Search Documents

By H. H. Hausner, O. V. Roman, F. V. Lenel, G. S. Ansell

The radial shrinkage during sintering of cylindrical compacts and loose aggregates of copper powder was measured. It was found to be nonuni-form from top to bottom of the samples and to depend upon the method of supporting them. The non-uniformity is due to the effect of gravity forces during sintering. Since gravity has an effect in sintering without externally applied stresses, no sharp dividing line can be drawn between conventional sintering and hot pressing. RECENT investigations of the sintering behavior of compacts1 and of loose powder aggregates2 have indicated that forces, other than those arising from surface tension effects, may play a role in shrinkage. In compacts it was shown that residual stresses from the pressing operation influence shrinkage behavior. In loose powder aggregates gravity forces due to the weight of the powder affect the ratio of shrinkage in the vertical and the horizontal direction. The main effort in the work reported here was to show that gravity plays a role also in the sintering of compacts. A few additional experiments were made confirming the effect of gravity in the sintering of loose powder aggregates. EXPERIMENTAL PROCEDURE Compacts and loose powder aggregates were prepared from irregularly shaped, electrolytic copper powder. Prior to use the powders were reduced 30 min at 400°C in dry hydrogen to remove surface oxides. Then the -325 mesh size fraction was separated from the -100 + 325 mesh fraction. The compacts were pressed at a pressure of 10,000 psi from 50 g of powder in a hardened steel die, 1 in. in diam. The height of the compacts was 0.725 i 0.005 in. An effort was made to get as uniform a green density distribution in the compacts as possible. The walls of the die were lubricated with a suspension of 3 pct of zinc stearate in acetone and the compacts were pressed using double action by first pressing the powder at 1200 psi with the die barrel supported, then removing the sup- ports and pressing to final pressure of 10,000 psi with the die barrel floating. The pressure was maintained for 10 sec. The compacts were sintered at a temperature of 925°C, generally for 1 hr. In order to maintain uniform temperature they were sintered in boats made from cylindrical copper blocks. The blocks were 2 in. in diam, either 2 or 2 1/2 in. long and, split to form the body of the boat and a lid. The body of the boat contained a cavity 1 3/8 in. wide, 1 in. deep and either 2 1/8 or 1 3/8 in. long. The longer cavity accomodated two samples, the shorter one only one sample. The uniformity of temperature distribution within the boats was checked with thermocouples welded to the top and bottom of the samples. The maximum variation between top and bottom temperatures was i 1/2°C. The actual sintering temperature was held constant within ±2°C. In order to determine the effect of gravity forces, i.e., the weight of the compacts, upon shrinkage, they were supported in the following ways during sintering: a) Full Bottom Support. The compacts rested either on a flat alundum disk or on alundum powders. b) Partial Bottom Support. The compacts rested on a graphite cylinder, 0.3 in. in diam which formed a projection on a larger graphite disk. It is difficult to balance the compact on the small projection. To avoid having the compact tip, a small hole was drilled through the compact and through the graphite disk and its projection. The graphite disk was then suspended from the lid of the boat by a thin iron wire which passed through the holes in the disk and the compact. c) Top Support, first type. A hole 3/32 in. in diam was drilled diametrically through the green compact 3/16 in. from the top of the compact. The compact was sintered suspended from an alundum rod (thermocouple protection sleeve) inserted into the hole. d) Top Support, second type. A hole was drilled axially through the center of the compact. The upper part of the hole from the top surface of the compact one fourth of the way down was 1/16 in. in diam; the lower part of the hole from the bottom surface three fourth of the way up was 3/32 in. in diam. The compact was suspended from the lid of the boat by an iron wire passing through the upper part of the hole and then tied into a knot. The loose powder aggregates were made by filling l in. deep, l in. diam cylindrical graphite molds with -325 mesh powder. To achieve uniform density in all the loose powder aggregates, the powders were settled in the molds by placing the

Jan 1, 1963

By H. Rosenthal, A. L. Jamieson

THE action of mercury on stressed brass to produce cracks was known before Moore, Beckinsale and Mallinson1 showed that actual season cracking did not occur spontaneously but could be induced by ammonia. These investigators studied other substances, including diphenylamine, without finding that anything other than ammonia could cause season cracking. Grimston2 reported season cracking in cartridge cases stored in wooden boxes wetted with dilute sulphuric acid pickling solution. Season cracking associated with sulphur dioxide, water vapor and air has been reported by Johnston,3 although he reported that trimethylamine and pyridine did not cause cracking. Jevons4 has ascribed season cracking of brass in certain instances to trimethylamine, "aldehyde amine," "ketone amine" and pyridine, but no experimental work was done evidently to prove this definitely. Pyridine was investigated by Morris,' who found it to have considerable cracking power. In the present investigation, the object was a qualitative evaluation of a number of representative amines with respect to their ability to cause season cracking. Thus it was desired only that an appreciable vapor pressure of each amine be obtained in order to make the test as severe as possible, without attempting to test equivalent concentrations for comparative purposes. METHODS Specimens Two types of specimen were used: I. Unannealed 70-30 brass cups formed from 0.040-in. thick sheet. Height of cup was 1 3/8 in. and diameter was 1 7/8 inches. 2. First draw pieces of caliber .50 cartridge cases in the unannealed condition (70-30 brass). The cups were representative of a thin wall and thin base specimen, whereas the draw pieces have a thick base (1/4 in.) and a thick wall (approximately 3/32 in.). Both types of specimens contained high residual stress and cracked in less than one minute in a solution of I per cent mercurous nitrate and I per cent nitric acid provided that this was preceded by a 30-sec. pickle in 40 per cent nitric acid. Specimens were prepared as follows: (I) degreased in trichlorethylene, (2) rinsed in H20, (3) pickled 5 min. in 10 per cent by volume H2SO4 (1.84 sp. gr.), (4) rinsed in H2O, and (5) dried. Amines Tested In selecting the amines, representatives of the three series of amines and one series of substituted amines were chosen. The aliphatic series was represented by the methyl and ethyl primary, secondary and tertiary amines. These are the simplest aliphatic amines. For the aromatic series, the phenyl primary, secondary and tertiary amines were selected as being the simplest. The heterocyclic series was represented by pyridine, which is a simple heterocyclic base (tertiary amine).

