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By C. van der Poel

When oil is displaced from a horizontal formation by another fluid of lower density, the latter tends to override the former in the shape of a tongue owing to gravity segregation. This gravity tongue has an adverse influence on the oil recovery. If the fluids are miscible, diffusion (mixing) takes place at the interfacial boundary of the gravity tongue. This mixing should have a favorable effect on oil recovery. The report describes a laboratory study of the magnitude of the mixing zone under various conditions, so as to assess the effect of diffusion on oil recovery both in laboratory experiments and under actual field conditions. The technique used enables visual observation and measurement of the size of the mixing zone in transparent glass-powder packs. The results show that in experiments in small models and cores the width of the mixing zone may well be of the same order of magnitude as the height of the model. In such cases oil recovery is favorably affected by mixing. It can further be concluded that, under conditions prevailing in the field, mixing of the injected fluid with reservoir oil is equal to that caused by molecular diffusion alone, eddy-mixing not taking place to any appreciable extent. A simple calculation, then, shows that molecular diffusion is too small for a beneficial effect to be expected from the injection of miscible fluids in horizontal or nearly horizontal reservoirs unless pay zones are thin. INTRODUCTION This paper gives results of experiments made on the mixing which occurs when a miscible displacement is carried out in a horizontal reservoir. This mixing takes place at the interfacial boundary of the gravity tongue formed when the lighter injected fluid overrides the oil present in the reservoir. The object of the experiments was to simulate the field case where, for example, propane with a viscosity of 0.075 cp under reservoir conditions displaces an oil of viscosity 0.6 cp. In the experiments the lighter fluid had a viscosity of about 1 cp and the heavier one a viscosity of about 8 cp, so as to obtain the same viscosity ratio. In order to enable the results to be compared with those published in the literature, a set of experiments with viscosity ratio equal to one was also performed. EXPERIMENTAL TECHNIQUE The technique developed for the purpose enables the width of the mixing zone to be studied as a function of time and place. A glass-powder pack is saturated with a water-glycerine mixture of suitable viscosity, which represents the reservoir fluid. The pack is then rendered transparent by dissolving sufficient ammonium thiocyanate in the mixture to obtain a solution with a refractive index matching that of the glass powder. Alkaline water to which phenol-phthalein has been added is used as the lighter and less-viscous displacing fluid. In those places where mixing or diffusion of the two liquids occurs, the slightly acidic ammonium-thiocyanate solution neutralizes the alkali in the water, and the glass pack shows up white against the red-colored invading water. If a black cloth is hung over the back of the apparatus, the transparent part of the glass pack appears black. In this way the position of the two phases and the transition zone between them is clearly visible, as shown in Fig. 1 (where the red-colored invading water is the grey-shaded zone lying uppermost). In all experiments the amount of alkali in the water was chosen such that the upper contour corresponded to a concentration of 5 per cent of the dense liquid. The lower contour is determined by the size of the glass grains and the thickness of the pack and, consequently, varies from experiment to experiment. Corresponding concentrations of the dense liquid range from about 97 per cent for packs of small grain size (permeability = 1 darcy) to about 95 per cent for those with large grains

By Edwin F. Brush, John Chipman

Published data on the activity of carbon in binary and ternary austenite at 1000°C are reviewed. The composition variables are . The coefficient, Vj, has the value for substitutional elements but may be assigned a ualue -1 for silicon to effect a simplification on the mathematical treatment. The activity coefficient PC = is obtained from gas equilibrium data. For the ternary systems studied the Henrian activity coefficient is given by the expression: The principle advantage in cornparison with the analogous expression in terms of atom fractions is found in the fact that for most systems the final term and in many the last two terms are zero. Values of the interaction parameters are tabulated and the graphical comparison of the equation with experirt~ental data is sho,wn in several figures. The thermodynamic properties of the solid solution, austenite, are of considerable importance in the heat-treatment of alloy steels and in other aspects of ferrous metallurgy. Early studies embodied in the Fe-C diagram have been extended to include other binary and some ternary diagrams. Our best hope of obtaining a useful thermodynamic treatment of reactions in complex alloy steels will not be found in quaternary and quinternary phase diagrams but in determinations of activities and interaction relations among the several solute elements. The foundation for such a development was laid by smith' in his early studies of the activity of carbon in Fe-C alloys and his subsequent work on Fe-C-Si, Fe-C-Mn, Fe-C-Ni, and Fe-C-Co solid solutions.2"4 Other observers have also made noteworthy contributions and these will be discussed and correlated here in the light of a somewhat simplified mathematical treatment of solute interactions. Fe-C AT 1000°C In a recent review of the thermodynamic properties of binary Fe-C austenite it was shown that the simple mathematical treatment employed by smith' was capable of describing all the published results on this solution. The treatment utilizes the atom ratio, yc = nC/nF,, rather than the atom fraction. The activity of carbon is proportional to the equilibrium gas ratio, either measured on a scalk in which the activity of graphite is taken as unity or, alternatively, aC may be set equal to yc at infinite dilution. In either case the ratio aC/y = (PC, the activity coefficient. It was found that the experimental data of smith1 and those of Diin-wald and wagner; Bungardt, Preisendanz, and Lehn-ert,' and Scheil, Schmidt, and Wiinnings at temperatures of 800" to 1200° C as well as reliable data on the solubilities of graphite and cementite could be represented by the equation for which graphite is the standard state: The data on alloyed austenite have been obtained at 1000°C. For this temperature, the "Henrian" activity coefficient (which is unity at infinite dilution) is: FOr an interstitial solute such as carbon in austenite it has been shown by statistical mechanicsg that the activity in the infinitely dilute solution is proportional to the ratio of the number of lattice sites occupied by carbon to the number of yet unfilled lattice sites. A variable zz proportional to this ratio serves as a useful measure of concentration:" in which b is the number of lattice sites provided by each atom of solvent; in austenite b = 1. The Henrian activity approaches zz at infinite dilution and the ratio a is the activity coefficient. The effect of a change in concentration is then given by: It has been shown further that in some systems the derivative in Eq. [4] remains constant over a wide range of concentrations. In such a case second-order terms become negligible and the Henrian activity coefficients is:

Jan 1, 1969

By S. Weinig, E. S. Machlin

IN a previous study of the grain boundary stress relaxation phenomenon,' the authors had arrived at the conclusion that two successive steps were involved in the complete relaxation of stress at a grain boundary. These two steps were grain boundary migration and grain boundary slip. It was further suggested that the slower of these two processes is rate controlling. In an attempt to ascertain the validity of the above, a study of grain growth kinetics on the same alloys used for the previous study was undertaken. Separate wire specimens, 0.030 in. diam, in the same as-deformed state (99 pct reduction in area) as in the previous investigation were heated to the various temperatures for a sequence of times. The compositions used and the temperatures of testing are summarized in Table I. A statistical determination of grain size was then made on each specimen, using the average length of traverse between boundaries as a measure of the grain size. Examples of typical results obtained are shown in Figs. '1 and 2. The grain growth law D = ktn was found to fit most of the data. Using this relation, values of the grain growth exponent n were calculated and the inter -esting dependence of n on solute content shown in Figs. 3 and 4 was then obtained. Also, it was found that the constant K which was obtained from extrapolation is roughly independent of solute content. (K is uncertain to within ±25 pct.) An estimate of the activation energy for grain growth was made using the technique of Burke? This method utilizes the plot of the reciprocal of time necessary for the grain size to increase from a definite starting size Do, to a final size D, for each isothermal heat treatment. The slope of this curve corresponds to the heat of activation for the process. In Fig. 5 the rate of grain growth is plotted against the reciprocal of absolute temperature. The activation energies were obtained from these curves and are summarized in Fig. 6. Discussion It is interesting to note that the same saturation in the variability with concentration has been found for the grain growth exponent n in this research as was found in the previous researches on both grain boundary stress relaxationa and internal friction of dislocation origin." The significant feature is that saturation in the variation of these properties has been found to occur at about the same level of solute concentration, namely, between 0.1 and 0.5 atomic pct. The only characteristic common to these different quantities is that solute adsorption at grain boundaries and dislocation can take place and affect these values in a similar fashion. Thus, it is concluded that the grain growth exponent n depends upon solute adsorption at the grain boundaries. It appears, therefore, that theoretical considerations leading to the contrary conclusions5,6 have not treated the real process by which solute atoms exert their effect on grain growth. Prior to the analysis of the observed activation energies, certain of the aspects of the aforementioned grain boundary stress relaxation investigation will be briefly reviewed. It was found that with the addition of solute atoms the grain boundary stress relaxation peak (internal friction vs temperature) decreased in intensity. Simultaneously a second peak was observed which increased with increasing solute atoms. Both of these peaks were shown to be the result of grain boundary stress relaxation. They have been termed, respectively, poire peak and solute peak. It was suggested that the solute peak was dependent upon grain boundary migration, whereas the pure peak was a manifestation of grain boundry slip. Activation energies for both peaks were obtained as a function of Solute content. The value of the activation energy in the temperature range corresponding to the solute peak was

Jan 1, 1958

By H. Bernstein

Grain coarsening tests were carried out on AI-4.5 pct Cu and AI-4.5 pct Si alloys. The effects of three variables, melt composition, pour temperature, and mold temperature, were determined. It was found that the macrostructure generally coarsened with increased pour and mold temperatures. Coarsening was extreme in the unrefined alloys but was retarded by the active grain refiners like titanium and columbium. The effect of boron was spectacular in suppressing coarsening tendencies. The results of the investigation support the carbide theory of nucleation as opposed to the peritectic theory. A REVIEW of prior work on the subject of grain refinement in the light metals indicated that, for the most part, it had been concerned with the positive effects of addition agents upon structure. This work produced various theories of refinement. Prominent among them were the peritectic theory and the transition element carbide theory. Certain inadequacies in the former theory appeared to be explained satisfactorily by the transition element carbide theory. In order to appraise these theories further, a study was undertaken of the permanence of grain refinement effects when subjected to thermal or chemical variations. It was considered that a study of this kind would be of practical value, since the light metals are exposed to thermal and chemical variations in the normal course of foundry operations. Accordingly, two alloys of commercial importance were selected for this investigation, the A1-Cu and A1-Si alloys. Experimental Procedure and Results Raw Materials: The base alloys, A1-Cu and A1-Si, were prepared from virgin aluminum and hardeners, induction melted, and pigged for remelting. The grain refiners, including titanium, columbium, zirconium, and boron, were added as master alloys. Analyses of the raw materials and base alloys are listed in Table I. Melting and Casting Practice: The metals were melted in clay-graphite crucibles in a Hevi-Duty pit-type resistance furnace, equipped with a Leeds and Northrup Micromax Recorder and Controller. After melt down of the base alloys, the additions were made. For each casting, approximately 80 grams of metal were poured into a preheated graphite mold held in a transite flask. The mold (Fig. 1) weighed 320 grams. To determine the effect of superheat upon structure, a set of melts was heated successively to four temperature levels, 705°, 775°, 845°, and 915°C, and test specimens were cast at each level. Prior to each pour, the furnace temperature was held constant for 20 min. Next, a set of melts was put through a superheat cycle and test specimens were cast at melt temperatures of 705" and 915°C successively. The crucibles then were cooled in air to 705°C as deter-mined by immersion thermocouple and additional test specimens were poured. The cooling interval was approximately 1 min. Another set of melts was furnace cooled with the cover slightly ajar and test specimens cast as before. The interval in this case was 15 to 20 min, varying with the superheat temperature. The mold temperature for all these tests was 400°C. To determine the effect of cooling rate without superheat upon structure, a set of melts was heated to 705°C, and castings were poured at mold temperatures of 205", 400°, and 540°C. An interval of 15 min elapsed between each pour. Mold temperatures were measured by a direct reading millivolt-meter, using a chromel-alumel thermocouple located at midwall thickness of the mold. To demonstrate the phenomenon of chemical coarsening, agents such as chromium and beryllium, which had acted as coarseners in a previous investigation,' were added to the A1-Cu alloy. Test speci-

Jan 1, 1955

By H. M. Myers, J. E. Funk

The two-phase flow of a drilling fluid in a diamond drill bit is investigated by deriving and solving the steady-state continuity and momentum equations. Parameters in this analysis are rotational speed of the bit, local rate of addition of drill solids, non-Newtonian nature of the drilling fluid and drilling rate. The describing equations relate the flow and pressure drop to the design characteristics of the bit. The equations are integrated numerically yielding the flow-rate pressure drop characteristics for the bit, flow distribution in the bit and velocity and static pressure as a function of position in each flow channel of the bit. Results are presented for a particular bit design. This paper shows that under normal drilling conditions certain parameters may be neglected in the hydraulic calculations for a diamond drill bit. Therefore, shortened forms of the equations presented can be used to fit the proper diamond bit to the drilling fluid hydraulic system. INTRODUCTION Like the conventional bit, the diamond drill bit is a key component in the circulating system of a well. The conventional rock bit is fitted to the circulating system by selecting the flow nozzles which provide the system with the proper flow-rate pressure drop relationship. Fluid behavior across the face of the diamond bit must be better understood so the bit can also be fitted to the circulating system. Data from field-operated diamond bits are presently available and do yield some information regarding the flow-rate pressure drop relationship. However, the number of factors affecting this relationship is quite large. Drilling parameters and conditions such as bit penetration rate, bit weight and rotational speed are important. Moreover, flow channels in the bit are part of the cutting head, and introducing drilled solids into the flow channels reduces the flow area, causes additional drag and influences the pressure drop. Many tests would have to be performed if field tests were required to study all parameters which might influence fluid behavior in the bit. A logical approach to this problem is to investigate analytically the fluid behavior in the bit, including parameters that are present under normal drilling operations. This approach, which seems to offer the best method for future studies, is presented in this paper. Following is the general procedure. 1. Equations describing the most general flow channel are written and include the addition of drilling solids (which is related to penetration rate), rotation of the bit, design parameters of the bit and non-Newtonian properties of the fluid. 2. A typical bit is designed and the bit parameters are substituted into the equations. 3. Parameters are assumed (penetration rate, rotational speed of the bit, mud weight, etc.). 4. The describing equations are numerically integrated to obtain the pressure drop across the face of the bit as a function of flow rate. 5. The pressure-drop contribution of each component (friction, acceleration, etc.) is obtained from the numerical solution, and those factors which largely influence the total pressure drop are identified. Classifying the drilling fluid is important in establishing the friction factor relationship since the frictional pressure losses are the main contributors to the total pressure drop. High-density drilling fluid is commonly assumed to be a Bingham plastic. 1-3 Govier4 presented a method for selecting a friction factor in the laminar flow region from the rheology properties of the mud and a modified Reynolds number. Metzner5 presented a criterion for selecting the friction factor in the turbulent flow region. The bit design used in conjunction with the solution of the equations has divergent flow channels. Stall, which is the backflow of fluid in the channels due to eddies that occur on the outer perimeter of the flow stream, can occur in these divergent channels (or diffusers). When stall does occur the static

