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By O. W. Ellis

Before entering upon a general discussion of the fascinating, but at present rather controversial, subject of gases in copper, the author feels that some attention should be directed to the work which has been carried out on the solubility of gases in metals. The outstanding contributions to our knowledge of this subject have been made by Sieverts and his collaborators(1) † and by Iwasé.(2) Both the German and the Japanese investigators employed apparatus of the same general design in their investigations. Full reference need only be made, therefore, to the German scheme, which is diagrammati-cally illustrated in Fig. 1. This, to use the words of Sieverts, which he employed in describing his arrangement of apparatus at the 1928 meeting of der Deutschen Gesellschaft für Metallkunde(10): shows a diagram of the usual mode of procedure. A quartz flask contains the metal (for high temperatures a highly refractory porcelain tube is used) and is connected with the rest of the apparatus by means of a stopcock. The other parts consist of a burette divided into 1/10 c.c., a leveling tube, and an adjustable mercury reservoir. The burette is connected on one side with the gas inlet and on the other side with the absorption flask; the connection can be interrupted by means of suitable taps. Another tap permits the connection of the flask and the Töpler pump. In an experiment the quartz flask is first exhausted and then a measured quantity of gas is let in from the burette. In the first place the volume of the flask when empty is found by calibration with an inert gas. The pressure is read off on the level tube of the burette, and the temperature measured by means of a thermocouple whose welded junction lies close to the outside of the quartz flask, which is heated in an electric furnace. In several experiments the quantity of absorbed gas was transferred to a burette by means of a pump and measured. Care was taken by Sieverts to cool the ground-in joint between the reaction flask (or tube) and the rest of the system. Suitable precautions

Jan 1, 1934

By N. M. Langdon

Spokane Meeting, September, 1909.) THE following corrections to the paper of Mr. Langdon (Bulletin No. 34, October, 1909, pp. 919 to 940), received after the publication of the paper in the Bulletin, will be incorporated in the paper as finally published in the forthcoming Vol. XL. of the Transactions, but are here presented for the information of members:' Page. 921. Table I., furnace M2, item 11. For " 8801 " read "0.8801." 922. Table II., furnace C, item 2, under gas. For " 0.011 C " read " 0.011 0." Furnace G, item 13, under gas. For " 5.074 air " read " 3.074 air." Item 15, 114.269 " should be " 4.289." Furnace H, item 2, under iron. For " 0.04 " read ".0.01." 923. Table II., furnace J, item 1, under iron. For " 0.95 " read " 0.93." Furnace N2, item 6, under gas. For " 0.66 CO," read 0.066 C02." 924. Table III., furnace C, item 17. For " 379 " read " 397." 927. Table IV., furnace C, item 4. For " 0.0124 " read 0.0424." Furnace G, item 15.. For " 4,060 " read " 4,066." 928. Line 2. Items 19 and 20 of heat-supply, should be items 20 and 21. 930. Line 3. Expunge remainder of paragraph after the word " supplied," and substitute the following : "As compared with the fusion-zone, the loss by radiation n C was 25.5 per cent. of the total (2,278 units) supplied to that zone, while in D it was 22.5 per cent. of the total heat (1,824 units) supplied to that zone. Finally, as compared with the reduction-zone, C lost by radiation 36.8. per cent. of the 1,580 units supplied to that zone,