Jan 1, 1944

By F. E. Crane, H. A. Kendall, G. H. F. Gardner

Two effects of a difference in density may be observed in miscible displacement. As the difference is increased from zero there is first a change in mode from multiple fingers to a single finger. A further increase results in a more rapid growth of the single finger. Miscible displacement with multiple fingers has been discussed by Blackwell, et al, whereas miscible displacement with a single finger has been discussed by Craig, et al. In the present paper experiments are described which bridge the gap between these extreme cases. INTRODUCTION Craig, et al,1 investigated the effect of gravity on frontal displacements for circumstances in which the gravity forces were significant. Blackwell, et a1,2 dealt with the other extreme in which gravity forces were negligible. The considerable difference between their results is illustrated in Fig. 1 where the breakthrough recoveries are plotted against the mobility ratio. The experiments described in the present paper were conducted to examine how the transition from the one extreme case to the other occurs when the gravity forces are gradually reduced. The transition is well illustrated by the production history after breakthrough. Fig. 2 shows how the number of pore volumes which must be injected at a constant rate to displace 98 per cent of the original fluid depends on the gravity force. For each mobility ratio there is a transition range, and a very significant change in the number of pore volumes occurs when this range is traversed. This range of the gravity force is physically linked with the formation of viscous fingers. A single finger is predominant for larger gravity forces; a multiplicity of fingers is formed for smaller gravity forces. Improved recovery and the occurrence of multiple fingers is concomitant with a large increase in the amount by which the fluids are mixed within the porous medium. The transition range depends on all the dimension-less groups which characterize the problem; but this dependence has not been exhaustively studied as yet and only fragmentary results are discussed in this paper.

By R. I. Jaffee, R. W. Wood, H. R. Ogden, D. N. Williams

D. W. Morgan, D. H. Polonis,and R Taggart (Uuivevsity of Washington)—Dispersion hardening in titanium-copper alloys is of particular interest to us in view of our current research activities in phase transformations in this system. We should like to raise questions concerning several points in the paper. The flow sheet for fabrication and heat treatment (Authors' Fig. 2) indicates that 0.045 in sheet is treated in air for a period of 30 min at 1625' F. Were any surface coatings used to reduce oxygen contamination at this stage? One might ask the same question about the 8-hr annealing at 1400F. Contamination during fabrication and heat treatment of such thin sections could be considerable without some protection. Although the authors state that no analyses were made, they note that contamination masks the distinction between base strengths of the different alloys. In this connection, what fabrication and heat-treatment procedures were used in obtaining the comparison specimens of unalloyed titanium? It would seem that oxygen contamination must cast doubt on the reliability of the proposed strength-mean free path relationship deduced from the data (Authors' Fig. 5). It is usual to evaluate dispersion hardening on the basis of yield strength rather than ultimate tensile strength, and accordingly we have replotted the authors' Fig. 1 to include yield strength. The yield strength data do not justify a discontinuity of 3 p at either 70" or 1000 OF. Can the authors substantiate their conclusion 1) with additional evidence? Otherwise it seems that they have succeeded only in pointing out the possibility of a linear relationship between yield strength (or Uts) and the logarithm of the nleall free path, comparable with that demonstrated for iron-carbon alloys (Authors' Ref. 2). Work in our own laboratories has shown that the hardness of the phase Ti,Cu is 235 Vpn, and that of a 1.5 pct (at.) (2 pct wt) supersaturated solid solution of copper in titanium is 190 Vpn. This small difference in hardness would suggest that Ti2Cu should not be a very effective dispersion-hardening phase. D. N. Williams, R. W. Wood, H. R Ogden, RI. L Jaffee (authors' reply)— This discussion brings out some interesting points with respect to the interpretation of our results, and also raises some questions regarding the experimental technique. We shall consider the latter questions first. Contamination during heat treatment was prevented by performing all heat treatments in argon-filled Vycor capsules. Fabrication was done in air, with the usually observed scaling. Scale was removed

Jan 1, 1962

By William A. Mitchell

AN X-ray diffraction pattern for "calcined cold precipitated ferric oxide" is reproduced diagrammatically along with data for other iron oxides by R. C. Mackenzie.1 This pattern, which shows spacings higher than those for any other form of iron oxide, was obtained from material prepared and photographed at several different times over a period of weeks, but later attempts to reproduce the results were unsuccessful the pattern of hematite being obtained every time.2

