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By J. P. Newell, R. W. Storey

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. AUGER mining is a form of continuous mining in that it completely replaces with a one-cycle operation the older conventional cut, drill, shoot, and load method of mining. Relatively new, having been utilized only within the last few years, it is even more continuous in its production of coal than some other forms of continuous mining being practiced in this country today. There are at present coal recovery augers in operation working along strip-mined highwalls from the outside. This paper will deal with underground mining, specifically with an experiment which was carried out with a machine developed for this purpose. The location of this experiment was in Pike County in eastern Kentucky in the upper split of the No. 3 Elkhorn seam. Coal height was 32 in. and roof conditions were very bad, with 10 in. of soft draw slate coming down with every cut in conventional mining. The coal is high-grade bituminous, excellent for metallurgical coking. Underground auger mining fills a need for a method of recovering coal in thin seams, under bad roof conditions or in split seams. In many cases it might save money by eliminating the handling of excessive quantities of rock. In fact, if the coal can be recovered, as in the case of this experiment, without mixing with any impurities outside the seam, it may be possible to load or ship a satisfactory product with little or no preparation or cleaning expense. The need for some economical method for recovering coal from thin seams is becoming more pressing as the more profitably mined seams are exhausted. Basic Principles of Auger Mining The principles of the auger, or screw conveyor, have long been used in drilling small diameter holes for blasting and other purposes. These same fundamentals apply to large diameter drilling. However, considerably more attention was given to designing a cutting head that would not pulverize the coal and consequently would require a minimum of power to drive it. The head, as designed for this job, consists of a cylinder 25 in. in diam with steel bits set in 3 positions spaced around the forward rim. A conventional coal drill bit, at the head of a bursting cone in the center of the cylinder, trails the forward rim slightly, see Fig. 1. The bursting cone and auger connections are anchored to the cutter barrel by 3 arms spaced at 120". This head design proved to be very satis-

Jan 1, 1953

By Herbert A. Stein, John B. Murdock

AN analysis of perlite expansion furnaces must be based upon one consistent theory which explains how and why perlite does expand when heated. There is more than one such theory, so to establish a basis for the rest of this paper, the authors will outline one theory and the data that support it before going into the construction details of different furnaces. JOHN B. MURDOCK, Associate Member AIME, is President, and HERBERT A. STEIN is Secretary, of the Perlite Corp., Phoenix, Arizona. San Francisco Meeting, February 1949. TP 2736 H. Discussion of this paper (2 copies) may be sent to Transactions AIME before Feb. 28, 1950. Manuscript received Jan. 3, 1949. Why Perlite Expands: Perlite is known to contain some dissolved or combined fluid, probably water, which is lost when the material is heated to fusion. It is generally agreed that when particles of this volcanic glass are heated to fusion in such a way that vaporization of this water into steam takes place at the same time as the glass becomes soft, the steam puffs up each particle into a mass of glass foam. It is a simple matter to expand perlite under a blow torch for demonstration purposes, but in commercial installations, the problem is made more complicated by the necessity of making efficient use of both raw material and fuel, and producing an expanded aggregate conforming to close specifications for size distribution and density, using many different types of perlite rock. The ability of a given operation to fulfill these requirements depends upon the proper handling of four variables. They are: (1) the nature of the perlite rock used, (2) the heating time taken to get the perlite particle up to its highest temperature, (3) the size of the particle, and (4) the maximum temperature the particle reaches. Types of Perlite Rock: Perlite may be classified in many ways, but the characteristics most easily correlated with its behavior in furnaces are its softening temperature, its effective water content, and its "liveliness." Actually there is a close correlation among these three characteristics so it is possible to describe a perlite using any one of them. Lively perlites always have low softening temperatures and high effective water contents, whereas the deader perlites have higher softening temperatures and lower effective water contents. These softening temperatures run from 1400°F to above 2000°F and the effective water contents run from over 2 pct down to 0.2 pct. Included in the category of lively glasses are the green pitchstone from the Edgar claim in Superior, Ariz., the red pitchstone on the Animas highway south of Lordsburg, N. Mex., and a gray glass from Beatty, Nevada. Examples of intermediate perlites (in order of decreasing liveliness) are the Guzman-Lobb perlite with obsidian

