree of invasion of the injected fluid. In the case of the displacement of oil by water, the assumption of dynamical equivalence between the water and oil will be strictly valid only by accident. Even if the oil viscosity should be the same as that of the water, the effective permeability to the oil in the presence of the connate water will in general be quite different from that of the water behind the water-oil interface flowing past the trapped residual oil. As a result the effective permeability for the stratum as a whole and rate of water invasion will change with time as the intrusion continues. The differential fluid motion in the individual strata will thus also vary with time. Qualitatively, it is easy to predict the resultant effects. If the permeability to viscosity ratio of the invading fluid exceeds that of the fluid displaced, the stratification and bypassing effect of the perme-

Jan 1, 1950

By Albert L. Toenges

C. P. HEINER*—I would like to ask Mr. Toenges about the highest rank coal. I did not get that clearly. What kind of coal is that? A. L. TOENGES (author's reply)— The coal in the Matanuska field ranges from high volatile "B" bituminus to anthracite. It all depends on which direction you go in the Matanuska field. C. P. HEINER—Is it a large reserve. A. L. TOENGES—That is what we hope. That is what we are trying to find out. B. W. DYER*—In those strip beds, I wonder how far back the coal would weather ? A. L. TOENGES—I never noticed particularly. B. W. DYER—The weathering does not extend back like it does in this country ? A. L. TOENGES—No, it does not. B. W. DYER—Is that due to the freezing ? A. L. TOENGES—Probably so. B. W. DYER—In this country, you would expect nothing but weathered coal. R. H. SWALLOW*—Along that line, you mentioned some of the seams were on fire. Did you ever know how far back they burned, or was it hard to tell ? A. L. TOENGES—The fires occurred in the mine. That one you refer to was from an inside fire.

Jan 1, 1950

By A. D. Hughes

C. W. MERRILL*—Mr. Hughes' paper not only is very well presented but is most timely in that it covers a subject of vital interest to the United States. Tin is one of the strategic metals which has not been found here in appreciable quantities. The total United States tin output since the first recorded production over 100 years ago would not supply current consumption for a fortnight. On the consumption side, tin is extremely important in national defense because of its use in tin plate which, in the form of tin cans, makes it possible to feed properly the armies that the United States recruits from its civilian population in emergencies. Moreover, the internal combustion engines so important in powering tanks, planes, and other war machines, require large quantities of tin alloys for bearings and for soldering. These considerations, along with the fact that Malaya, historically, has been the leading source of tin to the United States, make the kind of information that Mr. Hughes has presented so ably. a matter of vital interest. Your Chairman, Mr. Romanowitz, in his introduction, referred to the fact that I had been a member of the United States delegations to the three meetings of the International Tin Study Group. Some cominents on the Group's objectives and deliberations may be of interest. When it appeared that the International Tin Committee, the prewar producer's cartel, might soon revive its operations and extend its control agreement beyond the expiration date of Dec. 31, 1946, the United States Government became interested in some kind of an international trade organization concerned with tin which would give the consumers' interest equal representation with the producers' interests. An international meeting was called in London in October 1946 to consider this problem. I did not attend that meeting hut the result of the meeting was the organization of the International 'Tin Study Group which