Jan 9, 1953

By R. I. Lahring, C. G. Inks

A surfactant waterflood, using a block copolymer of ethylene and propylene oxide (PLURONIC L64*), wa., started in 1956 in Kansas to determine the commercial feasibility of such a process. The production formation was the Bartlesville sand at a depth of 1,400 ft. Leares in the test area had attained both primary and secondary production peaks, and were on a normal decline when the tests were initiated. The injection wells were taking water at a reasonable pressure and none of the operating conditions were particularly unusual. The leases were selected primarily because of normal operating conditions, and not because of any serious problems demanding remedie>,. Oil production and water injection data were recorded during the 10-year test period, and their compilation indicates that the surfactant resulted in an increase of about 9 percent in secondary oil production. Other benefits derived from the surfactant injection were lower injection pressure that resulted in reduced power consumption and reduced erosion of the pumps; and lower calcium scale buildup. These fringe benefits more than offset the cost of the surfactant used. Introduction During the past several decades, considerable research has been carried out on secondary recovery of crude oil that remains in the producing formation despite the most efficient, current primary production practices. Methods are constantly sought of increasing recovery of oil, while at the same time improving the economic efficiency of operations. One method that has received intensive study over the years is the use of a surfactant as a waterflood additive. Laboratory tests show conclusively that dilute solutions of surfactants remove considerably more oil from uncon-solidated sand cores than does water alone.'- The loss of surfactant by adsorption at solid-liquid interfaces has caused serious doubt that surfactants can be used economically as waterflooding additives. This is especially true with anionic and cationic surfactants, and to a lesser extent with nonionic surfactants. This work was undertaken to determine the effectiveness in increasing oil production by injecting water containing small quantities of a nonionic surfactant. The surfactant selected was PLURONIC L64*, a block copolymer based on ethylene and propylene oxide, having the following structure The selection of the test site, a typical shoe-string sandstone type of field located at Batesville pool, Toronto District of Woodson County, Kans., was made because of its normal primary and secondary recovery operating conditions, and not because of any serious operating problems. When the tests were begun, the field was experiencing the customary post-peak production decline of a waterflood. Using for the tests a field that was on a normal production decline, while maintaining constant all variables other than the addition of the surfactant. was of varamount importance if success or failure was to be attributed to a particular cause. It was reasoned that if a surfactant was added to the injection waters and nothing else was done to influence the oil production or injection of water, the effects of the surfactant on the flood could be determined precisely. Production History The first well in the tested field was drilled in 1935. Gas repressurization began immediately, but it was not until Aug., 1938, that the major portion of the field was developed. During the period of repressurization, 1,700 MMcf of gas was injected. As can be seen from the curves of Fig. 1, the production peak from gas injection was attained in 1937 and a normal production decline followed. Early in 1942, water injection wells were drilled and injection of water Was initiated. The amount of water injected increased as more injection wells were drilled until a peak injection rate of 2,700 BID was reached in

Jan 1, 1969

By John C. Bilello

The brittle fracture behavior of cold-worked sintered tungsten was studied over the temperature range 4.2° to 298°K using a high-sensitivity strain measuring system and electronfractography. Similar observations were made on a swaged electron beam zone-refined monocrystal. In sintered tungsten irreversible plastic deformation was observed during cyclic load-unload tests at stress levels well below the fracture stress for all temperatures, but general microyielding could be detected only down to 202°K. For the zone-refined samples macroyielding occurred at all test temperatures with evidence for twinning below -202°K. The fracture stress of the sintered tmgsten was virtually independent of temperature, while the zone-refined crystal showed a 2.3 times increase over the same temperature range. Electronfractography confirmed the presence of numerous rod-shaped and spherical submicroscopic voids which ranged in diameter from 1400 to 4300A in the sintered tungsten; no voids could be found in the zone-refined tungsten. Contrast effects observed on the replicas in the vicinity of certain voids indicated that plastic deformation could be induced by the local stress concentration. It has been suggested that the presence of these voids may be responsible for the low-temperature brittle failure of sintered tungsten. Based m this suggestim und on the evidence obtained here, a dislocatim model is presented to account for the brittle behavior of sintered tungsten. In this model slip, which is induced by the local high stress concentration in the region at the edge of a favorably oriented void, could cause the void to grow to a microcrack of critical size. STUDIES of brittle fracture in bcc metals have led to the well-known experimental relationships between grain size, yield stress, fracture stress, and temperature which have formed the basis for the various dislocation pile-up1-3 or interaction4'= models for slip-induced microcrack nucleation. While microcracks can be nucleated by deformation twins,6,7 there has been no direct evidence furnished by transmission electron microscopy to support conclusively either the Zener pile-up or Cottrell dislocation reaction models for producing micro-cracks in all "brittle" materials. In addition to the "inverse" grain size relationship for yield and fracture stresses the cottrel14 theory predicts that the fracture stress below the transition temperature should behave in a fashion similar to that of the yield stress above this temperature. Such behavior has been verified for several bcc metals.8-10 With reference to both grain size effects and the tem- perature dependence of the fracture stress below the transition temperature, the behavior of sintered tungsten appears anomalous. Early work by Bechtold and Shewrnon 11 showed no apparent temperature dependence of the fracture stress below the ductile-brittle transition temperature (DBTT). They attributed this result to the intergranular nature of the fractures observed. More recent work by Wronski and Four-deux12'13 on considerably purer material did not show any systematic relationship between the fracture stress and temperature below DBTT. The dependence of flow and fracture stresses on grain size is also not clearly established for sintered tungsten. Koo, for example, has shown that the DBTT for sintered tungsten depended chiefly on the annealing temperature and was relatively insensitive to the actual grain size achieved. Using electrofractography and transmission electron microscopy, Wronski and Fourdeuxl3 showed that numerous spherical and rod-shaped submicroscopic voids could be found in sintered tungsten but not in melted tungsten of nominally the same purity. They suggested that these voids could be responsible for the temperature insensitivity of the fracture stress below the DBTT. In the present work the temperature dependence of the fracture stress for high-purity commercially sintered tungsten has been determined. The presence of submicroscopic voids in sintered materials was confirmed, and these were studied in detail to examine the role they could play in nucleating brittle fracture. A dislocation model is suggested which could cause an inherent spherical void to lengthen into a Griffith crack of critical size. EXPERIMENTAL PROCEDURE Commercially sintered tungsten rod was obtained in the as-swaged condition from Sylvania. A zone-refined crystal was obtained from the same source. This crystal was grown by giving three zone passes (at 25.4 cm per hr) to a sintered rod of high-purity tungsten. The rod axis prior to cold working was -15 deg from the [110] direction. Originally the zone-refined rod was -6 mm in diam; it was reduced to -3 mm by eight swaging passes, at high temperatures, with each step having about the same reduction of area. The final swaging step gave a 7.5 pct reduction of area at 1050°C. All swaging operations were performed in a hydrogen atmosphere. For the sintered rod a similar working schedule was employed. Metal-lographic examination of the sintered material revealed that the cold-worked structure had an apparent grain diameter of -25 u transverse to the swaging direction (obtained by the intercept method). In the longitudinal direction cold-worked grains were approximately 1.5 to 2 times their diameter. No distinct fiber structure could be observed optically for the zone-refined rod. The cold-worked structure in the

