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By R. A. Morse, W. O. Keller

The properties of limestone reservoir rocks such as the distribution and degree of continuity of the pore systems, and the relative volumes and permeabilities of the systems making up the complex cause large variations between performance of individual limestone reservoirs and their susceptibility to secondary recovery methods. The effects of these factors on the mechanism of fluid flow cannot be adequately evaluated with presently developed concepts, laboratory data, and geological information. The observance and interpretation of the performance of individual limestone reservoirs provides, at present, the most adequate approach for evaluating the integrated effects upon performance of the many. now immeasurable variations in the properties of limestone reservoirs. INTRODUCTION The development and application of techniques for increasing the efficiency of oil recovery from natural reservoirs is a problem of primary importance to the industry. During the past several years, a great deal of effort has been expended by the technical personnel of the industry toward the improvement of present known methods of oil recovery. and evaluating the factors which control the susceptibility of particular reservoir types to economic application of secondary recovery methods. Providing adequate and accurate laboratory data on the properties of the reservoir rock and its contained fluids. together with good production statistics, are available, methods have been evolved for estimating with reasonable accuracy the performance of an oil reservoir under either continued natural depletion or conditions imposed by introducing additional displacing fluid into the reservoir from an extraneous source through the injection of gas and/or water. The susceptibility of limestone reservoirs to secondary recovery by gas injection is very much dependent upon gas-oil relative permeability relationships for the reservoir in question. In a rock formation in which the porosity is of the intergranular type such as is found in sand stones and some non-fractured dolomites, a representative sample of the pore structure can be obtained in a small core plug. In this type of reservoir, it has been shown that relative permeability data obtained from laboratory experiments can be Properly applied to evaluate the flow relationships actually observed during the depletion of a reservoir. In addition, a good idea of the fraction of the reservoir which will be swept by the injected gas may be obtained from the spacing pattern used and the permeability profile of cored wells. From these data, it has been demonstrated that reliable estimates of performance and recoveries under gas injection operations can be made for reservoirs in which the Porosity is of the intergranular type. Limestone reservoirs on the other hand often present much more complex problems. One reason that the performance of limestone reservoirs is so variable is that there may be, in reality. two or more pore systems, the integrated performance of which will depend upon the physical properties of each system and their inter-relationship. For instance, in a limestone reservoir, the main pore structure, as far as void spaces for storage of hydrocarbons is concerned, may be represented by the intergranular openings of the rock. Usually in limes and dolomites, the intergranular pore openings are very small and the matrix permeabilities extremely low. Often, as in the case of Many dolomite and oolitic lime reservoirs, this is the only pore system, and performance is observed to be very similar to that of a sand stone of similar permeability. However, in the great majority of' the limestone reservoirs, there is present, in addition to the intergranular pore system, a complementary system of openings caused by fracturing or solution.',' The openings in the latter system are usually many times more permeable than the intergranular pore system due to their much larger size, and may contribute almost all the fluid carrying capacity of the formation, even though their volume may be a very small part of the total pore space in the reservoir. Obviously, the performance of such a complex under either primary or secondary control will deend upon the distribution and degree of continuity of both systems, the relative volumes and permeabilities of the

Jan 1, 1949

By R. L. Bleifuss

The object of this study was to evaluate the oxidized taconites of the western Mesabi iron range and to establish a correlation between the various basic taconite types and their concentratability. The initial work included a study of the original mineralogical and stratigraphic facies of the fresh taconite and traced the oxidation and leaching patterns developed during the conversion of this material to oxidized taconite. Subsequent studies have extended this work to include the semitaconites and also the wash and heavy media ore types widely developed in the area. Each basic original mineralogical facies or taconite type produces during alteration an equivalent secondary oxidized facies which has a unique mineralogical composition and texture. These control the concentratability of the oxidized taconites. Actually the influence of the original mineralogical composition of the iron formation extends even further and determines whether the most likely product of oxidation and leaching will be a wash ore or a heavy media ore and even to the direct shipping ores where the ratio of hematite to goethite is largely determined by the original taconite type. The relationship between original taconite, oxidized taconite, semitaconites, and wash and heavy media ores is briefly summarized in Table I. The terms are not precise and in some instances tend to overlap. The table is intended to point out only the essential differences between the various materials. The original taconite was dominantly composed of mixtures of magnetite, iron carbonate, iron silicate, and quartz (chert). In a few thin stratigraphic units, hematite was present as an original constituent. The alteration of the original taconite to oxidized taconite has resulted from the circulation of ground waters through an initial fracture system related to minor structures in the iron formation. The chemical reactions have involved the oxidation and decomposition of original minerals such as magnetite, iron carbonate, and iron silicates to hematite or goethite. The alteration at this early stage is characterized by pseudomorphic replacement of the original minerals by oxidation products although retaining the major textural features of the original taconite. There was very little secondary migration of iron at this stage and the total iron content of the rock has been only slightly increased. Further alteration of this material to form a semi-taconite, a wash or a heavy media ore, involves extensive removal of silica in solution and significant redistribution of iron units. Wash and heavy media ores are developed by the growth of coarse secondary iron layers, dominantly goethite, coupled with the removal of silica in solution and decomposition of the cherty layers. This paper is concerned primarily with the materials classified as oxidized taconites which are characterized by oxidation of the original mineral constituents with little secondary enrichment. The area studied, shown on the index map, Fig. 1, extends some 30 miles along the strike of the Biwabik formation roughly from Hibbing to Coleraine. This study was greatly facilitated by the basic stratigraphic and mineralogical studies of Gruner1 and white2. The bulk of the material in this presentation represents a portion of the author's contribution to a study sponsored by the Great Northern Railway on the oxidized taconites of the western Mesabi.3 METHOD OF APPROACH A total of 106 drill holes, representing some 30,000 ft of drilling, were examined and sampled. The drill holes were logged and some 1500 composite samples were prepared for chemical analysis and bench scale metallurgical tests. These samples were analyzed for total iron and ferrous iron; and magnetite iron was determined by a standard Davis tube test at minus 200 mesh. Standard reduction roast tests using 150-gram samples of minus 10 mesh material were made on these 1500 composite samples with a mixture of H2, CO2, N2, and H2O at a temperature of 650°C. This roasted material was pulverized through 150 mesh and concentrated in the Davis tube. The iron recoveries and concentrate grades obtained on the roasted products were used to assess the concentratability of the oxidized taconites. Detailed mineralogical work was done on thin sec-