By J. P. Hammond, C. J. McHargue, S. E. Adair

Cold-rolled sheet textures have been determined for binary solid solutions of aluminum, columbium, tantalum, and zirconium in titanium. An alloy containing 3.8 pct Al had a (0002) [10101 texture, whereas alloys with the other elements had rotated (0002) [10101 textures similar to that of iodide titanium. THERE have been relatively few studies of the effect of alloying on deformation textures. A second element may be present in the base metal in solid solution and/or as a second phase. The literature offers no satisfactory explanation for the effects of solid solution alloying on textures noted thus far. For example, there is no satisfactory explanation of the difference in the textures of copper and a brass. The most complete study of the effects of solid solution alloying on deformation textures has been that of Brick, Martin, and Angier.¹ These investigators reported that the copper texture was retained by alloys of copper with up to 30 pct Ni, less than 5 pct Zn, less than 2 pct A1 or Co up to the limit of solubility. Copper containing more than 5 pct Zn, more than 2 pct Al, or the maximum soluble concentration of tin, silicon, or manganese showed the deformation texture of a brass. Bakarian² reported that additions of 0.20 pct Ca to 99.98 pct Mg or 2.0 pct Mn plus 0.15 pct Ca to magnesium resulted in entirely different textures than for the pure magnesium. The texture obtained for high-purity magnesium sheet showed the basal plane to be concentrated parallel to the rolling plane. The texture obtained for the alloy containing 0.20 pct Ca had the basal planes concentrated in elliptical areas whose centers were tilted 15" from the center of the pole figure toward the rolling direction. This split basal orientation was even more pronounced in the alloy containing 2.0 pct Mn and 0.15 pct Ca. Fuller and Edmunds" studied the rolled sheet textures in a zinc alloy containing 1 pct Cu and 0.01 pct Mn. The basal pole figure of this alloy contained a region of strong concentration not found in the pole figure for pure zinc.' In the above cases, results were discussed in terms of possible changes in slip and/or twinning systems and critical shear stresses. However, there were no experimental data to relate these speculations with the observed textures. It has been suggested that the deformation textures of titanium, zirconium, and beryllium could be directly ascribed to their low c/a ratios. The complex deformation mechanisms of titanium" also have been suggested to be characteristic of hexagonal close-packed metals with low c/a ratios. The purpose of this investigation was to study the cold-rolled sheet textures in binary titanium-base a alloys in which the c/a ratios were greater than, less than, and about the same as the c/a for iodide titanium. The annealed textures of these alloys will be reported in a subsequent article. Materials and Methods The chemical analyses of the metals used in this investigation are given in Table I. The alloys were prepared as 15 g buttons on a water-cooled copper block in a vacuum arc-furnace. The furnace was evacuated to pressures of the order of 10.' mm Hg, flushed with 99.98 pct pure argon, and melting was carried out in 0.2 atm pressure argon. Each button was remelted until radiographs and chemical analyses indicated complete solution of the solute elements. All buttons were forged and homogenized 72 hr at 500°C. The buttons to be rolled were ground and etched to sizes and shapes suitable for the rolling

Jan 1, 1954

By J. Chipman, N. J. Grant, E. C. Roberts

An equilibrium study was made of the distribution of chromium and oxygen between liquid iron, containing less than 1 pct Cr, and simple slags of the CaO(MgO)-Si02-FeO-Cr& type in the temperature range 1526' to 1734OC. The effects of slag oxidation, temperature, and basicity were observed. IN spite of the fact that chromium is one of the most important alloying elements in steel, and exists in almost all steels as a significant residual element, little research has been done to determine its behavior in basic steelmaking processes. Considerably more work has been done under silica-saturated acid slag conditions. Korber and Oelsen,' Herasymenko,' and others have generally agreed that in acid steelmaking practice the chromium in the slag behaved as if it were present as the chrom-ous ion (CrO). Work by Hilty- ir, high chromium slags also indicated that chromium may exist as CrO. In basic slag systems no equilibrium data exist. Based on individual studies of basic open hearth and electric furnace practice, Bardenheuer," Rock-rohr,% nd HauckQ oncluded that: 1—chromium recovery increased with decreasing basicity, and 2— chromium recovery increased with increasing temperature, although the effect was small. In similar studies Yavioskii and Dzemyen' concluded that: 1— slag FeO is the most important variable, 2—the basicity of the slag has no effect on chromium recovery, and 3—slag viscosity is not high even when 20 pct Cr,O, is present. Lapitskii\ oncluded that chromium recovery improved as the basicity of the slag decreased and increased with increasing manganese in the metal. Regarding the effectiveness of CrZ08 as a base or acid in basic slags, both Kristofferseno and Trojer" reported that Cr,08 was an acidic component requiring neutralization as 2CaO-Cr,O,. Experimental Procedure The experimental apparatus and procedure used for the present research were similar in most details to those used by Winkler and Chipman" and were described in detail by them. A magnesia crucible was used, holding 60 to 80 lb of Armco iron which was decarburized with hydrogen to about 0.010 pct C. Since all the metal samples solidified without gas evolution, this carbon level was assumed not to be significant. Synthetic slags made by mixing pure oxides were used throughout the study. Temperatures were measured by means of calibrated W-Mo thermocouples and were checked by Pt-Pt-Rh thermocouples. The range of temperatures covered in this study was from 1526" to 1734°C. The chromium content of the iron was in the range 0.032 to 0.82 pct, although the bulk of the tests showed 0.04 to 0.2 pct. The slags were of the CaO(MgO)-SiO,-FeO-Cr,O, type in which the Cr,O, content was from about 2 to 20 pct, although most of the slags showed from about 2 to 10 pct. The FeO range was from about 10 to 65 pct. CaO and SiO, were in the range of about 5 to 45 pct each, yielding a rather wide range of basicity values. The first 12 heats were made without a sulphur addition, and with only 30 min allowed for slag-metal equilibrium to be reached. In previous research it had been shown that less than 30 min was adequate to achieve equilibrium in slags free of Cr2O8.11,14.15 A study of the present data indicated that some of the tests may not have reached equilibrium in this time; accordingly four additional heats were made in which at least 1 hr was permitted for equilibrium to be reached. For reaching

Jan 1, 1955

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By P. de Vitry, Oliver Bowles

