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By A. Kounosu, T. Fujita, J. Shimoiizaka, K. Nakatsuka

Stable aqueous dispersion of magnetite colloid of about 10 nm in diameter was obtained by allowing an anionic or nonionic surfactant to adsorb on the hydrophobic surface of magnetite particles prepared by monomolecular adsorption of oleate. Sodium dodecylbenzene sulfonate, sodium oleate and poly (oxyethylene) nonyl phenyl ethers whose hydrophilic-lipophilic balance (HLB) are higher than 12 were suitable for giving a second adsorption layer to obtain a stable dispersion. Stability of the colloidal suspensions depends upon pH of the solution and is controlled by the dissociation of the adsorbed surfactant in the second layer. The addition of ethyleneglycol, which was used for lowering the freezing point of the dispersion, did not affect the stability when used in amounts smaller than 60% of water. Preparation of diester-based ferrofluids was also attempted by the same procedure using a nonionic surfactant as second layer molecule. Hydrophobic magnetite colloid, which had been preliminarily coated with mono-molecular oleate, was suspended in di(2-ethylhexyl) agipate, azerate, and sebacate respectively, and dispersion stability was investigated by adding various poly (oxyethylene) nonyl phenyl ethers of different HLB values. It was found that those with HLB values between 10.9 and 13.3 were suitable for this purpose. Stabilities of the dispersions in a magnetic field were investigated up to 1 T by applying an electromagnetic field. No separation of dispersant was observed and each magnetite dispersion displayed the characteristics of a magnetic fluid.

Jan 1, 1980

By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By M. Friedman

Applications of rock mechanics to the design of engineering structures in rock involve the assumption that the stresses are due entirely to the present applied loads. For instance, it is assumed that the vertical normal stress in undisturbed rock free of topographic effects is equal to the weight per unit area of the overburden. In fact, vertical dilatational strains associated with stresses of more than 100 times the present overburden pressure have been measured by strain-relief methods on outcrops. 1,2 The notion of residual strain (stress) or latent stress3 seems unassailable; and indeed this has long been recognized by metallurgists. It is difficult, however, to assess the residual component of the in-situ state of elastic strain with conventional strain relief methods employed in mines or down boreholes. That is, in principle, the in-situ state results from the superposition of present applied loads (natural or man- induced) and potentially recoverable elastic strains (stresses) that exist in a given volume of material even though there are no external forces across the boundaries of the body (Voight,4 and Fig, 1). Accordingly, only in unloaded blocks can the true residual strains be measured by strain relief methods. Using X-rays, the elastic strains locked within the quartz grains or crystals of a rock can be measured. These strains are known to persist even when the rock is reduced to small chips but to vanish when the rock is disaggregated and the grains are powdered. Although we have just begun to investigate the mechanisms by which the strains are stored (see Preliminary Results), we believe that "pressure solution'' at grain boundaries, secondary cementation under load, permanent ("plastic") deformation, and temperature changes are possible processes. In any event, in our study of naturally deformed rocks, it is significant that we are work-

Jan 1, 1972

By M. L. Fuller

MOST commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper' of this series, and in this paper, aging phase changes of zinc alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evalu-ated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable; from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0.03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change,

Jan 1, 1936

By C. Kolm, E. P. Warekois, S. A. Kulin

MUCH insight has been gained into the nature of the cold-worked state of metals in recent years through the use of modern X-ray techniques. These methods have revealed the existence of stacking faults together with regions of high internal strain and have provided means of measuring the atomic perturbations in plastically deformed metals. In view of the recent increased interest in the solid state, it is desirable to extend these techniques to the study of lattice imperfections introduced into semiconductors during plastic deformation. It is of particular interest to compare the state of imperfection sustained by metallic bonding with that sustained by the covalent bonding found in semiconductors. A knowledge of the imperfections which can exist in semiconductors is important from both a theoretical and a practical point of view since they can greatly influence many of the physical properties. In order to determine the possible existence of stacking faults in covalently bonded structures, precise measurements were made of the diffracted peak positions of plastically deformed germanium, gallium antimonide, and indium antimonide. These measurements were based on the theoretical treatment of Paterson1 and are similar to those employed by Warren and warekois2 in their studies of deformed a brass. In addition, diffraction peak profiles were measured on the annealed and plastically deformed materials in order to obtain information concerning the distribution of internal strains through the use of the Fourier methods developed by Warren and Averbach.3 EXPERIMENTAL PROCEDURES AND TECHNIQUES Because of the room-temperature brittleness of the semiconductors studied, it was necessary to plastically deform the materials at elevated temperatures. The brittle-ductile transition temperature ranges of GaSb and InSb are sufficiently low to permit hot-filing operations. Therefore, high-purity, polycrystalline GaSb and InSb were filed in an argon atmosphere at 400' and 300°C, respec-