Jan 1, 1969

By A. L. Labbe, J. J. Donoso

Hard-won experience in the operation of smelting plants has pointed the way to the most efficient design and economical operation of a baghouse system for recovery of metallurgical fumes. This paper treats of the principles governing bag filtration and the factors most directly affecting bag life. Methods for temperature conditioning of smoke previous to filtering are described and the evolution of bag shaking mechanisms is brought up to date. THE history of the bag filter process, as applied to the recovery of metallurgical fumes, goes back to 1876, when the Lone Elms Works of Joplin, Missouri, erected a two-section baghouse for filtering fumes from Scotch Hearth lead smelting furnaces. By modern standards this installation was crude, but the basic operating principles remain essentially the same today. Great progress, however, has been made in the mechanization of the process by the use of devices for mechanically and automatically cleaning bags of adhering fumes, in the use of instruments for recording and controlling the variables affecting baghouse operation, and in the conditioning of the smoke previous to filtering. The principles governing bag filtration of fumes were investigated in 1929 by A. J. Seitz of American Smelting and Refining Co., and he arrived at the following conclusions: 1. Pressure on Bags at Constant Volume: The rate at which the pressure builds up in a bag with constant volume is directly proportional to the time, with the same kind of smoke and dust burden (fig. 1). 2. Pressure on Bags for Change in Volume: With equivalent smoke and dust burden, the bag pressure increases with the square of the increase in volume. The rapid increase in pressure is due to (1) increase in volume, (2) increase in amount of dust on the bag, and (3) more intense packing of the dust at higher velocity (fig. 2). 3. Effect of Intensive Filtering on Pressure: Since the pressure builds up directly as the square of the volume, with the same smoke and dust burden, it is necessary to shake the bags in that increased ratio, and vigorously, to keep the pores of the bag open and pressure down. This increases the wear on the bags and the dust losses. 4. Effect of Shaking on Dust Losses: The losses are in direct proportion to the frequency of shaking because the loss takes place immediately after shaking, before the bag seals itself. Tests show that with hand shaking the last 20 pct of the removable dust requires seven times more shaking per unit weight of dust than the first 80 pct. 5. Effect of Fineness of Dust on Losses: The fineness of the dust particle increases the loss in two ways: (1) When the bag is clean a greater percentage of it will pass through before the bag seals itself; (2) fine material penetrates farther into the bag pores, building up pressure faster and necessitating more shaking, thereby increasing the loss. The physical principle of operation of the bag filter is simply the separation of solids from a gaseous carrier through a porous medium, and is analogous to the filtration of solids from liquid carriers. Basically, the mechanics of the process are as follows: Fume-laden gases drawn from the operating fur-

