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By John M. Campbell, W. E. Portman

A series of correlating charts have been prepared to enable the field engineer to predict the amount of stock tank fluid produced by stabilization of first stage separator fluid. The charts shown are particularly convenient for estimating the relative effect of temperature and pressure in economic studies. Further work is planned to investigate the factors affecting stage separation' yo supplement this preliminary work. The direct correlation of separation variables is dictated as a convenience to eliminate the trial and error calculation necessary when using the standard flash vaporization equations. These are obtained by a material balance using the equilibrium vaporization ratio K, and have appeared in the following, or similar. form many times in the literature. where La = mols of any component n in the separator liquid Ko — equilibrium vaporization ratio for any component at separator pressure and temperature Fa = mols of any component n in the feed Vn = mols of any component n in the vapor V = total mols of separator vapor These equations may of course be effectively and accurately solved by use of digital and analog computers. However, these are not usually readily available in field offices and the need often arises for fast results during routine operational problems. Consequently, many methods have been devised in an attempt to simplify the basic calculation.2-14 The methods proposed are generally satisfactory, but do not eliminate trial and error methods and the necessity of subsequent calculations to obtain the answer in volume terms. The purpose of this work. therefore, was to develop accurate charts that would give the result directly in gallons. When using stage separation the recoveries would be lower than those shown, for stabilization usually gives about 95 + per cent recovery on the potential stock tank components in the separator liquid. The recoveries are shown in terms of a 14 psi Reid Vapor Pressure product which has a true vapor pressure of 14.7 psia at 98°F. Consequently, this product represents a stable stock tank liquid under normal storage conditions. To estimate natural gasoline re- coveries by stabilization the volume shown may be multiplied by 1.20 for 18 Ib RVP natural gasoline and 1.36 for 26 lb RVP natural gasoline. PROCEDURE The five analyses shown in Table 1 were chosen since they were representative of wellstream compositions often found and had almost the same propanes plus liquid content, expressed in gallons per 1,000 std. cu ft of wellstream. The distribution of the components though is widely variant. A temperature range of 0-100°F. and a pressure range of 200 to 1,250 psia was chosen inasmuch as most separations fall within these limits The K values used were modified values of those originally published by Katz and Hachmuth.' In the range chosen these have generally given good results when predicting fluid recoveries. The choice was somewhat arbitrary, for the authors' personal experience has shown that

Jan 1, 1957

By R. M. Goldhoff, J. W. Spretnak, R. Speiser

IT has been observed by Grange and Garvey' that the homogenization of boron-treated steels could lead to complete elimination of the hardenability effect caused by boron. The experimental conditions leading to this conclusion involved the heating of steel specimens with and without boron at 2350°F for 24 hr. To prevent oxidation and decarburization, the specimens were encapsulated under vacuum in silica tubes. This observation of permanent deterioration of boron effect was noted in both a 0.63 pct plain carbon steel and a 0.25 pct C low alloy steel, both of which had been treated with ferroboron and homogenized at 2350°F for 24 hr. In another series of boron-treated steels which had been homogenized for shorter times, the effect was to reduce, but not completely eliminate, the boron effect. Under these circumstances, it was presumed that longer heating times would cause permanent deterioration of the boron effect in this series of steels also. Since the characteristic grain boundary constituent could not be formed in any of these steels after homogenization, it was concluded that possibly boron was being converted into an ineffective form through chemical combination resulting from prolonged heating at high temperatures. Assuming the validity of this observation, a series of experiments to establish the relationship between temperature of homogenization and kinetics of deterioration was contemplated. Initially an attempt was made to reproduce the results just described. For this purpose commercial lots of AISI 8640 and AISI 86B40 steels were used. The analyses of these steels appear in Table I. Hardenability evaluation was on the basis of the hardness of normalized sections. Grange and Garvey' pointed out that these steels are air hardening to some extent and such a technique can be used. For these tests the specimens were held for 20 min in a salt bath at 1600°F and then cooled in still air. Several evacuated silica capsules containing pairs of the test steels were made up and heated for 24 hr at 2350°F. A number of failures occurred among these capsules, but evaluation of the specimens successfully treated indicated a complete deterioration of the boron effect. However, examination of the surface of the treated specimens showed that some reaction, probably with the silica tube, had taken place, since none of the specimens was bright. One further test was made at 2350°F for 12 hr, using a pair of specimens wrapped in tantalum foil prior to encapsulation. These specimens appeared bright after treatment, and their hardenability evaluation showed that no deterioration had taken place. Since these steels are extremely sensitive to de-boronization at high temperatures and particularly at long times of holding, the experimental observations raised some doubt as to the real occurrence of the permanent deterioration effect. To resolve this question an experiment was undertaken in which the high temperature portion of the treatment was completed in vacuum. For this purpose a molybdenum wound resistance furnace capable of maintaining good vacuum was used. All the pertinent accessories to this furnace were machined from molybdenum stock in order to withstand the high temperature involved in the experiment. With this equipment a temperature of 2400 °F was obtained and held under a pressure of 5x10-" mm Hg for 24 hr. A specimen of each of the two test steels was suspended in the furnace and both were heated simultaneously. Temperature was measured with a standardized Pt—Pt-13 pct Rh thermocouple, whose millivoltage at 2400°F was extrapolated from the standardization equation, good up to 2200°F. The complete evaluation of these specimens is shown in Table 11. The hardness values attained by each steel after normalizing, both before and after the prolonged high temperature treatment, remain the same. A microscopic study of the decomposition products present in the microstructures of specimens at various points in the heat treatment correlated with the hardness values observed. It seems that no permanent loss of boron hardenability effect occurs, at least in these Grainal-treated steels, when deboronization is circumvented. Acknowledgments This work was conducted under the sponsorship of the Aeronautical Research Laboratory, Wright Air Development Center, under Contract No. AF 18(600)-94, and their support and permission to publish is gratefully acknowledged. A note of thanks is also extended to the Republic Steel Corp. for supplying the materials used in the work. References ' R. A. Grange and T. M. Garvey: Factors Affecting the Harden-ability of Boron Treated Steels. Tro.ns. ASM, 1946, vol. 37, p. 136.