Jan 1, 1964

By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing and shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subsequently mineralized by sulphides and barite. INTRODUCTION Buchans is 5 miles north of Red Indian Lake, in Central Newfound- land, at an elevation of 900 ft. above sea level and 400 ft. above Red Indian Lake, and is reached by a 37-mile private railway from Miller- town Junction. The first ore body found at Buchans was discovered some 30 years ago in the bed of Buchans River, by Matty Mitchell, an Indian woodsman employed by the Anglo-Newfoundland Development Co. Ltd. In the years following the discovery the ore was developed by shaft-sinking and drifting, with results indicating a lenticular ore body in a shear zone, containing about 100,000 tons of extremely fine-grained sulphide ore in barite gangue averaging about 0.05 oz. Au, 4 oz. Ag, 1.5 per cent Ch, 10 per cent Pb, 18 per cent Zn. Because a profitable metallurgical treatment for the ore was not found, the mine was closed down in 1911. In 1915, Mr. H. A. Guess, Vice President of the American Smelting & Refining Co., learned of the Buchans River ore body, and after metallurgical tests had been carried on from time to time in his company's testing plant a satisfactory separation of the sulphides by selective flotation was finally effected in 1925. Prospecting for additional ore bodies was begun in 1926, utilizing geophysical methods under the direction of Hans Lund-

Jan 1, 1937

By F. G. Jones, R. D. Pehlke, H. E. Gardner

The solubility of nitrogen in liquid Fe-18 pct Cr-8 pct Ni-0. 7 to 2.3 pct A1 alloys has been measured up to the solubility limit for the formation of aluminum nitride in the temperature range 1600° to 1700°C uszng the Sieverts' method. The solubility of nitrogen in 18-8 stainless steel increases with increasing aluminum content. Based on a nitride composition, AlN, the standard free energy of formation of aluminum nitride from the elements dissolved in liquid 18-8 stainless-steel alloys has been determined to be: ?G° = -42,500 + 20. IT in the range from 1600° to 1700° C. EVANS and pehlke1 have measured the equilibrium conditions for the formation of aluminum nitride, AlN, in liquid Fe-A1 alloys. The present study extends that work to the more complex solvent, liquid 18 pct Cr-8 pct Ni (18-8) stainless steel. Recent work by Small and pehlke2 has dealt with the effect of fourth-element additions on the solubility of nitrogen in 18-8 base alloys. They found the effect of aluminum additions, up to 0.74 pct, on the solubility of nitrogen to be small. The present study covered the range from 0.74 to 2.28 pct aluminum, and by extending the composition range may be used to better define the effect of aluminum on the nitrogen solubility in these alloys. EXPERIMENTAL PROCEDURE The Sieverts' method was used to measure the equilibrium solubility of nitrogen gas in liquid 18-8 stainless steel alloys containing 0.74, 1.49, 1.93, and 2.28 pct Al. The solubility was measured as a function of the nitrogen gas pressure at temperatures of 1600°, 1650°, and 1700°C. The apparatus used is the same as described by Small and Pehlke.2 The 100-g melts were made from Ferrovac-E high-purity iron, Crucible Steel Co.; 99.95 pct Cr, Union Carbide Corp.; 99.9 pct Ni, International Nickel Co.; and 99.99+ pct Al, Aluminum Co. of America. The aluminum was charged at the bottom of the crucible, surrounded by nickel and iron. The chromium was packed into the interstices to minimize vapor transport of the aluminum during initial melting. The hot volume of the system, measured for each melt with argon, ranged from 45 to 55 standard cu cm with a temperature coefficient of —8 x 10-3 cu cm per °C. The melt temperature was measured with a Leeds and Northrup disappearing-filament type optical pyrometer sighted vertically downward on the center of the melt surface. The temperature calibration of the system by Small and pehlke2 was assumed. Two problems are involved in determining the solubility product of a solid, metal nitride phase in liquid iron alloys. These are: 1) establishing the point of departure from Henrian behavior at the solubility limit of the metal nitride phase; and 2) determining the composition of the solid nitride which is precipitated. Determination of the solubility product of AlN was made by admitting small amounts of nitrogen into the reaction bulb until the deviation from Sieverts' law was clearly evident in the form of a pressure halt. To obtain the solubility product at several temperatures during one run the following procedure was used: 1) add increments of nitrogen to determine the Sieverts' law line at the lowest desired temperature; 2) continue to add nitrogen to precipitate a small amount of the nitride phase; 3) increase the melt temperature 50°C to dissolve the precipitated nitride; 4) repeat step 2 until either a nitride formed or the system reached ambient pressure; if a nitride formed at 1650°C, the sequence was repeated at 1700°C. The composition of the precipitated phase was checked by an X-ray diffraction pattern obtained from powder scraped from the surface of the solidified 1.93 pct A1 melt. RESULTS AND DISCUSSlON Solubility Measurements. Fig. 1 is a typical nitrogen-absorption curve obtained from measurements on a 1.93 pct A1 alloy. Since the initial absorption of nitrogen follows Sieverts' law the nitrogen solubility is plotted as a function of the square root of the pressure of nitrogen gas in the reaction bulb. The results of the solubility measurements for all alloys studied are summarized in Table I. The slope of the Sieverts' law line for each alloy was determined. Since this is also the solubility of nitrogen at 1 atm pressure of nitrogen gas, the latter designation is used for the data. It should be noted. however, that in most cases the value lies above the solubility limit for AlN. Fig. 2 shows the effect of aluminum on the solubility of nitrogen at this reference pressure and as a function of melt temperature. The solid portions of the lines represent attainable solutions; the dashed regions lie above the limit for precipitation of AlN.