Jan 1, 1951

By H. H. Hausner, H. S. Kalish

M. Hansen—This paper certainly is an interesting study. Although I have not had too much experience in the powder metallurgical methods of studying phase equilibria, I would like to say the following concerning the interpretations of the results obtained: 1. The existence of a zirconium-rich eutectic having a melting point close to 950°C and containing approximately 5 pct beryllium is well established. 2. Undoubtedly sintering of the original compacts (i.e., without repressing and resintering at 1350°C) resulted in a condition being far from equilibrium, even in the low-melting point zircon-rich region where undissolved zirconium particles have been observed. This means that only partial reaction between the component powders has taken place. 3. In preparing and handling powder mixtures for pressing and sintering, we have found that with powders differing considerably in density, and also in particle size, separation in layers of different composition may occur. This means that a concentration gradient would exist within such samples. This phenomenon may, at least to some extent, account for the difference in microstructure of the top and bottom regions of some of the sintered samples. If this is the case, density figures for some of the nominal compositions would not represent actual densities of those mixtures. 4. Fig. 1 shows that the low densities of mixtures with 40 and 60 pct beryllium sintered at 1350°C are changed to much higher densities if the products sintered at 1100°C are repressed and resintered at 1350°C, whereby an approach toward equilibrium takes place. This would mean that the low density and growth in volume is due to nonequilibrium conditions. If this is true, would it be justified, then, to conclude that "the remarkable growth of the alloys in the vicinity of 40 to 60 pct Be indicates the formation of a high-melting point phase, probably accompanied by a considerable change in volume due to a large alteration of the crystal structure from that of the original compounds"? If some compound formation has taken place already during the first sintering at 950" to 1350°C, more compound would be formed by repressing and re-sintering of the 1100" samples. This treatment, however, results in higher, rather than lower, densities. In general, the density-composition curve of alloy systems containing one or more intermediate phases is characterized by a more or less defined contraction (decrease in specific volume, increase in density) over the "theoretical" density. Does not discrepancy exist between the two statements that "growth of the alloy indicates the formation of a high-melting phase . . ." and "even at 1350°C, no indications of sintering have been observed"? 5. I am not sure that the explanation given for the fact that fig. 4 did not reveal as much eutectic as the top portions of the mixture with 2 pct Be, is correct. The density of the melt containing only 5 pct Be or even perhaps less, is not too much different from that of the nominal composition. The reason might be also that there was already some separation of the components in the pressed compact. 6. I do not understand why the microstructure of the bottom regions of the compact with 5 pct Be (fig. 6) is so different from that of the top regions (fig. 5). The compact was melted on sintering at 1100°C. Its composition lies close to the eutectic point. There should be at least some lamellar structure in the bottom regions too; otherwise, the composition of top and bottom must have been very different after sintering, because the eutectic is said to extend as far as the composition ZrBe2. In case the white and gray areas of fig. 6 are both gamma, and the black areas undissolved zirconium, this composition would be close to the phase coexisting with zirconium, that is, ZrBe2, according to the hypothetical diagram, or a compound richer in zirconium. 7. Figs. 9 and 10 are not mentioned in the text. 8. The great difference in microstructure of the composition 20 pct Be of figs. 8 and 14 on one side and fig. 15 on the other side proves that sintering at 950" and 1100°C results only in partial reaction of the powers. 9. The mixture with 60 pct Be (fig. 19) seems to consist of two phases, rather than one phase, one interspersed in a matrix of another. 10. The statement that the eta phase "may be an intermetallic compound or the product of a peritectic or monotectic reaction" seems to be misleading, because the product of a peritectic or monotectic reaction in this region of the system must be an intermetallic compound. 11. If there is some solid solubility of Be in alpha and beta-Zr, it would be expected to be higher in beta-Zr (b.c.c.) than in alpha-Zr (h.c.p.). The temperature of the polymorphic transformation of zirconium then would be lowered, rather than increased. In accordance with this, Battelle has found that the transformation point of titanium is decreased by beryllium. 12. In case the phases present in alloys with 80, 90, and 95 pct Be are identical (which appears to be correct), it is striking that the relative amounts of both phases (eta and beryllium) are not too different within this wide range of composition. With 60 to 65 pct Be

Jan 1, 1951

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By O. Jantti, Erkki Laurila, R. T. Hukki

INVESTIGATION of the methods of analyses for magnetite and ilmenite in the Otanmaki iron-titanium ore and respective mill products has resulted in certain improvements in the methods conventionally employed. The outcome of the investigations is summarized as follows: 1—Development of a diamond-drill core analyser for the determination of magnetic susceptibility of drill cores containing magnetic minerals. 2—Development of a magnetite-ilmenite analyser for pulverized products. 3—Development of a potentiometric method of chemical analysis for the determination of iron, vanadium, and titanium in succeeding steps from one test sample. 4—Proposal for a continuous and automatic magnetite assay method. Diamond-Drill Core Analyser The conventional method of assaying diamond-drill cores consists of splitting the cores, pulverizing them and running chemical analyses on representative samples. The physical properties of magnetic minerals, however, offer an entirely different approach to obtain similar final result by the measurement of respective magnetic susceptibilities in a properly designed instrument. This instrument is shown in Fig. 1. Essentially it consists of a magnetic unit, A, and of a meter unit, B. On top of A is a slot where a piece of diamond-drill core C is visible. The magnitude of disturbance in the original magnetic field caused by the magnetic minerals in the drill core can be observed from the microammeter. This reading is a function of the combined susceptibilities of all magnetic grains in the magnetic field. The magnetic unit is built of E-sheets of a shell transformer, as shown in Fig. 2. The primary coil and two identical secondary coils are wound around the central leg and end legs, respectively. The drill core under examination is placed into one of the air gaps as shown in Fig. 2. The number of ampere-turns of primary coil excited by 50 or 60-cycle ac give a maximum induction of about 600 gauss in the air gaps. The secondary coils are connected in series in the opposite direction. Thus their voltages compensate each other if no drill core exists in the air gap or if the susceptibility of the drill core is equal to zero. As soon as the susceptibility becomes greater than zero, the balance of the magnetic circuit is disturbed, resulting in increased voltage in the terminals of coil 1 and in a respective decrease of voltage in the terminals of coil 2. The voltage difference thus produced is a function of the effective susceptibility of the drill core. If the magnetic grains in the drill core are unevenly distributed, the voltage difference varies as the core is rotated around its own axis. The voltage difference is measured with a Bren-tan0 tube voltmeter. If extreme sensitiveness is desired, the established symmetry of the magnetic circuit does not allow reduction of the 0-voltage difference far enough. Therefore a compensatory voltage of a correct phase taken from the terminals