Jan 1, 1957

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953

By W. T. Olsen, R. Ulcer

WHEN a liquid alloy freezes, the solid first formed usually differs widely in chemical composition from that last formed, so that there is segregation in the alloy as cast. For example in the copper-nickel system (fig. 1) the first solid formed from a liquid containing 55 atomic pct Cu may contain as little as 38 pct Cu, while the last must contain well over 55 pct. Three factors may act to decrease segregation from the maximum possible. 1. Diffusion in the cooling solid tends to make the phase homogeneous, decreasing segregation. This may be important at slow rates of cooling. 2. Segregation is impossible without diffusion in the liquid. At extremely rapid rates of cooling there may not be enough time to allow maximum segregation. 3. Supercooling delays nucleation to temperatures well below the liquidus thereby decreasing segregation. Hence the first nucleus in the copper-nickel system may contain well over 38 pct Cu. At sufficient supercooling the first nucleus may form below the solidus, in which case there is no reason to expect any segregation whatever. From these considerations, we could predict that at sufficiently low rates of cooling the alloy would be unsegregated because of factor 1 and at sufficiently high rates of cooling there should also be no segregation because of factors 2 and 3. Considerable segregation should occur only at intermediate rates of cooling. We have demonstrated experimentally that segregation can be completely suppressed by rapid rates of cooling. For the alloys studied, however, these rates are too great to be attained in any commercial practice. An alloy of 55 atomic pct Cu, 45 atomic pct Ni was frozen by cooling at varying rates. The degree of segregation in the solid was determined by X-ray diffraction photographs. Slow rates were obtained by slowly cooling the furnace containing the liquid alloy; fast rates by pouring or ejecting droplets of the alloy into water or iced sodium hydroxide solutions. The cooling rate of the droplets can be cal-culated from their dimensions by assuming reason- able values of thermal conductivity.' The experi-ments were repeated with an alloy of 16.5 pct Cu and 83.5 pct Au. A single experiment also showed a 50 atomic pct Bi-Sb alloy had no segregation at the most rapid quench. The position of back-reflection X-ray diffraction lines is a highly sensitive function of the lattice constant, which in turn depends on the chemical composition of the phase. A phase of varying composition will give broad diffraction lines. By measuring the edges of these lines and making suitable corrections for intrinsic line width, it is possible to determine the range of lattice constants represented. These can be converted to chemical compositions from a lattice constant vs. composition curve. Results are shown in table I. In the copper-nickel system the greatest segregation is found at the slowest cooling rates, where the lowest percentage of copper theoretically possible is found. In the copper-gold system, on the other hand, the degree of segregation is decidedly less at the slowest rates of cooling, being greatest at 11,100°C per sec. At no rate is the theoretically lowest percentage of copper (12 pct) found. At the rates of cooling found in sand and die castings the degree of segregation is large and depends little on the rate of cooling. Acknowledgment Most of the material in this paper is abstracted from a thesis presented by William T. Olsen, Jr. in 1948 in partial fulfillment of the requirements for the degree of Master of Science at the University of California.

Jan 1, 1951

By P. R. Sperry, A. P. Beck

It has been shown1 that in poly-crystalline strips of high purity aluminum with a fairly random orientation distribution, grain growth progresses gradually until the average grain diameter reaches a value approximately equal to the strip thickness. Recent work at this laboratory led to the realization that grain growth might be impeded to a considerable extent in the presence of a sharply defined texture, where orientation differences between neighboring grains are small. In order to investigate this effect the following experiment was carried out with the same lot of high purity aluminum previously used for grain growth studies in randomly oriented material.' Very large grain size was developed by grain growth at 650°C in specimens of 0.200 in. thickness. These specimens were then rolled to a thickness of 0.050 in. or 1.25 mm—a reduction of 75 pct. In the rolled strip each large grain corresponded to an elongated area easily identified by etching. After annealing for 1 to 25 min at 600°C and re-etching, these elongated areas were again recognizable. Within each area, corresponding to a single large grain before annealing, there formed by recrystallization a multitude of new grains with a fairly well developed preferred orientation. The orientation and the size of the new grains formed in areas corresponding to different large grains, varied widely depending on the orientation of the parent grains with respect to the rolling direction and the plane of rolling. Many areas were found where the average grain size was considerably smaller than the specimen thickness. Such an area occurred in a specimen cut in half before annealing. One half, containing a portion of the area in question, was annealed 1 min at 600°C, the other half, with the remaining portion of this area, for 25 min at the same tempera-Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950