Jan 1, 1969

By C. C. Miller, C. A. Hutchinson, A. B. Dyes

This paper presents a simple and practical method for the estimation of effective permeability and reservoir pressures from the rise in bottom hole pressure when a well is shut in. The equations on which the method is based consider a stabilized well producing from a uniform formation when flow is shut off at the sand face followed by the unsteady state flow of a compressible liquid from regions far from a well to points closer in during the build-up period. An approximation for extending the method for two-phase flow in the reservoir is also presented. In order to compare the effects of extremes in the conditions existing at the external boundary of the reservoir, two general equations defining the build-up characteristics of the reservoir are shown: first, for a reservoir with constant pressure maintained at the radius of drainage, and second, for a reservoir with no influx over the radius of drainage. These equations define the build-up characteristics for the shut-in well as functions of time, the permeability and porosity of the drainage area, the viscosity and compressibility of the fluid flowing, the production rate prior to shut-in, and the radius of drainage of the well. When a well is shut in at the surface, rather than at the sand face, flow will continue into the well bore after shut-in due to the compressibility of the fluids in the bore. The effect upon the build-up characteristics of this flow into the well after shut-in has been studied by means of the electrical analyzer. From the basic relationships and consideration of the limitations due to continued flow after shut-in, methods have been developed for the estimation of the effective permeability of an area from the plot of the build-up characteristics of the well producing that area. Likewise, equations are presented for the estimation of the reservoir pressure from an early portion of the build-up curve. By means of the electrical analyzer, studies have been made concerning the variations in the build-up characteristics resulting from damaged or improved permeability in the immediate vicinity of the well bore. These studies show that the permeability estimated from the build-up curves represents the average effective permeability of the majority of the drainage area and that the permeability in the immediate vicinity of the well does not affect this estimate. Since the major portion of the drawdown is in the immediate vicinity of the well, variations in the permeability of this area greatly affect the productivity of the well as expressed by the productivity index. From pressure build-up and productivity index tests the ratio of the permeability of some arbitrarily specified area immediately surrounding the well and the effective permeability in the majority of the drainage area can be computed. This ratio is a measure of any damage to the well incurred in drilling or reworking and likewise any benefits as a result of remedial measures. In build-up tests and many other tests that are made on a producing well it is at least desirable, if not absolutely necessary, that the well be stabilized prior to testing. A method is presented here for relating the time required to stabilize a well and the reservoir and fluid properties. An equation is also presented for approximation of the length of shut-in time required to obtain sufficient build-up data for the estimation of permeability and reservoir pressure.

Jan 1, 1950

By L. K. Jetter, J. C. Ogle, C. L. McHargue

The preferred orientation developed in extruded aluminum rods has been studied as a function of extrusion temperature, extrusion speed, and position in the rod. Duplex <111> - <001> textures were developed for slow extrusion speeds at temperatures of 75° to 850° F and for fast extrusion speeds at temperatures of 75° to 450°F. The <001> texture component was shown to be primarily due to re crystallization occurring during fabrication. At fast speeds and billet temperatures of 650° to 850°F, complete recrystallization occurred and <115>or<118> textures were found. The nature of the structure has proved to be an important variable in the production and use of extruded products. Data on the flow of aluminum and aluminum alloys summarized by Smith,&apos; Hardy,&apos; and Locke3 show that the extruded product may possess a deformed, a partially recrystallized, or a completely recrystallized structure, and there may be important variations in the structure from surface to center and from front end to back end of an extrusion. This inhomogeneity in grain structure and preferred orientation affects both the mechanical properties of the extruded section and its response to subsequent heat treatment. Among the fabrication variables causing these differences are temperature, extrusion ratio, and extrusion speed. Preferred orientation which develops during the extrusion of rods is of the fiber-type and, in general, has been assumed to be similar to that developed in rods or wires fabricated by drawing through dies, rolling, or swaging.4 Because of the nature of the flow of metal being extruded, this assumption may be valid for material near the center of the rod but probably is not valid for the outer layers. In most face-centered-cubic metals a duplex fiber texture has commonly been reported in which the grains have either <Ill> or <001> directions parallel to the longitudinal axis. Sachs and fichiebold5 reported cold-drawn aluminum (99.6 pct pure) to have a single <Ill> fiber texture, and this observation was confirmed by Schmid and Wassermann.6 Hibbard, on the other hand, observed a minor <001> and a major <111> texture in 99.994 pct A1 cold drawn to 98 pct reduction in diam.7 He concluded that the <001> component resulted from a small amount of room-temperature recrystallization. Dayal8 concluded that the <001> component was an intermediate component which disappeared at high reductions in 99.5 pct pure Al. Kostron and schippers9 found duplex <111> — <001> textures in extruded 99.5 pct Al, as did Gow and cahnl0 and GOW11 for extruded rods of commercial and superpure aluminum. Similar duplex fiber textures have been reported for aluminum alloys by Kostron,= Unckel,13 and Van Horn.14 The present paper is concerned with the variation in texture with fabricating conditions and with the nature of the texture components in extruded aluminum rod (99.99 pct pure). EXPERIMENTAL PROCEDURE Ingots were chill-cast in cast-iron molds and machined to 3-in. diam by 6-in. long extrusion billets. These billets were upset to 3.125 in. diam and extruded through a flat-face 0.690-in. diam die. Quenching of the rods was accomplished by a water spray at the die face. The combinations of fabricat-

Jan 1, 1960

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.&apos; Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts&apos; Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg&apos;s method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

By C. Wachmann

The theory presented ill this paper makes possible examination of the phenomenological aspect of secondary oil recovery by alcohol flooding. Limitutions of the theory are contingent on three primary assumptions: (1) chemical equilibrium, (2) no fingering, and (5) no dispersion. The second assumption implies one-dimensional flow. In a geometric sense the theory extends the Buckley-Leverett construction to systems of two slightly miscible fluids and to systems of three components. This is made possible by considering single-phase fluids to be made up two phases, namely of an excess of one phase and a negative amount of the other phase. The procedure is discussed in the paper. The theory also permits direct determination of the relationship between the aqueous phase saturation and the concentration of water in the aqueous phase in a zone of variable composition. The velocity of planes of constant water concentration and of constant saturation can be computted likewise and the existence of saturation discontinuities inferred. Consequently the behavior of such a Zone, which may exist at some time between a displaced and a displacing fluid, May be determined. mathematical details are given in Appendices. Problems of experimental verification are pointed out on the basis of a supporting experiment. Implications of the theory and effects of violations of primary assumptions are discussed briefly. The major conclusion is that, if the primary assumptions are met, with pure alcohol and alcohol-rich .slugs piston-like displacement of oil and water is possible. INTRODUCTION The recovery of oil from porous media by alcohol displacement has been studied for several years. Extensive experimental investigations into alcohol flooding have been carried out in the laboratory although little has been done in the field. A large amount of practical information is available, the extent being indicated by the first three papers cited 1-3 and their respecrive bibliographies. This has permitted the Formulation of inferential theories. A more analytical approach in which theories are developed primarily by reasoning from known physical principles and relationships has, however, lagged behind. In fact, an analytically derived theory of alcohol displacement has not been available. The theory presented in this paper on oil and water displacement by alcohol from a porous medium is a result of the analytical approach. The theory is idealized, as certain assumptions had to be made to make the mathematics tractable and reduce complexity of argument. In particular, major assuptions concerning conditions of equilibrium, interfacial stability, longitudinal mixing, etc., led to the exclusion of fingering, for example, from all considerations. In many laboratory experiments reported in the literature fingering could not be avoided. There is, therefore, disagreement between theories based on experimental evidence available and the analytically derived theory presented here. This theory presented is based on known physical data and makes use of the Buckley-Leverett construction and its suggested extension. The mathematical derivation of the theory is given in Appendices. Three examples relevant to alcohol displacement are discussed to explain the use of this theory: (1) system of two immiscible fluids (the Buckley-Leverett case); (2) system of two slightly miscible fluids involving an extension of the Buckley-Leverett construction; and (3) system of three components, including injection of pure alcohol or alcohol-rich fluid as a special case, which involves a more general extension of the Buckley-Leverett construction. In these discussions strict assumptions were made to impose equilibrium conditions and exclude mixing and fingering. Effects of relaxing these assumptions and consequent extensions of the theory are indicated. The complexity of the alcohol displacement process makes experimental verification of the theory essential. Some relevant evidence is offered in this paper.