Jan 1, 1951

By R. T. Webber, B. B. Owen

THE vapor phase deposition of molybdenum and tungsten from the hexacarbonyls has been thoroughly investigated by Lander and Germer1 and shown to yield well-bonded coatings on a variety of hot metallic surfaces. They also demonstrated that chromium coatings2.3 could be similarly deposited, but did not investigate this metal extensively. Recently,4 conditions have been described by which this compound can be prepared in quantities sufficient for laboratory scale plating experiments, and it is the purpose of the present communication to outline the results of preliminary experiments upon the plating of chromium from its carbonyl. APPARATUS AND TECHNIQUE The apparatus used in these experiments is shown in Fig I. At one end, connected by a short length of rubber tubing, is a Cenco Hypervac 20 pumping continuously. At the opposite end is a needle valve which allows a small stream of purified hydrogen to flow through the apparatus. Connected in series are a trap T1, maintained at the temperature of dry ice and acetone, the plating chamber, and two traps T2 and T3 containing crystals of the carbonyl. T2 is kept in a constant temperature bath (not shown), while T3 is at room temperature. Stopcock S6 allows the hydrogen flow to by-pass the carbonyl traps. A McLeod gauge is connected so that it can measure the pressure at the pump through Ss, or the pressure at the plating chamber through S9 and S6. The standard (12 liter) volume connected by S5 is used to determine the volume included by S4, S6, Se, S10, the needle valve and the McLeod gauge. Knowledge of this volume allows calibration of the flow of hydrogen. The apparatus* is built entirely of pyrex, except for the needle valve, the rubber connection to the Hypervac, and the cover of the plating chamber. The plating chamber is water-jacketed, with a large brass top allowing insertion of the specimen to be plated. Set into the brass top is a ground glass stopper through which thermocouple leads are sealed. The thermocouple wires (pure Pt, and 87 pct Pt-13 pct Rh) serve the double purpose of measuring the specimen temperature and suspending it in the chamber. Surrounding the chamber is the coil of an induction heater, H. The apparatus is designed to allow variation of the following conditions: I, the specimen temperature, from room temperature to about 1000°C, 2, the carbonyl vapor pressure, from 40 to 220 microns, and 3, the hydrogen flow. In several runs, 0.8 to 1.8 pct of hydrogen sulfide was introduced through a needle valve that replaced S4. The vapor pressure of the carbonyl is

Jan 1, 1948

By R. E. Miner, J. K. Jackson, T. L. Wilson

THE nature of the decomposition reactions producing hardening in aluminum-rich A1-Ag alloys is now fairly well understood. The silver is not uniformly dispersed even at temperatures above the solvus line: rather, it is clustered into zones and associated with dislocations.' During quenching, nearly all of the silver segregates into zones' and some is attracted to dislocations, producing stacking faults. Growth of these faults produces the semicoherent y precipitate.1 During aging, the larger zones and the y precipitates grow at the expense of the smaller zones. The large zones persist up to about 350°C; where they redissolve in favor of the y' and y precipitates.' The equilibrium hcp y precipitate occurs both by a cellular reaction at the grain boundaries1 and by growth of the Y' plates to a critical size where incoherency results. Damask and Nowick 4 observed an internal friction peak in an A1-6 at. pct Ag alloy at about 140°C (0.25 cps). The peak was found to exhibit a systematic instability. After aging at successively higher temperatures between 155' and 23Z°C, the peak first migrated to higher temperatures while increasing in height, then returned to lower temperatures and decreased in height. After aging at temperatures above about 200°C, the peak position remained constant while the height decreased very slowly. In quenched specimens, elastic after-effect measurements inhcated a rapid initial transient in peak position from low temperatures up to 155°C. The authors concluded that a stress induced growth and resolution of the clusters and the 7' was the most reasonable mechanism to account for the behavior. It would seem, however, very unlikely that both the clusters and the y' precipitate would provide damping contributions whose relaxation time and activation energies were identical, which is required for them to produce the same internal friction peak. The present investigation was motivated by this apparent anomaly and the development of a very low thermal inertia torsion pendulum5 capable of monitoring transient behavior. Low frequency internal friction measurements were made on four binary A1-Ag alloys nominally containing 5, 10: 15, and 20 at. pct Ag. The results of measurements made on a 10 at. pct Ag alloy in the quenched condition are shown in Fig. 1. There are two peaks apparent in the spectrum, one centered at about 160°C, the second at about 210°C. The two peak spectrum was observed in each alloy, but it was best resolved in the 10 pct Ag specimens. Because of the instability in the internal friction, 4 it seemed possible that the second peak was not a peak at all, but simply a manifestation of a single, sharply transient, peak. This effect has been observed in Au-Ni alloys.6 The existence of the higher tempera-

Jan 1, 1970

By A. H. Daane, B. J. Beaudry

The Sc-Ti system was studied by thermal, metal-lographic, and X-ray methods. Scandium was found to transform at 1334 °C from a (hexagonal) to ß which was concluded to be bee since a continuous series of solid solutions is formed between ß scandium and ß titanium at elevated temperatures. There is a minimum in the solidus at 51 wt pet Ti and 1300°C, a monotectoid at 1050°C and 49 wt pet Ti, and a eutectoid at 875°C and 91.5 wt pet Ti. The maximum solubility of titanium in a scandium is 13.5 wt pet at the monotectoid temperature, while the maximum solubility of scandium in a titanium is 6.5 wt pet at 875°C. SCANDIUM, a member of Group 111 A of the periodic table, and now called a rare-earth metal,' has become of interest recently due to its low density (2.99 g per cc) and relatively high melting point (1539°C).Spedding,' et al. have described a method of preparation of pure scandium metal and have made a study of its basic properties. Since scandium is approximately 10 to 12 pet smaller in at. diam than the other rare earths while its electronegativity and valence are the same, a knowledge of its alloying behavior in contrast to these elements should be very helpful to fundamental alloy theory. Since scandium is quite scarce and difficult to prepare in pure form, its use as a structural material by itself seems quite unlikely. However, its use in special cases as an alloying addi- tive to other low-density materials is a possible application; the Sc-Ti system was chosen for this reason and for others of fundamental interest. Scandium was suspected of having a high temperature bee form as do some of the other rare-earth metals.3'4 Since titanium has a high-temperature bee form, a continuous series of solid solutions at elevated temperatures between ß scandium and ß titanium would prove the existence and structure of the high-temperature form of scandium. The existence of a continuous series of hexagonal solid solutions at room temperature was predicted by Burkhanov and Savitskiy,5 but Hias shown to be incorrect in early X-ray studies. EXPERIMENTAL METHODS Materials. The metals employed in this investigation were crystal bar titanium and distilled scandium prepared by the method described by Spedding,2 et al. The major impurities are listed in Table I in PPm. Alloy Preparation. All the alloys examined were initially formed in a nonconsumable electrode are-melting furnace under an atmosphere of purified helium or argon. A curve based on the observed weight loss of 0.6 pet* when titanium was melted