The conventional wire saw, introduced in the slate district of Pennsylvania by the Bureau of Mines in 1927, and used thereafter with remarkable success, consists of a three-strand steel cable having a diameter of 93/16 or 54 in. The equipment, methods used, and accomplishments have been described in previous reports.'-I Similar wire saws have been used extensively in Europe, in quarries and in shaping blocks and slabs. During the period 1932-1937, competition in European marble quarries was keen, prices were declining, and orders were not abundant. When orders were received, there was generally an urgent call for speedy delivery. Because of the diversification of demands, it was impossible to maintain in stock marbles of the color, size, and thickness called for, therefore the material generally had to be fabricated after the order was received. The wire saw enabled stone mills to fill such orders promptly. With skillful handling, 7/8-in. slabs could be cut accurately and rapidly with this equipment. It was found, however, that, as the three-strand wire became worn, the cutting speed dropped rapidly and the cut became less accurate. To overcome these difficulties the junior author of this paper, after much experimentation, developed a new type of wire consisting of a single ribbon-shaped strand, twisted as shown in Fig. I. To ensure straight sawing, the twist of the ribbon is reversed from right to left and vice versa every 25 ft. The reversal of the twist is shown in Fig. 2. This is not a new feature; it has been used to advantage with the three-strand wire both in Europe and America for several years. However, some difficulties arise in splicing the three-strand reverse-twist wire, and the claim is made that cutting is less accurate as the wire becomes worn. To make an endless belt, the ends of the single-strand wire are brazed together with Pyrophyllite is a hydrous aluminum silicate (A1²Si4O10(OH)²)1 that, occurs in both the foliated and the massive forms. The foliated variety resembles talc in that it has a greasy feel, a pearly luster, perfect basal cleavage, and usually is white, although in some deposits apple green, gray, brown, russet, and nearly black specimens may be found. The massive deposits of pyrophyllite yield pearl gray to light tan aggregates, some of which are so friable that they may be crushed with the hands into a fine gritty powder. Frequently specimens of the massive variety are studded with crystals of radial structure. The mineral has a specific gravity of about 2.7 and a hardness of 1 on Mohs' scale.' The chemical composition of commercial pyrophyllite reflects the mineralogy of the deposits, which, according to Stuckey12 contain pyrophyllite and quartz, together with chloritoid, sericite, and a few other minerals of negligible importance. The latter, he says, ('are noticed in but small quantities to the extent they might occur as accessory constituents of an igneous rock or as products of regional metamorphism or weathering. . . . Quartz is abundant everywhere except in the very best grades of pyrophyllite." Analyses of specimens from several deposits are listed in Table 1, showing that the silica content varies from 57 to 73 per cent and the alumina from 22 to 33 per cent. Oxides of iron and the alkaline metals are collectively present, with one exception, to an extent of about 1 to 1.5 per cent. Sources At present, North Carolina is the only commercial source of pyrophyllite, although the mineral has been found in small quantities in many parts of the world. The North Carolina deposits are in the "Carolina Slate Belt," which traverses the center of the state in a southwesterly direction. This belt varies from 8 to 50 miles in width. Two major deposits of pyrophyllite lie along its eastern boundary, in what is known as the Deep

Jan 1, 1942

By R. F. Domagala, M. Hansen, D. J. McPherson

On the basis of metallographic analysis, incipient melting data, thermal analysis work, and X-ray diffraction, phase relationships in the 0 to 50 atomic pct Cr region were carefully resolved. Phase relationships in the 50 to 100 atomic pct region were outlined. A single intermediate phase, ZrCr,, was established in the system. A eutectic and a eutectoid were found in the zirconium-rich region of the system, while a eutectic was located in the chromium-rich region. Limited solubility of chromium in both a and a zirconium was observed. THIS is another in a series of papers on zirconium-base binary phase diagrams based on a program sponsored by the Atomic Energy Commission. The Zr-Sn,' Zr-Si,' and Zr-Mo and Zr-W" systems have already been published. Previous work on the Zr-Cr system includes a partial diagram by Hayes, Roberson, and Davies' and a complete diagram by McQuillan." The phase relationships reported by these authors were determined with magnesium-reduced zirconium, whereas those reported herein are based on iodide metal. Some X-ray work on the intermediate phase in this system was also reported by Hayes et al., as well as by Wallbaum.' Comparisons with these data are made in the appropriate sections. Thermal analysis, metallographic and incipient melting techniques were employed to accurately resolve phase relationships in the 0 to 50 atomic pct Cr region, while the remainder of the diagram is outlined on a basis of cast structures and thermal analysis. A description and analyses of the metals used in the preparation of alloys for this study are included in Table I. A "low-hafnium" zirconium crystal bar (Westinghouse "Grade 3") was used. This material was produced by the decomposition of a volatile iodide onto a hot zirconium filament. The as-received crystal bar was coated with corrosion product from a standard autoclave test by which its grade designation is determined. A sand-blasting and subsequent HF-HNO, pickling treatment was employed to remove this contamination. The bars were cold-rolled to approximately 1/32-in. sheet, pickled again, sheared to 1/4-in. squares, washed with acetone, and stored for use. Ingot chromium metal from National Research Corp. and electrolytic chromium flakes from Johnson, Matthey and Co., Ltd., were available as alloy additions. The ingot chromium was received in granular form. The large granules were sized by crushing, treated for iron removal, rinsed with acetone, and stored. The flakes were broken to approximately 1/8 in. with mortar and pestle, cleaned with acetone, and stored for charging. Experimental Procedure A nonconsumable electrode arc furnace identical to that described by Hansen, Kessler, and McPher-son,' was used in this work. A 400 amp dc welding generator was the source of power. To insure homogeneity, ingots were melted in a water-cooled spun copper crucible, a total of four times without opening the furnace. No difficulties were encountered in the preparation of these binary alloys. Analyzed chromium contents were found to agree very well with the intended content. Melts of pure zirconium were interspersed in the course of preparing the alloys and their hardness was measured to keep a constant check on the melting technique. Vycor and quartz bulbs were used to contain the samples for isothermal annealing treatments. Vycor bulbs were employed for temperatures up to 110O°C, while quartz was used above this temperature. For treatments up to 950°C the bulbs were evacuated before sealing, but for higher temperatures a partial pressure of argon was admitted to the

Jan 1, 1954

By E. C. W. Perryman

The wide grooves formed at the grain boundaries when high purity aluminum is attacked by hydrochloric acid or sodium hydroxide have been attributed by earlier workers to the high energy of the grain boundary material. The effect has been investigated for high-purity AI-Fe alloys with up to 0.055 pct Fe as a function of iron content and heat treatment. It is shown that the explanation given above is untenable, but that the results can be explained on the assumption that iron segregates to the grain boundary in solid solution. IN 1934, Rohrmann¹ showed that aluminum of 99.95 pct purity suffered intercrystalline corrosion when immersed in 10 to 20 pct hydrochloric acid, and that the susceptibility to intercrystalline corrosion depended upon the heat treatment given. The greatest susceptibility was found for specimens quenched from a high temperature (600°C) and the lowest susceptibility for specimens cooled slowly from that temperature. Lacombe and Yannaquis2 have shown that super-pure aluminum (99.9986 pct) annealed at 600°C suffers intercrystalline attack in 10 pct hydrochloric acid and that this attack is intensified by anodic dissolution in the same solution at a current density of 10 milliamperes per sq dm. No difference in extent of intercrystalline attack was found between the 99.993 and 99.986 pct Al, which led the authors to suggest that impurities played only a secondary role in the mechanism of intercrystalline corrosion. It was found, however, that the attack at the grain boundaries depended upon the relative orientation of the grains, large differences in orientation favoring rapid attack. Boundaries where the two neighboring grains were similarly orientated showed high resistance to attack as did boundaries between grains which were in twin relationship. These observations led Lacombe and Yannaquis to suggest that the intercrystalline attack was due to lattice discontinuities present at grain boundaries. Assuming that the grain boundary is a layer three to five atoms thick and has a crystal structure which is a compromise between the two neighboring grains it is clear that the discontinuities will increase with increasing difference in orientation between the neighboring grains and hence the increasing tendency to intercrystalline attack. Roald and Streicher³ investigated the effect of heat treatment of aluminum alloys ranging in purity from 99.2 to 99.998 pct on the corrosion resistance in 20 pct hydrochloric acid and 0.30N sodium hydroxide. They found that in hydrochloric acid the intercrystalline attack appeared to be determined by the type and quantity of impurities present and by the relative orientation of the grains. No difference in the susceptibility to intercrystalline attack was observed between specimens quenched and those furnace cooled, from 575°C. In 0.30N sodium hydroxide some materials exhibited intercrystalline attack, this taking the form of V-notches. Rohrmann¹ offered no explanation for the greater susceptibility to corrosion of material quenched from 600°C. It seems possible that this difference is connected in some way with a different distribution of impurity elements in the quenched and slowly cooled specimens. The fact that Roald and Streicher8 observed no difference between quenched and slowly cooled specimens may possibly be due to differences in either rate of cooling or silicon content or possibly both. Both these would be expected to have an effect on the distribution of impurity elements. Although the rate of cooling used by Rohrmann was slightly more rapid than that used by Roald and Streicher the position cannot be clarified because Rohrmann does not give the silicon content and Roald and Streicher give the silicon contents of only a few of their alloys. That Lacombe and Yannaquis2 found no difference in corrosion behavior attributable to impurities between the two materials they used may be because both were of high purity compared with the aluminum used by Rohrmann.¹ Although they found no difference in the corrosion behavior of their two materials it is possible that the results obtained by Lacombe and Yannaquis may, nevertheless, have been influenced by impurity distribution, since, on the transition lattice theory of grain boundary structure, it would be expected that sparingly soluble impurities would tend to segregate to boundaries where the orientation difference is such that there is a greater density of atomic sites of suitable size to contain them. It was considered worth while, therefore, to examine the corrosion properties of a series of materials of differing impurity content with the objects of confirming the experimental observations made