Jan 1, 1965

By A. E. Bibb, J. R. Fascia

Single-crystal wafers of zirconium have been exposed to 680°F neutral water. The single crystals were of known orientation and weight-gain data as a function of crystal orientation were obtained. These data show that all the crystal faces studied obeyed a cubic rate law out to the time of transition whereupon the crystals corroded at an approximately linear rate. The time to transition varied from 114 days for (1074) crystals to about 325 days for the (2130) faces. The epitaxial relationship be-tween metal and monoclinic oxide was found to be (0001) H (111) and [1120] 11 [101]. A black tight adherent oxide layer was formed on the crystals in the pretransition range. This black oxide was found to be monocrystalline. The white corrosion product produced after transition was found to be polycrys-talline but highly oriented. X-ray line-broadening studies found that the black oxide was a highly strained structure whereas the white oxide was relatively strain-free. These results indicate a strain-induced re crystallization or fragmentation accompanies the change from protective black oxide to nonprotective white oxide. ZIRCONIUM alloys have been used quite extensively in high-temperature aqueous environments. Alloy additions can be made to commercial sponge zirconium which enhance the corrosion resistance of the zirconium in both water and steam media, which raise the tolerance limit for certain impurities detrimental to corrosion resistance, and which reduce the amount of free hydrogen pickup during corrosion. The development of the corrosion-resistant zirconium alloys has been a long and tedious job involving trial and error methods. This technique has been necessary because of a lack of fundamental data and hence understanding of the corrosion mechanisms. The objective of the work described herein was to provide some fundamental data with respect to the aqueous corrosion of zirconium crystals as a function of the orientation of the exposed surfaces. Hg. The zirconium chunk was then cooled to below the transformation temperature (862°C) and reheated to 1200°C for 8 hr. The ultimate size of the zirconium grains increased with the number of cycles. Rapid or even furnace cooling through the transformation temperature produces a considerable amount of substructure which was intolerable in corrosion experiments as it would be in the study of any crystallographically dependent property. It was found that a high-temperature a-phase anneal for approximately 4 days reduced the substructure below the limits detectable by visual or X-ray means. Crystals so produced were carefully cut from the massive zirconium chunk and oriented by standard back-reflection Laue techniques. The crystals were then mounted in a goniometer head and, by using the three degrees of freedom available, slices on the order of 0.015 to 0.020 in. were cut parallel to any desired crystal plane. These slices were then carefully polished on both sides to produce smooth flat faces, pickled to remove about 0.002 in. per face, annealed for 1/2 hr at &apos;750°C in a vacuum of approximately 10"5 mm Hg, flash pickled, and checked for orientation. The pickling solution was 45-45-10 vol pct HN0,-H20-HF and continuous agitation was provided to eliminate pitting of the slices. Any slice that was not within 2 deg of the desired orientation was discarded, and any evidence of substructure as indicated by the Laue spots was also grounds for discarding the sample. Thin slices were used for the corrosion tests because weight gain per area data could be obtained with only a minimum area exposed to the corrosive media that was not of the desired orientation. The thin single-crystal slices were of irregular shape and as a result the areas were determined by placing a crystal inside an inscribed square of known area, enlarging a picture of this assembly about X5, and tracing both the enlarged square and crystal with a planimeter. The zirconium used to produce these single crystals was crystal-bar grade, a typical analysis of which is given in Table I. An oxygen analysis on prepared crystals gave a concentration of 205 ppm. The hydrogen concentrations are believed to be less than 15 ppm due to the dynamic vacuum anneal given each crystal. Typical nitrogen values for zirconium treated in this manner are about 10 to 20 ppm. RESULTS AND DISCUSSION Single-crystal wafers have been exposed to de-oxygenated, deionized water in static autoclaves.

Jan 1, 1964

By Bruce Chalmers, D. C. Larson

Aluminum crystals with longitudinal-axis orientations of (111) . (110), and (100) were deforined in tension and annealed. The conditions of deformation were controlled so that the re crystallization nuclei originated in either the heavily deformed regions at saw cuts {artificial nucleation) or in the lightly deformed matrix (spontaneous nucleation). The artificial-nucleatioln experiments showed that in lightly deformed (110) and (100) crystals low-angle twist boundaries are most mobile, while in (111> crystals and heavily deformed (110) and (100) crystals high-angle tilt boundaries with near (111) rotations are favored. The spontaneous-nucleation experiments showed the existence of preferred orientations in the (111) crystals. The nonrandomness of the grain orientations is quantitatively determined through a comparison with the results which would he obtained from a randowl set of grain ovientations. PREVIOUS recrystallization studies have been performed on single crystals deformed in tension.1 7 The crystals used in these studies usually had random tensile-axis orientations and the extent of deformation was not a primary consideration. The present study concerns the recrystallization of single crystals with tensile-axis orientations of (Ill), (110), and (100). The emphasis of this work is on the influence of the tensile-axis orientation and the degree of deformation on both the nucleation and growth processes. The multiple-slip orientations were chosen because secondary slip or slip intersection promotes nucleation.1,5,8 These crystals recrystallize at lower strains than the crystals which are oriented for single slip. Also, the greatest variation in deformation behavior is exhibited by the multiple-slip orientations. The stress-strain curves for crystals with tensile-axis orientations of (111) are higher than the stress-strain curves for poly-crystals, and the stress-strain curves for crystals with tensile-axis orientations of (100) are lower (at large strains) than the stress-strain curves for the crystals which deform initially in single slip.g The recrystallization nuclei originated in either 1) the homogeneously* deformed matrix of the crys- tals or 2) the heavily and inhomogeneously deformed regions at saw cuts. The nuclei will be referred to hereafter as spontaneous and artificial nuclei, respectively. The two terms do not imply a difference in the nature of the nuclei; they imply simply a difference in the mode of introduction of the nuclei. During spontaneous nucleation very few (always less than ten) grains nucleate, while during artificial nucleation large numbers of grains nucleate. Only a fraction of the artificially nucleated grains penetrate very far into the deformed matrix during annealing. The grains that penetrate the farthest into the deformed matrix will be referred to as the dominant grains. EXPERIMENTAL PROCEDURE The thirty-five crystals used in this investigation were grown from the melt in milled graphite boats at a rate of 1.6 cm per hr. The crystals had dimensions of approximately 6 by 12 by 80 or 6 by 6 by 80 mm and the aluminum was of 99.992 pet purity. The as-grown crystals were annealed at 610°C for 24 hr and furnace-cooled. They were then heavily etched and electropolished in a solution of five parts methanol to one part perchloric acid. The crystal orientations were obtained by back-reflection Laue photographs and were accurate to ±2 deg. The tensile-axis orientations were (loo), (110), and (111). Two of the side faces of the (111) crystals were (110) lanes. The (110) crystals had both {100) and {110) side faces and the (100) crystals had (100) side faces. The crystals were deformed at a strain rate of 0.003 per min. Shear stress and shear strain were obtained by multiplying and dividing the tensile stress and strain, respectively, by the Schmid factor, m. For the (111) crystals m = 0.272 and for the (110) and the (100) crystals m = 0.408. The Schmid factor is effectively constant during deformation for all orientations. The deformed crystals were sawed into 1-in.-long specimens while the crystals were totally enclosed in a graphite boat. The sawing was performed very carefully in order to limit the plastic deformation to the sawed regions. The specimens were electropolished in the solution mentioned above to remove the sawed-end deformation as well as controlled amounts of surface material. A special stainless-steel grip was used to hold the specimens during the electropolishing treatment. The gripping faces were flat, with no teeth, to prevent the introduction of extraneous de-