Jan 1, 1962

DeLamar, the largest silver mine in the United States outside the Coeur d’Alene District in Idaho, came into production in April 1977. It is a joint venture of Earth Resources Company and Canadian Superior Oil Co., with Earth Resources being the operator. The property is a consolidation of several old operations dating back to the 1800s; the better known of these are the DeLamar and Sommer-camp mines. DeLamar is situated in southwestern Idaho near the Oregon border in the Owyhee Mountains, 88 km (55 miles) southwest of Boise, Idaho. Heavy snowfalls and very low temperatures are common in the wintertime. Planned production was 77,500 kg (2.5, million oz) of silver and 5 13 kg (16,500 oz) of gold per year. Expected life at a milling rate of 1,540 mtpd (1,700 stpd) was 20 years, with an ore grade of 144 g Ag and 1.58 g Au per mt (4.2 oz Ag and 0.046 oz Au per st). Present production is at the rate of 1,900 mtpd (2,100 .stpd). The total cost to bring the mine into production was reported to be approximately $22 million, and the mill was reported to have cost about $10,000 per daily ton of design capacity. At DeLamar, naurnanite (Ag2Se) is the principal silver .mineral occurring with acanthite (Ag2S) disseminated through quartz veins and a silicified rhyolitic ash-flow tuff of Miocene age. The mineralization is relatively iron and manganese free and is readily amenable to cyanidation giving recoveries of 85% silver and 92% gold, which occurs free. When the plant was started, considerable difficulties were encountered in handling the wet sticky ore because of the high clay content. Following primary crushing, the ore is stockpiled. Due to the sticky nature of the ore, the vibrating feeders initially installed under the stockpile were replaced by a reclaim hopper and an apron feeder which was fed 24 hours a day by a front-end loader. The minus 200 mm (8 in.) ore is fed to a 5.5 m by 2.75 m (18 ft by 9 ft) autogenous mill followed by a 2.75 m by 4.57 m (9 ft by 15 ft) ball mill and cyclones. The mills are equipped with 750 kw and 520 kw (1,000 hp and 700 hp) motors. Both mills discharge to the same cyclone feed sump and a portion of the cyclone underflow is returned to the autogenous mill. Cyclone overflow, which is 20% plus 74 microns (200 mesh), is leached in four agitators in series for 72 hours (45 hours at the 2,100

Jan 1, 1981

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

By Glen R. Neighbors, Sylvan Cromer

HIGH subsurface temperatures and pressures are making cementing operations more difficult as deeper producing horizons are being sought. Recorded bottom-hole temperatures above 200°F. and pressures in excess of 12,000 Ib. per sq. in., obtained by combining hydrostatic and pump pressures, are not uncommon. Insufficient time is available for proper placement of standard Portland cement, because of the shortened setting time produced by these excessive temperatures and pressures, therefore special types of cements have been developed to overcome these difficulties. From the standpoint of placement, the ideal slurry would be one that would remain fluid long enough to be placed, then harden rapidly, so that there would be a limited amount of contamination and the well could be placed on production in a minimum of time. It is highly desirable, therefore, that some method be devised to measure accurately the time that any slurry will remain in a fluid state while being pumped into the well. To study the effect of elevated temperature and pressure on fluidity, the authors have developed the pressure-type consistometer (Figs. I and 2) described below, and are presenting data obtained with it, using slurries of both quick-setting and slow-setting cements. Studies were made over a temperature range from 110° to 270°F., and a pressure range from atmospheric to 3000 lb. per sq. inch. APPARATUS The fluidity of cement slurries at atmospheric pressure is usually determined with the Halliburton consistometer1 or the Thickening Time Tester.2 These instruments are similar, in many respects, to an ordinary ice-cream freezer. The slurry to be tested is placed in a container that is rotated at a constant speed with an electric motor. Constant temperature is maintained by surrounding the container with a thermostatically controlled bath. The torque on the paddles, which is proportional to the force needed to shear the slurry, is indicated on a scale. The Halliburton instrument is calibrated from 0 to 100 poises against fluids of known viscosity. To permit direct correlation of observed elevated pressure data with those published at atmospheric pressure, the authors' designs of the slurry container, paddle, and torque indicator closely resemble those used on the Halliburton instrument. Duplicate results may be obtained at atmospheric pressure in either instrument. Instead of the atmospheric constant-temperature bath, one was built from a high-pressure steel bull plug. A Uni-Bolt union equipped with a blanking plug serves as the top, permiting the instrument to be opened or closed in less than one minute. The slurry container is built from Shelby steel tubing. A wrench socket welded to the bottom of the container engages a hexagonal nut on the top of the steel shaft that rotates it. This acts as a universal