By E. C. Franz

IN an effort to understand high cycle fatigue, as well as to study the mechanism of fracture in general, a number of researches have been undertaken whereby the fracture properties of a metal have been determined under conditions of repeated cyclic prestsain employing high strains with relatively few cycles. Liu, Lynch, Ripling, and Sachs' showed the effect of a definite strain history consisting of small increments of tensile or compressive prestrain upon the flow and fracture characteristics of metals after a limited number of repeated loadings. Liu and SachsW emonstrated by cyclic straining of the aluminum alloy 24s-T4 that the least reduction in ductility was obtained when the compressive stress was nearly equal to the tensile stress. Attempts have been made to correlate the reduction in ductility under such prestraining with conventional fatigue data, as was done by Liu and co-workers.' The following research was conducted to determine if such reduction as has been noted could be correlated with conventional fatigue data or whether the effect resulted from causes extraneous to the basic mechanism of fatigue failure such as strain aging. It might be pointed out in this connection that the reduction in ductility has occurred in alloys that might be susceptible to strain aging or similar behavior, such as alloy 24s-T4. In the present investigation, the test specimens were prepared from the aluminum alloy 75s-T6 and annealed electrolytic copper. Alloy 75s-T6 is a complex precipitation hardenable alloy, whereas electrolytic copper would not be expected to exhibit strain aging effects, particularly at room temperature. The experimental procedure consisted of prestraining test specimens repeatedly by increasing tension in small increments to various total prestrain values, followed by testing to failure in a tension test. The prestraining as well as the final testing was performed on a tensile machine using special fixtures9 0 maintain concentricity of the specimens. After prestraining, the specimens were unloaded as rapidly as possible and immediately reloaded so that the total time lapse between strains was held to a few seconds. Logarithmic or true natural strain was used in all calculations. The results are presented in Figs. 1 and 2. In Fig. 1, the retained ductility, area after prestrain area at fracture is plotted against the tensile prestrain, initial area area after prestrain as abscissa with the number of stress reversals executed to attain the required prestrain plotted as parameter. Several specimens that fractured during

Jan 1, 1955

By Jun Hino, P. G. Shewmon, P. A. Beck

THE investigations of Crussard,' of Guinier and Tennevin,' and of Dunn and Daniels," indicate that the subgrains formed in a cold worked and annealed metal are capable of growing at each other's expense during annealing, if the temperature of annealing is sufficiently high and the time is long enough. The results of Dunn and Daniels are particularly convincing in showing that subgrain growth is essentially the result of the free surface energy associated with the subboundaries. In subgrain growth, as in ordinary grain growth, energy is gained as a result of the decrease in total subboundary surface area per unit volume. Recently, Wood and Scrutton4 found that the rate of subgrain growth upon annealing increased very considerably, if simultaneously a creep strain was applied to the specimen at a low strain rate. Working with 99.98 pct pure fine-grained aluminum, these investigators found that the continuous X-ray diffraction back-reflection rings of material strained at room temperature remained continuous after heating for ten days at 250 °C. However, when heated at the same temperature under a stress of 1000 psi even for only three days, the formerly continuous X-ray diffraction rings broke up into numerous dots, which were fairly clearly separated from each other. The continuous X-ray diffraction rings were interpreted as indications of a very small subgrain size, not resolved by the X-ray diffraction method used. The breaking up of the continuous X-ray diffraction ring during annealing under stress was taken as an indication of a great increase in subgrain size, so that the individual subgrains could then be resolved. The effect of simultaneous strain at a low strain rate in accelerating subgrain growth, discovered by Wood and Scrutton and designated by them as "cell growth," is of fundamental importance. The experiments described in this note were carried out in order to confirm Wood and Scrutton's results by direct metallographic observation. Also, information was sought as to the minimum creep strain necessary to produce this effect. A fine grained high purity aluminum strip was prepared by alternate 33 pct rolling and annealing treatments for 1 hr at 350°C. Specimens cut from this strip were subjected to a relatively fast creep strain of 7.2 pct in 3.5 min at 300°C under a constant load initially corresponding to 1185 psi. The subgrains set up were large enough (about 0.015 to 0.03 mm) to be clearly observed (Fig. 1) at X200 magnification with polarized light, after electrolytic polishing and anodic etching, producing a fine oxide film." The corresponding X-ray diffraction pattern is shown in Fig. la. After the fast creep strain treatment a portion of the specimen was subjected to a creep strain of 8.3 pct in 44 hr at 350°C under a constant load initially corresponding to 320 psi. Another portion, annealed under the same conditions, but not strained, served as control specimen. The subgrain size of a typical area of the specimen annealed under strain and of the one annealed without strain is shown in Figs. 2 and 3 (X-ray diffraction patterns, Figs. 2a and 3a). Annealing without strain produced clearly observable subgrain growth (subgrain size: about 0.03 to 0.05 mm). The effect of simultaneous strain was to increase greatly the rate of subgrain growth (resulting in a subgrain size of approximately 0.05 to 0.13 mm), in accordance with Wood and Scrutton. In another experiment, the effect of the amount of simultaneous strain was studied. The initial subgrain structure was set up by fast creep, as described previously. The specimen was then heated at 350 °C under a constant load initially corresponding to 320 psi, as above, for 2.2 hr (0.24 pct strain), and 8.8 hr (0.58 pct strain). Comparison with the corresponding unstrained control specimens by means of X-ray diffraction showed that 0.58 pct strain definitely had an effect, but the effect of 0.24 pct strain was doubtful.