Jan 1, 1964

By B. E. Cornish

Most technical and statistical data published on pyrophyllite relating to production figures, uses, markets and sales, have in the past traditionally linked the mineral with talc and soapstone. This is due to several common superficial physical properties resulting in substitute uses and applications. However, these minerals are not similar in chemical composition and do not generally occur in a similar geological environment. Pyrophyllite now stands on its own in the marketplace-particularly in ceramic applications-due to the combination of excellent heat shock and creep resistance properties of the mineral. The increase in pyrophyllite use in the field of ceramics indicates the continuing realization of these marked unique properties. Several new fields of ceramic applications, previously the preserve of high-alumina materials, have been developed on the intrinsic properties of pyrophyllite. Pyrophyllite is an aluminum silicate with the molecular formula of AI2O34SiO2H2O. It would be more appropriate to group pyrophyllite with such materials as kyanite, diaspore, andalusite, and certain high-alumina clays in relation to its general applications (Stuckey, 1928). These materials all have good beat shock resistance properties at high temperatures and are widely used for the manufacture of refractories. For those reasons they are interchangeable in some applications. Pyrophyllite also has many uses in nonceramic applications, the most important to date being as a substitute for talc in fillers. The major pyrophyllite mining operations are located in the US, Japan, Korea, Canada, and Australia, where the mineral is widely used as a raw material for general ceramic, mineral filler, and dilutant applications. Commercial Applications Pyrophyllite was first used in the last century for lining stoves and fireplaces, and also in the carving and polishing of ornamental objects. The rise in industrial demand for new products and applications resulted in the introduction of pyrophyllite as an alternative, mainly for talc and soapstone. Industrial filler applications followed for paint, paper, cosmetics, rubber, pesticides, crayons and pencils, and bleaching soap. The first use of pyrophyllite in ceramic applications was prior to World War II, in the manufacture of ceramic cladding tiles in the US. This was followed by the production of kiln furniture refractories and whiteware when pyrophyllite was offered by suppliers in North Carolina as an alternative to some local clays. The largest tonnages of pyrophyllite used today are in refractory linings in steel ladles in Japan, as seen in Table 1. The consumption of pyrophyllite in Japan is second only to clay and chamotte among refractory raw materials used. Recently this technology has been adopted in Australia. Japanese and Australian practice has resulted in appreciable technical and economic benefits, particularly when pyrophyllite is used in combination with zircon. The potential growth for this application is substantial if US and European steelmakers follow. Investigation and research into the properties of pyrophyllite determined the following main advantages of pyrophyllite-based ceramics: high corrosion resistance for molten iron, steel, and slags; good heat shock resistance; good indices of deformation under load and hot creep resistance (refractories); and increase in mechanical strength of whiteware products promoted by a better distribution of mullite in finished products (also obtained at lower firing temperatures than normally required in production of triaxial ceramics). White cement

Jan 1, 1983

By R. E. Miner, J. K. Jackson, T. L. Wilson

A study has been made of the transformation kintetics and morphology in gas-quenched Fe-5 pct Ni alloys. Massive ferrite or nlurtensite was found to form at temperatures in agreement with earlier results. Surface Preparation appeared to have the greatest effect in determining the type of transformation Product formed. Grain size change, subgrain morphology, and dislocation densities of massive ferrite were essen-tinlly invariant functions of cooling rate. The mar-tens~tic structures were typical of transformation in austenite grains of the order of the sample thickness. BY introducing the idea of a massive transformation in dilute iron-base alloys, Gilbert and Owen in 1962 served to stimulate a closer inspection of phase transformations in ferrous systems.&apos; A wealth of literature has followed concerned with the morphology,2-5 transformation mode,2&apos;3&apos;6-8 and thermodynamics of transformations.2,5,9 interesting controversies have resulted from the experimental observations; closer attention has been paid to the definition of massive transformations and still to be resolved is the Ms temperature of pure iron. The purpose of this note is to report some observations made in a detailed kinetic and metallographic examination of the transformations that occur in gas quenched Fe-5 pct Ni. The results are pertinent to the Ms extrapolations that have been made for pure iron and the observed substructure of massively transformed alloys. PROCEDURE The material used in this investigation was cast as a 5 lb vacuum induction melted, carbon deoxidized heat. The ingot was hot worked to a strip 0.10 in. thick, decarburized, and cold rolled to final thickness. Specimens were punched to sample shape and decarburized in wet hydrogen at 600°C. The chemistry of test specimens is indicated in Table I. Samples 1 by $ in., by thickness were resistance heated and rapidly cooled in an apparatus as illustrated in Fig. 1. Similar helium quenching apparatuses have been described previously;2,6&apos;10 the distinguishing feature of this apparatus is the nozzle geometry. Twin nozzles with three convergent-divergent, sonic ports were mounted perpendicular to the specimen for quenching purposes. The specimen temperature was monitored with an intrinsic 3 mil chromel-alumel thermocouple spot welded to the specimen and con- nected to an oscilloscope. A single switch stopped the current flow through the specimen, opened a gas flow solenoid valve, and initiated an oscilloscope sweep. Cooling rates were read directly from a photograph of the oscilloscope trace and the quenching rates quoted later were made at a point immediately prior to transformation on the trace. All quenching studies were conducted either under a vacuum of 10"-5 torr or a helium atmosphere. The sample geometry was chosen large enough to permit optical and electron microscopy to be performed on samples. The samples were electropolished for both types of examination in a perchloric-acetic solution. Electron microscopy was conducted on a HU 11A microscope operated at 100 kv. Dislocation densities were determined at the same general operating reflection (110) on foils thick enough to produce Kikuchi patterns. RESULTS AND DISCUSSION Transformation Temperature Observations and OD-tical Microscopy. The quenching results of this study are illustrated in Fig. -2(a). Samples which were treated in the as-decarburized condition transformed in a manner similar to that reported previously—a decrease in transformation temperature occurred as the quenching rate increased until a plateau region was reached. Within the scatter of the results obtained here, there was no break in the transformation temperature-quenching rate plot. This suggests no change in transformation mode. Further metallographic examination confirmed this observation. A martensitic transformation was obtained for similarly treated samples except that the surface was first electropolished. The Ms temperature was approximately 85°C below the plateau determined for the unpolished samples and cooling rates as slow as 2000°C per sec were adequate for producing marten-site. The transformation temperatures are in gen- / STRIP SAMPLE / COPPER I SAX/-/}&apos; / CONNECTOR-----A f, SON|C poRTS AC LEADS 3j ]j"I rofe[ \ Mf/yinK/iKj&apos;&apos;^ THERMOCOUPLE X-(^—iie"s*c? &apos; LEADS 1 INCH Fig. 1-—Schematic scction of gas quenching apparatus