Jan 1, 1941

By J. E. Gould, H. J. Hand

MANY independent studies are being made on slag-metal relationships in the open-hearth furnace, and these studies cannot help but result in an ultimate improvement in the quality of open-hearth steel of both the open and killed types In maintaining quality control at the National Tube Company's plant, emphasis has been placed on an evaluation of the iron oxide content of the steel in as quantitative a manner as possible, in order that the most desirable level of oxidation might be obtained for a given type of steel, and to secure a more precise basis for final deoxidation In the past, various methods were used for estimating FeO content of the metal at tap to ensure uniform and thorough deoxidation of killed steel, avoiding over-deoxidation to minimize the amount of inclusions present and to make as sound a steel as possible For the open-type steels, such control involves obtaining the necessary level of oxidation for the most suitable action of the steel in the molds to provide good surface quality and cross section for the specific grade involved While rapid analytical methods are available for determination of FeO in the liquid metal, such methods are still not sufficiently rapid for routine control on the open-hearth floor, nor do such analyses provide information as to what causes high or long FeO values The method of sampling can still be considered a problem in view of the variability encountered in taking simultaneous duplicate tests With the accurate rapid methods now available for determining carbon in the metal, estimating slag basicity and obtaining temperatures of liquid metal, it was believed possible to determine the influence of the various furnace reactions in establishing the state of oxidation at a given time Simultaneous slag and metal tests were used in this analysis, aided by statistical methods, to determine the factors that affect the metal FeO, and also to make a quantitative evaluation of these factors Data obtained are from actual furnace operations, the metal test being of the spoon, Herty type, and taken in duplicate. Metal temperatures were taken with the open-tube bath pyrometer developed by the Research Laboratory of the United States Steel Corporation This method of taking open-hearth metal temperature was invented by Collins and Oseland,1 and was developed into its present form by L 0 Sordahl,2 of the Research Laboratory The instrument and its mode of operation have been fully described by Sordahl and Sosman in three publications 3,4,5 Slag components were obtained by chemical analysis Data were taken from four 165-net-ton furnaces during the working period of the heat Recognizing that additions of ore affect the

Jan 1, 1942

By A. G. H. Anderson, A. W. Kingsbury

Silicon bronzes containing ken are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 etermined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at iioo°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West? have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,l,2,7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. Preparation of Samples Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 1/8 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1943

The Inspiration ore body was discovered in 1904, but a 50 -ton mill which was installed to treat the disseminated copper ore promptly failed. The original Inspiration Company then gave way to another, backed by W. B. Thompson, which found 40 million tons of ore. Control then passed to Anaconda and Dr. Louis Ricketts took charge as consulting engineer. He abandoned the mill which had been partially built (to the horror of the stockholders, according to Ira Joralemon) and spent a year and a million dollars experimenting with flotation. The first large copper flotation plant was then built and recovered 50% more copper than had previous gravity mills. It, of course, was highly successful and became the forerunner of modern flotation plants. Inspiration is distinctive as the first fully integrated copper operation in the United States. Three open pits supply sulfide ore to the concentrator and mixed oxide and sulfide ore to a vat leaching and electrowinning operation with leached ore also being sent to the concentrator. In addition, dump leaching supplies pregnant solution for scrap iron precipitation. Inspiration has recently constructed an electric furnace smelter and also operates a continuous casting and rod plant. The new primary 54 in. by 74 in. crusher was completed in May of 1972 and replaced an older unit which was in the way of the open pit development. It is of an unusual circular silo design, which permits dumping 0 from two positions at 90 from each other. One dumping position is in line with the spider, while the other one is at right angles to it. A box girder splitter bar hung from the dump pocket slopes downward from the second dump point, across the spider cap, and rests on the pocket bottom. This splitter was not installed to protect the spider but was to aid in distributing wet ore being dumped from that position to both sides of the spider. Any large amount of wet ore delivered to one side of the spider would pack in the crusher cavity. The round front wall of the 18 ft (5.5 m) deep pocket is unlined except for light steel protection at the top, while the straight back wall is lined with vertically positioned railroad rails. Water for dust suppression is sprayed into the pocket through a cluster of 3/8 in. (9.5 mm) nozzles at the back of the pocket. About 5 gpm (19 lpm) of water are mixed with 90 psi (620 kPa) air upstream of the nozzles to produce a fog which is effective in dust control. The 54 in. Allis -Chalmers gyratory is placed mostly within one quadrant of the circular enclosure to permit placement of the apron feeder on the lowest level in the proper position to transfer crushed ore to the