Jan 1, 1959

By R. L. Wilcox, M. L. Fuller

MOST commercial alloys undergo changes in phase composition after casting. This is a natural result of the fact that the alloys are not in a state of phase equilibrium as cast and phase changes will therefore take place, with more or less rapidity, in an attempt to attain equilibrium. The practical aspect of aging in zinc-alloy die castings concerns the changes in physical properties and in dimensions that may accompany aging phase changes. Harmful alterations have been reduced to a minimum and zinc-alloy die castings are being produced today that are so stable with respect to dimensions and physical properties that they are entirely suitable for most practical purposes1. In the first paper2 of this series, and in this paper, aging phase changes of zinc alloy die castings have been investigated and the possible influence of these changes on dimensional changes of the castings has been evaluated and compared with the dimensional changes actually experienced. The change of dimensions has been selected for practical comparison in these papers because the effect of phase changes on the dimensions of a casting is directly calculable from X-ray crystal-analysis data of the phase structure. The die-casting alloys considered contain, in addition to zinc, 4 per cent of aluminum, about 0.03 per cent magnesium, and from 0 to 3 per cent of copper. It was shown in the former paper that the eutectoidal decomposition of the beta aluminum-zinc phase, while intrinsically capable of causing a considerable shrinkage, can have very little effect on the observed shrinkage of die castings because it takes place within a few days of aging, whereas the observed shrinkage continues for five weeks. It was therefore concluded that the other existing phase change,

Jan 1, 1935

By H. C. Vacher

THE limiting concentrations of carbon and oxygen which may co-exist at equilibrium in liquid iron are important in determining the degree to which liquid steel may be refined before it is deoxidized. Most refining processes depend upon the oxidation of a highly carburized iron which invariably results in contaminating the steel with oxygen. The oxygen .thus introduced presents many problems to the refiner, who in turn has attempted to rid the steel of this impurity by deoxidation with elements such as manganese, silicon and aluminum. The importance of the limiting concentrations of carbon and oxygen is accentuated in view of a number of recent researches which have indicated in many instances the existence of relations between oxide inclusions and dissolved oxygen and physical properties and chemical behavior of steel. The determination of the equilibrium concentrations of carbon and oxygen existing in iron under steelmaking conditions is obviously of fundamental importance. It has been generally assumed that the product of the equilibrium concentrations of carbon and oxygen in liquid iron is a constant and that this product is directly proportional to the carbon monoxide pressure in equilibrium with the liquid iron. Herty1,2 has computed values for this product based on open-hearth data which are all in the neighborhood of 0.01 to 0.03 (per cent. FeO X per cent. C) for temperatures in the vicinity of 1550° to 1600 C. and one atmosphere pressure. Kinzel and Egan3 have attempted to determine the value of this product by exposing liquid iron to carbon monoxide at one atmosphere pressure. The value reported by them was 0.0005 at 1550°. C. In. order to apply certain equations to the rate of carbon elimination in the open-hearth process, Feild4 found it necessary to assume. a value of 0.0102 at 1580° C. for this

Jan 1, 1931

By C. F. Quest

THE steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more compre-hensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collec-tion of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combina-tion of tables and an equation. The latter include work by Campbell2,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Tensile strength = 41500 + 770C + 1000P + yMn [1] y was a variable depending on the carbon and manganese content of the steel and was listed in tables, Webster investigated acid Bessemer steel and developed the equation Tensile strength = 38000 + 800C + xP + yMn [2]