Jan 1, 1952

By Oren C. Baptist, Eliot J. White

Samples of four reservoir sands having different degrees of water sensitivity were subjected to several laboratory tests to determine differences in capillary behavior attributable to clay-mineral effects. The degree of water sensitivity was estimated by the difference between gas and water permeability. Unsaturated pore volumes determined with mercury injection were comparable to irreducible water saturations determined with the semipermeable bar-rier method only for the non-sensitive sands that contained small amounts of non-swelling clay minerals. Irreducible saturations were independent of salinity of the water, which suggests that most residual water is adsorbed 0.7 a film over solid surfaces and that internal retention by clay minerals is relatively insignificant. The water-sensitive sands imbibed water to higher saturations than did non-sensitive sands, and this result is believed to be a combination of the effects of clay minerals and preferential wettability; however, the relative importance of each of these effects is riot determinable. Thus it is concluded that the semipermeable barrier method is the best of the laborafory methods used for estimating formntion water .saturations in the sands studied. INTRODUCTION This investigation is a continuation of studies of the role of clay minerals in petroleum production in the Rocky Mountain area. Previous work has shown large differences in gas and water permeability in numerous reservoir sands; these water-sensitivity effects observed in the laboratory have been correlated with well behavior in the field, and the degree of water sensitivity imparted to reservoirs by the various clay minerals has been determined.'.' The effect of interstitial clay minerals on formation water3 saturations is not so well known. It has been reported that formation water saturations probably are higher in clayey than clean sands,' but this effect has not been evaluated in the laboratory, and the relative effect of the various types of clay minerals on formation water saturation has not been determined. The clay-mineral groups of most importance to this study and to petroleum production in general are kaolinite, illite, and montmorillonite. The minute layers of montmorillonite are loosely bound to one another so that water enters between them, causing great expansion of the particles. Kaolinite and illite do not exhibit interlayer hydration, but they do immobilize considerable amounts of water owing to their large surface areas, which are of the order of 15 to 97 m2/gm of clay.5 The four Wyoming sands used in this study were selected to represent a wide range of water sensitivities. These sands, with the number of wells and fields from which the samples were obtained, are: Second Frontier, five wells in two fields; Newcastle, six wells in one field; Tensleep, two wells in two fields; and Lower Muddy, five wells in one field. EXPERIMENTAL METHODS AND PROCEDURES Water-displacement data were obtained by the semipermeable barrier method," using both fresh water and brines having either 16,500 ppm sodium chloride or calcium chloride. A displacement pressure of 35 psi was found to be sufficient to obtain the practical irreducible water or brine saturation (IWS, IBS) in most samples. Mercury-injection data were ob-tained with equipment and pro-cedures similar to those described by Purcell.7 Exceedingly high pressures are required to attain complete mercury saturation by this method; however, since saturations in most samples change very little with large pressure increases above 1,000 psia, the maximum pressure used was 1,400 psia. To facilitate comparison of mercury-injection and water-displacement results, it is convenient to express mercury-injection data in terms of unsaturated pore volume. The abbreviation, (100 - SHg)min, is used to denote the pore volume unsaturated by mercury at 1,400 psia injection pressure. Gas permeabilities, ki, were deter-mined by the method proposed by Klinkenberg.8 Methods of determining types and amounts of clay minerals by X-ray diffraction analyses, as well as methods of determining water permeability, have been described previously.' The imbibition characteristics of

Jan 1, 1958

By D. S. Hutton, W. C. Leslie

S. Floreen (1nteumtio)lal Nickel Co.)— One fairly simple way to differentiate between embrittlement due to surface microcracks or due to a dislocation barrier effect might be to load a brittle rock salt crystal in tension to some stress just below the fracture stress and then immerse the loaded crystal in water. If a surface film is retarding plastic flow then one should observe some plastic deformation of the rock salt as