Jan 1, 1954

By V. J. Berry, J. D. Pendergrass

Well pressure transient tests provide a means for directly obtaining information about formation pressure and reservoir flow capacity. Such tests have also been proposed for determining presence and location of faults or other reservoir closures and for measuring oil in place. For mathematical convenience, most theoretical studies have considered the reservoirs to be homogeneous. Definitive information is not yet available to show whether the actual presence of nonuniformities will make pressure transient behavior different from that of a uniform reservoir. The conclusions reached from actual transient tests are questionable, therefore, insofar as they rely on the original assumption of homogeneity. One type of nonuniformity commonly assumed to exist is that of stratification. In most reservoirs the strata are thought to be in vertical communication. Equations for the transient flow of a single-phase, compressible fluid in a one-well, bounded, circular reservoir have been solved for several situations involving crossflow between multiple strata of various thicknesses and permeabilities. The results show that except for the very early flow period, which usually is too short to be analyzed, the transient performance observed at the well is substantially identical with that of a homogeneous reservoir having the same dimensions and having the same steady-state flow capacity. Thus, stratification does not adversely affect interpretation of well transient tests. This conclusion holds for all commonly encountered combinations of reservoir thickness and external radius. Deviations are observed for unusually thick reservoirs whose outer radii are relatively small. The results of these studies also show that the presence and the amount of stratification cannot be simply diagnosed from reservoir pressure transient data when there is crossflow between strata. INTRODUCTION The last decade has brought wide acceptance of the transient well pressure test for determining reservoir parameters. Following the original work of Hurst and van Everdingen,1 the mathematical theory was thoroughly explored. Numerous authors have suggested how to determine static reservoir pressure, permeability-thickness product, original oil in place and reservoir limits for different reservoir geometry. The same mathematical techniques have been used to predict the transient performance of a reservoir over a long period of time. Most of the theoretical work has been for homogeneous, isotropic systems. Some results have also been presented for a homogeneous, anisotropic reservoir.2 Petroleum reservoirs are not homogeneous. The deposition process seems to favor creation of a stratified formation. This concept is sufficiently well accepted so that the most natural extension of the transient flow theory beyond the homogeneous case is to a stratified formation. Results for a stratified reservoir with no vertical communication between layers can be obtained from the results for a homogeneous reservoir. Lefkovitz, et a1,3 have given a thorough treatment of the two-layer case. Two recent papers4,5 have treated the case of a two-layered reservoir with vertical communication or crossflow, between layers. Russell and Prats4 find that, after a relatively short time, the two-layered reservoir with crossflow exhibits a simple exponential pressure decline. From this time forward, the behavior is not distinguishable from the behavior of a homogeneous reservoir having the same steady-state flow capacity. The results of Katz and Tek 5 are equivalent. Russell and Prats4 also speculate that a multi-layered reservoir with crossflow will behave as a homogeneous system after long enough production time "... providing the contrast in kh between layers is not too great". They also suggest that, at intermediate times, "... the relative positions of the layers with respect to each other will have a great influence on the production behavior and on the time at which the previously mentioned large-time approximation might be valid". Katz and Tek5 remark upon the mathematical difficulty of treating a reservoir having many layers or strata. If relative position of the layers is also

By F. J. Fayers, J. W. Sheldon

A theoretical discussion is presented of the behavior of the interface between two fluids of different physical properties when displacement is occurring along a thin tilted bed. An approximate equation of motion is deduced for the motion of the interface, suitable boundary conditions are derived and the conditions necessary for the approximation to be valid are determined. Steady-state behavior and the circumstances under which a steady-state interface can develop are discussed. Finite-difference solutions of the equation of motion for two characteristic water-drive problems are presenled. The theory of displacement in a thin bed may be regarded as being the porous-medium-equivalent of the classical "shallow-water wave" theory of hydrodynamics. INTRODUCTION The solution of moving interface problems are important in predicting the behavior of oil reservoirs under various conditions of production. Kidder4,5 has obtained analytic solutions for the fingering problem and for another particular case of the motion of the interface between two immiscible fluids of unequal density in a porous medium. In the present analysis, we analyze the problem of the motion of an interface along a slightly dipping bed whose length is long compared with its thickness. The requirement of a thin bed is necessary in order to give a simple differential equation for the motion. The two fluids are of unequal density and mobility. In the derivation of the equation of motion, it is assumed that the lighter fluid is being injected at constant rate at the high end of the porous layer, while heavy fluid is produced at the low end of the layer. The analysis applies equally well, however, to the reverse procedure in which the heavier fluid is injected at the low end of the tilted layer. It will be shown that the behavior of the system is critically dependent on which fluid has the higher mobility and that the interface can in certain circumstances achieve a simple progressive steady-state shape. The fluids may be considered to be immiscible or miscible. It is assumed, however, that the thickness of the interface region is negligible in comparison with other dimensions of the system, and that the strength of the saturation or concentration discontinuity remains constant during the motion. In conjunction with Buckley-Leverett theory and areal sweep-out calculations, the tilted interface problem is one of the fundamental problems of reservoir engineering; it defines the very important underpassing and overpassing phenomena associated with water-drives, gas-drives and secondary recovery operations. The tilted interface problem has been dealt with previously by Dietz.2 In the present paper, we endeavor to derive the pertinent mathematical results more rigorously, and in doing so we obtain modifications in both the differential equation and boundary conditions for those given by Dietz. We also attempt to show the connection between these results and some of the recent work on the stability of interfaces. Finally, we attempt to demonstrate the practical importance of the thin bed theory by showing the difference in behavior of two characteristic waterflood problems. In the favorable mobility case recovery is improved by increasing production rate, while in the unfavorable case undercutting or overcutting is minimized by reducing the displacement rate. PROPERTIES OF THE EQUATION OF MOTION Fig. 1 illustrates a porous layer of constant thickness H and tilt 8 with Fluid 1 of mobility ?l and density pl below Fluid 2 of mobility ?2 and density p2. The fluids are incompressible and flowing with volumetric flux q along the layer. Both the slope a of the interface with respect to the bed and the curvature of the interface are assumed to be small. What is meant by "small" is indicated in the derivation given in Appendix A of an approximate equation of motion for the interface. Other symbols are defined in the "Nomen-