Jan 1, 1940

By Richard J. Borg

The vapor pressure of Cd in equilibrium with CdSb in the presence of excess Sb has been measured using the Knudsen effusion method over the temperature range 276° to 379°C. The free energy of formation of CdSb is given by AF° = -1.58 + 1.53 x l0-4 T, kcal per mole. The enthalpy and entropy are obtained from the temperature coefficient of the .free energy. CADMIUM and antimony have almost imperceptible mutual solid solubility but form a single stable intermediate phase, CdSb. This phase, according to Han-sen,l extends from about 49.5 at. pct to 50 at. pct Cd at 300°C and has the orthorhombic structure. The free energy of formation of CdSb can be calculated from the vapor pressure of Cd for compositions which contain less than 49 at. pct Cd. The appropriate reaction and formulae are given by Eqs. [I] and [2]- CdSb(s, ~ Cd(g)-, +Sb(s) [1] Since Sb is in its standard state, Af - N,,AF'-,, = NcdRT In a,, = NcdRT InP/PO [2] In Eq. [2], P, is the vapor pressure of Cd in equilibrium with the alloy, and Po is the vapor pressure in equilibrium with pure solid Cd. It is implicit in this calculation that the free energy only slightly changes within the narrow limits of the single phase field. Thus, the value obtained from the antimony-rich boundary is truly representative of the stoi-chiometric compound. The results reported herein are obtained from a mixture near the eutectic composition, i.e. 59 at. pct Sb. Only two previous investigations" of the free energy of formation of CdSb have been made. Both relied upon the electromotive force method, and measurements were made over relatively narrow temperature ranges which strongly influences the reliability of the values of AH and aS. EXPERIMENTAL The eutectic composition is prepared by fusing reagent grade Cd and Sb by induction heating in vacuo with the starting materials held in a graphite crucible having a threaded lid. The material obtained from the initial melt is pulverized, sealed under high vacuum in a pyrex capsule, and annealed at 420°C for two weeks. X-ray analysis"gives the following lattize parameters: a = 6.436A, b = 8.230& and c = 8.498A using Cu Ka radiation with A = 1.54056. These values are in fair agreement with the result? previously reported by Al~in:4 i.e. a = 6.471A, b = 8.253A, and c = 8.526A. Vapor pressures are measured using an apparatus which has been described elsewhere,= however, with a single important modification. Knudsen effusion cells are made of pyrex with knife-edged orifices made by grinding the convex surface of the lid on #600 emery paper. Photographs taken at known magnifications using a Leitz metallograph enable the determination of the orifice area. Numerous calibration measurements of the vapor pressure of pure Cd give close agreement with values previously reported5,= thus indicating that no significant error can be ascribed to the substitution of glass cells for metal cells used in previous work. Because the vapor pressure of Cd is reliably established and because it is difficult to obtain Clausing factors for the glass cells, the final values used for the orifice areas are calculated from the calibration measurements of the vapor pressure of pure Cd. Effusion runs are started in an atmosphere of purified helium which is quickly evacuated as soon as the cell attains thermal equilibrium. Less than one minute is necessary to obtain high vacuum after evacuation begins, and the temperature seldom varies by more than 0.5oC from the value obtained prior to pumping out the helium. RESULTS The results of this investigation along with other pertinent data are tabulated in Table I. Fig. 2 is the familiar graph of log P against T-10 K. At least mean squares analysis of the data presented in Table I yields the following equation: log1DJP = 8.790 - 6472 x T"1 [3] The deviations of the individual measurements from the values calculated with Eq. 131 are given in column six of Table I; the average deviation is 4.0% of the calculated value. Although the partial molal properties change significantly with composition within the single phase region, the integral thermodynamic value should remain relatively constant. Hence the results of the following calculations, which use the data obtained for the eutectic composition, are probably representative of the equi-atomic compound. Eq. [4] describes the vapor pressure of pure Cd as a function of temperature and may be combined with Eq. [3] to

Jan 1, 1962

By H. B. Pulsifier

The following report on the structure of copper is the result of work done in the laboratory of the Rome Wire Co. early in 1925. Previous work had indicated to the author that excellent results might be expected if a suitable technique in surfacing and etching could be developed. The resources of the Rome Wire Co. enabled this metal to be studied more intensively than previously, although none of the materials were investigated exhaustively. The material presented is hardly more than a preliminary summary of the most obvious character of the metal; a much longer research would have been necessary to solve many of the pressing problems connected with the casting and working of copper. The Rome Wire Co. has generously released the paper; to Dr. E. H. Darby, technical supervisor of the company, are due particular thanks for his appreciation of the importance of metallographic study of copper and for his effective support in the prosecution of the work and in making its publication possible. Dendrites, Cells and Granules The microscope reveals at least three orders of structural units in copper, as in other metals. The largest structural units are the dendrites —spine-shaped crystals building up the masses of metal when it solidifies from a melt or is crystallized from solutions by chemicals or electricity. The nucleus cells, commonly called "grains," are the largest and most conspicuous units of recrystallized solid metal; the limitations of their growth usually confine their sizes to microscopic proportions, although in "single crystals" they may become as large as the piece of metal itself. The granules are the microscopic fine-structural blocks or laminations that build up the nucleus cells; they are revealed when metal is etched with suitable chemicals. The granules are commonly visible at 500 diameters magnification and are plainly visible at 1000 diameters; magnification of the granular surfaces up to 6000 to 9000 diameters shows no finer units, not because of lack of optical resolution but because the chemical attack has left an unfeatured smooth surface.

