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By L. L. Handy

The development of a theory for miscible liquid displacement requires evaluation of the variables which affect growth of the mixing zone between solvent and displaced oil. Factors which appear to be important are individual fluid viscosities, viscosity ratios, flood rate, fluid densities, flow characteristics of the porous medium and molecular diffusion coefficients of the fluid components. The primary purpose of this paper is to evaluate diffusion effects. Theoretical treatments to date have been limited to floods for which the viscosity ratio is one. Two principal theories have been proposed. Von Rosenberg adapted for porous media a theory derived for capillary tubes by G. Taylor.' ,' In this theory molecular diffusion perpendicular to the direction of flow is a primary factor in sharpening the flood front. Slow floods give sharper fronts for a given distance traveled than fast floods. An alternative theory considers miscible liquid displacement as a statistical problem.3,4,5 Diffusion is not an important factor in this theory, but it leads to the same general type of equation as von Rosenberg's. Both theories predict S-shaped concentration profiles with the same dependence on distance traveled. The statistical or "dispersion" theory predicts rate independence, however. To supplement rate studies a direct measurement of a diffusion effect would be helpful in evaluating which of the two proposed mechanisms best describes miscible liquid displacement for one-to-one viscosity ratio systems. No quantitative theory has been proposed for floods in which a low-viscosity fluid displaces a high-viscosity fluid. It might be anticipated, however, that the extensive fingering observed in floods with adverse viscosity ratios would increase opportunities for an exchange of components between displaced and displacing liquids by a diffusional process. Even if molecular diffusion were not an important mixing mechanism for one-to-one viscosity ratio systems, it could be significant in systems with adverse viscosity ratios. METHOD FOR EVALUATING DIFFUSIONAL MIXING In solvent flooding the displacing liquid can become mixed with the displaced liquid by a number of processes; in general, either mechanical or diffusional in character. To evaluate the contribution of diffusion, a method was sought that would distinguish diffusional mixing from mechanical mixing. Suppose two soluble tracers are added to the displacing liquid and that one tracer has a diffusion coefficient much greater than the other. Then, if diffusion is important during miscible liquid displacement and if diffusional transport is primarily transverse to the direction of flow, substances with high diffusion coefficients will have sharper concentration profiles than those with comparatively low molecular diffusion coefficients. In order to have material balance the profiles for the two tracers must intersect. For one-to-one viscosity ratios the intersection would occur at the 50 per cent concentration point. It is generally assumed that diffusion in the direction of flow is negligible. This assumption appears reasonable because flow velocities are ordinarily orders of magnitude greater than diffusional velocities. If this is not a valid assumption, however, the shapes of the fronts will be further degraded by longitudinal diffusion. The effects of rate and molecular diffusion coefficients are the opposite for longitudinal diffusion to those for lateral diffusion. Higher rates or lower diffusion coefficients would tend to give sharper fronts. The double tracer method offers several unique advantages in evaluating effect of molecular diffusion. First, the method gives a direct measure of the effect of diffusion on mixing zone size. Second, the effect of a difference in diffusion coefficients is determined from a single experiment. Comparison of several experiments at different rates is not required. Third, the method is applicable for any viscosity ratio. Fourth, the method is unaffected by density differences between the two fluids which might result in rate dependent gravity effects. EXPERIMENTAL PROCEDURE Suitable tracers are substances whose diffusion coefficients differ as widely as possible, but whose adsorptions on rock surfaces is negligible. The two tracers selected were methanol and sucrose in water solutions. The approximate diffusion coefficients for methanol and sucrose, as given in the International Critical Tables, are 1.3 X 10-5 and 0.3 X 10-5 m2/sec, respectively. Concentrations in the water solutions were 200 gm/liter of solution for both methanol and sucrose. These high

By E. Martinez

Samples of chrysocolla, a hydrated copper silicate, from several sources were submitted to differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). Pure samples of chrysocolla are difficult to obtain, but comparison of the thermograms revealed that certain reactions occurred in all the samples and it is believed that these are due to chrysocolla. Endothermic reactions occurred at 50' to 175°C, 350° to 650°C, and 980° to 1100°C each of which caused a weight loss. The first was due to loss of absorbed water, the second to a dehydroxyla-tion, and the last to conversion of cupric oxide to cuprous oxide. In addition, two exotherms were detected at 685° to 695°C and 935° to 950°C. Infrared spectra of heated samples indicated the exotherms were due to changes in the Si-O bonds leading to the formation of cristobalite. The results suggest that thermoanalysis may be a more sensitive and reliable method for detection and identification of chrysocolla than X-ray diffraction, infrared spectroscopy, or optical techniques. The recovery of copper from oxide ores has been the subject of much research in recent years. One of the principal oxide copper minerals is chrysocolla, a hydrated copper silicate. The information available indicates that it has widely varying properties depending on the origin of the sample. Chrysocolla usually is found associated with cuprite, malachite, azurite, and native copper. Most of these other minerals are recoverable by present day flotation practice, but chrysocolla is lost in the tailings.1,2 Reagent combinations that are successful in laboratory chrysocolla flotation with ore from one source have been found to be ineffective with another. 3 The copper segregation process offers an altemative to beneficiation of oxide copper ores.4'5 The process is of particular interest in processing ores that cannot be treated by conventional hydrometal-lurgical methods because of high acid consumption.6 Fuller understanding of the properties of chryso- colla may prove of value in the search for improvements in both the flotation and segregation processes. Chrysocolla samples from Arizona, Nevada, Chile, Australia, and South Africa were studied by differential thermal analysis (DTA) and thermal gravimetric analysis (TGA). In addition, a sample from Miami, Ariz., was submitted to X-ray diffraction, infrared spectrophotometry, and surface area determination. EQUlPMENT Differential thermal analysis (DTA) detects, amplifies, and records exothermic-endothermic reactions occurring in a sample as its temperature is raised at a constant rate, usually 10°C per minute. A unit made by the Robert L. Stone Co. was used in this study. The tests can be run if desired with a gas streaming through the sample. A thermobalance records weight losses or gains in a sample as its temperature is raised at a uniform rate. The gravimetric analyses (TGA) were run on a Chevenard thermobalance converted electronically for graphic recording. A heating rate of 5°C per minute up to 1100°C was used in these tests. A Perkin Elmer Infrared Spectrophotometer, Model 221, was used with sodium chloride optics obtaining IR spectra in the 2 to 15 region. A pressed pellet technique with potassium bromide was used in preparing the samples. DESCRIPTION OF SAMPLES Chrysocolla is found in the oxidation zones of copper deposits commonly associated with malachite, azurite, and limonite. It is described as varying in composition and in color from bluish green to brown or black. Inclusions of other minerals are usual so chemical analysis of chrysocolla samples may be suspect. However, it is considered by many to be a solid solution of CuO, SiO2 and H2O with a general formula of CuO.SiO2.2H2O or 2CuO.2SiO2. 3H20. Chukhrov7 has described a sample from the Urals as CU3,5(OH)2 (A1Si3) O10.nH2O and stated that chrysocolla is a montmorillonite-type mineral. On the basis of X-ray analyses, DTA, and infrared spectra of chrysocolla from the Inspiration Mine, Ariz., Sun8 concluded that there was no substantial evidence to classify it as a montmorillonite mineral. Chrysocolla samples from many sources throughout the world were used in this investigation. The following is a brief description of each:

Jan 1, 1963

By R. G. Ward, A. E. El-Mehairy

A technique was developed to calculate the density of liquid metals from the profile of a weighed levitated drop obtained by emitted light photography and calibration. The density of liquid copper was determined over the temperature range 1370" to 2100°K and expressed with the equation: The molar volumes and thermal coefficients of expansion are calculated. Copper, upon melting, was found to expand 3.34 pct. A knowledge of the density of liquid metals is essential as it is a parameter appearing in most theories of the liquid state. The liquid density is also necessary for the calculation of the commercially important contraction occurring on solidification. Unfortunately good density values are rarely available and the present work was undertaken to establish a new method of density determination free from the limitations of the existing methods. For liquid metals with high melting points, the variation and the limited number of density values reported in the literature have been caused primarily by difficulties in technique, a matter which has been adequately discussed by Urbain.' In all the methods used for measuring the density of the high-melting liquid metals there are sources of error, and corrections have to be made. For example, in the method of balanced columns, the formation of gas bubbles in one or both arms was a great source of error. In the pyknometer3 and immersed-sinker methods, corrections of certain volumes for thermal expansion to the operating temperature exceed 4 pct. In the maximum-bubble method5 a correction for the thermal expansion of the bubble-tube is used (about 1.6 pct); a second correction takes into account the change in the volume of liquid displaced by the bubble-tube (about 3.5 pct). Another method used is based on the shape of a drop of liquid, at rest on an inert refractory plaque, obtained photographically or radiographi-cally. The volume is calculated from the shape, which is sensitive to the surface tension and supporting material, by some intricate empirical relation. The drop contour changes with 90 deg rotation of the support.7 The application of all methods is limited by reaction between liquid metal and the apparatus. The successful stabilization of a mass of liquid metal during levitation melting8 afforded a technique for measuring the density of liquid metals out of contact with solid materials. The technique was developed by using copper as the density of liquid copper has already been studied extensively, thus allowing comparison with the new method. It consists of calculating the volume from the dimensioned profile of the levitated drop obtained by emitted-light photography and careful calibration. The molten egg-shaped drop spins around the magnetic axis of the coil (lined vertically) at a speed which seems to increase with increasing temperature. The method does not involve corrections and the experimental setup allows the use of vacuum or special atmospheres. The maximum operating temperature is limited by excessive evaporation of metal from the droplet. EXPERIMENTAL Levitating System. A stabilizing ring was used in conjunction with a 3-turn levitating coil energized by a 450-kc per sec, 10-kw Toccotron with a high current-low voltage output stabilized to f 1 pet.' APyrex glass tube with a Pyrex Optical flat window inserted through the coil and ring allowed the use of special atmospheres during levitation melting, as shown in Fig. 1. Optical System. Fig. 1 shows the optical arrangement used to photograph the profiles of the drop, parallel and perpendicular to the vertical spinning axis, simultaneously on the same frame of a high-speed 35-mm film. The optical system was adjusted to avoid any distortion of the profiles and to ensure that both profiles are in focus. The length of path from object to objective was about 30 cm, and a magnification factor close to 1 was obtained with the single-lens reflex-camera system. Temperature Measurement and Control. In operation, the specimen temperature was constant to 5 C for a fixed power input to the levitating coil and fixed rate of gas flow through the tube. The temperature was measured by an automatic two-color pyrometer (Coloratio) checked at the melting