May 1, 1910

By C. S. Barrett, O. R. Trautz

PREVIOUS investigations have shown that lithium is body-centered cubic from near its melting point to the temperature of liquid air1,2,3 Nevertheless there was an incentive to search again for a transformation at low temperatures: C. Zener4,5 has remarked that the low value of the elastic modulus (11 - C12)/2 of body-centered cubic metals and alloys implies a rapid increase in free energy with decreasing temperature, which would favor the occurrence of a transformation; also the shear movement to which this modulus applies is one that can transform a body-centered cubic structure into a slightly distorted face-centered cubic structure. It was confirmed that lithium does not transform spontaneously at liquid nitrogen temperature, but it was found that a transformation can be induced at this temperature by cold working the metal,6 and at slightly lower temperatures a different transformation occurs spontaneously. Transformations were also found in solid solutions of magnesium in lithium. THE NATURE OF THE TRANSFORMATIONS Before presenting a detailed treatment of the technique used and the specific data obtained, it would be well to give a brief survey of the general characteristics of the transformations. A new crystal structure begins to form spontaneously in a specimen when it is cooled below a critical temperature. In lithium the structure appears to be close-packed hexagonal; in the Li-Mg alloys most of the diffraction lines (but not all) are near those for hexagonal lithium. The transformation proceeds as the temperature is lowered and soon stops if the temperature is held constant or raised. The course of the transformation on cooling is indicated by the curve at the lower left of Fig I. This curve is drawn in stepped fashion because the transformation goes by discrete steps with audible clicks. Because of the similarity to the decomposition of austenite into martensite in steels, it seems appropriate to designate the beginning of the spontaneous transformation on cooling as the Ms point. On heating to room temperature after the low temperature treatment only the usual BCC structure is found. On heating, the low temperature modification begins to disappear at a temperature which will be designated as Ac. The transformation on heating is halted when the rise in temperature is halted. The temperature must be raised 40 to 50°C above Ac before the reversion is complete-an interval which is sensitive to the rate of heating and to the time of holding at temperatures above Ac. This behavior on heating thus has similarities also to the formation of martensite in the cooling of steels.

Jan 1, 1948

By A. Keil

TO measure the absolute conductivity of metallic specimens it is generally necessary to have exact geometrical shapes and good electrical contact with the test-piece. To overcome limitations of the standard methods, an electronic conductivity-meter* Trade name, Sigmatest; model Dr. F. Forster; Reutlingen, Ger-many. has been developed, which works on the principle of inducing high frequency eddy-currents in the specimens and measuring the reaction of these curients on a measuring coil.',' To attach the instrument to the test specimen, a flat area of about 10 mm diam is all that is necessary. The reading is taken off a scale calibrated in pet of International Annealed Copper Standard. The induced eddy-currents are propagated in a circular motion parallel to the surface. Thickness of the layer included in a measurement depends on the frequency used. With a frequency of 60 kc per sec, the penetration of the currents was 0.8 mm at the upper limit of the scale, and 2 mm at the lower limit. The method is limited to nonferrous metals and other applications have been described elsewhere." The object of the present investigation was to detect the formation and growth of surface layers of differing conductivity, and to determine the depth to which these changes could be observed. A well known phenomenon which illustrates the problem is the internal oxidation of certain silver alloys containing base metal solutes, such as copper or cadmium, when they are annealed in an oxidizing atmosphere.4, 5 Until now, the only methods available for following these phenomenon have been metallo-graphic examination and hardness tests.0, 7 Changes in mechanical properties of copper alloys by internal oxidation were recently discussed in a more general way by Martin and Smith." When measuring these conductivity changes it must be remembered that the only absolute values of conductivity are those of 1) the nontreated homogeneous specimen, and 2) the final values obtained with a surface layer of depth comparable to the penetration of the eddy-currents. All intermediate values refer to the mixed conductivities of the transformed surface layer and the untransformed alloy, and are thus readings of relative value only. Experimental Results Specimens were annealed for 1/2 hr at 800°C in hydrogen, and the internal oxidation was carried out by thermal treatment in air at 800°C. Fig. 1 shows the results of the first series of experiments. With internal oxidation of a solid solution of 8 pet Cd in silver, the conductivity rises continuously until the surface layer formed has become thick enough to be the deciding factor (about 400µ). Precipitates of CdO are mainly in the form of points, Fig. 2, and, as a result, the electric contact between the silver crystals is not distorted by them. Brine11 tests were run with a 1.25 mm ball and a 7.812 kg load. The specimen annealed in hydrogen and oxidized to a depth of 400µ had a hardness of 40 Bhn,