Jan 1, 1926

Alexander N. Winchell, Butte, Mont. (communication to the Secretary): Mr. Spurr calls attention to the fact that an ore-deposit may be due to a succession of concentrations at different geological epochs. He cites an example of such a condition on Napoleon creek, a branch of Forty-Mile creek, Alaska. It will perhaps be of interest to call attention to another example of the same general character, not so remotely situated. The example referred to is located on Pole creek, a tributary of Cherry creek, in the extreme northeastern part of Madison county, Montana. An excellent geological map of this region is to be found in the Three Forks folio (No. 24) of the United States Geological Survey. According to this map, Pole creek, in its upper course, occupies the contact between the " Flathead " formation, which Peale correlates with the Middle and Lower Cambrian, and an area of gneisses and schists supposed

Jan 1, 1903

By Persifor Frazer

The following notes on the Whopper and adjoining mines in the Gunnison district of Colorado mere made in the spring of this year. The time chosen for the author to visit the region was, unfortunately, the most unfavorable of an exceptionably unfavorable year. About the middle of May all the hill slopes, which at this period of the pear are generally covered with pasture, were thickly covered with snow. The unusually large precipitation of this Tear caused loacal mountain torrents at every few hundred feet, which wore away the oft foothills into gulches, gouged great chasms out of the roads, and transformed miles of usually dry soil into dangerous quagmires. Travel was totally interrupted for weeks, except on horseback or afoot, and even then with great difficulty and some danger. The Whopper mine is situated on the Whopper Mountain, about two miles from the headwaters of Rock Creek, and on the right hank of that stream. The Whopper Creek flows into Rock Creek horn the east, and, by a precipitous descent, offers excellent facilities for its utilization as a source of power. This stream, which pours past the picturesque Whopper Cabin about thirty tons of water a minute, has a fall of 100 feet in 400 yards, and is said to be a stream of some size, even at the seasons of the year when drought prevails. The Whopper claim extends down the hill a distance of about 250 feet to its intersection with the Whopper Creek (on the other side of which is a small tunnel on its extension called the "Teller") and over the steep hill northwest to the limits of the claim about 1250 feet. The part of the mountain in which this mine is situated is remarkable for its splendid forest, the spruce, fir, and quaking asp covering the mountain-sides with a green growth of valuable timber. The distance from Gothic City to this mine is about eight miles along the valleys of East River and Rock Creek, and on the divide which separates them. The elevation of Gothic City is given from the engineer's notes as 9500 feet above sea-level, and the mean of several observations with a Beck watch-barometer made the elevation of Whopper Cabin (which is about fifteen feet above the floor of the Whopper upper tunnel) about 1260 feet above Skiles's Cabin in Gothic City. The record of this instrument must, how-