Jan 1, 1963

By H. H. Klepfer, M. E. Snyder

UNTIL very recently, the commercial availability of the rare earths as metals has been very limited. Fabrication of mill products from these metals has not been studied in most cases. This note reports the results of the development of fabrication techniques for thulium. Thulium has a melting point of about 1550°C and a hexagonal close-packed crystal structure. It oxidizes in air to give a black oxide (TmzO,). The procedures for producing thin thulium foil were developed on one ingot weighing about 220 g and were subsequently applied in processing about a pound of metal to foil. Several alternates for the various fabrication steps were investigated and will be discussed. The metal fabricated was in the form of commercial chill-cast ingots 1 in. in diam and 2 in. long weighing approximately 220 g. Impurities in the ingots were reported by the vendor to be 4000 ppni tantalum, 2000 ppm calcium, 200 ppm nickel, 100 to 200 ppm iron, 100 ppm europium, and less than 100 ppm copper, lutetium, and ytterbium. In addition to these impurities, several salt-like inclusions as large as l/8 in. in diam were revealed along the center line of the one ingot sectioned. Preliminary tests indicated that small wafers cut from the as-cast ingot would not fabricate readily by rolling. Forging of copper-jacketed wafers was therefore attempted. At 1550"F forging was satisfactory but an apparent reaction of copper with thulium demanded investigation of lower temperatures. Therefore, the remainder of the test ingot was forged at 1450°F—with only minor cracking. All ingots forged were inserted into copper tubes of 1 in. 1D and 0.125-in. wall thickness. The jackets were sealed by flattening the ends of the tubes and welding under helium. Heating time at 1450°F was 30 min. Press forgings of 1/8 in. per pass were used, followed by 10 min reheats. When the ingots had been squared and reduced to 0.250 in. in thickness, the original copper jacket was stripped off and replaced by a new jacket in preparation for hot rolling. Hot rolling at 1450" F without edge cracking was readily accomplished after forging. Excellent results were obtained with 10 pct reductions of thickness followed by 5 to 10 min reheats. After reduction of thickness from 0.250 to 0.100 in. the copper jacket was removed. It was found, in fact, that hot rolling in air was possible. A tenacious black oxide similar to that seen on zirconium was formed during 3 min reheats at 1450°F. Reduction in air to 0.010 in. foil was possible taking 10 pct reductions per pass. The oxide coat formed during hot rolling in air could best be removed by sand blasting and pickling. Common pickling solutions containing polar solvents were found to attack the metal too rapidly and a concentrated nitric-hydrofluoric acid mixture attacked neither the oxide nor the metal. The most satisfactory pickling solution was 52 vol pct concentrated nitric acid-48 vol pct glacial acetic acid. After forging to 0.250 in., vacuum annealing and cold rolling was found to be another satisfactory alternate to hot rolling in copper jackets. After forging. a hardness of Rockwell B76 was found. Annealing in vacuum (2 X l0-5 mm of Hg) for 1 hr at 1200"F did not alter this value. Annealing at 1470"F for 1 hr brought the hardness down to R;]63. With cold rolling (5 pct per pass) the hardness returned to about R,1:76 after 20 pct reduction and edge cracking became noticeable. However, cold rolling to a total of 40 pct reduction in thickness (RI,,83) was possible before edge crack propagation became serious. Good surface finish was obtained, and the metal loss due to oxidation was minimized by cold rolling and vacuum annealing. Using this procedure the yield of 1.25 in. wide by 0.010 in. thick foil from a 1-in. diam ingot was about 40 pct.

Jan 1, 1961

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By Steve H. Carpenter, Henry E. Otto

The explosive welding of metals is dependent upon the production of a jetting action caused by the collapsing of one metal plate against another. Successful welds are generally accomplished if the yield strength of the metals is in the range of 10,000 to 90,000 psi and the sonic velocity of the metal is greater than the detonation velocity of the explosive if direct contact explosive is being used.' Should the detonation velocity exceed the velocity of sound in the metal it may still be possible to obtain the jetting action and a good weld. However, in most cases where a high detonation velocity is used complications arise because of reflected shock waves which tear the bond apart as fast as it is put together.' Explosive welding of lead presents several problems since its yield strength and sound velocity are very low. Various values have been published3-5 for the velocity of sound in lead ranging from 2000~ to 23004 m per sec. Most of the high-order explosives have detonation velocities on the order of 6000 to 8000 m per sec, which precludes their use. The dynamites have a lower detonation velocity of around 2800 m per sec which is still somewhat too high. Lower-order explosives such as ammonium nitrate (1070 m per sec) must be used to weld lead in the as-received condition if the explosives are used in direct contact. Rather than use low-order explo'sives it was decided to alter the sonic velocity of the lead. The sonic velocity is directly related to the modulus of the material according to the following expression: Fig 1—Interface of explosive weld of lead to steel. Lead is on top As-polished Magnification 75 times as well as the yield strength. Bolling et al. 6 show that the shear modulus of lead single crystals increases from about 0.72 X1011 dynes per sq cm at 300°K to about 0.98 X1011 dynes per sq cm at 0°K, an increase of approximately 3 5 pct. This gives an increase in the sonic velocity of around 700 m per sec. Hence, the sonic velocity of lead at cryogenic temperatures is approximately equivalent to the detonation velocity of the low-order dynamites. We have obtained high-quality lead to steel explosive welds using a 40 pct dynamite in direct contact with the lead. Prior to detonation the lead was chilled with liquid nitrogen (78°K) to increase the strength and sonic velocity. Welds were made while the lead was cold. Specimen sizes were 3 by 6 in. A preset angle of 5 deg with a 0.10-in. standoff at the base was the geometrical setup used. The amount of explosive used for optimum welding of an 1/8 -in. -thick lead sheet to a steel plate was found to be 7 g per sq in. A PETN sheet explosive line wave generator was used to insure a linear detonation front through the dynamite. A photomicrograph of a lead-steel weld is shown in Fig. 1. The typical wave effect that constitutes a good explosive weld is present. When tested in shear, the weld failed in the lead, indicating that the bond is stronger than the lead base metal. Higher-order explosives were also tried without success. We believe this indicates the importance of matching the detonation velocity and the sonic velocity for successful explosive welding. Note Added in Proof. High quality explosive welds of lead to steel have recently been obtained at ambient temperature using a low velocity (1000 M per sec) free running dynamite. The weld interface obtained is comparable to Fig. 1. 'S. H. Carpenter, R. H. Wittman, and R. J. Carlson: Proceedings of the First International Conference of the Center for High Energy Forming, Syracuse University Press, syracu.se, N. Y., in press. 'A. HI Holtzman and G. R. Cowan: Welding Risearch. Council Bull., No. 104, April, 1965. 'Metals Handbook, 8 ed., p. 1062, Metals Park, Ohlo. 'J. M. Walsh, M. H. Rice, R. G. McQueen, and F. L. Yarger: Phys. Rev., 1957, vol. 108, pp. 196-216; 'L. V. Al'tshuler, K. K. Krupnikov, B. N. Ledener, V. I. Zuchikhin,