Jan 1, 1959

By I. L. Dillamore

I. L. Dillamore (University of Birmingham)—The different textures developed in various fcc metals have long awaited satisfactory explanation and it has now become clear that these differences are related to parallel differences in the deformation characteristics of the metals. Liu is correct, therefore, in seeking to account for the observed textures in terms of the flow mechanisms but I believe, for the reasons outlined below, that the particular interpretation of flow mechanisms proposed by Liu is open to substantial objections. By considering the forty-eight possible designations of the twelve octahedral slip systems found in fcc metals as distinct and separate deformation modes, Liu has fallen into the error of assuming that only positive glide dislocations associated with each system are present. In fact both positive and negative dislocations will be present and the only difference between for instance the systems B4 and B4' (in Liu's notation) is that under a stress of given sign the direction of motion of a dislocation is reversed on changing from B4 to B4'. For both orientations positive and negative dislocations will be present. In considering possible dislocation interactions it is, therefore, inadmissible to differentiate between R4 and R4' as Liu does. Liu considers those dislocation interactions which give the biggest reduction in energy to be the most favorable and neglects, on the grounds that they will form strong barriers to slip, interactions between dislocations with perpendicular Burgers vectors. Setting aside interactions between positive and negative dislocations of the same slip system, which must occur regardless of the combination of slip systems chosen, the biggest reduction in energy occurs for the Lomer-Cottrell interaction and it is Lomer-Cottrell barriers which are thought to provide the stronger dislocation obstacles. On the other hand the intersection of dislocations with perpendicular Burgers vectors is thought to be a low-energy process which contributes only a fairly small temperature-dependent part of the total work hardening. On this basis it seems doubtful whether the reduction in energy through possible dislocation interactions provides a reasonable criterion for choosing the operative slip systems. From the point of view of texture development it is unsatisfactory to ignore the slip rotations leading to an end position and to neglect to consider the stability of the chosen end point. It is also unsatisfactory to treat the two stress axes as interchangeable since, if the stress system is idealized as biaxial, one stress is compressive and the other is tensile. For the same reason the rotations of the two stress axes are not made compatible simply by assuming that the same slip directions are responsible for the rotations of the two stress axes. It is, in short, essential to treat the two stress axes as acting together on the same slip systems. Turning to the question of the difference between the copper-type and the brass-type texture, there now remains little doubt that the difference is attributable to differences in stacking-fault energy (y), as noted by Liu, but it is doubtful whether the temperature dependence of the texture in copper and in silver is due to increasing stacking-fault energy with increasing temperature. The results of Swann and Nutting42 cited by Liu were obtained in Cu-A1 alloys and the apparent increase in stacking-fault energy on raising the temperature may be influenced by short-range ordering. In pure metals such effects are absent and the only data available on the variation of y with temperature are those of Buhler et a1.43 for silver. They report a minimum at 200°C which does not fit the hypothesis put forward by Liu. It is much more likely that thermal activation of cross slip is important in determining which texture develops, as proposed by Dillamore and tors. These workers have proposed an explanation for the differences in observed texture among the fcc metals and the pole figures predicted consist of an orientation spread which is in better agreement with observation than the limited number of discrete orientations suggested by Liu. The theory of Dillamore and Roberts is also able to account for the differences between aluminum and copper which Liu still leaves unexplained. Y. C. Liu (author's veply)—The writer appreciates the interest of Dr. Dillamore, but must discuss some of his comments in order to avoid cross purposes. The phrase, "forty-eight slip systems," which appeared twice in the text—in the caption of Fig. 1 and the first paragraph in the Discussion—might unfortunately have led Dr. Dillamore to disagree

Jan 1, 1965

By I. N. Zavarine

AUSTENITE is often defined as a solid solution of carbon or carbide in a nonmagnetic form of iron. Conversely, magnetic measurements are often used by investigators for the purpose of detecting the degree of austenite decomposition after an iron alloy has been subjected to certain thermal or mechanical treatments. Association of the magnetic state with the gamma-phase decomposition is often extended to the alloys of iron with elements other than carbon. Definition of austenite as a nonmagnetic solid solution cannot be accepted in the light of available information without certain reservations. The relation of magnetic transformations with the gamma-phase decomposition in the complex alloys of iron has never been rigorously proved. The present investigation deals primarily with the magnetic trans-formation that occurs in carbon steels during the quenching process. The work was further limited to a study of magnetic transformation in carbon steels quenched at such rates as are necessary to retain the product of austenite decomposition in a martensitic state.