Jan 1, 1953

By J. H. Frye, J. L. Scott, J. W. Woods

THERE are at least two effects of temperature on the stress required to produce plastic flow. 1) Metals plastically strained for the same amount at different temperatures possess different stress-strain curves and different internal structures (e.g., nature and density of imperfections). 2) There is both experimental and theoretical evidence that the stress necessary to produce plastic flow may vary with temperature even though the internal structure remains constant.1-5 Much of the data in the literature is difficult to interpret because these two effects are simultaneously present. In the work reported here, they are considered separately. Standard 0.505 in. tensile specimens were prepared from high-purity Mond nickel and OFHC copper. Nickel specimens were annealed in hydrogen at 1150°C for 30 min and furnace cooled. This produced an average grain diameter of 1.4 mm. Copper specimens were annealed in vacuum at 525°C for 6 hr and furnace cooled. This produced an average grain diameter of 0.11 mm. Nickel tensile specimens were prestrained in tension at 500°K, whereas copper tensile specimens were prestrained in tension at room temperature. All specimens were cooled to 74°K and heated to room temperature. After these treatments all of the tensile specimens of a given set possessed identical structures. All specimens were returned to the tensile machine and tested at various temperatures and constant cross-head speed. Many of the tensile curves showed well defined yields but, in order to minimize personal judgment, the yield was always chosen as the stress corresponding to 0.2 pct plastic deformation. Results are summarized in the graph of yield vs temperature of test, Fig. 1. All of the specimens corresponding to any one line have had identical treatments and, therefore, have identical internal structures. Thus, each line gives the relation between yield stress and temperature for one constant internal structure. The lowest line, which is for annealed nickel, shows no measurable variation of yield with temperature. This is similar to Blewitt's6 results on copper single crystals, but a variation in yield with temperature was found by Andrade and Henderson' in single crystals of nickel, and by Car-recker and Hibbard8 in annealed polycrystalline copper. The three other lines, which are for prestrained materials, show that there is a linear relation between yield stress and temperature when the internal structure remains constant. Such a relation might be expected from a rate equation such as that of Kauzmannl on the assump- tion that the activation energy is either independent of or linear with temperature. These results would also be expected if the shear moduli of copper and nickel are linear functions of temperature for, as Cottrell and Stokes have pointed out," in all dislocation theories of strength the flow stress appears proportional to the shear modulus of the material. In copper and nickel, since the modulus of elasticity decreases roughly linearly with increase in temperature," it is probable that the modulus of shear also decreases approximately linearly with increasing temperature. A detailed discussion of the effect of these and other factors on the temperature dependence of flow stress in face-centered-cubic metals has recently been given by Seeger.4

Jan 1, 1958

By A. T. Corey, C. H. Rathjens

INTRODUCTION Although the oil industry has been aware of the directional variability of permeability in porous rock, the directional variability of relative permeability has been largely ignored. Yet it is apparent that such an effect must be present in a system in which the distribution of oil and gas within the porous matrix is controlled by capillary forces. It is easy to visualize a rock composed of layers of fine and coarse material such that gas flow across the bedding planes would take place only after the average oil saturation had been reduced to a very low value. The fine layers, because of their greater capillarity, would remain saturated and act as barriers to the flow of gas after the coarse layers had been desaturated. Flow of gas parallel to the bedding planes would obviously take place at a much greater liquid saturation. Without more complete information concerning the geology of a reservoir than is generally available, it is not possible to predict exactly how such phenomena would affect the over-all performance of an oil field. It is possible, however, to predict qualitatively the effect of stratification on relative permeability measurements made on laboratory cores. In this investigation the effect of stratification was studied analytically by assuming that two porous materials with different capillary pressure-desaturation curves (but identical relative permeability curves) were in contact and in capillary equilibrium. As a qualitative check on the analytical results, cores having various degrees of visible stratification were used for relative permeability measurements made with fluids flowing both parallel and perpendicular to the bedding planes. A quantitative check was considered impractical because of the difficulty of devising models in which two materials of predetermined properties could be joined without the plane of contact becoming a discontinuity. THEORETICAL CONSIDERATIONS AND ASSUMPTIONS The assumption of capillary equilibrium in an oil-gas system implies that the difference in pressure between oil and gas is everywhere the same. This means that the curvature of the interfaces must be everywhere the same in order to satisfy the equation where PC is the pressure difference between phases, y the interfacial tension and r, and r2 are the major and minor radii of curvature. Depending on the pore size distribution of coarse and fine layers, the volumetric percentages of oil and gas in these layers will differ when equilibrium exists. The exact relationship can only be determined by obtaining the complete capillary pressure-desaturation curves for each of the porous materials in contact. It has been pointed out elsewhere' that the capillary pressure-desaturation curves of sedimentary porous materials can often be approximated by the relation where C is a constant and Soe is the effective saturation to oil based on a percentage of the pore volume effective to flow. In the same paper it was indicated that, as a first approximation, the values of oil relative permeability are given by and the values of gas relative permeability by For this analysis Eqs. 2, 3, and 4 were assumed to apply to each of two components of a hypothetical porous rock in capillary equilibrium. It was also assumed that each of the components had a residual wetting phase saturation of 20 per cent so that 80 per cent of the total pore volume was effective to flow. The permeability of the coarse stratum was taken as 100, and its displacement pressure was such that C in Eq. 2 had the numerical value of 1. The corresponding values for the fine stratum were 10 for the permeability and 10 for C. Units are not specified because they do not enter into the final results. The choice of the permeabilities and displacement pressure ratios was made to expedite the calculations. Any reasonable rock properties could have been chosen without changing the results qualitatively. Several arrangements of the two components were studied. Table 1 summarizes the resultant permeabilities obtained for four types of arrangement. RELATIVE PERMEABILITY CALCULATIONS The first step in the computation of relative permeability for the composite cores was the plotting of the capillary pressure-desaturation curves and the relative permeability curves for the individual components according to Eqs. 2, 3, and 4. At arbitrary