Jan 1, 1881

By Persifor Frazer

THE following notes on the Whopper and adjoining mines in the Gunnison district of Colorado were made in the spring of this year. The time chosen for the author to visit the region was, unfortunately, the most unfavorable of an exceptionably unfavorable year. About the middle of May all the hill slopes, which at this period of the year are generally covered with pasture, were thickly covered with snow. The unusually large precipitation of this year caused local mountain torrents at every few hundred feet, which wore away the soft foothills into gulches, gouged great chasms out of the roads, and transformed miles of usually dry soil into dangerous quagmires. Travel was totally interrupted for weeks, except on horseback or afoot, and even then with great difficulty and some danger. The Whopper mine is situated on the Whopper Mountain, about two miles from the headwaters of Rock Creek, and on the right bank of that stream. The Whopper Creek flows into Rock Creek from the east, and, by a precipitous descent, offers excellent facilities for its utilization as a source of power. This stream, which pours past the picturesque Whopper Cabin .about thirty tons of water a minute, has a fall of 100 feet in 400 yards, and is said to be a stream of some size, even at the seasons of the year when-drought prevails. The Whopper claim extends down the bill a distance of about 250 feet to its intersection with the Whopper Creek (on the other side of which is a small tunnel on its extension called the "Teller ") and over the steep hill northwest to the limits of the claim about 1250 feet. The part of the mountain in which this mine is situated is remarkable for its splendid forest, the spruce, fir, and quaking asp covering the mountain-sides with a green growth of valuable timber. The distance from Gothic City to this mine is about eight miles along the valleys of East River and Rock Creek, and on the divide which separates them. The elevation of Gothic City is given from the engineer's notes as 9500 feet above sea-level, and the mean of several observations with a Beck watch-barometer made the elevation of Whopper Cabin (which is about fifteen feet above the floor of the Whopper upper tunnel) about 1250 feet above Skiles's Cabin in Gothic City. The record of this instrument must, how-

Jan 1, 1881

By C. F. Quest, T. S. Washburn

The steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more comprehensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collection of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combination of tables and an equation. The latter include work by Campbel12,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Teosile etrength = 41500 + 770C + 1000P + yMn [1 y was a variable depending on the carbon and manganese content of the steel and was listed in tables. Webster investigated acid Bessemer steel and developed the equation: Tensile strength = 38000 + 800C + xTP+ yMn [2]

Jan 1, 1940

By C. F. Quest, T. S. Washburn

The steel industry has a definite need in its tonnage mills for a formula relating expected tensile strength to the analysis of the steel. The McWilliam-Barnes1 and other less comprehensive formulas are used for this purpose, but these formulas were designed for an analysis range that does not include the medium manganese and silicon-bearing steels. This type of steel is being produced to meet the demand for tensile strength slightly higher than that of ordinary structural steel but not high enough to justify expensive alloy steels. The purpose of this paper is to present a somewhat more comprehensive formula based on data accumulated over a number of years by the Inland Steel Co., and to discuss the method followed in obtaining a formula to fit the data. The resultant formula admittedly is still weak in some respects, but for the expanded analysis range appears to be an improvement over the other formulas. It is hoped that with the collection of more data and possible collaboration with other mills studying this problem it will be possible to work out a more nearly perfect formula. Several publications have been issued on this subject. In some, the equation type of relation was evolved while others made a combination of tables and an equation. The latter include work by Campbel12,3 and Webster.4,5 Campbell classified the steels as acid and basic and applied a different formula to each. For basic steels, he used the equation: Teosile etrength = 41500 + 770C + 1000P + yMn [1 y was a variable depending on the carbon and manganese content of the steel and was listed in tables. Webster investigated acid Bessemer steel and developed the equation: Tensile strength = 38000 + 800C + xTP+ yMn [2]