Jan 1, 1950

By P. Duwez, L. Zwell

In recent years, the problem of pressing metal powder in a die has received much attention. The question has been the object of a Symposium held in New York in March 1947 under the sponsorship of the AIME; an excellent review of the subject may be found in Ref. 1. Various experimental techniques have been used to study the behavior of the powder in a die cavity. Two methods have been particularly successful; one consists of measuring the density distribution²,³ and the other makes use of a lead grid in the powder during pressing.4 In the present study, the pressure at various points on the bottom and the sides of a die 1.50 in. in diam was measured by means of small piston dynamometers and resistance sensitive strain gauges. In order to correlate the results with previous investigations, the pressure distribution inside the compact has also been determined by an indirect method based on density measurements. Strain Gauge Measurements of Pressure on Side and Bottom of Die A schematic drawing of the die used for measuring side pressures is shown in Fig 1. The pressure gauge consists of a 0.25-in. diam piston A which transmits the pressure to a dynamometer B, on which two Baldwin Southwark type 4-14 strain gauges are fastened 180" apart. Because the installation of several dynamometer assemblies along the side of the die would have been difficult, the pressure distribution was obtained in successive tests in which the distance from the gauge to the bottom of the compact was adjusted to different values by changing the length of the bottom piston. The dynamometer, disassembled from the die, was calibrated under compressive loads and showed a 1.00 ohm change of resistance for every 15,300 psi change of pressure (750 lb load change). All the strain gauge measurements were made with a null type Leeds and Northrup Wheatstone bridge. The sensitivity of the method was better than 1 pct and the accuracy was within 2 pct. These values were considered satisfactory in view of the rather large scatter in the measurements introduced by the random variation in packing the powder in the die. The stable ambient conditions and short time involved in the taking of observations made temperature compensation unnecessary-. The pressure distribution on the bot-

Jan 1, 1950

By E. P. Klier, S. M. Grymko

The transformations in eutectoidal systems have been extensively studied as they occur in steels.&apos; As a consequence of these studies the martensite, bainite and pearlite reactions found for most steels are widely recognized. Further, because of the work of Smith and Lindlief2 and of Greninger and Troiano3 these reactions, except for the bainite reaction, are considered as typical for all eutectoidal systems. The primary alloy studied by Smith and Lindlief2 was a CuAl alloy of near eutectoid composition as was the alloy more recently studied by Mack.4 The transformations in these alloys were, for the most part, studied metallo-graphically, while an X ray analysis of structures was essentially wanting. It has appeared desirable, therefore, to investigate selected CuAl alloys at and slightly away from eutectoid composition. For this purpose three alloys were prepared containing 10.5,11.9 and 13.5 pct A1 respectively. The results of a metallographic and X ray analysis of structures obtained for isothermal transformation of the ß-phase are reported here for the 11.9 and 13.5 pct A1 alloys. Introduction The phase equilibria in the CuAl alloys of immediate concern are indicated in the equilibrium diagram section presented in Fig 1.5 The equilibrium and transition structures which have been reported in this system are as follows: a = copper rich terminal phase (f.c.c.) ß = high temperature eutectoidal phase (b.c.c.) r2 = aluminum-rich intermediate phase (r-brass structure) a&apos; = modified a-phase postulated by Bollenrath and Bungnrdt.26 ß1 = ordered ß (b.c.c.) ß&apos; = martensite structure: A1 < 13 pct (near h.c.p.) ß" = ß&apos; of Smith and Lindlief2 7&apos; = martensite structure: A1 > 13.5 pct (h.c.p.); ß2 of Bollenrath and Bungardt.26 The eutectoid transformation can be suppressed at sufficiently high cooling velocities. The ß-phase is then retained to about 500°C where ordering sets in. The ordering interval is not satisfactorily known but indirectly appears to be non-suppressible. Subsequent to the ordering reaction and consequently at lower temperatures, the ordered ß1 decomposes to a marten-sitic structure. The kinetics of these reactions and in particular those of the martensite reaction have an important bearing on the results obtained in this investigation. Since some confusion exists concerning certain reported aspects of these reactions, they will be considered in some detail. THE MARTENSITE REACTION The martensitic structure is formed on cooling through a critical range6