Jan 1, 1957

By R. M. Genevray, M. B. Bever, E. J. Suoninen

THE martensitic transformation in the ß-phase of the Cu-Zn system has been the subject of several investigations. The transformation is known to be reversible and to be affected by stress. Its temperature range has been determined as a function of composition. In the investigation reported here, the effect of tensile stresses on the transformation was investigated quantitatively. Some information was also obtained on the thermoelastic behavior of the martensite formed in the first stages of the transformation. Most of the experiments were done with alloy E of an earlier investigation;' this alloy analyzed 60.49 pct Cu and 39.51 pet Zn by weight. The methods of shaping and heat treatment were also essentially the same as those previously used. The stress was applied to the specimen immersed in a cooling liquid. The transformation was followed by measuring the electrical resistance with a Kelvin bridge and the elongation with a cathetometer. Fig. 1 shows the M, temperature as a function of stress. Resistance and strain measurements gave essentially identical values. The results suggest a roughly linear relation between M. and in the range investigated, up to 12 kg s mm". At higher stresses, plastic deformation begins to interfere seriously with this relationship. The increase of M, with stress is consistent with published work on the effect of stress on the martensitic transformation. The slope of the curve, 4°C per kg mm ", is of the same order of magnitude as the corresponding value calculated for steel.' Fig. 1 also shows the difference, AM, between the temperature of 50 pct transformation on cooling, as measured by changes in length, and that of 50 pct reverse transformation on heating. This difference, which may be considered a measure of the hysteresis, increases with stress; the decrease at highest stresses is probably associated with plastic deformation. Preliminary work using only resistance measurements was done with an alloy containing 60.15 pct Cu and 39.79 pct Zn by weight. The results indicated higher values o-F M, in agreement with the known variation of M. with composition.' The effect of stress on M, (2°C per kg mm-') was of the same order of magnitude as that shown in Fig. 1 for composition E. An increase in hysteresis with stress was also found. The following experiment was made in order to investigate a partially transformed structure. A specimen of alloy E was cooled to — 85°C under a stress of 4.7 kg mm-'. Under these conditions, the martensitic transformation started but did not go to completion. The stress was then released and the specimen cooled to — 105°C. Fig. 2 shows the measured elongation c. The first change in the slope of the curve indicates the beginning of the transformation under stress. Removing the load at —85°C caused a decrease in length to the value corresponding to the elastic elongation of the parent phase resulting from the applied stress. Hence, the marten-site formed in the first part of the experiment apparently disappears completely and without hysteresis upon the release of the stress. The increase in length on further cooling indicates renewed formation of martensite. These conclusions are consistent with the concept of "thermoelastic" martensite," which has been confirmed by test." Acknowledgments The authors are greatly indebted to Professor M. Cohen for his advice and encouragement. They also thank F. Paxton for assistance. Thanks are due the American Brass Co. which supplied the alloys. References E. Kaminsky and G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1936) 6, p. 984. A. B. Greninger and V. G. Mooradian: Trans. AIME (1938) 128, p. 337. "J. E. Reynolds, Jr. and M. B. Bever: Trans. AIME (1952) 194, p. 1065; Journal of Metals (October 1952). 'A. L. Titchener and M. B. Bever: Trai~s. AIME (1954) 200, p. 303; Journal of Metals (February 1954). " 3. A. Kulin, M. Cohen, and B. L. Averbach: Trans. AIME (1952) 194. p. 661; Journal of Metals (June 1952). "J. K. Pate1 and M. Cohen: Acta Metallurgica (1953) 1, p. 531. 'C. Crussard: Comptes Rendus (1953) 237, p. 1709. ' G. V. Kurdjumov: Zhur. Tekhn. Fiziki SSSR (1948) 18, p. 999. G. V. Kurdjumov and L. G. Khandros: Dokl Akad. Nouk. SSSR (1949) 66. p. 211.