Jan 1, 1978

By J. G. Thompson

Determinations of the hydrogen content of irons and steels invariably are subject to two serious difficulties: (I) the determination of amounts of 0.001 per cent or less of any constituent requires an analytical procedure of unusual precision and accuracy, and (2) the hydrogen content of many samples is dccidedly not stable; i.e., there is no assurance that the content at the time the analysis is made is the same as it was when the sample was taken or at some previous time in the history of the piece. In respect to both the precision and speed of the determination, the vacuum-extraction procedure for the determination of hydrogen possesses advantages over the vacuum-fusion procedure, which has been the recognized standard for the detcrmination of other gaseous elements in sted-— oxygen and nitrogen for example. The basic facts upon which the vacuum-extraction procedure is based—i.e., the evolution of gas from solid steel when it is heated in vacuum, and the fact that the evolved gas is rich in hydrogen—were observed by Graham1 many years ago. Subsequent investigations have shown that hydrogen exists in steel chiefly as interstitial solid solution (i.e., in atomic dispersion) and perhaps to some extent as hydridcs that are unstable and decompose to form atomic hydrogen. In either case practically all of the hydrogen in steel at elevated temperatures exists in the atomic condition and consequently is able to diffuse readily through the metal. In contrast to this, other gaseous elements, such as oxygen and nitrogen, normally are present in steel chiefly in the form of relatively stable compounds such as oxides or silicates and nitrates; i.e., the oxygen and nitrogen atoms are fixed in stable combinations and are not free to migrate. The only oxygen or nitrogen that can diffuse in steel is the small amount in solution (atomically dispersed) and the rate of diffusion of these atoms is much less than that of hydrogen because of their greater atomic volume and lower mobility. Consequently, it is possible to extract most or all of the hydrogen from solid steel in a reasonable time at moderately elevated temperatures, but the procedure is not applicable to the determination of oxygen or nitrogen. It is only within the last decade that these observations have been developed into an analytical procedure for the determination of hydrogen. Apparatus and Procedure The apparatus used at the National Bureau of Standards,6 for the determination of hydrogen by the vacuum-extraction procedure, is shown schematically in Fig. I. The specimen, freshly cleaned and dried,* is suspended on a fine wire within the quartz furnace tube that is connected to the reservoir system and analytical train.

Jan 1, 1945

By C. B. Smith, A. G. Guy

The power and convenience of tensor analysis are employed in deriving the equations that describe three-dimensional diffusion in an n-component system plus vacancies. A "Kirkendall coordinate system, '' defined in principle by Kirkendall markers, is used in defining the intrinsic diffusion coefficients that are of primary interest. The defining equations are then transformed to local cartesian coordinates and to fixed cartesian coordinates, the latter being convenient for experimental measurements. Finally, it is shown how the intrinsic diffusion coefficients can be calculated from the experimentally determined quantities. It is generally recognized that any treatment of the essential diffusion phenomena in metallic systems—the jumping of atoms from one lattice position to another—must be based on movement of the atoms past Kirkendall interfaces.' A logical extension of this idea is the proposal that, fundamentally, diffusion must be described mathematically in terms of "Kirkendall coordinates." The basic equations thus obtained may then be transformed into other coordinate systems, when such transformation leads to simplification of either the experimental or mathematical treatment of diffusion data. Tensor analysis is clearly the appropriate mathematical tool for this purpose, since it provides methods both for determining general equations that are valid for all coordinate systems and for conveniently transforming the equations from one coordinate system to another system related to the first in some known fashion. For the present purpose three coordinate systems are used, and it is convenient to begin with a description of the relations among these three systems. FICK LAW FOR KIRKENDALL COORDINATES The reference coordinate system, and the one that is useful for most experimental measurements, is a cartesian coordinate system, xi (i = 1, 2, 3), fixed with respect to some point in the specimen, such as an end of the alloy bar undergoing diffusion. A second set of coordinates, the Kirkendall coordinate system, is one that in principle can be described by the location of inert markers (Kirkendall interfaces). A convenient mathematical relation between Kirkendall coordinates, x'i, and the reference cartesian coordinates, ii, is obtained by specifying that the Kirkendall coordinate system coincide with the cartesian system at time, t = 0. After diffusion has occurred for some time, t = t, the Kirkendall coordinate system will differ from the reference system in the manner shown schematically for the one-dimensional case in Fig. 1. The third coordinate system is Darken's1 local cartesian-coordinate system, xi, which is identical with ii in orientation and units, but which moves with the point under consideration in the Kirkendall coordinate system. Even though most diffusion problems are essentially one-dimensional, there is an advantage in first carrying out the analysis of the three-dimensional problem to gain a clearer insight into the assumptions that are made in the usual one-dimen-