Jan 1, 1950

By Paul Averitt

require both time and money. Any attempt to secure a quick answer will yield a figure that very likely cannot be substantiated, and certainly will not yield information in the detailed form now desired. It will be about 10 years before a completely new estimate can be prepared for the coal reserves of the United States at our present rate of progress, though of course, much information will be available in the interim. We would like to present such information as we obtain in the form most acceptable to the industry, and to that end we are working closely with coal resource committees of the AIME, the National Bituminous Coal Advisory Council, and the Bureau of Mines. DISCUSSION G. H. Cady*—Mr. Averitt&apos;s description of the nature of the coal resources investigations of the United States Geological Survey and the progress of this work is very timely in view of the general interest in the subject of coal resources. The Federal Survey is obviously taking the "long view" with respect to the appraisal of the coal resources as part of the preparation of the general geological map of the country and the attendant determination of the quantity of all mineral and fuel resources. It is apparently for regional surveys of the conventional type that the detailed procedures employed by the Federal Survey are applicable. Even if so it is somewhat unexpected to find the same criteria for evaluation will be applied to the country as a whole. The work on coal resources appraisal has been proceeding at various rates in a number of coal producing states for various periods. Undoubtedly since there has been no common practice in the method of appraisal the states each have worked independently and independently of the Federal Survey, and each has adopted certain practices to meet local conditions. I do not know how much consideration has been given by the U. S. Geological Survey to these practices. It seems probable that such consideration might result in important modifications of the standards which apparently have been set up by the Federal group in line with local requirements. It is the practice in some state surveys to present the facts in regard to the occurrence and distribution of coal beds and their variations in thickness down to thicknesses of 1 to 1 1/2 ft in relatively narrow stages up to maximum thickness. It is then possible for any one using such figures to compile quantitative estimates of workable coal at various minimum thickness limits. This is a desirable objective where surveys are detailed and information correspondingIy good. However, vast quantities of coal lie in beds that are relatively thin about which little information is available and the quantity of such coal might affect the final appraisal to the extent of several thousand million, depending upon the minimum limitation observed. Thus in the case of Illinois a difference of 1 ft in average thickness of coal in the coal field would make a difference of approximately 35 billion tons in the estimated quantity present. One is dealing with a very large area and small differences in thicknesses are very irnportant in the overall picture. The estimate of 10 years to accomplish the sort of detailed appraisal outlined by Mr. Averitt is viewed somewhat skeptically and certainly would require many more trained geologists than seem to be available. The requisite detailed mapping and study are very time consuming not only because of the geological field work required, which is difficult in certain seasons, but also in order to assemble data from company and personal files, and to study drill records and cores, and to sample and analyze the coal. Unless the staff of geologists could be increased in the order of several hundred per cent the prospects are that the appraisal of the type suggested will require many decades not just one. The permanent value of such appraisal, however, is not questioned and it should be expedited as rapidly as means allow. Satisfactory appraisal is not easily achieved and will vary from time to time. The main function of a geological survey is to collect and present the facts that will make possible appraisal in terms of existing conditions by individuals, particularly engineers, qualified by training and expcrience for making such estimates. Thickness and character of the coal bed, nature of the overlying and underlying strata, position, thickness, and character of "partings," relationship to other coal beds, and a variety of other factors must be assembled by the geologist in order to present a complete picture of the geological setting. The economic and engineering factors are in general outside the field of geological experience. The geologist should see to it that the pertinent geological facts are available; much more information than simply thickness and depth of the coal beds is essential to meet all the requirements of appraisal in the future as well as at present. With respect to the present demand by engineers and coal mine operators and others for a rapid re-appraisal of the available coal resources, in the light of existing practices and those in immediate prospect, the Federal procedure of systematic mapping and appraisal is scarcely in line. It will be necessary for those particularly interested in having such an estimate made to establish standards with respect to the various factors involved so that the scope of the geological work can be definitely restricted for the various coal fields. There is little use in setting up general standards since no such standards will be applicable to all fields. Thus it is folly to establish a standard minimum thickness to be generally applicable which is one-half to one-third the minimum minable thickness in some fields. The greatest difficulty in appraisal of the presently actually workable coal bed lies in the variation in the importance placed on roof, floor, structural conditions, bedded impurities. sulphur content and other factors that affect judgment relative to the value of a coal bed. It is doubtful whether any appraisal will have universal approval in view of the variable factors involved. For this reason if none other, the facts should be carefully and painstakingly assembled after the manner of a systematic geological survey such as that advocated by Mr. Averitt. Only upon the basis of sucb information can reliable estimates be made in line with selected conditions. Paul AveRitt (author&apos;s repty)— In this paper I discussed, but did not define as such, two major phases of our activities on coal, which are closely related, and which normally we in the U. S. Geological Survey see as an integrated whole. It is understandable, therefore, that Dr. Cady should assume that my remarks applied only to the current work on coal reserves with which I am directly concerned. In view of Dr. Cady&apos;s discussion, however, I think a brief summary of the two phases of U. S. Geological Survey activities on coal will be appropriate. The long-term function of the U. S. Geological Survey on coal investigations is to make detailed geologic studies, involving the preparation of detailed geologic maps showing the outcrops and correlations of coal beds, direction and dip of coal-bearing rocks, nature and thickness of overburden, location of faults and fold axes, and similar features. Such studies also yield many measured sections of coal and associated strata, which show variations in the thickness of the beds, and the intervals between coal beds. Taken as a whole, detailed geologic studies provide much useful information for mine operators and engineers. As Dr. Cady points out, this type of geologic work is arduous and time consuming, but it provides the basic data that are necessary both in the development of our coal fields, and also in the preparation of coal-reserve estimates, which are discussed in the next paragraph. The U. S.