Jan 1, 1968

PURPOSE OF UPDATED ESTIMATE FOR MINERAL INVENTORY BLOCKS During the production stage of an open pit porphyry copper mine it was observed that the expected production grade, as determined from the block inventory estimates, often differed greatly from the head grade of ore delivered to the mill. It was determined that, for purposes of production scheduling and monthly forecasting, better in situ grade estimates for mining blocks were necessary. Because all of the bench blastholes were being sampled, and periodic holes were being drilled into the next underlying bench, much more sample data existed than was being used for estimating the grade of nearby mining blocks. It was reasoned that, by periodically updating the mineral inventory block file over the benches scheduled for mining in the next time period using all existing data, better estimates and forecasts for production grade could be made. BLASTHOLE SAMPLE DATA MANAGEMENT The collars of all blastholes in each mined bench were surveyed and assays run on the cuttings representing the full 12-m (40-ft) bench height. The blastholes range from about 5 to 6 m (16 to 19 ft) apart along the front of the bench as well as perpendicular to the front. Overbreakage often left larger spacings between successive blasts. Fig. 17-1 is a plan map of blastholes on a typical mine bench. All blasthole data were keypunched to a format resembling that of the 12-m (40-ft) composite assay data file as follows: [Collar Coordinates Compite Assoy Hole ID Northing East Elewotion Total Copper Oxide Copper] Because of the many blasthole samples available, and in order not to use excessive computer time for running kriged estimates for 30.5 X 30.5 X 12-m (100 X 100 X 40 ft) blocks adjacent to and beneath the mined area, the decision was made to average all the blastholes falling with each 15.2 X 15.2-m (50 X 50-ft) mined block, and use the mean value of the samples as a regionalized variable for purposes of assigning kriged estimates and estimation variance to adjacent unmined blocks. In other words, instead of using individual blasthole samples for making kriged estimates, the holes were grouped by blocks and assay values were averaged and assigned to the centroid of the holes within the block, which was then treated as a single regional variable for purposes of kriging. See Fig. 17-2. VARIOGRAM COMPUTATIONS AND KRlGlNG RESULTS With the many blasthole samples it was possible to compute directional and vertical experimental variograms for both sulfide and nonsulfide copper assays falling within the enriched mineral zone for the full 12-m (40-ft) sample support. Due to the close spaced drilling, excellent definition of the experimental variograms was possible, and the spherical model exhibited good fits. A three-dimensional kriging program was then run over the two or three mine benches involved in the inventory update, and estimated grades reassigned to all mining blocks falling within the range of the new blasthole assay data according to the anisotropisms of the deposit. Better confidence limits could then be assigned to scheduled mining blocks and better short- range forecasts made. An interactive kriging computer program was also applied for the purpose of determining the kriging variance or estimation of error for larger, irregular mining blocks representing the monthly production from a particular bench. The interactive program permitted the operator to enter the limits of the irregular block onto the screen of a cathode ray tube (CRT) as a series of points around the perimeter of individual gridded blocks making up the larger irregular block. The computer then was programmed to calculate the kriging variance of the larger block using all samples fall- ing within range. Thus the limits of estimated grade could be established at any confidence level. Fig. 17-3 illustrates the output from the interactive kriging program showing the sample points entering into the grade and kriging variance computations, and also the kriging coefficient assigned by the computer to each sample.

Jan 1, 1980

By Fred H. Poettmann

The vaporization characteristics of carbon dioxide in a League City natural gas - Billings crude oil system were studied at three temperatures, 38°. 120°, and 202°F and for pressures ranging from 600 to 8,500 psi. Variation of carbon dioxide concentration up to 12 mole per cent in the composite showed no effect on the equilibrium vaporization ratios (K values) of the hydrocarbon constituents or on the K value of carbon dioxide itself. It was shown that carbon dioxide is more soluble in crudes than in distillates which is contrary to the behavior of methane. A working chart of carbon dioxide K values is presented. INTRODUCTION The study of the equilibrium vaporization ratios of mixtures of paraffin hydrocarbons has been rather thorough.2,6,7,8,9 In the past few years considerable attention has been paid to the vaporization characteristics of the so-called noncondensable gases such as nitrogen, carbon dioxide, and hydrogen sulfide in mixtures of hydrocarbons. since they usually occur to some extent in most crude oils and natural gases.1,3,4,5 Knowledge of this behavior is useful to both the production and refining phases of the petroleum industry. This paper reports the equilibrium vaporization ratios (K's) of carbon dioxide in a mixture of League City natural gas and Billings crude oil, and compares them to those obtained in a natural gas-distillate system. The equilibrium vaporization ratios for the hydrocarbon components in this system had previously been studied by Roland.' In addition to the determination of the K values for carbon dioxide, the K values for methane and ethane were also determined in order to observe what effect, if any, the presence of carbon dioxide had on these K values. The concentration of carbon dioxide was also varied in order to observe the effect of this variable on the carbon dioxide K values. EXPERIMENTAL PROCEDURE The apparatus used in this study cotlsisted of a stainless steel equilibrium cell of about 2 liters capacity. The cell was mounted on trunions permitting rocking in a thermostatically controlled oil bath. Two high pressure valves fitted with steel tubing were mounted on the top of the cell. one was used for sampling the equilibrium gas phase and the other for sampling the equilibrium liquid phase by means of an induction tube within the cell. Stainless steel tubing from the bottom of the cell led to a mercury reservoir and manifold which was connected to a free-piston type pressure gauge manufac- lured by the American Instrunlent Ctr. and to a volumetric. putrip. The temperature of the oil bath was measured by means of a ralibrated mercury-in-glass thermometer. The recorded temperatures are believed to be accurate to ±0.5 °F. The pressures are correct to 22 psi. The crude oil used in this study was stock tank oil obtained from the Wilcox formation in the Billings Field, Noble County. Okla. The natural gas was obtained from the League City Field. Galveston County, Tex. The oil was treated with anhydrous calcium sulfate in order to remove the last traces of water. To insure a supply of constant composition gas at room temperature the cylinders of League City gas were cooled to about 30°F, inverted, and the condensed liquid was allowed to drain from the cylinders. The analysis of the gas and crude are tabulated in Table I. The carbon dioxide came from Pure Carbonic, Inc., and was .stated to have a purity of 99.5 per cent or better. The procedure used to obtain samples of the equilibrium liquid and vapor was similar to that employed by others making use of the rocking type equilibrium cell.6,7,8 The equilibrium cell was evacuated and calculated quantities of carbon dioxide, natural gas, and crude oil were charged to the cell to the desired pressure. In charging the equilibrium cell an attempt was made to maintain the ratio of the natural gas to crude oil as close as possible to that employed by Roland. After the cell was charged, samples of

Jan 1, 1951

By L. M. Pidgeon, K. T. Aust

There has been considerable interest in the possible use of titanium in magnesium alloys.' Zirconium has shown some promise in this connection2 and its general similarity with titanium suggests that the latter might act in a similar manner. A literature survey revealed that quantitative data on the Mg-Ti system was unavailable. Several patents3 have claimed that titanium additions from 0.2 to 4 pct to magnesium alloys were possible, but no mention was made as to the form in which the titanium existed in the alloy. Kro114 succeeded in introducing only traces of titanium into magnesium by bubbling TiCl4 through the metal under argon or by reacting it with sodium titanium fluoride. The application of theoretical data given by Carapella5 based on Hume-Rothery's principles, involving atomic size factor, crystal structure, valency and the electro-chemical factor, suggests that a Mg-Ti alloy is a favorable case, and the system appeared to warrant experimental examination. Experimental Procedure and Results THERMAL ANALYSIS If titanium is appreciably soluble in magnesium, a change in the melting point of the magnesium might be detectable using standard cooling curve methods. Magnesium was melted in graphite crucibles under an argon atmosphere, the assembly being enclosed in a silica tube. Graphite thermocouple protection tubes served also to stir the melts. The apparatus was very similar to Fig 1, with the addition of a refractory and baffle system to prevent undue heat losses from the top of the crucible. Chromel-alumel thermocouples were calibrated using Al of 99.97 pct purity. Dominion Magnesium Limited sup- plied redistilled high purity magnesium of the analysis given above. Titanium was added in three different forms: 1. Titanium powder —100 mesh, from the Titanium Alloy Manufacturing Co., Niagara Falls, N. Y. 2. Sheet titanium from the U.S. Bureau of Mines, produced by Mg reduction of TiCl4. 3. Magnesium —50 pct titanium master alloy from Metal Hydrides Inc., Beverly, Mass. The melting point of the high purity magnesium used was measured experimentally as 651.0°C. More than a dozen tests were conducted using titanium from the three sources referred to above, in calculated additions up to 20 pct titanium, at temperatures between the melting point and 1000°C and holding periods up to 6 hr. In no case was evidence obtained of solubility of titanium in magnesium, using inverse-rate and time-temperature curves. The melting point of the magnesium was unchanged within the accuracy of measurement, namely -+0.5°C; and no other thermal arrests were detected. Metallographic investigation of the thermal analysis billets indicated that the titanium additions were apparently mechanically entrapped in the magnesium in segregated areas. Consequently, these samples were not analyzed for titanium. The master alloy proved to be a mechanical mixture of titanium particles in a magne- sium matrix. These results indicated that the titanium solubility, if such existed, could not be obtained by the usual thermal methods. X RAY DIFFRACTION INVESTIGATION In an effort to detect solubility of titanium in magnesium, samples were investigated using both the Debye-Scherrer and the Focusing Back-Reflection methods. Filings from samples of the thermal analysis billets and from pure magnesium were annealed in argon one hour at 350°C to relieve mechanical strain. Measurements made of the interplanar spacings showed no difference between the Mg-Ti samples and pure magnesium. The interplanar spacings could be measured to within 0.0002A, and the greatest variation found was 0.0004A, in the back-reflection method. The diffraction lines for magnesium were not shifted by the titanium additions indicating that the solid solubility of titanium in magnesium is of a very low order—less than 0.5 pct. From both diffraction methods, a d or interplanar spacing of 0.817A was obtained for the redistilled high purity magnesium. This latter value is not given in the standard X ray diffraction cards for magnesium metal or vacuum distilled magnesium. Theoretical calculations for a close-packed hexagonal space lattice for magnesium indicate that the planes {2134) should give a line which was found. The relative intensity for this reflection at 0.817A is slightly less than that at 0.870k for magnesium. SOLUBILITY OF TITANIUM IN LIQUID MAGNESIUM The Mg-Mn system was examined by Grogan and Haughton6 who were