Jan 1, 1957

By L. Mair

A STUDY by J. R. Low, Jr.1 on the effect of quench aging on the Charpy-impact specimens of semikilled 1020 steel disclosed that a decrease in cooling rate from 1275°F raised the transition temperature. This was demonstrated in his investigation by controlling the cooling rate of impact specimens to duplicate that of a heavier plate and com- paring the properties with air-cooled specimens and quenched specimens. The transition temperature of the samples that had been cooled at a rate estimated to be similar to that of an air-cooled 3/4 in. plate was approximately 45ºF higher than the quenched samples. The transition temperature of the air-cooled series was between that of the slow-cooled and the quenched series. On the basis of this work, it appeared that the cooling rate of plates after rolling in a hot mill would have a bearing on the brittle fracture of the

Jan 1, 1955

By P. Stark, B. S. Lement

ACCORDING to Hanemann1 the hardness of retained austenite in a 1.7 pct C steel is increased by subsequent tempering. He reported that the hardness of this constituent increases only slightly on tempering to 300°F, rises more rapidly above this temperature, and attains the same value as the tempered martensite present in steel at approximately 480°F. The variation of hardness of both retained austenite and martensite with tempering temperature as obtained by Hanemann1 is shown in Fig. 1. Hanemann attributes the increase in hardness of the retained austenite essentially to continued formation of fine needles of martensite on tempering. Although he did not explain the actual mechanism involved, work hardening of retained austenite by the plastic deformation associated with such martensite formation appeared to be a possibility. Recently Lement, Averbach, and Cohen2 reported the existence of subgrains, about l000Å in diameter, in retained austenite and suggested that they may be delineated by a subboundary carbide. This raised the possibility that carbide precipitation might be responsible for the hardening reported by Hanemann. In view of these conflicting possibilities, an investigation" was carried out on a high purity, Fe-C alloy containing 1.7 pct C in order to clarify the nature of the phenomenon involved in the reported hardening of retained austenite. This investigation involved correlation of changes in microhardness and microstructure of the austenite as a result of tempering. Microhardness tests were made with a Tukon tester using a 25 gram load and a Vickers diamond. It was found that two groups of austenite hardness values were obtained after tempering at a series of temperatures up to 450°F, which was the highest temperature at which retained austenite regions could be identified microscopically. One group represents a high hardness level which in-

Jan 1, 1955

By Paul B. Crawford, Bobby L. Landrum

Electrical model studies have been made of the effect of unsymmetrical vertical fractures on production cnpacity. The study war restricted to the case of two vertical fractures originating at the well and extending out into the reservoir for various distances and orientations. The ratio of the short fracture length to the long fracture length was varied from 0.1 to 1.0 in successive studies. The angle separating the two fractures was varied from 0 to 180 degrees. The most effective fractured patterns were obtained when the fractures were oriented 180 degrees. It was found that when the total fracture length was equal to 0.2 of the drainage radius, the increase in production capacity may vary from approximately 1.55 to 1.95. depending upon the ratio of the short fracture length to the long fracture length and the angle separating the two fractures. If the total fracture length were 0.5 of the drainape- radius. poroduction cavacitv., increases varving 1.95 to 2.65 were observed, depending on the angle between the fractures and the ratio of the .short fracture length to the long fracture length. The fractured well production capacity decreased aPproxin?ately I to 10 per cent as the angle separating the fractures was varied from 180 to 90 degrees. It was dependent on the particular fracture. The commercial application of reservoir fracturing techniques has caused an interest to be expressed in the effect of vertical and horizontal fractures on production capacities. Some data have indicated that substantially vertical fractures may be created in some reservoirs. It is believed that the fractures are possibly unsymmetrical, that is, one fracture may extend due north 100 ft and a second fracture on the opposite side of the well may extend south or southeast only 50 ft. The total fracture length, ratios of the lengths and angles of separation may vary considerably. For this reason variations in these factors were considered. The study was restricted to the case of two vertical fractures originating at the well and extending out into the reservoir. It is not known that such will occur in a reservoir, but the results may be of value in interpreting or studying fracturing applications. PROCEDURE An electrical model was used in this study of the effect of unsymmetrical vertical fractures on production capacity, A wooden tank 30 in. in diameter and approximately 2 in deep was coated with paraffin wax. A copper band was situated at the periphery and a single wire electrode was positioned at the center of the tank. The ratio of the reservoir radius divided by the