Jan 1, 1970

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald&apos; who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall&apos; who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956

By Frederick N. Rhines, Robert F. Mehl

It has been shown elsewhere1 that the data on the rates of diffusion in solid metals are fragmentary and in many cases unacceptable. As a result, relatively little is known concerning the factors determining rates of diffusion and the variations in these rates with temperature. The first form of Fick&apos;s law (equation 1 below), in which the diffusion coefficient D is assumed invariant with composition, has been recognized for many years as only an approximation. The differential equation representing the second form of Fick&apos;s law (equation 4 below) has only recently been integrated by Matano,2 and unfortunately only in cases where a full diffusion-penetration curve (concentration-distance curve) has been obtained can the Matano solution be applied. The proper analysis of diffusion data is thus confined to the data of Grube and Jedele and of Jedele. 8 These data are essentially for one temperature alone and do not furnish any information on the variation of the activation heat of diffusion, Q, with concentration: no information exists on the variation of Q with concentration within a single solid solution field. 11 Much of the argument concerning the properties of metals that determine D and Q has been drawn from data in which variations of the quantities with concentration are unknown, for these data have been taken from experiments that could not furnish this information. Speculation concerning the properties of metals that may be effective in determining D and Q on the basis of data in which the chosen D and Q values are averages over wide concentration ranges of values at particular concentrations, ranges often of 100 per cent, is likely not to be fruitful.

Jan 1, 1938

By R. C. Buehl, M. B. Royer

High manganese slags of low phosphorus and iron content are produced by air oxidation of high phosphorus spiegeleisen in a basic-lined converter. Control of phosphorus and iron within specification limits for ferromanganese ore feed is obtained by a unique cyclic operating procedure. Various types of slags, or synthetic manganese ore, can be made. AN affiliated paper&apos; describes the production of high phosphorus spiegeleisen containing 14 to 23 pct Mn and up to 4 pct P in an experimental blast furnace from open-hearth slag or manganiferous iron ore. This phosphorus content is too high for use of the spiegel in normal steel-production operations. Consequently, a preferential separation must be effected whereby the manganese is concentrated in a product that is usable in industrial operations. The preferential separation methods being investigated for this phase of the work are confined to pyrometal-lurgical processes for ready incorporation into steel-plant operations. It is fortunate that manganese is more actively oxidizable than iron or phosphorus, and therein lies a preferential separation method for isolating manganese from these two elements. Silicon is more strongly oxidizable than manganese, and its oxidation precedes, or occurs simultaneously, with manganese. Therefore, manganese and silicon are separable into a high manganese oxide slag phase while the phosphorus and iron remain in the molten metallic state. Complete separation of these elements represents an ideal condition which is not generally attainable in actual operations. This pyro-metallurgical method for separating manganese from phosphorus and iron by preferential oxidation was investigated by blowing 500 lb of metal in a basic-lined vessel to obtain preliminary information on the effectiveness of the procedure. Certain conditions of attainment in the separation process are desirable in any method for removing manganese from high phosphorus spiegeleisen, such as: 1—High recovery of manganese in the oxidation product; 2—the product to be of equal or better quality than ferromanganese-grade ore—48 pct Mn minimum, less than 10 pct SiO2, and Mn-P ratio of 300:1; and 3—attainment of the enumerated objectives in a product amenable to industrial handling, such as a slag of high manganese content that will flow from the processing vessel and of sufficient fluidity for ready separation of metallic granules that may have become mixed with the manganese slag phase. Previous Work Recovery of manganese from low grade ores and industrial byproduct slags by smelting to spiegeleisen, with subsequent oxidation to synthetic ferro-manganese-feed ores, has been a subject for periodic investigation during the past four or five decades in the United States and Germany. Joseph&apos; and associates of the Bureau of Mines North Central Experiment Station, Minneapolis, Minn., smelted manganiferous iron ores of the Cuyuna range, Minn., to spiegeleisen and subsequently tried air and ore oxidation procedures for concentrating the manganese into synthetic ferrograde manganese ore. Joseph&apos;s results on the operation of a side-blown basic-lined converter for air oxidation of manganese from molten spiegeleisen were so discouraging that the procedure was abandoned after 11 blowing tests. Much slag was thrown from the converter vessel; phosphorus content was four to five times the maximum allowable for ferro ore; and a manganese-iron ratio of only 2 or 3:1 was obtained in the slag instead of the required 8:1. Oxidation of manganese from spiegeleisen with about 0.5 pct P, by adding iron ore to molten spiegel in an experimental open-hearth furnace, proved moderately successful in Joseph&apos;s experiments. The main drawback to the operation was the necessity for over-oreing for effective oxidation of the manganese with consequent too high iron oxide residual in the slag. Furthermore, the phosphorus content was proportional to the iron concentration and therefore much too high, so that several hours of reduction by a carbonaceous material were required to adjust the iron and phosphorus to the desired content of high grade ferro feed. A troublesome feature of the slag product of the spiegel oxidation process was its lack of fluidity if the silica content was less than 10 pct, the concentration considered desirable for the synthetic ore. Approximately twice the desired concentration of silica was required to impart enough fluidity for transfer from the vessel by pouring. The acute shortage of manganese in Germany