By R. F. Stewart, A. W. Hall

A method has been developed for continuously measuring the moisture content of coal. The method is based on the thermalization of fast neutrons by hydrogen in the coal. Neutrons from a small radio-isotope source penetrate the coal, are scattered by hydrogen, and measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. In a pilot-scale system, moisture was measured continuously within 0.2% in coal moving at rates up to 20 tph. The method is adaptable in industry for continuously measuring the moisture content of coal at high tonnage flow rates. Such an application would permit continuous recording of moisture in coal without sampling and facilitate quality control. An automatic and continuous method of measuring the moisture content of coal is needed by the coal industry. Automatic control of the coal quality would reduce the cost of coal preparation, improve the product, and thus indirectly increase the use of coal. Moisture in coal can be determined by several methods, but the time required to obtain samples and analyze them by existing methods makes it difficult, if not impossible, to control the quality of the product. Both producers and consumers need a method for continuous and instantaneous measurement of moisture content without sampling in order to regulate process equipment and keep the moisture content of coal within specifications. At the Morgantown, W. Va., Coal Research Center we are developing a nuclear method for continuous measurement of moisture in coal. This method is based on the thermalization of fast neutrons by hydrogen in the water and organic matter of coal. Neutrons from a small radioisotope source penetrate the coal, are scattered by hydrogen, and are measured by a thermal neutron detector. The number of thermal neutrons counted can be directly correlated with the moisture content of coal. Design of a moisture meter based on neutron thermalization depends on many variables, any or all of which can affect the sensitivity of the meter. These factors include those related to the nuclear aspect; type and size of neutron flux and source, type of detecting device, and background count; and those related to the coal being tested: rank, particle size, and ash content. A survey was initiated to eliminate the relatively insignificant factors and to ascertain the magnitude of the major effects. Such information was necessary to fully evaluate the technique and to establish design criteria. Coal contains a relatively large amount of hydrogen in the organic coal substance and the water of hy-dration of the shaly material as well as in the moisture. To apply this concept of moisture measurement to coal requires that the organic substance in coal from any one seam of a particular mine be uniform in hydrogen content. The difference in total hydrogen content of wet and dry coal is relatively small, so that a moisture measurement based on this concept requires a measurement between two large numbers to a high degree of precision. Thus, it was necessary to develop a highly precise instrumentation system for continuous measurement and to obtain a physical arrangement permitting measurement of moving coal with a minimum effect from density variation. EXPERIMENT WITH TRAYS OF COAL Tests were conducted with metal trays containing SO to 100 lbs of coal to develop an instrument system of high precision. A scaling system with a maximum instrument error of 0.2% was used to test different types of thermal neutron detectors. The most suitable type of detector was a boron-10-lined proportional counter tube. While this type of detector showed satisfactory stability, extensive testing disclosed a long-term count reduction probably due to some type of deterioration in the detector. However, development of an electronic system using dual detectors eliminated this deterioration as a serious problem. (The second detector would be used to measure a reference drum of dry coal — the difference in count rate between the wet coal and dry reference coal being a direct measure of moisture content.) Table I, column 1, shows typical results with a 1-curie plutonium-beryllium neutron source and a thermal neutron detector beneath a tray of coal and illustrates the precision of measurement. Consecutive measurements (indicated in Table 1, columns 2-5) of thermal neutrons at various times and positions be-

Jan 1, 1968

By H. L. Sauder, J. L. Newman, C. Waddell

An instrument capable of measuring subsurface flow rates is described. The instrument is self-contained and may be run on piano wire line. It detects flow by means of an impeller suspended between two torsion wires. The force of the well fluid striking the impeller causes the impeller to rotate, exerting a torsional force to the wires. This force is determined by recording the angle of rotation of the impeller on film using a battery-driven, clock-controlled camera. The impeller is sensitive to flow in either direction and the same instrument can be used to measure injection as well as production rates. Changes in direction of flow, such as might be caused by thief zones, are measurable and are indicated by a reversal of the direction of rotation of the impeller. Adjustment of the sensitivity of the instrument to measure a wide range of flow rates is accomplished by the use of different size torsion wires. An umbrella-type fluid trap, which contacts the casing or wellbore, diverts the flow through the flow tube. The fluid trap remains closed while rurrning in the hole and can be opened at any point in the well. The instrument with the trap closed is 1 3/4 in. OD and may be run through 2 in. tubing. Successful flow profiles have been made on wells with flow rates ranging from 60 BID to 4,000 B/D at surface pressure up to 4,500 psi. The instrument is designed for high-pressure and high-temperature operations. INTRODUCTION The need for an instrument that will measure flow rates in a wellbore is as old as reservoir engineering itself. A number of such devices have been designed within the past few years. Some of these have been described in the literature1,2,3,4,5,6 One of these devices1. a hot-wire anemometer type, made many successful jobs in dry gas producing areas. Difficulty was encountered when this flowmeter was used in wells producing liquids and development work was initiated to overcome this difficulty. The present flowmeter is the result of this work and provides an instrument with a wider range of application in the industry. Consider- able development work has been done on the tool involving many changes in the mechanics of recording the flow readings, however, the basic principle of flow detection has remained the same since its inception. PRINCIPLE OF OPERATION The basic principle of operation of the flowmeter is the utilization of a portion of the kinetic energy of flowing well fluid to impart a rotational force to an impeller suspended between two torsion wires. This impeller, Fig. 1, is a screw-type propeller with the blades having a pitch angle of 40. As the well fluid passes through the instrument it strikes the impeller. The resulting force rotates the impeller and twist\ the torsion wires to a balance point at which the torque imparted to the wires balances the force required for the impeller to deflect the well fluid. The impeller is symmetrical and a change in direction of the flow results in a reversal of the direction in which the impeller is deflected. Thus the direction of the flow as well as its velocity is indicated. A dial is attached to the impeller by means of a hollow tube through which the upper torsion wire extends. The angular position of the impeller is recorded by photographing the dial at frequent intervals. In any given set of torsion wires the modulus of shear and polar moment of inertia remain constant and the deflection varies directly with the applied torque. The deflection imparted to the torsion wires also varies as the square of the fluid velocity. Further, the velocities represented by any two given deflections hear the following relationships: and Where V = velocity of flow stream and O ;= deflection. This is the basic relationship which is used to calculate the relative velocities represented by a given set of deflections where the velocity represented by any one of the deflection readings is a known quantity. For a given torque, the deflection of the torsion wire varies inversely as the fourth power of the wire diameter. Wire sizes ranging from ,005 in. in diameter to .022 in. in diameter can be used. The range of