Jan 1, 1950

By Michael Hoch, Walter C. Wyder

The isothermul section of the Nb-Ti-Zr-O system at 1500°C was investigated using X-ray dzffraction and metallographic techniques. UP to 66.7 at. pct 0, the system contains nine four-phase regions. Tsopleths at 10, 20, 30, 40, 50, and 55 at. pct 0 weye constructed. The purpose of this investigation was to determine the general shape of the quaternary equilibrium phase diagram of niobium, titanium, zirconium, and oxygen at 1500°C. The system was truncated at 66.7 at. pct. O., PREVIOUS INVESTIGATIONS The Ti-Zr-O system was investigated in this laboratory.' The binary systems of interest have been compiled and discussed by anssen2 and Levin, McMurdie, and Ha11. Elliott4 has determined the Nb-O system by metallographic and X-ray diffraction techniques. He shows the existence of three oxides, namely NbO, NbO2, and Nb2O5. At 1500°C the solubility of oxygen in niobium is about 4 at. pct. No solid solubility region is shown for either NbO or NbO2. EQUIPMENT The same equipment as that for the study of the Ti-Zr-O system was used. The X-ray diffraction patterns were analyzed with the help of the ASTM card set5 and NBS circulars.6 MATERIALS The niobium powder (99 pct pure), the titanium powder (99.6 pct pure), the niobium pentoxide, and the zirconium dioxide used in this study were purchased from the Fairmount Chemical Co., Newark, N.J. The zirconium powder (99.4 pct pure) was obtained from the Charles Hardy Co., Inc., N.Y. Reagent-grade titanium dioxide was purchased from the Matheson Co., Inc., Norwood, Ohio. The oxides were dried in air at 700°C for 24 hr before use. Though the materials used were not "hyper-pure," the impurities present do not affect the results (lattice parameters, phase boundaries), within the experimental accuracy. PROCEDURE Samples of the desired compositions were made up, in mole pct, from the materials listed above. In some cases the intermediate binary compounds, such as NbO and TiZrO4 were prepared beforehand and used in the preparation of the samples. This technique enabled equilibrium to be reached from two sides. The components of each sample were mechanically mixed in a mortar and pestle and pressed into 3/16-in. diam pellets. The pressures used in compacting were of the order of 50 to 100 x 103 psi. Sintering was accomplished by heating the samples in a tungsten crucible (3/4-in. high, %-in. diam, 1/8-in. wall, lid with XB-in. hole). The pellets were separated from each other and from the crucible by means of small spiral coils of tungsten wire placed between the stacked pellets and on the bottom of the crucible. The sintering time was from 4 to 12 hr at 1500°C under a vacuum of 6 x 101-5 to 1 x 10-6 mm of Hg. All samples were reground after the first or second heating repressed, and reheated. In most cases: equilibrium was obtained after the first heating, as the X-ray diffraction pictures after each heating remained unchanged. Quenching of the samples from 1500°C was at first only possible by allowing the crucible and its contents to lose heat by radiation. The temperature dropped from 1500° to 900°c in approximately 1 1/2 min, which was considered adequate when compared to the times used by other investigators to reach equilibrium in the temperature range of 1000°c and lower. Later, a new technique for faster quenching of the samples was cleveloped. This technique involved the removal of the samples from the crucible, whereupon they were quenched by coming in contact with the water-cooled copper base of the furnace. This manipulation was performed without breaking the vacuum. The sample pellets were placed on a tungsten wire rack inside the crucible. The wire rack passed through the hole in the crucible lid, where it was connected to a small nonmagnetic chain. The chain was fed to the side of the furnace by means of a brass rack which fitted between the body and lid of the furnace. Suspended at the end of the chain, near the furnace wall, were three magnetic washers. With the use of a strong

Jan 1, 1962

By Zay Jeffries

From the title of this chapter the reader could expect an attempt to out- line the anticipated shape of things to come, mineralwise. We have no crystal ball and if we possessed one we could claim no expertness in its use. In the first place no one can tell the future status of man. No one has any way of knowing to what extent peace will prevail, nor to what extent changes may occur in national sovereignties or forms of government or in international relationships. So future man is an uncertainty. Nor can we predict new developments that may result in significant changes in man's status or in the mineral industry or both. If, for example, this chapter had been written in the middle 1930's, nearly everything that has happened since in the fields of atomic energy and space technology would have been missed. Yet what vast changes these I have made in the status of man! Also the changes in the mineral industry have been important. A writer would have been bold indeed had he prophesied that uranium would play such an important role. But we need not confine our foggy vision to these fields. The steep rise in the use of aluminum, titanium, and germanium reflects the unpredictable in what may be thought of as the more normal pursuits. This should not discourage one from using the past and currently observable trends as bases for limited predictions. To do this, however, it is desirable to make certain assumptions about man's status without pretense that these assumptions have a high probability of fulfillment: 1. Only minor changes will occur in the geographical boundaries of the nations of the world. 2. World War III will not take place in the near future. 3. As a consequence of (2), man will not destroy himself by wanton use of atomic weapons. 4. Disarmament will take place, if at all, gradually rather than all at one time. Under the above assumptions the world will enjoy a period of relative peace even though the status may be one of an armed truce. The assump-

Jan 1, 1964

By P. R. Smith, R. A. Walters

Borates have been mined in the desert areas of California and Nevada for more than 100 years. To about 1890, playa surface mining provided the chief sources of boron minerals. Underground mining of colemanite and later of borax and kernite was predominate until about twenty years ago. Open pit mining of the large deposits of borax and kernite near Boron, California has been most significant for the past twenty years. Mining of colemanite in the Ryan, California area, near Death Valley, began in 1907. Following the discovery of the large deposits in the Boron area (about 1957), mining in the Death Valley area became nearly nonexistent. Only small tonnages were mined for special uses. Little mining was done in the Boraxo area near Ryan. The first claim was made in about 1915. In 1960 the area became the property of the Kern County Land Company, which was acquired by Tenneco Oil Company in 1967. In 1976 the various boiate properties and claims in this region were acquired by American Borate Corporation. The open pit mine is now approximately 122 m (400 ft) deep, 910 m (3000 ft) long and 305 m (1000 ft wide). The borates in the Boraxo pit consist primarily of three minerals. These are about 50% colemanite (CB6011 5H20), about 40% probertite (NaCaB50g 5H20), and 10% ulexite (NaCaBgOg 5H20). The colemanite, along with boric acid and high-grade colemanite ore from Turkey provide the only sodium-free borates for production of textile grade fiberglas. When heated to its decomposition temperature, colemanite decrepitates to a fine powder, which is the basis for the concentration process. The gangue minerals in this deposit are primarily calcite and clays, including bentonite. The ore body has a very low arsenic content, which is a desirable feature. Test work had been done with samples prior to the results discussed herein. This paper will discuss results of test work which were the basis for erection of a plant, and the subsequent plant operations. Laboratory Calcination and Air Tabling Tests Laboratory calcination tests showed that substantial upgrading of the borate could be accomplished by calcining followed by screening of the calcined material. Removal of the + 28 mesh calcine resulted in borate losses of less than 10% with a rejection of 40 weight % or more of the calcine. The minus 65 mesh calcine generally met the requirement of containing 48%, or more, B203. The minus 28 plus 65 mesh material contained an intermediate quantity of borate and would require additional treatment. Testing demonstrated that ore would not have to be reduced to a size finer than 19 mm (3/4 in.) prior to calcination. A temperature range from 400 to 455OC (750 to 850°F) was apparently satisfactory. Calcination at a temperature of 48Z°C (900°F), or higher, was unsatisfactory due to fusion. All laboratory calcination tests were static tests conducted by placing small covered charges in a laboratory furnace for 40 min. In all tests vapor issues from the furnace for 5 to 7 min. Following this period the ore could be heard "popping," due to decrepitation of the colemanite. The reaction generally continued for approximately one-half hour. Various size fractions of the calcination products from laboratory tests were subjected to laboratory air tabling tests, usually after removing the plus 28 mesh material. Laboratory air tabling tests were conducted employing a Whippet V-80 model air table manufactured by Sutton, Steele and Steele Co. now known as Tripple S Dynamics. Variables include both end and side-tilt, speed of vibration, and quantity of air rising through the deck. In addition to the variables in the machine itself, the feed rate is also a rather critical variable. Testing demonstrated that all - 28 mesh size fractions of the calcine could be successfully concentrated to 48% F2O3 or greater. For the finer material recoveries into the concentrate were between 85 and 90% of the borate. With the coarser material a substantial amount of middling was produced which required cleaner tabling. Laboratory calcination and air tabling tests indicated a process whereby the borate could be concentrated to about 50% B203 with borate recoveries approaching 90%. Moreover, the iron content of the concentrate was well below the required specification of 0.3% Fe2O3. Pilot Plant Calcination Following the laboratory test work described above, pilot plant testing was conducted to prove the process, provide data for engineering studies, and provide product for a prospective purchaser. The kiln used was 0.9 m-diam (3 ft) by 9.0 m (30 ft) long and had a belly section 1.2 m-diam (4 ft) by 2.74 m (9 ft) long near the discharge end. The kiln was operated at a speed of 0.7 rpm. Gas was fired into the kiln at an average rate of 27.1 m3/hr (958.4 cu ft per hr). The air to gas ratio used was 10:1. The ore was fed to the kiln countercurrent to the flame and discharged through a hopper into a screw conveyor which discharged to a 1.2 m (48 in.) Sweco separator. The separator had 28, 65, and 150 mesh screen cloths, with the plus 28 mesh fraction being discarded. The minus 28 mesh fractions were later subjected to air tabling. The exit gases, containing some calcine dust, were swept through two cyclones to recover the dust. The gases then were scrubbed in a Ducon scrubber; very little dust reported past the first cyclone. The dust from the first cyclone was also saved in drums. In addition to the gas rate, the flue gas velocity, after