Jan 1, 1934

By Cyril Wells, Robert F. Mehl

THE practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out 1,13 This importance ties chiefly, though by no means only, in the study of carburizing and in the study of reactions involved in the eutectoid inversion in steel The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in y-Fe and their mutual effects are measured with precision The present paper reports the results of meas¬urements of diffusion coefficients D of manganese in -y-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients [$] Data on the rate of diffusion of manganese in y-Fe have been reported by Fry2 and by Paschke and Hauttmann 3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq cm per sec at 960°, which will be shown to be incorrect by many orders of magnitude Paschke and Hauttmann gave a rough value of 9 6 X 10-8 sq cm per sec at 1400° Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon METHOD AND MATERIALS Method -The method employed is identical with that used earlier 5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded The diffusion anneals were performed in argon, except one (test 18) in which hydrogen was employed for purposes noted below The temperatures reported are accurate to about 3° and constant within I°C , the diffusion times are reported to the nearest half hour The specimens were furnace-cooled after the diffusion anneal at about 2° per min Layers, usually 0 004 in thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0 01 per cent Mn, the distances of these layers from the interface was measured to ±0 0002 in The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions e The D values calculated by these two methods do not differ appreciably 5 The Grube solution was used except in tests in which the effect of concentration upon D was greater than 50 per cent, in such cases the Matano method, which explicitly provides for the variation of D with concentration,1 is the more reliable In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer In 3 of the 30 tests, however, this is not justified, and the D values

Jan 1, 1941

By W. C. Ellis, E. S. Greiner, M. E. Fine

Discontinuous changes of Young's modulus, internal friction, coefficient of expansion, electrical resistivity, and thermoelectric power are evidence for a transition in chromium near 37OC. Although the X-ray diffraction pattern gives no clue, a difference between the thermal expansivity and the temperature dependence of the lattice parameter suggests a crystal-lographic change. Young's modulus data disclosed another transition near THE thermal dependence of a number of proper- ties of chromium indicates a transition occurring over a temperature range near room temperature. Bridgman' noted this first from a minimum in the electrical resistivity near 12°C. In a sample of greater purity, Sochtig' observed the minimum at 41 °C. Erfling3 reported an inflection in the thermal expansivity curve at 36°C. These temperature-dependence curves are reversible with no hysteresis being detected. No discontinuity or inflection has been observed in the heat capacity' or the paramagnetic susceptibility.' Likewise, no one has noted a change in crystal symmetry. In the present investigation Young's modulus, internal friction, coefficient of expansion, electrical resistivity, illustrated in Fig. 1, lattice constant, Fig. 2, thermal electromotive force, Fig. 3, and paramagnetic susceptibility, Fig. 4, were measured over an extended temperature range. The samples were prepared in two ways: (1) By cold pressing a sintered electrolytic powder compact,' and (2) by electroforming from an aqueous solution. The electroformed samples were prepared by R. A. Ehrhardt and G. Bittrich by plating on copper or nickel tubes from an aqueous solution according to the method of Brenner, Burkhead, and Jennings.' The pressed powder samples (method 1) were finally annealed at 1400°C in purified helium: the electroformed samples, packed in powdered chromium, were vacuum-annealed at 1000°C. From the composition of the original powder' the purity of the pressed powder samples is estimated to be 99.8 pct Cr. Spectrochemical analysis furnished by E. K. Jaycox, revealed only slight traces of impurities in the electroformed sample (less than 0.001 pct), neither iron nor nickel being detected. Chromium deposited by this method is reported to contain approximately 0.05 pct 0.- Methods and Data Young's Modulus: For measurement of Young's modulus, an annealed, pressed powder sample, 0.114 x0.237x1.845 in., and an electroformed sample, 0.10 in. od, 0.01 in. id, and 1.86 in. long, were prepared. The resonant frequencies of the rod samples in forced longitudinal vibration were measured at a series of temperatures from —192" to 200°C by a method previously de~cribed.6,7 Because the samples were nonferromagnetic, iron- silicon or molybdenum permalloy tips (0.013 in. thick) were soldered to the ends. The softening temperature of the solder limited the temperature of measurement. Young's modulus, E,, of chromium at temperature, T, may be calculated from the resonant frequency of the composite rod, f,; the thickness of the tips, t; the length of the chromium sample at 25°C, l,.; the density of chromium at 25°C, pc (7.20 g per cc);5 and the thermal expansivity, Al/l25. Modulus differences for two temperatures, ET and E, are accurate to +0.002x10" dynes per cm2. ET = 4PAlc+2tyf Young's modulus at 25°C, Fig. la, is 28.2~10" dynes per cm' (40.8xlO" si) in wrought chromium (upper curve). The modulus of the electroformed sample is apparently lower due to cracks. From the modulus measurements two transitions were observed: one with a critical temperature at 37°C, the other at —152°C. Internal Friction: The internal friction, 1/Q, was determined from the width, Af, of the strain amplitude-frequency curve at 0.707 times the strain amplitude at resonance;' the internal friction, 1/Q, then equals Af/f. Fig. lb shows a sharp peak in internal friction at 38°C. The internal friction of the electroformed sample had a similar maximum. Thermal Expansion: The expansivity measurements, shown in Fig. 2, covering the temperature range —195" to +400°C were made by D. MacNair in an interferometric dilatometer8 sing a sample consisting of three pyramids 0.25 in. high prepared from wrought electrolytic chromium. Below —120°C the experimental points deviated up to ±2x10 from the drawn expansivity curve in Fig. 2 because of decreased precision of the quartz wedge thermometer at low temperatures. Near 38°C the thermal expansivity curve, Fig. 2, goes through an inflection corresponding to a minimum in the coefficient of expansion, Fig. ld, and a relative volume decrease on heating. Electrical Resistivity: The variation of electrical resistivity with temperature measured by the po-tentiometric method is also shown in Fig. l. The resistivity of the wrought chromium (upper curve) at 20°C is 13.6 microhm-cm; of electroformed chromium (lower curve) 12.8 microhm-cm. The lower value reflects higher purity and agrees closely with a published value." A minimum at 40°C occurs in the resistivity curves of both samples. No conclusive evidence for a transition near — 150°C was observed, but the points, Fig. 1, appear to deviate from a smooth curve between —120" and —160°C.