Jan 1, 1956

By J. P. Hammond, C. J. Sparks, C. J. McHargue

IN a study of the effects of solid solution alloying on the deformation texture of titanium, an alloy containing 3.8 pct A1 was found to develop a (0001) [1010] texture instead of the texture characteristic of pure titanium.ls2 A short investigation has been made of the change in texture with aluminum content. Alloys containing 0.27, 0.47, 1.05, and 1.43 pct A1 were prepared by vacuum arc melting, using iodide titanium as the base material. Homogenized ingots were reduced 90 pct in thickness by cold rolling. Pole figures were obtained using the usual film techniques. Fig. 1 shows that the change from the tilted to the nontilted (0001) position is gradual. The dashed contour lines in Fig. 1 indicate the extent to which data was collected. The addition of 0.27 pct A1 resulted in a decrease in the transverse spread of basal poles. With increasing aluminum content, the amount of the tilt becomes less and the region of highest intensity takes the shape of a ring about the center of the pole figure. For aluminum contents greater than 1 pct, the (0001) [1010] texture is definitely present—the sharpness increasing as the amount of solute is increased.* It is interesting to note that Williams and Eppel-sheimer9 eported for commercial grade titanium a high intensity region 20" toward the rolling direction from the rolling plane normal in addition to. one 30" toward the transverse direction. Their basal pole figure was similar to Fig. 1, row inree. The observation that the texture changes gradually with solute concentration is similar to the results of similar studies on copper." At the present time these effects are not clearly understood. Acknowledgments This work was sponsored by the Aeronautical Research Laboratory (WCRRL), Wright Air Development Center, under Contract NO. AF' 33(038)-19574. The authors are grateful for the aid received and permission to publish these results.

Jan 1, 1958

By D. P. Koistinen, K. E. Beu

THE application of the integrated intensity X-ray diffraction method to the measurement of retained austenite concentrations in hardened steels has been fully described.'-' In developing this particular method, the assumption was made that the samples used would have flat surfaces which were free from voids and in which austenite was homogeneously distributed. The original calculation procedure' was modified to include the constant factor G which relates the intensity of a given diffraction line to the concentration of the component giving rise to that line. In order to include A (0) in the constant factor G, it was further assumed that the geometrical conditions relating the X-ray beam, camera cylinder, and sample surface were precisely met.V has been demonstrated that these geometrical conditions can be met experimentally without difficulty in many cases;' however, for those samples which have irregular surfaces or where it is impossible to locate the sample in the proper position with respect to the X-ray beam and film cylinder, it is desirable to evaluate experimentally what effect these nonideal conditions have on the reliability of the austenite determination. This note decribes the results of such experiments. SAE 1095 bar stock was used throughout and all samples were heat-treated as follows: 1600°F for 1 hr in a neutral atmosphere, brine quench, and 300°F temper for 30 min. To control heat-treatment conditions as closely as possible, all samples were plated with 0.002 in. copper to protect the immediate surface from the heat-treating atmosphere. After heat treating, the samples were deplated electroly-tically so that only the copper was removed. The heat-treated surfaces thus obtained were nearly as bright and polished as the original surfaces before copper plating although no mechanical work was done on the samples after heat treating.

Jan 1, 1954

By P. W. Neurath, R. E. Waite

INFORMATION is available on the effect of stress on permeability, coercive force, and hysteresis for a variety of materials' but for the technically important grain-oriented 3 pct Si-Fe' the stress effects are not adequately covered in the literature; in addition, most of the stress data do not permit estimation of what would happen to the 60 cycle watt losses of the material under stress. Direct measurement of these effects therefore has been made and appears to be of considerable theoretical as well as practical interest. Losses were measured on the central 25 cm portion of 40~3~0.035 cm samples which could be stressed in a small tensile machine built for this purpose. Under tension the following effects, illustrated in the figures by a particular example, were observed: 1—"Unstrained" material of commercially acceptable loss level shows no change or a small increase in loss at low elastic stresses. For the sample shown in the figures, this is illustrated during the initial run, where a 7 pct increase is observed (Fig. 1). 2—There is no additional change in loss when the sample is further strained up to the elastic limit (Fig. 1). Within that limit the loss-stress curve is reversible. This is not illustrated in Fig. 1. 3—Even in the plastic range only small increases in loss are observed as long as the sample is kept under stress (Fig. 2, point N); often no increase can be observed (Fig. 1). 4—A large increase in watt losses is observed after removal of the stress subsequent to plastic deformation (Figs. 1 and 2). 5—All, or nearly all, of the foregoing increase in loss due to plastic deformation can be eliminated by a reapplication of tensile stress but returns upon removal of this stress. This is illustrated in the third run (Fig. 3). This run remains within the elastic limit and shows the reversibility of the stress-loss curve under this condition. These findings have been confirmed on large Samples (approximately 200~10~0.035 cm and larger) except that under 1 no initial increase in loss was ever observed on these. The accuracy of the watt loss measurements is of the order of 1 pct. Neither bending of the sample in the tensioning device nor a redistribution of flux along the width of the sample accounts for these results. They therefore must be explained on the basis of either a change in the domain configuration due to stress or a change in the domain wall mobility. Acknowledgment The assistance of Mr. Robert L. TenBroeck with the instrumentation is gratefully acknowledged.