Jan 1, 1950

By David R. Mitchell, E. C. Carris

THE particular field of application of machines utilizing air currents as the primary separating medium is in the cleaning of fine sizes of bituminous coal. Approximately 18,000,000 tons of bituminous coal was cleaned by air machines in 1947, but such machines have not yet been applied in the cleaning of anthracite. This chapter is limited to a description of the processes in which the separation between coal and refuse depends mainly on a difference in specific gravity. Dry processes depending on differences in coefficient of friction, shape, or other property, are described in chapter 17. The possibility of using air for the separation of coal from refuse was recognized early by mining men and many attempts were made to develop commercial machines. Some of these early machines are described by Berrisford,1 Chapman and Mott,2 and Mitchell.3 Only two machines are extensively used today in the United States, the Stump air-flow jig and the American oscillating table. GENERAL CHARACTERISTICS OF AIR CLEANING MACHINES The principles of gravity concentration and the properties of air as a medium for separation were explained in chapter 9. It was pointed out that because of the low density of air a medium of sufficient density has to be built with the material itself. Hence there must be some device to impart to the bed the necessary mobility for proper classification. It was also noted that the compressibility of the air may cause "geysering" of the bed and disturbance of the hindered-settling classification if the correct balance of conditions is not maintained. Most devices use a vertical upward current of air through the bed of material. They differ by the method of imparting mobility to the bed and the method of removing the refuse. In general terms, the air machines can be divided into three types: 1. Pneumatic jigs where the air current is pulsated. 2. Pneumatic tables where the refuse is diverted from the direction of flow of the clean coal by a system of riffles fixed to the deck.