Jan 1, 1953

By J. F. Martin, L. M. Melnick, R. Rapp, R. C. Takacs

Recent studies on the determination of hydrogen in steel have shown that the hot-extraction method for removing hydrogen from a solid sample is preferable to its removal from a molten sample by vacuum fusion or by fusion in vacuum with tin. A number of techniques are available, however, for determining the hydrogen so extracted. They include: thermal conductivity, gas chromatography, pressure measurement before and after catalytic oxidation of the hydrogen to water and removal of the water, and pressure measurement before and after diffusion of the hydrogen through a palladium membrane. These techniques have been evaluated on the basis of initial cost, maintenance, speed and accuracy of analysis, and applicable concentration range. The results of this study showed that the palladium-membrane technique is best suited for routine use. FOR some time investigators have been concerned with the origin, form, and effect of hydrogen in steel. In such stdies&apos;, the analysis for hydrogen constitutes one of the most important phases. It is quite apparent that the results for hydrogen concentrations in a given steel are dependent on the method of obtaining the sample, storage of the sample until analysis, preparation of the sample, and analysis of the sample, including all the facets inherent in the calibration and operation of an apparatus for gas analysis. There are a number of means available for determining hydrogen. This is a critical study of some of the more common techniques in use today. In most conventional melting and casting methods, hydrogen concentrations of 4 to 6 parts per million (ppm) in steel are quite common. Because of the undesirable effects of hydrogen on steel there has been increased use of techniques such as vacuum melting,&apos; vacuum casting, and ladle-to-ladle stream degassing, which lower the hydrogen content to levels on the order of 1 to 2 ppm. Therefore, the method used for determining hydrogen in steel must be sensitive and precise. In any analytical procedure for gases in metals there are two distinct operations—the extraction of the gas from the metal and the analysis of the extracted gas. To extract the gas from the steel, three methods have been employed: 1) fusion of the sample with graphite at high temperature; 2) fusion with a flux, such as tin, at a lower temperature; and 3) extraction of the hydrogen from the solid sample at a temperature below the melting point of the steel. Fusion with graphite is the least-acceptable method. The blank in this method is higher and more variable than in either of the other two methods. The hydrogen fraction of the total gas composition usually is between 10 and 50 pct; thus, a larger analytical error is possible. The vacuum-tin fusion4 extraction of hydrogen is probably the most rapid method in use today; the extraction time is usually about 10 min. However, with this system a bake-out of the freshly charged tin for 2 hr is necessary and a change of crucible and a charge of fresh tin are required after each day of operation whether one or thirty samples have been analyzed. In addition, frequent checks of blank rates are required since CO and Na are continually being given up by the steel samples dissolved in the tin bath. The composition of the gas in this method lends itself readily to analysis; although the hydroge concentration may fall to as low as 50 pct, more often it is above 90 pct, thus allowing a more precise analysis (because of less interference from other gases). In 1940 ewell&apos; published the hot-extraction method for extracting hydrogen from the solid sample, comparing analysis for hydrogen extracted at 600°C with similar analysis for the gas extracted at 1700°C by fusion with graphite. Good agreement for hydrogen was obtained between these two methods, provided sufficient time was allowed for extraction at the lower temperature. carsone obtained good results in his comparison of this hot-extraction method with vacuum-tin fusion. Subsequent work by Geller and sun7 and Hill and ohnson&apos; has shown that steel samples should be heated to at least 800°C to effect the release not only of the diffusible hydrogen but also of the "residual" hydrogen that may be present as methane. Since the rate of evolution of hydrogene9l0 depends on such factors as sample size and composition, thermal history, and extent of cold work, a fixed extraction time is not possible. Extraction times of 30 min are normal, but 2 hr are not unusual. Induction or resistance heating may be used in the hot-extraction method. With resistance heating the

Jan 1, 1964

By J. Downie, H. A. Kendall, G. H. F. Gardner

Some cases of the motion of two miscible fluids in uniform linear models are discussed. There is no bulk flow through the models, and the convection currents are caused solely by density gradients. Horizontal, vertical and inclined positions of the models are treated separately. Analytical formulas for the motion of a narrow transition zone between the fluids are obtained and compared with measurements, and the limitations are discussed. Observations of the ultimate stabilizing effect of diffusion on the motion me compared with the theory. It is shown that fluid motion in an inclined model with a constant rate of bulk flow can be directly deduced from the cases discussed, provided the viscosity ratio is small. INTRODUCTION In some reservoirs, convection currents caused by variations in the fluid densities may be significant. For practical purposes it may be desirable either to minimize the effect, particularly in miscible displacement, or to maximize the effect as in some schemes for the production of heavy crude oils by combustion. Experiments by Craig, et al,l have shown the effectiveness of gravity in reducing the efficiency of a miscible displacement when the mixed zone between the displacing and displaced fluids is narrow compared with the height of the system. The presence of a board transition zone from one fluid to the other has been shown by Perkins, et al,2 to nullify considerably the influence of a difference in density. Indeed, the theoretical discussion given by Perrine3 has shown that when the transition zone exceeds a certain critical length the efficiency approaches 100 per cent. Many additional results 495 have been published on miscible and immiscible displacements which show the importance of density difference and also mobility ratio. The aim of the present paper is to discuss some cases of gravity segregation of miscible fluids in linear models such as are often used in the laboratory to evaluate recovery processes, and to supply additional experimental evidence in support of the conclusions. An attempt is made to calculate simply the magnitude of the fluid motion caused by density pdients and mobility ratios, and to quantify the modifications in the fluid motion produced by the combined effect of molecular and convective dispersion. However, it should be pointed out that the uniform permeability of the models and the use of only a single pair of fluids (whereas several pairs of fluids may be employed in a recovery scheme) severely restricts direct conclusions about natural reservoirs. For conciseness, the motion generated by density gradients is emphasized for the case of no bulk flow through the models. This is not a drastic limitation because, as shown in Appendix A, a fluid motion with a constant bulk flow through any linear model is equivalent to a fluid motion with no bulk flow in the same model inclined at a different angle to the horizontal, provided only that the density is a linear function of the viscosity of the fluid mixture. HORIZONTAL MODEL In this case the model is assumed to have a rectangular cross-section with a horizontal breadth b, vertical height and a great length L. Throughout.the paper it will be assumed that x-axis points along the length, the y-axis along the width and the z-axis along the height. Thus, in the present case the x, y plane is horizontal. Initially, the transition zone between the fluids is assumed to be thin and parallel to the y, z plane. An example of this situation in a practical problem arises in a scheme for using air for cushion gas in the storage of fuel gas in aquifers. 6 With the passage of time the denser fluid sinks and spreads along the bottom of the model while the lighter fluid rises. The interface extends from the top plane of the model to the bottom. Experiments have shown that for practical purposes this interface may be treated as a plane surface at all times. The surface is significantly curved, however, for viscosity ratios greater than about 10. Other complications arise with large viscosity ratios because of the nonlinear dependence of the viscosity on the composition of the mixture, so that the simple results given here are restricted to fairly low viscosity ratios.