Jan 1, 1940

By M. M. Mebta, G. W. Dean, W. H. Somerton

With the advent of underground heating operations, interest has developed in the alteration of rock properties by high-temperature treatment. In the present work a number of sandstones were heated to temperatures in the range of 400°C to 800°C under both atmospheric and simulated reservoir pressures. Pertneabilities increased by at least 50 per cent and sonic velocities and breaking strerlgths decreased by an equivalent amount. Differential thermal expansion and other reactions of constituent min-era1 grains are the causes of these alterations. INTRODUCTION In the underground combustion of petroleum reservoirs, temperatures of the order of 600C are reported to have been reached in the combustion zone.' At this temperature rocks are subject to extensive thermal alteration. Temperatures of this magnitude and higher may also occur in subsurface formations when subjected to bottom-hole heating, thermal drilling operations, and underground nuclear explosions. Temperatures of this magnitude might also be generated by conventional rock drilling methods at points of bit-tooth contact. In earlier work, the permanent deformation of rocks resulting from heating was reported. Major structural damage of rocks occurs due to differential thermal expansion of mineral constituents. A number of mineral alterations including crystal inversions, loss of water of crystallization and dissociation, may also contribute to changes in physical structure and properties of rock. In the present work, samples of three typical sandstones were heated to several temperatures up to a maximum of 800C and then allowed to cool to room temperature. Heating was done under both atmospheric pressure and simulated reservoir pressure conditions. Physical properties of the samples were measured before and after heating and comparisons made. Measured properties included permeability, sonic velocity, breaking strength and fracture index. Changes in physical properties were compared to changes in mineralogical characteristics as determined by thin-section. X-ray diffraction and chemical tests. EQUIPMENT AND PROCEDURE Two outcrop sandstones (Bandera and Berea) and one sub-surface sandstone (St. Peter) were selected for the tests. These samples have a wide ranee in composition and physical properties as shown in Table 1. The first series of tests was made on 2-in. diameter by 5-in. long test specimens. Test specimens used in all later work were 3/4-in. diameter by 1 1/8-in. long, this being the specimen size required for heating at simulated reservoir pressures. After careful washing, the cores were oven dried at 100 ± 5C for a minimum of 24 hours before the tests were run. Test specimens were heated in an electric furnace at a constant rate of temperature increase of 3C per minute. When maximum temperature of the run was reached, the sample was allowed to soak for one hour. The furnace was then cooled to room temperature at the same rate of 3C per minute. The entire heating operation was designed for reproducibility without subjecting the test specimens to excessive thermal shock. For samples heated under simulated reservoir pressures, a pressure cell designed by Dean was used (Fig. 1).3 The core sample was inserted into a thin-walled (0.006 to 0.01-in.) copper cup which was then mounted in a high-pressure cell. Provisions were made for the application of internal pore pressure as well as confining pressure. Tests showed that the thin-walled copper cup closed tightly around the core and satisfactorily transmitted confining pressure to the core. The core was heated by placing the entire cell into the electric furnace. The heating program was the same as that used in the atmospheric pressure runs: tempera-ture rise of 3C per minute to maximum temperature of the test, soaking at maximum temperature for one hour, and cooling at a rate of approximately 3C per minute. The cell was designed to withstand 5,000 psi at 1,000C. However, since it was considered likely that repeated heating and cooling would in time weaken the steel, 2,000 psi at 850C was set as a working limit. In the present series of tests, the pore pressure was held constant at 750 psi and the confining pressure at 1.500 psi. The pressure source was a high-pressure nitrogen tank. The two pressures were controlled manually but are accurate well within ± 50 psi.

Jan 1, 1966

By N. A. D. Parlee, E. M. Sacris

OVER 55 years ago, Sieverts and Hagenacker1 and Donnan and shaw2 made determinations of the solubility of oxygen in liquid silver, over a rather short range of temperatures (973° to 1125°C), using quartz bulbs, mainly at 1 atm. From the results of their investigations, Mizikar, Grace, and parlee3 plotted % O vs 1/T and obtained the following straight-line equation for solubility at 1 atm: log % O = 723.7/T - 1.0949 Recent work on the kinetics of the Ag-O2 system394 indicated there might have been some error due to reaction with the direct heated silica bulbs. Thus it became important to redetermine the solubility with the silver contained in a better refractory such as alumina, and by induction heating where the walls of the container were not so strongly heated. It was also desirable to extend the temperature range. A modified Sieverts apparatus of fairly standard type was used except that a special type of reaction tube was employed, Fig. 1. Dried argon with a guaranteed purity of 99.9 pet, and dried medical-grade oxygen with a guaranteed purity of 99.6 pet containing a little nitrogen, were the gases used. The measuring system consisted essentially of a manometer and a water-jacketed 100-cc gas buret with an open-end vertical tube parallel to the buret. This tube has the same diameter as the buret in order to give the same capillary effect on the mercury. A screw leveling device was used with the buret leveling bulb to help provide accurate pressure readings. A 2-mm ID capillary line connected the buret to the reaction chamber, helping to reduce the dead volume, which was determined with argon. The heating medium was a 2.5-kw output induction furnace. The induction coil was made of a 3/16-in. copper tubing with eight turns and an inside diameter of 4 cm. The reaction bulb was made of a quartz tube 18 cm long and 3 cm in inside diameter, Fig. 1. Inside the quartz tube were two alumina crucibles (Mor-ganite Triangle RR, XN10 and XN5) one inside the other. Below these two was an alumina disk. The disk prevented the corners of the outer crucible from expanding against the quartz tube. The solid sample (99.994 + pet Ag), which had been previously cleaned by air oxidation and repeated removal of scum, was placed inside the inner crucible. An alumina disk with a hole at the center covered the two crucibles. In order to decrease the dead volume, an evacuated quartz "filler" tube was placed on top of the crucible cover. The part of the reaction tube above the spherical joint was made up of Pyrex glass with a flat glass top. It was here that a prism was placed to facilitate the use of an optical pyrometer, previously calibrated at the freezing point of silver. This type of reaction bulb and furnace assembly was specially designed for this work, and used in preference to the relatively new water-