Jan 1, 1962

By A. G. H. Andersen, A. W. Kingsbury

SILICON bronzes containing iron are used to a considerable extent in industry, under the trade name of P.M.G. alloys. Various classes of wrought alloys fall in the composition range 1.5 to 3.5 per cent silicon, and 0.5 to 2.5 per cent iron. Castings may contain as much as 6 per cent silicon and 3 per cent iron at present. The constitutional diagrams of these alloys are thus of considerable practical importance. Copper-silicon-binary alloys have been thoroughly investigated by a number of workers, the latest reports being those of C. S. Smith1 and of A. G. H. Andersen.2 Although much work has been done on iron-copper alloys,3 recorded investigations on the copper-rich copper-iron binary constitutional diagram are not numerous. Tammann and Oelsen4 determined the solubility limits of iron in copper by means of magnetic measurements, and found that the solubility of iron in copper amounts to a fraction of one per cent at 400°C., increasing slowly to one per cent at 800°C. From 800°C., the solubility increases rapidly and attains 4 per cent at 1100°C. Hanson and Ford,5 using electrical resistivity measurements and the microscope, determined a somewhat different solubility limit. Of earlier X-ray works on the copper-iron system, very little has been published. The work by Bradley and Goldschmidt6 on copper-iron-aluminum alloys includes some information on the copper-iron binary. These investigators conclude that substitution of iron in the copper lattice decreases the spacings, which is contrary to the evidence of the present work. Hanson and West7 have investigated the ternary alloys of copper with iron and silicon. Although their diagrams are valuable contributions to the understanding of these alloys, they did not recognize the kappa phase,12, 7,8 and their diagrams do not everywhere conform to the phase rule. The present work contains a check by means of X-rays of the solid solubility limit of iron in copper, and an X-ray investigation of the ternary-phase diagram, which, owing to present conditions, it became necessary to curtail considerably. PREPARATION OF SAMPLES Castings weighing about 75 grams were melted under vacuum. The charges were made up of ingot iron, copper cathodes from Laurel Hill, and refined silicon supplied by the Electrometallurgical Co. Alundum crucibles were generally used. The exceptions were alloys 77 and 78, which were melted in graphite crucibles. The ingots were annealed at 800°C. for one week, then samples were cut for chemical analysis. Longitudinal sections of the binary alloy ingots were hammered into plates 3 in. thick. Wherever possible, these plates were homogenized at temperatures ensuring

Jan 1, 1942

By Henry Fay

LAWRENCE ADDICKS, New York, N. Y., (communication to the Secretary *).-There are two points regarding gun erosion on which I want to say a few words: The first is about the analogy to hardening of wire by drawing and the second the possible role played by thermal conductivity of the metal. The ductile metals do not necessarily become brittle when cold-worked as it is possible to draw copper from 3. in. in diameter soft rod down to the finest hair wire without annealing. This results, as stated in the paper, informing a hardened core with a very hard skin. The electrical conductivity is depressed some 3 per cent. and the tensile strength nearly tripled. A soft copper wire 0.08 in. in diameter and 6 in. long may be twisted 150 or more turns before the wire will snap under torsion. A hard-drawn wire will break after perhaps a dozen twists, the skin breaking down at one spot. Just wiping the wire with a cloth clamp with dilute nitric acid has a remarkable effect in increasing the number of twists without appreciably lowering the tensile strength, showing the skin to be very thin. On the other hand, pickling the rod, from which the wire is to be drawn, in dilute nitric acid also greatly increases the number of twists which can be applied to the resulting wire. This indicates that the copper oxide scale produced when the wire bar is rolled hot is more or less rolled into the rod and may have much to do with the skin effect. We also know that if the conditions of drawing are not correct, the heat of deformation in the die may produce quite an annealing effect. The application of this analogy to what occurs in a gun to produce the effects noted offers some difficulty. The second point is that as the temperature of the surface of the gun bore has undoubtedly a great deal to do with the amount of erosion, one natural remedy would be to conduct the heat away fast enough to keep this temperature within desired limits. This brings up the question of the thermal conductivity of the metal of which the gun is made. We know that the conductivity of pure metals is greatly altered by alloying and that the alloy is usually, though not always, lower in conductivity than the metal before alloying. This is interesting when it is considered that the high-nickel and manganese-steel alloys show greater erosion as stated. Would it not be instructive to study the question from the point of view of heat conducted away from the eroded surface?

Jan 3, 1917

By E. R. Atkins, G. H. Smith

Results of laboratory tests are presented to show that lire value of "m", in the Archie expression dernlined by the shapes of the particles in the system. Tile value of m "the shape factor", is constant for a system of particles of a given shape for a range of F - + values. Applying this concept, one can predict F - + relationships for mixtures of particles with different shapes, and these predicted relationships are useful in electric log interpretation. It is suggested that an equation of the form 1/F -10mcan be used to describe the properties of natural formations containing varying amounts of sand and clay. From this work and values of "a" and "m" reported in the literature, it appears that in many cases rocks in the same geological horizon have a common primary porosity but contain varying amounts of a particular clay. It is concluded that the equation can be applied to a rock-water system only when values of "a" and "m" have been established for the particular system. INTRODUCTION The petroleum literature contains many reports of the results obtained by determining formation resistivity factor F and porosity + of rock samples from oil fields all over the world. The usual practice is to use data from a large number of samples from a number of fields to find an average relationship between F and +. Several such average relationships have been advanced. In the absence of data on a particular formation or field, it has been the practice to use the average relationships to give a rough approximation of the F - + relationship. The purpose of this paper is to report on basic relationships that exist between F and + for naturally occurring particles in water solutions. Other workers' have found the same relationships apply to the diffusion of hydrogen through packed beds of dry particles. In the work discussed here, relationships for application to unconsolidated sands or shales containing mix- tures of particle shapes are derived. These relationships, developed for unconsolidated formations, may apply to consolidated formations. EXPERIMENTAL To evaluate F- relationships for unconsolidated rocks, the results of laboratory measurements on simple slurries of clay or sand will be used. Such laboratory studies are concerned with the electrical behavior of water-containing rocks. The wet rock constituents are electrically similar in slurries and in rocks. Archie2 defined formation resistivity factor as All resistance measurements were made using a 1,000-cycle impedance bridge with an oscilloscope as the null detector." The accuracy of this bridge was better than * 0.15 per cent. For the particular apparatus employed, no additional reactance was required to achieve balance for samples with resistances between