Jan 1, 1962

By D. H. Polonis, J. G. Parr

IN a recent paper on titanium-rich Ti-Fe alloys,' the hardness of quenched powder specimens was given, together with the amounts of martensitic a they contained. The values disagreed in two respects with previous determinations that Worner² made on lump specimens: 1—Some martensitic a' is formed in powder specimens of alloys containing up to 12 atomic pct Fe. On the other hand, Worner reports that, although his results on quenched lumps are not conclusive, alloys containing more than about 4 pct Fe "appear to consist of retained ß'' although they "may not be strictly unaltered solid solutions." 2—According to Worner, quenched lump specimens show a maximum hardness at a composition about 3.5 pct Fe. Earlier -experiments by the authors showed a maximum hardness of martensitic alloys in powder form at 10 pct Fe. Accordingly, more experiments have been conducted in order to confirm these differences and to determine with more accuracy the minimum composition of quenched lump specimens that consist entirely of retained ß. Lump samples?x?x1/20 in. were quenched from 1000°C in helium and, on the whole, showed similar hardness values to the specimens that Worner water-quenched from 950°C. The hardness curve the authors obtained shows a more pronounced peak, but in other respects it is very similar to Worner's curve (Fig. 1). While it was possible to make fairly reliable measurements of the percentage of martensitic a in quenched powders (by Geiger spectrometer), the solid samples allowed only approximate estimates to be made from visual observation of line intensities on film. Retained ? begins to appear in quenched lumps containing 0.2 pct Fe; at 2.2 pct Fe there are approximately equal quantities of ß and a'; in a 4.7 pct Fe alloy only a trace of a' appears. These results are represented as a curve on Fig. 1. The hardness and constitution of powder samples were verified by repeating both types of quenching experiment described in the earlier paper.' Identical results were obtained by the two methods, and they agreed with the figures published previously (Fig. 1). The appearance of the martensitic structure under the microscope is shown in Figs. 2 and 3. The mar-tensite needles are coarser in the lump; otherwise the structures are similar. Three conclusions are made at this juncture: 1— The properties of quenched lumps reported by Worner are confirmed, on the whole. The differences between them and the properties of powders are probably due to an effect of specimen size. Differences of behavior in various sizes of specimen have been observed previously in martensite reactions in Fe-Mn alloys3 and in Cu-A1 alloys. 2—The maximum hardness of both quenched lumps and quenched powders appears at a composition where martensite formation has all but ceased. In this respect, powders and lumps behave similarly. 3—Martensitic a' has essentially the same microscopic appearance both in powders and lumps. Acknowledgment This work is part of a program sponsored by the Defegce Research Board of Canada, Project No. 425.

Jan 1, 1956

CONTENTS PAGE Bronze Bearing Metals. By G. H. CLAMER 1729 Pennsylvania Railroad Anti-friction and Bell Metals. By F. M. WARING . . 1733 The Tin-plate Industry. By D. M. BUCK. Discussed by G. H. CLAMER, J. W. RICHARDS 1735 The Aluminum Bronze Industry. By W. M. CORSE 1738 Bronzes, Bearing Metals, and Solders. By G. K. BURGESS and R. W. WOODWARD. Discussed by G. H. CLAMER, R. T. ROBERTS 1742 Babbitts and Solder. By G. W. THOMPSON 1751 The Cadmium Supply Of the United States. By C. E. SIEBENTHAL. Discussed by M. L. LISSBERGER, C. W. HILL, F.- F. COLCORD . . .. . . . . 1752 Solder, Its Use and Abuse. By M. L. LISSBERGER 1759

Jan 12, 1918

By Quentin D. Singewald, B. S. Butler

Some of the broader relations between structure and ore deposition along the London fault, deduced from a thorough study of the geology of the eastern part of the Mosquito Range, should be of general interest to economic geologists. The first part of this paper is a generalized statement of the geology of the region in which the London fault is located; it may be supplemented by reference to several earlier publications by the writers and to the U. S. Geological Survey's Professional Paper 148, on the Leadville district. The second part deals with the structure of both the fault and the disturbed zone adjoining the fault. The third part discusses the salient features of the ore deposits, particularly emphasizing structural control. The two generalized maps are complementary to one another but contain too many data to show on a single small map. The London fault is between Leadville and Alma, and the ore deposits along it are said to lie in the Alma district. Field work in this district, during six summers since 1927, has been a part of the cooperative work of the U. S. Geological Survey, the State of Colorado, and the Colorado Metal Mining Board. The writers have made use of work by R. D. Butler, J. W. Vanderwilt and R. E. Landon. G. F. Loughlin and C. H. Behre, Jr., who have worked on the west side of the range, have contributed valuable suggestions. Mining men of the district have aided in many ways. General Geology Pre-Cambrian Rocks.—The oldest rocks in the district are schists, correlated with the Idaho Springs formation of the Front Range. Quartz-mica schist predominates, but other types occur locally; almost everywhere the rocks show considerable lit-par-lit injection. Intrusive into the schists are two varieties of granite, only one of which is widespread. It is a fine-grained, porphyritie, gray granite correlated with the Silver Plume granite of the Front Range. Near the head of Buckskin Gulch a

Jan 1, 1937

By H. W. Paxton, C. C. Busby

IT has been shown previously' that strain aging can markedly improve the tensile properties of low carbon martensites, especially the yield-tensile ratio, without seriously affecting the ductility. In view of interest in high strength steels, an investigation has been made of the effect of strain aging following tension or rolling on the tensile properties of A1S1 4340 in an attempt to obtain a tensile