Jan 1, 1950

By G. T. Smith, R. C. Moyer

Cadmium, along with other impurities such as lead, gallium, germanium and indium, is characteristically found associated with zinc ores, the average ratio of zinc to cadmium being about 200 to 1. The increasing demand for cadmium has led most zinc producers to develop a means for its recovery. The separation and recovery of this byproduct constitutes an important development in the metallurgical field. Zinc sulphide concentrates, principally from domestic sources, are processed at Donora Zinc Works and they assay approximately 60 pct zinc, 30 pct sulphur, 0.37 pct cadmium, and 0.8 pct lead. Concentrates are roasted to convert zinc sulphide to zinc oxide. Sulphur evolved as sulphur dioxide is used to manufacture 60º Baume sulphuric acid by the lead chamber process. The roasted calcine is sintered to remove the remaining sulphur and volatile impurities. Fume from the sintering machines is collected by Cottrell pre-cipitators and sent to the Cadmium Department for cadmium removal. The sintered product, a crude zinc oxide, is then mixed with coke and salt and charged into horizontal retorts for reduction to zinc metal. Furnace residues are then passed through a Waelz kiln which recovers practically all of the remaining zinc as an oxide. This oxide is collected by Cottrell precipi-tators and returned to the sintering plant for further processing. The following discussion covers operating procedure, and equipment used in the Cadmium Department for the manufacture of cadmium and its byproducts. (See attached Flow Sheet, Fig 1.) The production of cadmium may be divided into several steps, each of which will be discussed separately. These steps are as follows: 1. Raw Materials—Sinter Plant Cottrell dust, acid sludge and sulphuric acid. 2. Sulphating—Separation of lead. 3. Purification—Separation of impurities other than zinc. 4. Precipitation—Separation of cadmium from zinc. 5. Briquetting—Preparation of sponge for charging to furnace. 6. Smelting—Distillation of cadmium metal. 7. Remelting—Casting into commercial shapes. 8. Recovery of Rare Metals—Separation of germanium, gallium and indium. Raw Materials The raw material, or Sinter Plant Cottrell dust, from which the cadmium is manufactured, is recovered by Cottrell units collecting fume from two Dwight-Lloyd sintering machines. An average analysis of this dust is 36 pct zinc, 1.5 pct sulphur, 17 pct lead, and 5.5 pct cadmium, with associated elements in smaller amounts. A lesser tonnage of material removed from the sintering machine fans, and called fan cleanings, is also treated for cadmium. It is lower grade material and analyzes approximately 41 pct zinc, 1.2 pct sulphur, 14 pct lead, and 4 pct cadmium. Cottrell dust and fan cleanings are delivered to the Cadmium Department by monorail crane in bell-bottomed dump buckets. Acid sludge and 60" Bauine sulphuric acid are received from the Acid Department. The acid sludge is a mixture of lead sulphate, sulphuric acid and zinc sulphate, and is recovered mainly from the floors of the acid chambers or storage tanks. The acid sludge is delivered to the Cadmium Plant in a lead lined bucket. The 60º Baume sulphuric acid is delivered through a lead pipe to a lead lined storage tank. Sulphating Four well ventilated lead lined sulphating tanks, 8 1/2 ft in diam by 12 ft deep, are used. These are steel tanks lined with 20 lb lead on the bottom and 16 lb lead on the ides, equipped with Hastelloy side agitators. 15 hp motors drive 24 in. propellers at 450 rpm. There are water connections to stuffing boxes to keep sludge from entering the bearings. The tanks are covered with removable wooden lids and are connected to marine plywood

Jan 1, 1950

By W. J. Parton

The efficient recovery and preparation of small sizes of anthracite called No. 4 Buckwheat (3/32 by 1/32 in.) and No. 5 Buckwheat (1/32 in. by 0), pre-sent a difficult problem to the anthracite operators. In many instances preparation of these sizes, particularly No. 5 anthracite, is extremely inefficient. In many of the older preparation plants, inadequate facilities, and often none at all, were provided as an integral part of the plant for cleaning this fine anthracite. Consequently, much of the material smaller than 3/32 in. was discarded. As the demand for these sizes increased, facilities for preparing the fine sizes were often crowded into existing structures with consequent sacrifices of capacities and efficiency. In addition to this condition, the methods of preparing the finest sizes are being developed in an attempt to improve their efficiencies. Because the demand for small sizes of anthracite still is increasing, many operators would benefit by investigating and improving the cleaning equipment employed on these sizes. The object of this paper is to de- scribe a stationary screen device from which the underflow is restricted by orifices, called a launder screen, along with operating results of several applications of this screen; a settling tank in which two classified products are produced by the installation of a cylindrical partition of smaller diameter than the original tank, one product being recovered from the small tank created by the partition and one product from the space between the inner and outer tank walls; a small pocket classifier or hydraulic trap for use in removing high ash particles from a sludge flow; the classification or segregation of sludge solids occurring in a 16 in. diam pipe flow by analysis of samples procured at different zones; and the operating results of a Fahrenwald sizer, as well as the performance of the concentrating tables handling the classified products. These simple devices were employed at the collieries of the Lehigh Navigation Coal Company Incorporated, Lansford. Pa., in order to improve preparation results on the fine sizes of anthracite. Launder Screens The launder screen is a screening and dewatering device which probably could be used advantageously in the flow diagram of many fine coal plants. Fig 1 shows that it consists of a stationary screen constructed by placing 6 in. high partitions every 6 in. along a launder. Holes are then drilled on 6-in. centers across the bottom of the launder to receive pipe bushings of the desired diameter. The screen cloth is tacked on top of the partitions. When water and solids are fed to the screen, only a small portion of the total water is removed through the orifices in each compartment so that the water in the feed is distributed evenly over the whole length of the screen. The screening action which results is very efficient because the solids are kept in a fluid condition for the full length of the screen. Blinding of the screen can be minimized by the use of screen cloth