By H. L. Luo

SYSTEMATIC investigations of the Fe-Ga system have been reported only very recently."' The maximum solid solubility of gallium in a-Fe is nearly 50 at. pet at 900°C. However, from Ref. 1, it was not evident that the a-Fe solid solution could be retained successfully beyond 17.38 at. pet Ga by solid-state quenching. The present investigation reports the retention of a-Fe solid solution at 50 at. pet Ga by quenching from the liquid. An ordered phase of CsC1-type B2) structure was observed between 34 - 50 at. pet Ga. Since it was considered very probable that the CsCl structure would occur at high temperatures, alloy filings were also quenched by the conventional quenching technique. In addition to the CsCl phase, a second ordered phase of BiF3-type (DO3) structure was found in the range 25 - 30 at. pet Ga. Alloys were prepared from elements of 99.99 pet purity or better, induction-melted in alumina crucibles under hydrogen. After reweighing, the alloy ingots were cast into wires under argon. From the weight losses and the reproducibility of the lattice parameters, compositions were estimated to be within ± 0.3 at. pet. The techniques of quenching from the liquid state were reported before.3-5 Prior to quenching, a small section of cast alloy wire (30 - 50 mg) was melted in an alumina insert under an argon flow. The quenched specimens were in the form of flakes, typically 1 sq mm in area. For solid-state quenching, alloy filings passing 200 mesh were sealed under a reduced helium atmosphere in a thin-bottom silica tube. After heating for -30 min at the desired temperature in a vertical furnace, the sealed tube was rapidly dropped into ice water so that the thin bottom of the tube broke on impact. The quenched alloy filings were always ferromagnetic and could be collected by a magnet. X-ray diffraction patterns were taken with iron-filtered cobalt radiation in a 114.6-mm-diam Debye-Scherrer camera. High-angle lines were always resolved and spacings were computed relative to ? (CoKa1) = 1.78890Å. Lattice parameters were obtained from extrapolation against the Nelson-Riley function. The variation of lattice parameter with composition is shown in Fig. 1, together with the data of Dasarathy and Hume-Rothery.1 Uncertainties in the present measurements are within the dimensions of the symbols or indicated by error bars. X-ray diffraction lines indicative of CsC1-type ordering could be clearly identified for alloys of 34 - 50 at. pet Ga quenched from the liquid and alloys of 35 - 41 at. pet Ga quenched from -975°C. Within experimental error, no difference in

Jan 1, 1968

By J. M. Seeman, R. A. Dodd

If some solution-quenched supersaturated aluminum solid solutions, e.g.., Al(Cu), are plastically deformed at room temperature and then aged at 200oC, the hardness may first decrease before increasing in the usual manner ' A similar transient softening is observed, even in the absence of plastic deformation, when a thin foil or small-diameter wire Al(Cu) specimen is rapidly quenched from the solution-treatment temperature and then aged.' Also, some solution-quenched and neutron-irradiated alloys undergo an initial hardness decrease during subsequent aging.3 The usual explanation of the transient softening in the above examples involves the effect of vacancies introduced by plastic deformation, rapid quenching, and neutron irradiation, respectively However, the mechanism of softening is not unequivo-cably established. In the first-noted case, Gane and parkins' observed that the softening was approximately proportional to the difference in the atomic diameters of solute and solvent, and it was argued that, if a large relative difference in atomic diameter promoted vacancy-assisted room-temperature solute diffusion to dislocations, dislocation climb occurring during subsequent aging at 200°C could cause transient softening. Some substantiation of this theory was offered by the additional observation that discontinuous yielding of solution-quenched polycrystalline Al(Cu) tensile specimens was suppressed by interrupting the test for a short aging treatment at 200°C. Of course, reversion (resolution of GPI) at 200°C would also cause softening, and Sil-cock4 expressed the opinion that the softening in the case of Al(Cu) must be partly associated with reversion. Also, Hirsch5 commented on the possibility that, if jogs cause hardening, an anneal at 200°C should straighten the jogged dislocations and result in softening. However, parkins' has re-expressed his belief that these mechanisms are not entirely consistent with the observed serrated stress-strain curves. Experimental. New data has now been obtained for Al(Cu), Al(Ge), Al(Mg), and Al(Zn) primary solid-solution alloys. These alloys were prepared from metals exceeding 99.99 pct purity, and specimens 4 by 4 in. diam were solution-treated, quenched, deformed 10 pct in compression at room temperature, and aged at 200'C in a cottonseed oil bath for various times. Generally, these operations could not be carried out in rapid succession, so the alloys were stored in a freezer between treatments to minimize aging. The variation in hardness with aging time, Figs. 1 to 4, was determined by microhardness testing with a 3.0-kg load. At least five readings were averaged to obtain each data point, and all measurements were taken about the center circumference of each cylinder (region of maximum deformation). Each specimen was used to obtain only one data point, i.e., specimens were not replaced in the aging bath after measurements were made. In