Jan 1, 1957

Discussion of the paper of F. C. NEWTON, presented at the New York meeting, Feb-ruary, 1915, and printed in Bulletin No. 9S, February, 1915, pp. 473 to 477. H. 0. HOFMAN, Boston, Mass.-The results of these large-scale experiments, which were carried on at Perth Amboy, show that there are many differences between theoretical conceptions and their applications to work on a large scale. The author has given reasons why the results of bringing a desilverizing kettle to the high melting point of the zinc-silver alloy, Zn3Ag2, melting at 665° C., are not satisfactory. In all probability the alloy is dissolved in the lead; it may also be decomposed by the lead; the practical result is that this high temperature does not work. It remains now for the laboratory man to carry on systematic experiments

Jan 5, 1915

By L. F. Mondolfo, W. T. Collins

A study of the relationship between undercooling for nucleation and structure in Sn-Cu alloys with 0.1 to 5 pct Cu has shown that in hypereutectic allojls the halo of tin that surrounds the primary crystals of Cu3Sn5 is larger, the larger the undercooling for nucleation o,f the tin. This increase of halo size results in a decrease of coupled eutectic, and, in alloys far from the eulectic composition, may produce its complete disappeavance, with the formation of a divorced eutectic structure. This was confirnred by the excrrnination of other alloys in which divorced eutectic slructuves are formed, and leads to the conclusion that they ave only an extrenle case of halo forrtzalion , which results when the two phases freeze one at a time and solidification of the first is completed Defove the second starts. It was also found that under proper conditions of nucleation all types of eutectic structures can be formed in the sartte system , and therefore divorced eutectics, like normal and anomalous, are not characteristic of the syslett~, but are mainly controlled by nucleatiorz. Dizlovced eutectics are formed when the phase that tutcleates the eulectic vequires a large undevcooling for ils nucleation and when the cotnpositiorz of the alloy is far from the eutectic., on the side of the primary phase that does not nucleate the other phase. It is recommended that the tevm "divorced" be used in preference to degenerate because it is more desct-iptice of the morphology and mode of forinalion of the structures. ThE variety of structures found in eutectic alloys has been extensively investigated and classified. The most accepted classification is the one by ~cheil,' in which three different types of eutectic were distinguished: 1) normal, 2) anomalous, 3) degenerate (divorced). ATornlal eutectics are typified by the simultaneous growth of the two phases ("coupling") by which the two phases appear as interpenetrating crystals. The presence of a crystallization front, in which the two phases grow side by side, creates the eutectic grains, with the boundaries where the fronts meet. The presence of eutectic grains is the .distinguishing feature of a normal eutectic, according to Scheil. Straumanis and Brakss2 examined the Cd-Zn system and showed that there was a crystallographic relationship between the phases. Later, others4 also investigated additional systems and found definite crystallographic relationships in the coupled eutectics. The anornalous eutectic shows much less coupling than the normal; the two phases are intimately mixed but 'grow without a uniform crystallization front—a consistent crystallographic relationship— and the eutectic grain is conspicuously absent. As in the normal eutectics faster rates of growth result in a finer structure, but there is not the typical uniform spacing of normal eutectics. The degenerate eutectic shows no coupling; in fact the two phases attempt to minimize their area of contact and to form separate crystals. It has been suggested5" that slow cooling may favor this type of structure. Scheil believes that normal eutectics are formed when the two solid phases are present in more or less equal proportions, whereas both anomalous and degenerate eutectics form when one of the phases is present only in small amounts. spengler7 extended much farther this qualitative relationship between the eutectic type and the ratio of the two phases, and added a relationship to the melting point of the constituents. On this basis he proposed two equations for determining into which of Scheil's classifications an alloy belongs. The first equation is: where TI is the melting temperature of the lower-melting component, Tp of the higher-melting component, and Te the eutectic temperature. The second equations is: where is the volume percent of the lower-melting phase and $2 of the higher-melting phase at the eutectic composition. If 0 and/or 4 are in the range 0.1 to 1, a normal eutectic is formed; if in the range 0.01 to 0.1, anomalous; if less than 0.01, degenerate. Although the examples given by Spengler show a good agreement with the formulas, chadwick found that the Zn-Sn eutectic is normal to all growth rates, even though the volume ratio is 12/1, and Davies9 reports that the A1-AlgCo2 eutectic is normal, with a volume ratio of more than 30/1. Many more discrepancies of this type can also be found. Neither Scheil nor most of the other investigators have considered nucleation as a factor in the formation of divorced eutectics. Daviesg states that divorced eutectics form when neither phase acts as

Jan 1, 1965

BULLETIN 177. The decline and ultimate production of oil wells with notes on the valuation of oil properties, by C. H.- Beal. 1919. 84 pp., 4pls., 80 figs. BULLETIN 179. Abstracts of current decisions on mines and mining, reported from September to December, 1918, by J. W. Thompson. 1919. 166 pp. TECHNICAL PAPER 214. Motor gasoline; properties, laboratory methods of testing, and practical specifications, by E. W. Dean. 1919. 33 pp., 2 figs. TECHNICAL PAPER 219. Combustion and flue-gas analysis, by U. S. Fuel Administration. 1919. 12 pp., 5 figs. TECHNICAL PAPER 223. Cost-keeping for small metal mines, by J. C. Pickering. 1919. 46 pp. Only a limited supply of these publications is available for free distribution. Publications should be ordered by number and title. Applications should be addressed to the Director of the Bureau of Mines, Washington, D. C.

Jan 7, 1919