Jan 1, 1950

By J. F. Radavich

Many heats of steel of low carbon value have been known to produce brittle pieces of steel. The brittleness is believed to be due to the impurities located within the grain boundaries. Such brittle steels have been examined with an optical microscope to ascertain the nature and the amount of the impurities present at the grain boundaries. Due to the relatively low resolving power of the optical microscope, the impurities are not visible in fine detail. The writer obtained some sheet steel and proceeded to determine the location of the impurities and to show the application of the electron microscope to the study of grain boundaries. One sample was known to be capable of becoming embrittled, whereas another sample was believed to be much less susceptible to embrittlement. Treatment of Specimens The specimens were embrittled by annealing above the A3 point under mildly oxidizing conditions. One piece of ingot iron could not withstand a 90" bend, whereas another piece of ingot iron was not affected and could withstand a 90" bend. The brittle piece was then annealed at a high temperature in a hydrogen atmosphere. The annealed ingot iron was termed cured and could withstand a 90" bend very easily. The three specimens examined will be designated as brittle, good. and cured in the discussion that follows. Procedure The sizes of the specimens were as follows: one piece of brittle ingot iron-3/8 by 35 in.; one piece of good ingot iron-96 by 1/8 in.; one piece of cured ingot iron-36 by 54 in. The specimens were too small to be polished by hand and therefore were mounted in bakelite. The polishing procedure was carried out in the conventional manner with the use of 1/0 through 3/0 papers, and the final polish was done with alumina on a billiard cloth. The specimens were then etched in a 4 pct solution of picral in alcohol, and then they were examined through an optical microscope. An area was chosen that showed distinct grain boundaries, and an effort was made to keep near this area when pulling the replicas REPLICA TECHNIQIJE The replica technique used in the preparation of the replicas for examination under the electron microscope is described in Electron Metallography.&apos; It consists essentially of the following steps: 1. Obtaining a suitably etched specimen. 2. Applying a swab of ethylene di-chloride on the surface. 3. Applying a formvar solution on the surface. 4. Placing a screen on any desired spot. 5. Breathing on the fornivar layer. 6. Applying scotch tape on the screen and film. 7. Pulling the film and the screen up with the Scotch tape. 8. Separating the screen from the Scotch tape. This replica technique is very similar to the one described by Harker and Shaefer. However, with the added step, the percentage of replicas removed is very much higher regardless of the length of the time from the etching of the specimen to the actual pulling of the replica. The replicas were then shadow cast with manganese at a filament height to replica distance ratio of 1 1/2:7. This produced a very high contrast replica for use in the electron microscope. One of the dificulties encountered with this study was the restricted area of the specimen. The width of the specimens was the same as that of the 200 mesh nickel supporting screen. In order to increase the effective area, the screens were cut down as shown in Fig 1. The arrow indicates the direction in which the replica was pulled. This operation made it possible to obtain a large percentage of good replicas. Fig 3 shows an electron micrograph of a brittle piece of ingot iron and a grain boundary that was polished mechanically. The surface is very rough probably due to the incomplete removal of the flowed layer by the picral etchant. The grain boundary does show evidence of impurities. It was decided to electropolish the specimens to obtain a much smoother surface than the one obtained by mechanical polishing. ELECTROPOLISHING The specimens were cut in half to expose the metal on the back side. The exposed metal had sufficient area to make good electrical contact and electropolishing was carried out easily. The conditions for electropolishing were 0.9 amp, 35 volts, and 25 sec. in an electrolyte composed of 850 cc of ethyl alcohol, 100 cc distilled water, and 50 cc of perchloric acid. The polished specimens were then etched in the 4 pct picral solution for a shorter time than was necessary for