Jan 1, 1981

By E. J. Nielsen, P. R. Strutt

A study has been made of the progressive changes in the distribution of etch-pit structures occurring during high-temperature creep in copper + 7 wt pct Al single crystals oriented with a [113] tensile axis. The two equally stressed glide systems with the highest Schmid factor would be expected to form subboundaries of the type predicted by Kear.2 The alignments of etch-pits on sections parallel to different (111} planes consistent with these types of boundaries were not observed. However, they were consistent with planar subboundaries (on a macroscopic scale). From an analysis of Amelinckx1 it may be shown that stable cross-grid dislocation boundaries may form in the primary slip planes. These boundaries form when dislocations with a Burgers vector not in the slip plane move into the plane by combination of climb and glide. THE geometry of subboundaries formed by the interaction of dislocations of two glide systems has been analyzed by Amelinckx,1 and the particular types produced by deforming fee crystals are predicted by ear.' In this paper types of boundaries which may be formed when climb as well as glide occur are discussed as this is relevant in high-temperature creep. It is assumed in the present investigation that the etch-pits observed in Cu + 7 wt pct A1 on surfaces parallel to {111} planes delineate the sites of dislocations. Although there is no direct evidence for this previous work on a-Cu/Al single crystals by Mitchell, Chevrier, Hockey, and Mon-aghan,3 would show this assumption to be reasonable. The alignments of etch-pits which form during creep are studied on sections parallel to each {111) plane. It is then deduced that these alignments are consistent with a specific type of planar subboundary. The Cu + 7 wt pct A1 single crystals had a [113] tensile axis and Fig. 1(a) shows schematically the relation of the slip planes and slip directions (as represented by tetrahedron ABCD) with reference to the tensile axis. The two equally stressed glide systems with the maximum Schmid factor namely ß-AD and (a-BD, from the analysis of Kear,2 would be expected to form the boundaries shown in Fig. l(a) and (b), also Fig. 5(a) and (b). EXPERIMENTAL PROCEDURE The a-Cu/Al single crystals were grown and annealed in a "gettered" argon atmosphere. Chemical analysis showed the aluminum content to be uniform in each crystal and the difference between crystals was maintained to an accuracy of ± 0.25 wt pct. The initial dislocation density and mean subgrain diameter after annealing was -106 cm-2 and 250 µ, respectively. Surfaces parallel to (111) planes were produced by specially developed electrolytic machining processes. The {111} faces were next electropolished for 5 min in a solution consisting of 25 g chromium trioxide, 113 ml glacial acetic acid and 40 ml water; the applied potential was 8 v. Dislocation etch-pits were revealed using l an etchant described by 1 ml bromine, 45 ml HCl, and - 250 ml water. RESULTS In crystals strained into secondary creep at higher stresses (443 and 750 g - mm-2 at 650° C aligned rows of etch-pits parallel to slip plane traces were evident in sections parallel to the (1111, (ill), and (111) planes, see Fig. 3. As well as the longitudinal alignments in Fig. 3, well formed randomly oriented arrays indicative of an equiaxed subgrain structure are evident. At the lower stresses (100 to 230 g . mm-2) only an equiaxed structure formed during creep. The sections in Fig. 3 are from a crystal crept for 70 hr at 650°C with a CRSS of 443 g.mm-2. Two identically oriented crystals were also deformed at the same temperature and stress for 5 min and 4 hr. In the crystal crept for 5 min, the etch-pits were randomly distributed with no tendency for directional alignment, see Fig. 2(a). As shown in Fig. 2(b) aligned arrays were evident after 4 hr creep but they were not nearly so well defined as in Fig. 3. The alignments (parallel to the arrows) in Fig. 3 are consistent with the existence of boundaries in the two main slip planes a and ß. The way in which this is deduced is seen by reference to Fig. l(c), where the existence of boundaries in the a and ß planes is verified by sectioning parallel to a,ß, and d. The (111) and ß(111) planes intersect the d(111) plane along BC [101 ] and AT [011] and alignments parallel to [101] and [011] are clearly evident in Fig. 3(c) in a section parallel to the d(111) plane. Similarly the a, and ß planes in Fig. l(a) intersect each other along DC [110] and hence there will be an alignment parallel to [110 ] in sections parallel to the a-plane and the ß-plane; this is evident in Fig. 3(a) and Fig. 3(b). It is interesting to note that alignments of etch-pits consistent with the boundaries predicted by Kear2 were not observed; see Figs. l(a) and l(b). The geometry of boundaries in {111} planes as shown in Fig. l(c) is discussed later. In Fig. 4(a) the individual etch-pits are resolved and the alignments are exactly parallel to the slip trace direction [101]. However, in some areas alignments deviate away from the slip trace direction by as much as 10 to 15 deg, this is evident in Fig. 4(b), and in Fig.

Jan 1, 1969

By G. D. Rieck, M. M. P. Janssen

Chemical diffusion coefficients and heats of activation for diffusion in the NizAh fy), NiAl (6), and Ni3A1 (E) intermetallic phases and the solid solution of aluminum in nickel (( phase) were calculated from layer growth experiments. No finite diffusion coefficient for the NiAl3 ((3) inter metallic phase could be calculated. The values of the diffusion coefficients are dependent both on the method of calculation and the type of diffusion couple. The heat of activation for diffusion in the y phase was found to be 47 kcal per mole in the temperature range oj 428" to 610°C. Heats of activation of 41, 12, and 48 kcal per mole were found for diffusion in the 6, E, and ( phases, respectively , in the temperature range of 655" to 1000°C. Experiments with markers in the diffusion zone demonstrate a very pronounced Kirkendall effect. It appears that only aluminum atoms take an active part in the diffusion process during the formation of the 0 and y phases at temperatures of about 600°C. During the formation of the 6, E, and < phases at higher temperatures only nickel atoms are moving. It is suggested that the great stability of the intermetallic compounds in the Ni-A1 system governs the Kirkendall effect. SOME factors controlling layer growth during inter-diffusion in the Ni-A1 system (phase diagram, see Fig. 1) were studied by Castleman and Seig1e.l&apos;~ They found the NiA1, ((3) and NiAl3 (y) intermetallic compounds to appear in the diffusion zone of Ni-A1 couples at annealing temperatures of 400" to 625°C; the NiAl (6) and Ni3A1 (E) intermetallic compounds appeared in y-Ni couples at annealing temperatures of 800" to 1050°C. These authors carefully examined metallographically Ni-A1 couples after 340 hr annealing at 600°C. Besides the (3 and y phases they found very thin layers of the 6 and E phases. ~n~erman~ and Castleman and Froot4 observed a much more rapid growth of the 5 and E phases at 600°C in Ni-A1 couples in case a crack was present at the /3-A1 interface. Numerous layer thickness measurements carried out by Castleman and Seigle on the y phase prove that the layer growth of this phase obeys the parabolic law after a certain transient period. From this they concluded that the layer growth of the y phase is controlled by volume diffusion. The growth of the 13, 6, and E phases appeared to be volume-diffusion-controlled also. The authors estimated that at 600°C and at atmospheric pressure Dp was 1.8 x lo-"ll sq cm per sec, D, 9.1 x 10" ™ sq cm per sec, Qp 27 kcal per mole, and Qy 31 kcal per mole. The present work was carried out to obtain more quantitative data about the kinetics of growth of the phases of the Ni-A1 system and the reactions that occur during the formation of these phases. Because in this system the diffusion process results in the formation of several distinct intermetallic compounds, the current term reaction diffusion is used in the title of this paper. In order to obtain layers of the fl phase compound of uniform thickness, a new technique for preparing diffusion couples was developed. The kinetics of growth of the y phase in 6-Al, E-Al, and Ni-A1 diffusion couples was studied at different temperatures. The kinetics of growth of the 6, c, and ( phases in Ni-y, Ni-6, and Ni-c diffusion couples was also studied at different temperatures. The calculation of the diffusion coefficients Dp and Dy by Castleman and Seigle are critically considered in this paper; by means of a revised method of calculation more reliable val-ues of , and Dg were found. These values are in good agreement with the values of the diffusion coefficients obtained by the method of Boltzmann-Matano. From the temperature dependence of the diffusion coefficients the heats of activation for diffusion were calculated by means of an Arrhenius-type equation. The investigation of the Kirkendall effect has been used to obtain information about the ratio of the intrinsic diffusion coefficients of the separate atoms5 and the mechanism of diffusion. Moreover porosity as a result of a distinct Kirkendall effect would be of practical importance in connection with the bonding of diffusion coatings. The analyses of the diffusion couples were carried out by metallographic methods. The values of the concentrations at the phase boundaries and the concentration profile in each of the phases, which are needed for the calculation of diffusion coefficients, were obtained by electron-pro be X-ray microanalysis. EXPERIMENTAL PROCEDURE A) Materials for Diffusion Couples. The intermetallic compounds 6 (50 at. pct Ni) and E (74 at. pct Ni) were prepared from the pure metals by high-frequency induction melting in argon atmosphere. Use was made of aluminum wire (99.99 wt pct Al) and nickel sheet (99.95 wt pct Ni). The 6 and E phase melts and the nickel shiet (thickness 0.1 and 0.5 mm) used for preparing diffusion couples were annealed for 64 hr at 1200°~ for homogenization and grain coarsening (final crystal size 1 to 3 mm). composition and homogeneity of the intermetallic compounds were checked by mi-crohardness measurements and X-ray diffraction. From the 6 and E phase melts discs of 0.5 mm thickness were prepared by means of a water-cooled rotat-