Jan 1, 1952

By Paul A. Filteau

Asbestos ranks among the leading minerals produced in Canada. It is also mined in Russia, Rhodesia, South Africa, Cyprus, Italy, the U.S.A., Japan, China and several other countries. The most abundant variety, chrysotile, and also the most valuable form of asbestos produced, makes up 90% of the world's supply. In Canada, chrysotile is found in the provinces of British Columbia, Ontario, Newfoundland as well as in Quebec, the latter accounting for almost 90% of all the fibre produced in this country. A number of developments emerging this year could make 1968 a record production and export year for Canada's asbestos mining industry. Asbestos fibre consumption in increasing in the U.S., Canada, up 10% to date this year, Japan and in Latin America. Demand in Western Europe is again on the upswing, following a cut-back last year. As a result, shipments from Canadian mines for the first eight months of this year reached some 916,968 tons versus 873,402 in 1967, an increase of 43,566 tons or 5%. Indications are that Canadian asbestos production will for the first time ever top 1.5 million tons in 1968.

Jan 1, 1969

By Frank Firmstone

When in charge of the Glen don Iron Works, the importance of good methods of filling was forcibly brought to my attention, and it occurred to me that the first step toward the discovery of the best plans was the accumulation of exact information as to the distribution actually effected by various chargers; also, that something could be done in this direction by careful measurements in the furnace, to be afterwards recorded for comparison on drawings. The figures shown herewith have been prepared from such measurements, and nearly all of them refer to Glendon, where the fuel used was anthracite and the ore-mixture about threequarters of New Jersey magnetic ores and one-quarter of brown-ores from the vicinity of the works. Every occasion furnished by the blowing-in of furnaces was utilized, but the data accumulated rather slowly in this way; and, opportunity oEering to make special trials at no great expense, the figures from 2 to 7 were thus obtained. The trials were made by dumping a hopperful (6 barrows) of material at once into the furnace, and, when all the fuel of a round (12 barrows) had been put in, the profile of the upper surface was obtained by stretching a steel tape across the top on a diameter and at a known height. By measuring down from this with a graduated rod, the profile was easily obtained with sufficient accuracy, especial pains being taken to get correctly the crests of the ridges and the bottoms of the hollows, as many intermediate points being included as seemed necessary. This was repeated on another diameter when there was occasion. The same course was followed for the limestone and ore.