Jan 1, 1957

By R. G. Schaal

The Magma Mine at Superior, Arizona had an unimpressive beginning as a. worked out silver mine that was purchased in 1910 for $130,000 and then incorporated into the Magma Copper Company which has been continuously mining the deposit since 1915. Copper is the principal metal produced. However, zinc, gold, silver and iron have also contributed to the total metal product. Prior to 1973, the production rate of 1500 tons per day was maintained by hoisting 4 and 5 ton pay-loads at speeds up to 1100 FPM through four small hoisting shafts. The hoists used included 8' and 7' diameter double drum, double clutched doc. and a.c. motor driven geared units built as early as 1917. One old timer that did yoeman's service for many years was an 8' Bollen Pulley with a.c. geared drive that utilized an endless rope system with mechanical grip and release mechanism built into the pulley's throat. Primary power for all of these old production hoists was 25 Hertz. Exploration that was completed in 1967 developed a reserve of 10 Million tons of 5 per cent copper which was sufficient to justify new capital expenditures for enlargement of productive facilities to 3300 tons per day. To reach the new reserves a 22' I.D. concrete lined vertical shaft was sunk to an initial depth of 48431. A 12 ½ diameter adit was bored from the mill side of the mountain to intercept the shaft at a point about 1100' below the collar. This 9200' long adit provides the right-of-way for the mine to mill railway and egress for heavy supplies from rail head as well as a conduit for potable water, electric power, compressed air and mine drainage. Mine operating levels begin 3582' below collar and thereafter have been cut at 100' vertical intervals. Skip loading stations have been installed 4282' and 46821 below collar with an in-shaft skip dump station located 800' below collar. This provides for 4500 tons of storage above the mine to mill train loading station located 1100' below collar. Ore and waste are moved horizontally from stope chutes and drift headings by rail haulage to transfer raises which channel all material to the two mentioned skip loading stations. The 22' diameter shaft crossection is arranged with the two skip compartments on the south side separated from the manway and utility compartments by the cage compartment. The cage counterweight operates in a portion of the southwest quadrant of the shaft. The hoisting plant consists of two conventional Nordberg double drum, single clutch, geared, d.c. motor driven units that are identical except for the drives and automatic controls. The drums are 15' diameter x 105" face with LeBus grooving for 2-1/8" diameter wire rope wound in three layers. Mechanical design emp1o::ed is the same as has been used for the past twenty- five years. One drum is attached to the main shaft by 2 large bolted integral shaft flenge. The loose drum is engaged by a 4-arm positive tooth clutch meshing with radially cut teeth of the clutch ring which is bolted to the drum. The drums are one-piece steel plate weldments having a finished weight of 60 tons each and are mounted upon a 36" diameter shaft that also weighs 60 tons. With the addition of brake rings, clutch, bull gear and rope, the total dead weight adds up to nearly 250 tons that is supported by just three double row spherical roller pillow block bearings. There is no bearing between the drums. All pinion shafts as veil as all head sheave journals are supported in the same type of antifriction bearings.

Jan 1, 1975

By C. C. Clark, J. S. Iwanski

The purpose of this investigation was to study mi-crostructural changes that take place in a commercial nickel-chromium-iron alloy, such as Incoloy "901," over long periods of time at temperatures up to 13 50°F and to correlate such changes with creep-rupture properties. of the alloy. In the course of the investigation, some microstructural changes were observed which correspond to microstructural alterations found in previous studies of Inconel "X." Microstructural phases have been identified in both alloys with the aid of electron and X-ray diffraction and an electron probe microanalyzer. The materials used in this investigation were from commercial heats of the following chemical composition: Pct Cr Pct Ni Pct Mo Pct Fe Pct Cb Incoloy "901" 12.51 43.67 5.72 Bal. -Inconel "X" 14.61 73.44 - 6.61 1.02 Pct A1 Pct Ti Pct Mn Pct Si Pct C Incoloy "901" 0.10 2.46 0.46 0.24 0.05 Inconel "X" 0.70 2.43 0.51 0.36 0.04 Long-term creep-rupture tests were conducted on Incoloy "901" at temperatures of 1000°, 1200°1 and 1350°F. A summary of these results is shown in Table I along with the results of a long-term creep-rupture test conducted on Inconel "X" at 1500°F. The heat treatments given the specimens are also shown in Table I. When the creep-rupture results on Incoloy "901" are compared with shorter-tertn data, there is no evidence of any undue deterioration of the creep-rupture strength with time, nor is the elongation decreased more than would be expected from the influence of time alone. INCOLOY "901" PHASE IDENTIFICATION Microscopic examination of the Incoloy "901" specimens reveals a dark etching grain boundary constituent in the specimen which was under test for about 11,500 hr at 1000°F. This grain boundary constituent was seen to increase in size as the test temperature was increased to 1200" and 1350°F, Figs. 1, 2, and 3. Simultaneously, an acicular structure of definite crystallographic orientation appears within the grains of the 1350°F specimen, Fig. 3. Under examination with the electron microscope, a fine precipitate is observed in the 1200 °F specimen. Fig. 4. It becomes considerably larger in the 2850-hr 1350°F specimen, Fig. 5. In a few areas the precipitated particles have been replaced by, or transformed to, small needles or platelets. After 7380 hr at 1350°F, Figs. 3 and 6, the needles are much larger and have replaced nearly all of the fine precipitate. X-ray diffraction studies detected the presence of hexagonal Laves phase and hexagonal n phase (Ni,Ti) in the 1350°F specimens, Table 11. Only the Laves phase was detected by X-ray diffraction in the 1200°F specimen and none was detected in the 1000°F specimen. In this latter specimen, however, the small quantity of precipitate in the grain boundaries (presumed to be Laves phase) precludes its detection by X-ray diffraction. Composition of the hexagonal Laves phase is not yet known, although its diffraction

Jan 1, 1960

By P. R. Sahm, T. V. Pruss, D. A. Gandolfo

Cb 3 Sn powders were hot-pressed to estahlish densi-fication conditions and assess the possible use of such compacts in multiphase structures with ceramic or magnetic inclusions. Superconducting transition temperatures, Tc, were measured as a function of powder particle size, pressing temperature, and second-phase admixtures. The highest transition temperatures were found in coarse powder (5 to 500 u) compacts and were only weakly depended on pressing temperatures up to 1200°C. Fine powders (below 5 p), however, both single-phase CbsSn and Cb3 Sn-composites, showed a stronger dependence on hot-pressing temperatures. While Al2 O3 phase admixtures did not affect T, much more, a Pronounced T, degradation was observed upon the addition of ferrimagnetic Fe2 Mno. 5 Zno.5 O4 powders. Likewise, critical current densities, Jc, at 4.2° K were lowered appreciably in the ferrite doped samples, whereas the neutral A1203 inclusiow gave slightly improved Jc values. MULTIPHASE structures in electronically active materials have recently gained in interest as pointed out by Galasso in a review article.' In superconductors the most widely reported group are eutectic alloys which have been mostly investigated with respect to the proximity effect.2"4 In addition, "artificial eu-tectics", for example in the form of mercury-vycor glass sponge5 or fine niobium wires imbedded in a copper matrix,= have been prepared to attain higher critical fields and critical current densities. The idea was to enhance flux pinning phenomena by second-phase inclusions or ho1es. 7 Flux pinning should also be possible by the introduction of insulator inclusions into a superconducting matrix. Ceramic-metal combinations are most easily produced by hot pressing (= pressure sintering), as it permits an almost unlimited selection of material combinations. Cb 3 Sn has been prepared by vapor phase growths or in the form of thin films. Large compacts must be sintered,1° however, and normally present difficulties. At temperatures below 1350°C insufficient densities are obtained and at higher temperatures the loss of tin due to dissociation upsets the stoichiometry. Hot pressing is a natural approach to circumvent the problems, since one can obtain satisfactory densities despite low sintering temperatures. This work was mostly concerned with establishing conditions to hot press Cb3 Sn and Cb3 Sn multiphase structures (= composites), because no data are presently available, and to evaluate these with respect to their transition temperatures. However, a few measurements on critical current densities were also carried out, in particular to assess the value of ferrimagnetic inclusions. I) EXPERIMENTAL PROCEDURE The experimental procedure involved the preparation of feed material and powders, hot pressing, and evaluation of the resulting ingots. As no attempts were made to synthesize Cb3Sn from the elements during hot pressing, feed material had to be produced. For this purpose, a stoichiometric Cb-Sn powder mixture was compacted into a 3-cm-diam ingot (80,000 psi) and then inserted into a quartz tube and evacuated. Rf heating was employed. Above the tin melting point (230°C) liquid tin was forced out of the ingot, but was pulled back by capillary action after approximately 0.5 hr of continuous pumping at 700°C. Thus, it appears that evacuation at this temperature caused desorption of impurity gas creating wetting surfaces which, later on, favored alloying at relatively low temperatures. After a presintering period of 17 hr at 800°C, the quartz tube was tipped off and sealed into another such larger-diameter tube which, in turn, was connected to a pump system. This configuration permitted a temperature treatment at 1400°C, carried out for 65 hr, without collapsing of the glass walls or unfavorable chemical interaction of Cb3Sn with the quartz. The resulting material was