Jan 1, 1968

By G. R. Speich

The distribution of carbon and the type of substructure in iron-carbon martensites containing 0.02 to 0.57pct C has been studied in the as-quenched condition and after tempering at 25" to 700°C by using electrical resistivity, internal friction, hardness, and light and electron microscope techniques. in marten-sites containing less than 0.2 pct C, almost 90 pct of the carbon segregates to dislocations and to lath boundaries during quenching; in martensites containing greater than 0.20 pct C, appreciable amounts of carbon enter normal interstitial positions located far from defects. Tempering martensites with carbon contents below 0.20 pct at temperatures below 150°C results in additional carbon segregation to dislocations and to lath boundaries but no carbide precipitation whereas -carbide precipitation occurs in martensites with carbon contents exceeding 0.2 pct. Above 150°C, a rod-shaped carbide (either Fe3C or Hagg) is precipitated in all cases. At 400°C, spheroidal Fe3C precipitates at lath boundaries and at former aus-tenite grain boundaries. At 400" to 600"C, recovery of the martensite defect structure occurs. At 600" to 700°C, recrystallization of the martensite and Ost-waW ripening of the Fe3C occur. The effects of the carbon segregation that occurs during quenching and the subsequent substructural changes that occur during tempering on martensite tetragonality, hardness, and precipitation behavior are discussed. A mathematical analysis of carbon segregation during quenching is presented. RECENT studies of the strength of low-carbon martensitel-4 emphasize the importance of carbon segregation to the martensite lath boundaries and to the dislocations contained between them during quenching. Unfortunately, very few studies of the tempering of low-carbon martensites have been conducted, so the exact nature of this segregation is poorly understood. In fact, most early tempering studies5,6 were restricted to carbon contents greater than 0.20 pct. Moreover, these studies did not determine the amount of carbon segregated to the martensite substructure during quenching so that the initial state of the martensite was not established. Aborn7 studied the precipitation of carbide in low-carbon martensite during quenching but did not establish whether carbon segregation occurs prior to carbide precipitation, nor did he study the subsequent tempering sequence in detail. In the present work we have used electrical resistance and internal friction measurements, supplemented by electron transmission microscopy to establish the carbon distribution in as-quenched specimens. Specimens thin enough to avoid carbide precipitation (but not carbon segregation) were employed. The redistribution of carbon on subsequent tempering below 250°C was followed by measurements of elec- trical resistance. Additional studies were made on specimens tempered at 250" to 700°C to elucidate the overall tempering behavior of low-carbon martensites, including the formation of cementite and recrystalli-zation of the martensite. EXPERIMENTAL PROCEDURE Eight iron-carbon alloys with 0.026, 0.057, 0.097, 0.18, 0.20, 0.29, 0.39, and 0.57 wt pct C were prepared as 8-lb ingots by vacuum melting. Typical impurities in wt ppm were 40 Si, 20 Mn, 30 S, 10 P, and 10 N. These alloys were hot rolled to 3 in. plate at 1095°C) (2000°F). The hot-rolled plates were surface ground to remove scale and the decarburized layer, then cold rolled to 0.010 in. sheet. Specimens cut from the sheet were austenitized for 30 min at 1000°C (1830°F) in a vacuum tube furnace in which the pressure did not exceed 2 x 10-3 torr. Chemical analysis of specimens after austenitization indicated no decarburization at this pressure. Immediately before quenching, the furnace was filled with prepurified helium. The specimen was then pushed rapidly through an aluminum foil gasket, which sealed the bottom of the furnace, into an iced-brine bath (10 pct NaC1, 2 pct NaOH). The quenching rate at the M, temperature is about 104&apos;c per sec for 0.010 in thick specimens, as calculated from Newton&apos;s law of heat flow2 using a heat transfer coefficient of 25 ft-&apos;. This quenching rate is sufficiently high so that all the alloys transformed completely to martensite throughout the entire 0.010 in thickness and no carbide precipitation occurred in the martensite. All specimens were immediately transferred to liquid nitrogen after quenching and stored there until needed. Tempering below 250°C (480°F) was done in silicone oil baths thermostatically controlled to *;"C. Tempering above 250°C was done in circulating air furnaces or lead pots with the specimens contained in evacuated silica capsules. Electrical resistance was determined by measurement of the potential drop across both a standard resistance and the specimen, connected in series. All resistance measurements were made in liquid nitrogen (77K, -196°C) to minimize thermal scattering of electrons and thus maximize the contribution of impurity scattering to the resistance. Specimen dimensions were 5.10 by 0.19 by 0.025 cm. Although the precision in the electrical resistance measurements was +0.1 pct, the electrical resistivities could only be measured with an accuracy of +5 pct because of uncertainty in the specimen dimensions. Internal friction measurements were performed in an inverted pendulum apparatus at vibration frequencies of either 1.9 or 66 Hz. The specimen dimensions were 5.10 by 0.375 by 0.025 cm. Hardness measurements were made with a Leitz-Wetzlar microhardness machine with loads of 100 g. Specimens were examined by light microscopy after etching in 2 pct Nital and by electron transmission microscopy after preparation of thin sections by electrolytic thinning in a chromic-acetic acid solution.