Jan 1, 1956

By W. R. Hibbard

IN ref. 1, on the basis of tension and torsion experiments with single crystals of a brass, the values given in Table I were obtained for elastic coefficients. It was pointed out by Zener that the values for the 71.2 pct Cu were not satisfactory, since they resulted in a negative value for the bulk modulus, namely —4.17X1012 sq cm per dyne. In reevaluating the data of this investigation, it was determined that the reason for this negative bulk modulus lay in the extrapolation of the reciprocal Young's modulus to the zero value of the orientation function shown in Fig. 5 of ref. 1. This extrapolation was reevaluated by the method of least squares (50 pct probability) and a new value of the coefficient S,, was determined as 18.9220.42X 10M sq cm per dyne in lieu of the value originally reported of 18.82x10 sq cm per dyne. This new value of S, leads to a new value of S, of — 9.43 X101" sq cm per dyne. The values of the other coefficients are unchanged. results. This value compares with the value of 12.3X10 sq cm per dyne reported by Schmid and Boas? The new results are summarized in Table 11. These results follow similar qualitative trends, previously published,' relative to the effect of zinc content. However, the derived values of C11, C,, C,, and K are so sensitive to the uncertainty in the first decimal place of the S, values that they are probably not useful. This uncertainty must also apply to the previous results of Masima and Sachs," who obtained S, values from a similar extrapolation drawn wholly above their data points. Acknowledgments Advice and assistance on the statistical methods were obtained from R. W. Guard. The calculations were carried out by Miss E. Saacke.

Jan 1, 1958

By Wm. C. Phelps, R. E. Grace

b R.c c)nduciivity of slags and glasses is of particular interest when viewed as an activated ionic flow process. The ionic conductivity, for example, has been found to obey the Easch-

Jan 1, 1958

By E. A. Kaarsberg

The electron photomicrographs shown in this paper are of samples of the A.P.I. Reference Clay Minerals Montmorillonite No. 27 and Kaolinite No. 4 and of a shale from Spraberry Oilfield in Texas. These samples are part of a larger collection whose physical properties, composition and internal structure were previously studied by ultra-sonic and X-ray methods. ' Elastic anistropy was indicated in the montmorillonite and shale samples by sound velocity measurements parallel and perpendicular to the bedding. In the montmorillonite the velocities parallel and perpendicular to the bedding were 2.12 and 1.92 km/sec respectively, a difference of about 11%; in the shale the same velocity measurements were 4.18 and 3.75 km/sec, a difference again of about 11%. Within the bedding plane the sound velocity was also found to be independent of direction. The electron photomicrographs of the montmorillonite sample, which are shown in Fig. l(a) and (b), clearly indicate the preferred orientation of the mica-like clay particles parallel to the bedding. In Fig. 2(a) and (b) similar orientation in the shale sample can be seen although not quite as clearly. This is probably because, in addition to the clays illite and chlorite, the shale sample contains grains of quartz, calcite and dolomite which do not as readily show an alignment pattern as the clays do. This suggests that the elastic anisotropy of these two samples is derived from a preferred alignment of component mineral grains which are themselves elastically anisotropic. The bulk elastic properties of these two samples therefore appear to be much like those of mica. Velocity measurements were made on the kaolinite sample in three directions at right angles because no bedding could be discerned in it. The values ob-

Jan 1, 1967

By H. R. Skewes

IN the course of small seale experiments on the electrodeposition, of copper, extremely brittle deposits were obtained from electrolytes prepared by leaching calcined chalcopyrite with aqueous sulfuric acid. It was not possible to strip the metal without fracture after it had been deposited from such electrolytes onto smooth oiled copper sheets, the usual plant procedure for the production of so-called starting sheets. The embrittlement did not occur with electrolytes made either by leaching the calcine with water or by treating an acid leachate to remove iron as hydrous ferric oxide. The electrolytes which produced brittle deposits were found to contain molybdenum in concentrations of 10 to 25 mg per 1, whereas those which produced ductile deposits contained <0.5 mg per 1. Synthetic electrolytes having the composition: Cu", 40 gpl; Fe", 0.5 to 1.0 gpl; Fe3+, 0.5 to 1.0 gpl; and H,SO,, 10 to 50 gpl, were prepared from reagent-grade salts; by adding ammonium molybdate, the embrittling effect of the higher concentrations of molybdenum (VI) was strikingly confirmed. The brittle deposits contained up to 0.03 pct Mo. The importance of oxidation state of the molybdenum was demonstrated when the electrolyte containing it was circulated continuously through a bed of fine copper metal during deposi- tion. Under these reducing conditions, the cathode deposit was ductile and molybdenum could not be detected. Molybdenum has not been recognized as one of the metals causing embrittlement of copper nor is it listed among the usual impurities. In most elec-trowinning plants there is a purification step which removes iron from the leachate before electrolysis. In these cases molybdenum would be coprecipitated with hydrous ferric oxide. In the case of the large leaching plant at Chuquicamata, Chile, where the leachate is reported to contain considerable molybdenum, it would be reduced to a lower oxidation state during removal of chlorine by means of cement copper. This may explain why the embrittling effect of molybdenum has not been reported previously. Moreover, in copper refining plants where soluble anodes have been prepared by a high temperature smelting process, it is most unlikely that any molybdenum would remain with the copper, whereas the calcines in this work were prepared in a fluidized bed reactor at a temperature not exceeding 720°C. Acknowledgment This work is part of an investigation on the roasting and extraction of copper from sulfide ores sponsored jointly by Mt. Morgan Ltd., Queensland, and the Mt. Lyell Mining and Railway Co. Ltd., Tasmania.

Jan 1, 1958