Jan 1, 1969

By N. J. Grant, C. Stein

A more complete determination of the chromium-rich portion of the Cr-Ni phase diagram was made, based in part on resistivity measurements. The existence of a eutectoid reaction at 1215°C,made,based in addition to the previously reported eutectic reaction at 1343°C, was confirmed. Metallographic studies, lineal analysis, and diffusion-couple evidence were utilized to support Metallographicand extend the findings of the resistivity measurements. Delineation of the a chromium solvus line shows that the maximum solubility of nickel in a chromium decreases rapidly from 25 wt pct Ni at the eutectoid temperature to 16 wt pct. Ni at 950°C. IN recent years alloys of high chromium and nickel content have become of more interest as better performance of metals at higher temperatures is sought. It has become increasingly important, therefore, that the Cr-Ni binary diagram, which is composed of two of the elements commonly found in many high temperature alloys, be known more accurately. In particular, the chromium-rich portion of this diagram has for a long time remained incompletely determined and has been reported in the literature with a great deal of conflicting evidence. In general, electrolytic chromium of nominal purity was used by most of the earlier workers, who, except for Jenkins et al., made no further attempt to purify the metal. In the present redetermination of the chromium-rich portion of the Cr-Ni phase diagram, every effort was made to use the purest component metals available and to retain this purity throughout the preparation of the alloys and their subsequent handling. Early work by Voss, Bain," and Phebus and Blake4 indicated that the Ni-Cr binary diagram was a simple eutectic system with rather extensive terminal solid solutions. Later, Nishigori and Hamasumi," Tasaki, Weaver and Jellinghaus,' Matsunaga, and Jette, Nordstrom, Queneau, and Foote attempted to determine the limits of the phase fields. Except for Jette and coworkers, the other investigators agreed that the temperature of the eutectic reaction occurred between 1320" and 1340°C and at a composition of 50 or 51 pct Cr. There was, however, considerable disagreement as to the melting point of the chromium-rich alloys and the limits of the solid-solution fields. As a result of the studies of Jenkins et al., the liquidus and solidus curves up to 80 and 90 pct Cr, respectively, were outlined. In addition, the solid-solution phase fields at higher temperatures had been investigated and showed only two phases. The boundary of the chromium-rich a phase was not determined precisely according to these authors, but indications were that it tended to confirm the earlier work of Nishigori and Hamasumi. A more recent investigation by Taylor and Floyd,'" using X-ray methods, essentially corroborated the diagrams proposed by Jenkins et al., and by Wise and Eash (see Fig. 1). Again, no indication of a third phase in the chromium-rich portion of the diagram appeared. The earlier observations, however, are not substantiated by the modifications to the Ni-Cr binary diagram proposed by Bloom and Grant." In the investigation carried out by Bloom and Grant, X-ray methods showed that an eutectoid reaction existed at approximately 1180°C, in addition to the eutectic reaction at 1343°C (see Fig. 1). Their determination of the melting point of pure chromium was 1930°C (later revised to 1903"C)." Experimental Procedure and Results The chromium used for this study was electrolytic chromium, made available by the United States

Jan 1, 1956

By Irving B. Cadoff, Alvin A. Machonis

The resistivity, Hall coefficient, Seebeck coefficient, and thermal conductivity were measured as a function of temperature for cation-rich alloy single crystals covering the composition range across the PbTe-SnTe system. Alloying of PbTe with up to 20 pct SnTe was found to have little effect on the energy gap. Above 20 pct SnTe the alloys were "p" type but below this range the sign could be varied by heat treatment. The lattice thermal resistivity of the compounds SnTe and PbTe is raised by alloying one with the other. Z values in the order the interesting values obtained. THE PbTe-SnTe system has several interesting features. For one, PbTe is a useful thermoelectric material and the possibility of improving its figure of merit by alloying with SnTe, an isomorphous compound, has been suggested since these pseudo-binary solid solutions generally have a more favorable ratio of electrical conductivity to thermal conductivity than either of the components.' Other interesting features relate to the conductivity mechanism, band structure, and stoichiometry of the compounds and their alloys. PbTe is a semiconductor with an energy gap of about 0.29 ev2 at room temperature whose conductivity sign and magnitude can be varied from "n" to "p" by controlling the proportion of lead and tellurium with respect to the stoichiometric ratio.3 Excess lead results in "n"-type conduction. SnTe is found to exist only as a "p"-type material of relatively high conductivity. This behavior is attributed to stoichiometric deviation by Brebrick4 but Sagar and Miller proposed that the behavior of SnTe must be due in part to the presence of an overlapped band. An investigation of alloys of this system, therefore, might give additional information which would permit one to evaluate which of the two proposals is the more appropriate one. Abrikosov et al.' studied the room-temperature electrical properties of these alloys and reported data for Seebeck coefficient and resistivity on poly-crystalline alloys. The present work is a more exhaustive survey of the PbTe-SnTe system. Re- sistivity, Hall coefficient, Seebeck coefficient, and thermal conductivity were measured over a wide temperature range for single crystals at 10-pct intervals of lead/tin ratio across the pseudobinary system. The relative concentration of tellurium was controlled so as to obtain metal-ion excesses in all cases. SAMPLE PREPARATION The crystals were prepared by melting elemental lead, tin, and tellurium in weighed proportions in evacuated Vycor capsules. The lead and tellurium were high-purity grades obtained from American Smelting & Refining Co. The tin was supplied by Comico. The proper calculated proportions of lead, tin, and tellurium were weighed and charged into prepared Vycor capsules prior to evacuation. The capsules were prepared from 15-mm Vycor tubing. A sharp point was worked on one end of the tube. A pyrolytic graphite coating was deposited on the Vycor walls by heating the tip to 800°C in an atmosphere of acetone-saturated argon. An additional coating of graphite was deposited on the pyrolytic coating from an Aquadag suspension. Above the coated tip the tube was reduced in diameter to form a constrictive neck. To avoid scratching the graphite coatings the charge was placed in the tube above the constriction. After a low-temperature bake, the evacuated capsule was sealed. On subsequent heating the charge melted down into the lower portion of the capsule. The crystals were grown by lowering the capsule through a Bridgman-Stockbarger furnace. The lowering rate was 1 in. per 8 hr. The upper portion of the furnace was set for 950°C and the lower portion for 800°C. In general the yield of single crystals was about 25 pct. The mixed compositions were, as expected, the most difficult to grow. The finished crystals were sectioned into 5/8-in. slices. The tip, end, and middle slices from each crystal were analyzed by X-ray fluorescence to determine the lead-to-tin ratio. The resulting values were used to plot a composition vs distance plot for each crystal. Slices were selected from each crystal, with the aid of the composition plots, to cover the complete range of compositions at 10-pct intervals. In general, the slices selected were taken from the seed end of the crystal where the longitudinal segregation (as determined from the X-ray fluorescence analysis) was a minimum. Laue single-crystal analysis and metallographic analysis was used to verify if a slice was single or polycrystal. Any grain boundaries were clearly visible in the as-cut and polished condition. In ad-

Jan 1, 1964