By Nicholas J. Grant, Hanna Ibach, Bill C. Giessen

The system Ta-Rh was investigated over the entire comnposition range using metallogvaphic and X-ray techniques as well as thermal analysis. Terminal solubility limits, solidus temperatures, and the crystal structures of two new intermediate phases were determined. There are five intermediate phases: o, tetragonal, isostructural with o(Fe-Cr); a1, orthorhomnbic : a2, orthorhombic, isostructural with CozSi; 0 3, a high -temperature phase of unknozun structure; and a TaRh3, cubic, AuCu3 structure. a, aL, a,, and a melt peritectically; and a TaRh, has a maximum melting point. Five peritectic and one eutectic reactions occur. THE Ta-Rh phase diagram has not been fully treated in the literature; however, two inter metallic phases have been described.&apos;-&apos; This study attempts to work out the diagram covering the details of phase boundaries as well as the crystallography of the intermediate phases. EXPERIMENTAL METHODS Starting materials were tantalum powder of 99.8 pct purity, supplied by National Research Corp., Cambridge, Mass., and rhodium powder of 99.9 pct purity, supplied by Bishop Co., Malvern, Pa. Analyses as given by the manufacturers are presented in Table I. In addition to the spectroscopic analysis, an oxygen analysis has been made of the tantalum powder. After preliminary trials, the standard procedure employed in making the alloys was as follows (see Ref. 4 for further details). The powders were weighed, mixed manually, compacted under 16,000 psi, and arc-melted at not more than 500 amp under thoroughly titanium gettered welding-grade argon of 400 mm Hg pressure. The gettering process was repeated after each melt. It had been shown previously5 that under these conditions no oxygen pick-up exceeding 0.001 pct in a hafnium button could be detected. The buttons, ranging from 5 to 10 g in weight, were inverted or, if possible, crushed and remelted three times. Melting presented no difficulty, except for tantalum-rich al- loys, which showed considerable spashing during melting. The average weight loss of 1 wt pct rose to 2.5 wt pct in these cases. Subsequent melting, however, resulted in losses of less than 0.1 wt pct. The melts obtained frequently showed small in-homogeneities, mostly in the tantalum-rich part of the system below 25 at. pct Rh. This was not due to insufficient blending of the elements, but to crystallization taking place from the cooled bottom. This condition was not improved by further re-melting; therefore the following precautions were taken. Cross sections of as-cast buttons were made. For the investigation only buttons were used where these inhomogeneities did not exceed 1 at. pct (estimated from the amounts of haSeS resent). In addition, only the center portions of such buttdns were utilized to minimize errors. Smaller buttons showed smaller concentration gradients and were used as a check. Finally, all alloys were homogenized to eliminate coring (see below). After this, the error in alloy composition due to inhomogeneity was cl at. pct. In order to confirm the concentrations of the alloys and to provide an impurity check, wet-chemical analyses and oxygen-fusion analyses of four key alloys were carried out. The results, together with the concentrations as calculated with the weight balance method, are presented in Table 11. It was found that for three alloys the agreement is very good (< 0.2

Jan 1, 1964

By Oliver Bowles

Dimension stone is a term applied to stone sold in blocks or slabs of specified shapes and usually of specified sizes, contrasted with crushed, broken and pulverized stone covered in another chapter. Dimension stone includes cut stone, rough building stone, ashlar,* rubble, monumental stone, paving blocks, curbing, flagging, and many types of ornaments and novelties carved from stone. Riprap-large, irregular blocks used for shore protection-is classed with crushed and broken stone. Composition, Varieties, and Properties Dimension stones are of many kinds. The principal varieties are granites, trap rock (diabase, basalt, and gabbro), sandstone, limestone, and marble. Slate is covered in a separate chapter. Granite is a visibly granular crystalline rock consisting essentially of feldspar, quartz, and mica or hornblende. The basaltic rocks are darker in color than the granites. They contain little or no quartz and consist largely of plagioclase feldspar, augite, pyroxene, and hornblende. They are classed commercially as black granites. Limestone consists essentially of calcium carbonate. Dolomites and magnesian limestones used as dimension stone are classed with the high-calcium limestones. Marble is a crystalline form of limestone, but in the trade, any carbonate rock which will take a polish is called a marble. Many limestones which are fossiliferous but which will take a polish are sold as a decorative stone for lobbies of hotels and office buildings. Sandstone consists essentially of silica in the form of sand grains cemented into a coherent mass. Although rock occurrences are numerous and widespread, the exacting requirements of use condemn all but a small fraction of them for commercial use as dimension stone. No deposit that has closely spaced joints or planes of weakness can be used because sound blocks of moderate to large size are demanded. Uniform texture and grain size, constant and attractive colors or color pattern, and freedom from impurities that may cause stains or deterioration usually are demanded. Hardness is a variable property. Granites and diabases are as hard as or harder than steel, while limestones and marbles may be scratched with a knife. The hardness of sandstone depends upon the degree of cohesion of the grains. Workability depends to a considerable extent on hardness, but the degree of hardness has little influence on use except where stones are subjected to abrasion as on steps or floors. "Texture" as applied to stone relates to the arrangement, uniformity, and size of the constituent grains. Stones are of many colors and thus can satisfy a variety of tastes. For monumental stone, a marked contrast between polished and tooled surfaces is preferred in order that inscriptions may be read easily. Strength requirements usually may be disregarded because any sound structural stone suitable in other respects is almost invariably many times as strong as would be required for any ordinary use. The pressure on the base course of the Washington Monument, Washington, D. C., is less than 700 psi, and highgrade granites, limestones, sandstones, and marbles will sustain a crushing load of 10,000 to 25,000 psi. A structure made of stone with a crushing strength of 15,000 psi would have to be nearly 21h miles high before crushing of the lower courses would occur. However, stone disintegrates more readily under severe

Jan 1, 1960