Jan 1, 1950

Minerals: When man first picked up an appropriately shaped stone and fastened it to a stick of wood to create a primitive axe or hammer he started down the long road of mineral dependency that has continued until today (Fig. 2). Though he did not realize it, that man and his stone axe created an extremely simple form of mineral economy. The struggle against extinction from that day has been fought with minerals. In addition to providing himself with a means to fight for survival, he also exhibited an increase in intelligence. As his curiosity was stimulated, his ability increased to provide himself with better mineral and metal weapons and tools. Today, when we examine the artifacts of past civilizations, we measure the degree of development that had been attained by the variety of metals and minerals possessed and how they were used. The metals employed are so characteristic of the level of intelligence that we have named the various stages of human progress by the metals that were most commonly utilized. Thus, mall went through the Stone Age, the 13ronze Age, the Iron Age and now has reached the Steel Age. The first period of mineral development, the Stone 4ge, began during late Pliocene time. In this first mineral age, prehistoric man began to shape stones by chip- ping off small pieces until the stone assumed the crude form he wanted. As his intelligence increased, he progressed to finer workmanship and turned out finished spear heads and barbed arrows. Throughout this very

Jan 1, 1950

By D. Harker, E. Epremian

The constitution of the nickel-tungsten system has been studied by a number of investigators, the most recent of which are Ellinger and Sykes.1 On the basis of metallography, electrical resistivity and hardness measurements and some X ray diffraction work, they constructed a consitution diagram (Fig 1). Ellinger and Sykes report a0 for the alpha face-centered cubic phase (nickel saturated with tungsten) as 3.66?.‡ The gamma phase (tungsten saturated with nickel) is given as body-centered cubic, but no value of a. is recorded. At 43 pct tungsten by weight (approximately 20 at. pct) a beta phase is reported, but structure and lattice parameter are not known. Primarily on the basis of metallographic evidence, they conclude that beta is a new phase and rule out the possibility of formation of a superlattice since they- observe a new phase in the microstructure. Grube and Schlecht2 report an ordering reaction in a system similar to the Ni-W (Ni-Mo) and Harker3 has shown that NirMo forms a superlattice upon the pre-existing face-centered cubic lattice of the alpha phase. Elliniger arid Sykes observed a change in the diffraction pattern of a 4.3 pct W alloy upon aging and attributed it to the formation of a new phase. Thus, there appears to be some question as to the character of the beta phase reported by Ellinger and Sykes. The purpose of the present work is to determine precisely the structure and nature of the beta phase in the Ni-w system of X ray diffraction methods. Experimental Procedure One inch diameter ingots of 43.66 pct, 40.15 pct and 34.06 pct .tungsten by weight (19.8, 17.6 and 14.1 at. pct respectively) were melted and cast under vacuum from electrolytic nickel and pure wire filament grade tungsten. The ingots were soaked for 16 hr at 1300°C in a hydrogen atmosphere furnace, then swaged at this temperature and finally drawn to 0.020 in. diam wire. Some of the bar stock was retained in 1/2 in. diam rod for hardness and metallographic studies. Wire samples for diffraction work were sealed in evacuated quartz tubes and subjected to the various solution and aging heat treatments in a hydrogen furnace. X ray photograms were taken in a Debeye-Slierrer camera using copper K radiation filtered by nickel foil. Results X RAY DIFFRACTION The lattice parameters of the alpha and gamma phases at saturation were determined by an X ray photogram of the 19.8 at. pct W alloy after solution heat treatment at a temperature well within the alpha-gamma range above the peritectoid temperature (17 hr at 1150°C—oil quenched). The alpha phase was found to be face-centeted cubic with a. of 3.594 ± 0.001?, while the gamma phase was determined as body-centered cubic with a. of 3.158 ± 0.001?. Exactly the same phases and parameters were ohtained with the 17.6 at. pct W alloy for the same solution heat treatment. Thorough analysis was made of an X ray photogram of a 19.8 at. pct alloy sample in the quenched and aged condition (solution treated 1T hr at

Jan 1, 1950