Jan 1, 1970

By M. Gell, G. R. Leveran

The high- and low-cycle fatigue properties of the nickel-base superalloy, Mar-MBOO, in columnar-grained and single-crystal forms were determined at room temperature. It was found that the fatigue lives of these materials were greatly affected by the size of preexisting cracks in MC-type carbides contained in the micro structure. Most of the data falls on two curves given by: (zN)&apos;/A€= K, where Nf is the number of cycles to failure, Af is the total strain range, and K is a function of carbide size. No difference was observed in the fatigue behavior of the columnar-grained and single-crystal materials for the same MC carbide size. Matrix slip and crack initiation occurred at precracked MC carbides and, to a lesser extent, at micropores. Fatigue crack propagation was mainly in the Stage I mode, i.e., on cry stallo graPhic slip planes. The Stage I fracture in these materials was unusual in that distinct features were observed on the fracture surfaces. In high-cycle fatigue, these features resembled those commonly observed on the cleavage fracture surfaces of bcc and hcp materials. Yet, in this study, the cracks propagated slowly in a cyclic manner. In low-cycle fatigue, the Stage I facets contained equiaxed dimples, similar to those observed on the tensile fracture surfaces of ductile materials. These observations indicate that both local normal and shear stresses are involved in these Stage I fractures. A model is proposed to explain these results based on the weakening of the cohesive energy of the active slip planes by reversed shear deformation and the fracture of the bonds across the weakened planes by the local normal stress. RECENT developments in casting technology have produced cast nickel-base superalloys in columnar -grained and single-crystal forms.1&apos;2 The tensile and creep properties of the nickel-base superalloy, Mar-M200, cast in these forms have been shown to be superior to the corresponding properties of the conventionally cast polycrystalline material.lp2 This improvement in properties results, in part, from the elimination of grain boundaries in the single crystals and the alignment of the grain boundaries parallel to the stress axis in the columnar-grained castings. As part of a program to evaluate the fatigue properties of nickel-base superalloys cast in single-crystal and columnar-grained forms, a study has been made of the cyclic deformation and fracture of Mar-M2OO at room temperature. M. fiFl I .hininr Mpmher AIMF ic ^pninr Rocoarrh Accn^iata anH I) EXPERIMENTAL PROCEDURE The composition range of Mar-Ma00 in weight percent is: 8 to 10 Cr, 9 to 11 Co, 11.5 to 13.5 W, 0.75 to 1.25 Cb, 1.75 to 2.25 Ti, 4.75 to 5.25 Al, 0.01 to 0.02 B, 0.03 to 0.08 Zr, 0.07 to 0.12 C, bal. Ni. All of the castings met the above specifications. The castings were solutionized for 1 to 4 hr at 2250°F followed by aging at 1600°F for 32 hr which resulted in a 0.2 pct offset yield stress of 150,000 psi at room temperature. The microstructure of the material consisted of cuboidal, coherent particles of ordered, fcc Ni3(A1,Ti) (commonly designated y&apos;), approximately 0.3 p on edge, distributed in an fcc y solid-solution matrix. MC carbides together with shrinkage and gas micropores were also distributed throughout the materials. The MC carbides and micropores were located preferentially in the interdendritic interstices, as well as in the grain boundaries in the columnar-grained castings. The (100) direction of all the single crystals and the common (100) axis of the grains in the columnar materials were aligned within about 5 deg of the specimen axis. Fatigue testing was carried out in the high-cycle (HCF) and low-cycle (LCF) fatigue regions, with the major difference being gross yielding of the specimen occurred during the first cycle in the LCF region. This division also corresponded with the more usual one in which the life of a specimen in LCF is less than lo4 cycles and that in HCF is greater than lo4 cycles. The designs of the high-cycle fatigue and low-cycle fatigue specimens are shown in Figs. l(a) and (c), respectively. The gage sections of both HCF and LCF specimens were electropolished prior to testing. The HCF specimens were tested in an MTS, closed-loop, hydraulic fatigue machine at 10 cps in air. The specimens were cycled between a tensile stress of 5000 psi and a maximum tensile stress which ranged from 35,000 to 125,000 psi, Fig. l(b). The LCF specimens were cycled under strain control from zero to a maximum tensile strain, Fig. l(d), in a Wiedemann-Baldwin testing machine. The experimental procedure has been described elsewhere.3&apos;4 Both HCF and LCF tests were interrupted periodically in order to replicate the development of slip and cracking at the specimen surface. This was accomplished by placing plastic replicating tape around the gage section of the specimen while the specimen was in the mahine. The size of the MC carbides for all specimens was measured on a polished longitudinal section through the gage section after fatigue testing. The method of measurement consisted of carefully scanning the entire polished section in order to locate the largest MC carbides. Photographs were then taken of the six longest carbides oriented approximately normal to the

Jan 1, 1969

By P. Gordon

An isothermal jacket microcalorimeter, supplemented by metallographic, microhardness, and X-ray measurements has been used to study the isothermal annealing of high purity copper after room temperature tensile deformation. The amount of stored energy released during annealing has been measured as a function of deformation in the range 10.8 to 39.5 pct elongation. The data have shown the major heat effect to be associated with recrystallization and have allowed an analysis of the recrystal-lization kinetics and the calculation of activation energies of recrystallization. WHEN a metal is deformed plastically, some of the energy expended is dissipated as heat during the working process, while the remainder is stored within the metal in the form of lattice distortions and imperfections. During subsequent heating of the metal, the distortions and imperfections can be largely annealed out and the associated stored energy released as heat. It is apparent that measurements of the evolution of stored energy during such annealing may produce important information concerning the nature of the annealing mechanisms and the imperfections involved. Some excellent studies of this type have been made in the past, notably those of Taylor and Quinney,&apos; Suzuki,2 Bever and Ticknor,3 Borelius, Berglund, and Sjöberg,4 and Clarebrough et al.5,6 None of this work, however, employed isothermal techniques, with the exception of the Borelius studies&apos; in which only the early annealing stages were investigated. Since isothermal measurements, as compared with heating or cooling curve, have the merits that 1—they reveal the kinetics of a process more clearly, 2—the results obtained are more easily applied to theory, and 3—most fundamental investigations of annealing using techniques other than calorimetry have been carried out isothermally, it was considered important to apply calorimetry to the study of the isothermal annealing of metals. Accordingly, an isothermal jacket calorimeter of the Borelius type,&apos; supplemented by metallographic, hardness, and X-ray measurements, has been used to study the annealing of high purity copper after room temperature tensile deformation. Experimental The microcalorimeter has been described fully elsewhere." Briefly, the specimen to be studied is placed in a constant temperature environment of virtually infinite heat capacity achieved, as shown in the drawing of Fig. 1, by means of a vapor thermostat. A high thermal resistance is provided between the sample and the environment and a sensitive differential thermopile (see Figs. 2 and 3) arranged with half its junctions in contact with, and thus at the constant temperature of, the environment, and the other half in contact with the sample. A reaction in the sample develops a small difference in temperature, AT, across the thermopile, which is followed by a recorder-galvanometer set-up as a function of time, t, and is converted to reaction heat per unit time, P, by the use of the equation AT P=a?T + b AT dt The constants, a and b, in Eq. 1 are determined by a simple calibration, making use of the Peltier heat developed by a small current run through the junction of a thermocouple located in an axial hole in the specimen (Fig. 2). In its present form, the limit of sensitivity of the calorimeter is a heat flow of 0.003 cal per hr. The copper used was the spectroscopically pure metal supplied by the American Smelting and Refining Co. in the form of 3/8 in. diam continuously cast rod, reported to be 99.999+ pct Cu. A small amount of the copper was available at the start of this work and is referred to hereafter as lot A. A second batch, lot B, was obtained later, most of the results described subsequently being for this lot. As will be seen, there is some indication that lot A was somewhat purer than lot B, but it is not known whether this difference was present in the as-received metal or arose during subsequent handling. The two lots of copper were remelted and cast into two 1½ in. diam ingots in vacuo, using high purity graphite crucibles and molds. The ingots were upset several times to break up the large cast grains, and then rolled and swaged to rods 0.391 in. in diameter, using several intermediate anneals with about 40 pct reduction in area between anneals. The penultimate anneal was 2 hr at 350°C. X-ray examination showed no marked general preferred orientation in the resulting rods. The grain structure typical of the two rods is shown in the micrograph of Fig. 4." It was found to be virtually im- possible to get an unambiguous measure of the absolute grain size in the two annealed rods because of the profusion of annealing twins and the lack of regularity of the grain boundaries. However, counts of the number of boundaries intersected per unit length along a random line on a polished section, making a correction for the proportion of boundaries (about half) estimated to be twin boundaries, gave a figure of about 0.015 mm for the average grain diameter. The grain size of the rod from lot A was about 5 pct smaller than that from lot B. The rods were cut into 1 ft long bars and these deformed in tension at room temperature to various total elongations in the range 10.8 to 39.5 pct. A strain rate of 1 pct per min was used. The deformed bars were then stored in a dry ice chest until such time as samples were to be cut from them. Five bars deformed as indicated in Table I were used for the subsequent tests. In all cases, all the calorimeter.