Jan 1, 1965

By Goro Shimaoka, Kichizo Niwa

IN the past, the crystalline states of graphite in cast iron have been studied by many investigators. Recently several authors 1-4 have published interesting information on the crystal texture of the individual graphite grain, especially spherulites in nodular cast iron. In regard to the crystal structure of graphite, Lipson and Stokes0 howed by powder X-ray analysis that most of the crystals contain about 14 pct rhombohedra1 structure (ß-form) which differs from the hexagonal structure (a-form) in the sequence of layer stacking. Hoerni6 onfirmed the existence of the ß-form in a single crystal with electron diffraction by Kossel-Moellenstedt's method. Furthermore, Hoerni and Weigle7 found extra reflections in electron diffraction patterns, which are given by a unit cell twice as large as the usual one in the basal plane. Recently, Lukeshs observed graphite twinning and satellite reflections in his X-ray work and considered them as evidence for the existence of an orthorhombic superstructure. Owen and Street" and Matuyama" studied the structures of graphite crystals in several types of cast iron, using the X-ray powder method, and they showed that the graphite crystal contains a certain amount of the ß-form, an amount which varies with the sources of the cast iron used. The present study was made in order to secure structural information on graphitization in cast iron. Electron diffraction studies on the structure of single graphite flakes segregated from molten carbon or silicon-rich iron at 1200" to 1500°C are reported. Experimental Honkeiko pig iron (4.05 pct C, 1.59 pct Si, and 0.65 pct Mn) was used as the solvent of carbon or silicon. The pig iron was melted in an open furnace and a small quantity of metallic silicon was added to the melt at 1300°C. The melt was heated to 150O°C, and then retort black carbon or metallic silicon was added little by little. The components added to the bath contained approximately 5.0 pct C and 2.0 pct Si in the carbon-rich material, and 3.8 pct C and 5.4 pct Si in the silicon-rich iron. These two types were held at 1500°C and then cooled without graphitizing by cutting the heat sup-

Jan 1, 1958

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947

By B. D. Cullity

Gold and beryllium form an intermediate phase composed of the two metals in equal atomic proportions and having the formula AuBe. According to Winkler,' this phase probably exists in two modifications: beta, stable below about 600°C, and alpha, stable between 600°C and the melting point, about 740°C. Only the low-temperature beta form will be considered in this paper. Experimental Procedure The gold used had a fineness of 999.75 to 999.85, balance mainly silver, and the beryllium purity was better than 99.8 pct. AuBe was prepared by melting the constituents in a beryllia crucible in an evacuated induction furnace. After melting and thorough mixing, the alloy was allowed to solidify in the crucible. No difficulty was encountered in obtaining a homogeneous ingot. Both chemical analysis and microscopic examination of the ingot showed that the alloy was essentially one phase, containing 50 at. pct gold. The alloy was quite brittle and powder samples could easily be prepared by grinding in an agate mortar. The X-ray diffraction patterns were made with CuK-alpha radiation in a Debye-Scherrer powder camera 57.3 mm in diameter. The film was placed unsym-metrically in the camera in order to afford a basis for film-shrinkage corrections. A sample homogenized at 500°C gave the same diffraction pattern as a sample taken from the as-melted ingot. General Results The diffraction pattern of AuBe was readily indexed on the basis of a simple cubic lattice with ao = 4.659 + 0.001kX. If the unit cell is assumed to contain four AuBe "molecules," the calculated X-ray density is 13.46 grams per cc as compared with the measured density of 13.55 gm per cc. The only missing reflections in the diffraction pattern are (100) and (220) (see Table I). Since these missing reflections are not those characteristic of body or face centering, the lattice of AuBe must be simple cubic. To locate the positions of the atoms within the unit cell, two possibilities had to be considered: I. The structure was disordered and there were eight positions to be filled by an LCaverage" gold-beryllium atom. That the structure was disordered seemed unlikely since the lattice parameter did not vary with composition in alloys containing sornewhat more and somewhat less than so at' pet gold, indicating a fixed composition for AuBe.

Jan 1, 1947