Jan 1, 1968

By C. F. Floe, N. J. Grant, A. Joukainen

A CCORDING to Guertler,¹ Smith and Hamilton were the first to study the Cu-Ti alloy system, but because of the presence of large amounts of impurities their data are inconclusive. Hensel and Larsen² in 1930 and Kroll³ in 1931 determined the high copper end of the diagram. In 1939 Laves and Wallbaum,4 in a short summary of compound determinations in titanium binary alloys, mentioned the existence of a face-centered cubic compound, Ti2Cu, with 96 atoms per unit cell, and also a compound, TiCu3, which was said to have a deformed hexagonal close-packed structure in which ordering had been observed. The existence of a compound, TiCu, was also found but the crystal structure was not determined. Craighead, Simmons, and Eastwood determined the effect of copper on the allotropic transformation in titanium. The investigation was limited to alloys containing from 0 to 5 pct Cu, using titanium of fairly high impurity content. Experimental Procedure The methods used for determination of the diagram included metallographic examination and X-ray and thermal analyses. The system was first worked out using the higher purity "Process A" sponge titanium and oxygen-free copper. The high titanium region was next determined more accurately using iodide titanium and vacuum-melted, oxygen-free copper. Preparation of Alloys: The alloys were prepared by arc melting under prepurified helium atmos- pheres in water-cooled copper crucibles. The high purity iodide titanium alloys were prepared by melting three compositions along with a specimen of unalloyed titanium in a single charge. A multiple crucible was used which consisted of a copper plate with four cup-like depressions. The unalloyed titanium was melted first and acted as a getter for any oxygen and nitrogen in the melting chamber. Since these elements harden titanium, the hardness of the standard specimen was an index of the highest probable contamination of the alloy melts. The sponge titanium alloy melts weighed from 100 to 200 g each and the iodide titanium melts from 20 to 25 g. In order to insure greater homogeneity most of the alloys were melted, turned, and remelted twice. The larger buttons made from sponge titanium were sectioned or crushed before remelting. These alloys up to 30 pct Cu were further homogenized by forging at 925°C. They forged readily up to 20 pct Cu but numerous cracks were formed in the alloys containing from 20 to 30 pct. Above 30 pct Cu the sponge titanium alloys were homogenized by heating for 200 hr at 850°C under prepurified helium. Similarly, the iodide-grade titanium alloys containing up to 3 pct Cu were homogenized at 1000°C for 24 hr and all others at 880°C for 200 hr.

Jan 1, 1953

By C. W. Haworth, M. G. Hall

THE diffusion of copper in silver has been studied by Sawatzky and Jaumot1 and Cahoon and Youdelis.2 Sawatzky and Jaumot measured tracer diffusion in single crystal specimens but the 12.9 h half-life of CU64 limited the time of the diffusion anneal to about 50 hr, and in consequence the minimum temperature of the investigation was 716°C. Cahoon and Youdelis employed polycrystalline diffusion couples, and measured the interdiffusion coefficient over the range 0 to 2 at. pct Cu. These experiments were performed at temperatures down to 630°C and a discontinuity in the Arrhenius plot was observed at -700°C. The high D-values at lower temperatures were attributed to the effect of grain boundary diffusion. The present experiments were undertaken to investigate this anomaly and study the low temperature region of the diffusion of copper in silver. The method employed single crystal samples and a plated source of copper. Silver single crystals 2½ by 4 in. sq were grown from zone-refined silver bar (>99.99 pct Ag) by the Bridgeman technique, and $ in. thick slices were cut by spark machining. The specimens were electro-polished, and a 2 µm layer of copper was electroplated on to the planar surface at one end of each specimen using a potentiostatic voltage source. The following solution was used for plating: CuSO4 . 5H2O 125 gm H2SO4 (S.G. 1.8) 53 ml H2O 1000 ml The diffusion couples were sealed in capsules, in an argon atmosphere, and were annealed at either 701, 597, or 498°C. The temperature measurements were made to an accuracy of *l°C After the anneal, the penetration of copper into the silver was determined using an electron probe micro-analyzer. 100 sec scaler measurements of the intensity of Cu Ka! X-radiation were performed at 2 to 5 µm intervals along a line normal to the source, with a beam potential of 25 kv. Allowances were made for the background radiation, and the dead-time of the counting system in the normal way, and the intensity ratios were corrected to weight concentration by the method of Duncumb & de-Casa.3 For the analysis of the diffusion profiles, it was first observed that the copper layer did not completely dissolve in the host crystal for the specimens annealed at 498 and 591 whereas for the specimen annealed at 701°C, a single phase solid solution was formed. For the 498" and 597°C specimens, the concentration of copper in the silver at the interface was therefore constant throughout the anneal and the analysis for a

Jan 1, 1970