Jan 1, 1956

By W. A. Backofen, D. L. Holt

Push-pull fatigue tests have been carried out at 4.2°K, 77oK, and room temperature on two poly crystalline materials of widely different stacking-fault energy (?): pure copper (? - 70 ergs per sq cm) and the Cu-8 wt pct A1 alloy (? - 2.8 ergs per sq cm). Constant stress-amplilude was imposed and measurement was made of the plastic-strain amplitude (ep) at saturation. Lives extended from 104 to 106 cycles. Designating lives at the various temperatures by NRT, N77, and N4.2. the ratios N77/NNT and N4.2/N77 ranged from 3.5 to 18 under the condition of common Ep . Metallo-graphic examination revealed different crack morphology in Cu-8 Al fatigued at room temperature, and at 77" and 4.2oK. At room temperature, cracks lay in or near grain and lain boundavies; at 77o and 4.2oK. cvacks were transcrystalline. Tests on single crystals of Cu-8 A1 showed that such a change in the cracking mode in polycrystallitle material accounted for a factor of- about 3.25 in N77/NRT . The longer life at lower tewperatztre (conslant cp) has heels attributed to two deuelopinents: a reduced production of the dislocation tangles and subgrain boundaries which serve as paths of rapid cracking, and suppression of oxygen chetni-sorption at the crack tip It was concluded that in both materials the luller accounted for an extension of the life at 4.2oK beyond that at room temperature by a factor of 15. XV ECENT experiments on the fatigue of Cu-A1 alloys in the so-called high-cycle range (greater than lo4 cycles) have emphasized the importance of stacking-fault energy (y) as a quantity affecting crack propagation rate and fatigue life.1,2 It was found in comparisons at essentially fixed plastic-strain amplitude that crack growth rate decreased by a factor of about 5 over the composition range from copper (? - 70 ergs per sq cm) to Cu-8 wt pct Al (? - 2.8 ergs per sq cm). The argument was made that, when stacking-fault energy is high, cross slip and climb are favored, so that dislocation tangles and/or subgrain boundaries form more readily under cyclic loading. Since the boundaries and tangles act as paths of rapid crack propagation ,3, 4 life is shortened as a result. However, when stacking-fault energy is reduced (as by alloying), cross slip and climb become more difficult, with the result that substructure formation is retarded and growth rate is also reduced. A purpose of the present work was to investigate the substructure effect in relation to temperature. As temperature is lowered, ? is varied only slightly (if at all), but decreased thermal activation can interfere with cross slip and climb. Thus substructure formation could be curtailed and life increased. Fatigue life in the high-cycle range is also known to be strongly influenced by environment. Working with copper, Wadsworth and Hutchings observed that life in a vacuum of 10-8 mm Hg exceeded life in air by a factor of 20.5 They isolated oxygen as the agent that furthered cracking. While the details are still unclear, a requirement in any mechanism of oxygen-accelerated cracking is that there be chemisorption at the crack tip. That could prevent welding on the compression half cycle,= interfere with reversal of slip,1, 6 or aid in breaking metal-metal bonds at the crack tip.5&apos;7 In the work being reported here, temperature was lowered by immersion in liquid nitrogen and helium, which also served to reduce both the oxygen concentration and chemisorption rate. A possible effect upon life, i.e., a lengthening, had to be recognized. Several researchers have determined fatigue lives at low temperatures presenting their results in the form of stress amplitude (S) vs cycles in life (N) curves.8-11 Such curves reflect, primarily, the fact that metal is strengthened by lowering temperature; effects of substructure and changing environment tend to be masked. The difficulty can be overcome by comparisons based on identical plastic-strain amplitudes, and in the present work the dependence of life on both plastic strain and stress amplitude was established. EXPERIMENTAL Materials. The principal materials were polycrystal-line copper (? - 70 ergs per sq cm)" and the Cu-8 wt pct Al alloy (? - 2.8 ergs per sq cm),I3 the latter being near the limit of solubility of aluminum in copper and having, therefore, the lowest stacking-fault energy in the CU-Al system. Specimens were machined from 0.118-in.-diam cold-swaged rods of high-purity (99.999 pct) copper and the Cu-8 Al alloy, the latter produced initially in a graphite boat by induction vacuum melting a mixture of 99.999 pct Cu and 99.99 pct Al. The machined specimens were annealed to produce mean grain diameters of about 0.070 mm in copper and 0.190 mm in the alloy. Specimen dimensions are given in Fig. 1. Values of the tensile yield stress, ultimate strength, uniform strain (determined by the Considgre construction), and reduction of area, for both materials at 4.2oK, 77oK, and room temperature, are listed in Table I. The tensile apparatus in which these results were obtained has already been described.14 Apparatus. Specimens were fatigued in push-pull with a machine that is illustrated schematically in Fig. 2. The specimen is first soldered into the top grip (1) with Woods metal, and the grip is then screwed into the inner tube (2) which is connected to the drive rod of the Goodmans vibration genera-

Jan 1, 1968

By C. G. Bieber, J. R. Mihalisin, R. T. Grant

A growing demand for longer service life of gas turbines has placed increasingly rigorous requiret~rents upon superalloys employed for that application. Long-titne testing at high temperature has revealed that phase transformations occur in all superalloys. A common one of particular interest is o formation. Presented here are studies made to identify a and to characterize its formation and effect on properties in three cast nickel-base superalloys—IN 100 alloy, alloy 713C, and alloy 713LC. Methods are discussed by which o can be eliminated or inhibited in IN 100 alloy and alloy 713C. Evidence was obtained to indicate that some types of o may be more detrimental than others. Limitations in the electron vacancy approach to o prevention are pointed out, and it is shown how alternative approaches, such as reducing a complex superalloy matrix to the form of a pseudo-ternary system permitting equilibrium diagram treatment, lead to additional insights into the formation of in these alloys. AROUND 1960. Beiber1 developed IN 100 alloy, which still remains one of the strongest commercially available nickel-base superalloys. The principle used in the design of this alloy was to produce large quantities of y&apos; phase in a y matrix through the use of copious amounts of aluminum and titanium. In 1963, ROSS&apos; showed that when certain heats of this alloy were held for a long time at 1650°F they formed an acicular phase, subsequently identified as a.3 a is a hard and brittle phase first discovered in the Fe-Cr system by Bain and Griffiths.4 They termed it the "B" constituent. Subsequently this same phase was found in other systems, primarily those of the transition elements, and acquired the name "a" by which it is now known. The crystal structure of the a phase was first determined in the Fe-Cr system in 1950.5 It was shown to be tetragonal with a c/a ratio of about 0.52. as is the case with a found in other systems. This characteristic crystal structure is now the means by which a is identified. In superalloys, such as IN 100 alloy. large amounts of o impair the high-temperature creep strength and drastically reduce room-temperature tensile ductility. Discovery of o phase in some heats of IN 100 alloy quickly led to investigations of other superalloys for similar transformations. It was found that many of the stronger, more highly alloyed. super-alloys were indeed susceptible to o formation. This investigation has been concentrated on three commercial alloys: IN 100 alloy, alloy 713C, and alloy 713LC. J.R.MIHALISIN,MemberAIME, and C.G.BIEBER are with The International Nickel Co., Inc., Paul D. Merica Research Laboratory, Sterling Forest, Suffern, N. Y. R. T. GRANT, Member AIME, is with The International Nickel Co., Inc., Pittsburgh, Pa. Manuscript submitted May 22. 1968. IMD A detailed study has been made of the phase transformations and their relation to a formation along with a consideration of electron vacancy approaches for predicting a-forming propensity in these alloys. EXPERIMENTAL PROCEDURE Phase transformations were studied by light and electron microscopy, electron diffraction, microprobe investigations, and X-ray diffraction. Specimens for light micrographic examination were prepared by conventional grinding and polishing followed by etching with glyceregia (2:l HC1/HNO3 + 3 glycerine by volume). Photomicrographs of stress-rupture specimens were taken adjacent to the fracture unless otherwise noted in the text. Negative replicas for electron microscopy were taken from surfaces electropolished with a solution of 15 pct H2SO4 in methanol. For carbon extraction replication, a solution of 10 pct HC1 in methanol was used. A Siemens Elmiskop I was used for all electron microscopy. Selected-area diffraction studies were made at 80 kv using evaporated aluminum for standardizing the patterns. A nondispersive electron microprobe attachment was used to analyze the extracted precipitates chemically. The fluorescent X-rays were recorded using a flow counter containing P10 gas (90 pct Ar-10 pct methane) with a beryllium window and a single-channel pulse-height analyzer. The pulses from the analyzer were passed to a scaler-ratemeter and differential curves of counting rate vs pulse amplitude were obtained. The base line of the analyzer was driven with a synchronous motor at 0.5 v per min and a channel width of 0.5 v. The time for 105 counts was printed out for each 0.5-v increment. The microscope was operated at 80 kv with beam currents of 1 to 20 pa. This equipment detects elements from atomic number 13 to 40. X-ray diffraction studies were usually made on residues electrolytically extracted in 10 pct HC1 in H2O, although in one case a pattern was obtained from an etched surface of a metallographic specimen. A Siemens Crystalloflex IV was used with iron-filtered CoKa radiation. X-ray patterns were recorded using a goniometer speed of : deg per min. The scintillation counter and pulse-height analyzer operated at a channel height of 10 v and a channel width of 12 v. The equipment was calibrated with a powdered gold standard. The residues usually contained a number of phases. several of which could not be found in the ASTM card file. In addition, as is shown for the case of a phase in IN 100 alloy, other phases had a somewhat different lattice parameter from that reported in the ASTM card file, making it difficult to separate and identify constituents by comparison with ASTM d spacings. For these reasons, phases were identified on the basis of the lattice parameter obtained by indexing the ob-

Jan 1, 1969

By T. A. Rickard

Flaubert, as we know, laid stress on the selection of the right word, le mot juste, the precise epithet, the word that belongs to the thing. A sentence, or even a paragraph, may be spoiled by the use of a word that is not proper, that does not fit or is foreign to the meaning intended. An Australian mining expert is reported to have said: You have a property of considerable value, and what I saw warrants a good development of very rich cubicular galena, with gossan intermixed. &apos;Cubicular&apos; means `belonging to a small bedroom&apos;, a `cubicle&apos; being a sleeping compartment. He meant `cubic&apos;, of course. This is a malapropism, and reminds me of the lady from Chicago that, on her return from Europe, said how much she had enjoyed the rural parts of France, because, among other things, it was "so delightful to hear the French pheasants singing the mayonnaise to the tune of the Los Angelus". It is impossible to amalgamate coal-tar thoroughly with the pulp in the agitating-tank. In metallurgy, `amalgamate&apos; refers to the combination of mercury with one or both of the precious metals, forming an amalgam, which is an alloy of mercury with another metal. It differs from other alloys, such as brass or bronze, in being made without the aid of heat, inasmuch as mercury is molten at the ordinary temperature. The word comes to us from the Greek. through Old French and means `something soft&apos;. It is a mistake to use technical terms, having a specific meaning, for purposes that are foreign to that meaning. The writer of the quotation is not discussing any combination of metals; he is dealing with the physical process of mixing and is using &apos;amal-

Jan 1, 1931