Jan 1, 1899

By G. Sachs

According to Tammann,' the explanation of the effect of mechanical deformation in producing changes in the properties of metals is one of the most important problems of physical metallurgy, taking rank with the study of the constitution of alloy systems; and this problem has long attracted the attention of practitioner and scientist alike. Its solution was not advanced materially until Tammann2 set up his translation hypothesis with its crystallographic basis, while other hypotheses, such as the amorphous metal hypothesis of Beilby3 and Rosenhain,4 have been shown by more intensive studies to be less and less satisfactory. The principles of the Tammann translation hypothesis have proved to be useful even up to today and in spite of all of the recent accumulation of experimental data, while the differences of opinion which have arisen relate to the extent to which the hypothesis accounts for the observed changes Ïn properties and to what extent further assumptions are necessary. Stimulated by the proposals of Tammann, there soon developed a lively experimental activity which aimed at the elucidation of the structural or crystallographic changes produced by the mechanical deformation of metals. Parallel movements of crystal "blocks" along definite crystal slip planes had already been observed by Ewing and Rosenhain5 in 1900, in metals which had been moderately deformed but without shedding light on the crystallographic nature of the processes accompanying more severe deformation. The solution of this important problem was not advanced until a much later date, or until the methods of X-ray crystal analysis had become available. Shortly after the discovery of the diffraction of X-ray by crystals, symmetrical diffraction effects were

Jan 1, 1931

By Morgan Walker

Intermittent injection of gas in gas-lift pumping is a variation of the common practice in that the gas is delivered to the well for a short period, called the "on time," followed by a period during which none is admitted, called the "off time," instead of being admitted continuously at a constant rate or by intermittent flowing in which it is occasionally delivered to the well in just sufficient quantity to flow off the accumulated head of fluid. The term "gas" is used throughout this discussion but it should be remembered that in so far as the operation is concerned either air or natural gas may be used. The equipment at the well is the same as commonly used in gas-lift installations and gas may be admitted to either the tubing or the casing. It seldom occurs that all the wells on a lease can be pumped economically by intermittent injection from one header. Wells that have flow characteristics which permit their being handled together have their intake lines grouped at a central compressor station. Well groups may consist of two or more wells. The total volume of gas delivered by each group of compressors goes to one well at a time through a quick opening valve, each well connected to the header receiving its charge of gas in turn. Special cases may require a deviation from this arrangement. The distribution of the gas to the different wells is effected by an automatic timing device which operates quick-opening valves on the intake lines. The timing mechanism may be actuated by electricity, liquid or gas pressure, The essential factor in the operation of the timing mechanism is that as one intake valve is closed another must be opened. Water-operated Timing Device Timing devices operate the intake valves either directly, or indirectly by pilot valves. Of the former type one that is operated by water and has given satisfactory service is shown in Fig. 1 and can be made on the lease. The horizontal cylinder is a piece of 10-in. casing about 7 ft. long, closed at each end and free to oscillate about a fulcrum at the center.

Jan 1, 1929

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By R. L. Orr, J. D. G. Masse, Ralph Hultgren

The relative partial molar enthalpies of gold and tin in liquid Au-Sn alloys have been measured from Xsn = 0.474 to 0.510 at 696°K, slightly above the melting point of solid AuSn. Within an average precision of 6 cal per g-atom, the data are represented by two smooth curves, which satisfy the Gibbs-Duhem relationship and which do not show any anomalous behavior in the range of composition studied. The results give no support to the hypothesis that atomic associations in the equiatomic liquid alloy resemble those in solid AuSu. LITTLE has been firmly established as to the nature of atomic distribution in liquid metallic phases. A favored hypothesis assumes the existence of atomic groupings in the liquid phase which are similar to those in solid phases occurring at lower temperatures. Beginning with this hypothesis, it is often possible to adjust the values of certain parameters (such as degree of association) so that approximate agreement is achieved with certain features of the X-ray diffraction pattern of the liquid, even though many other possible structures might satisfy the data equally well. Thus, in this manner, the structure of liquid tin has been described as a dispersion of fragments of gray tin in a matrix of metallic tin.1 Four X-ray diffraction studies2"5 have been made of the liquid alloy of composition AuSn at temperatures slightly above the melting point of the solid. Each investigator concluded, on somewhat different grounds, that the liquid consisted to a large extent of arrays of atoms similar to the solid, with admixture of more disordered arrays. Solid AuSn has the nickel arsenide crystal structure: each tin atom has six nearest neighbors, all gold atoms; and each gold atom has six tin and two gold atoms as nearest neighbors. It remains highly ordered to the melting point. The liquid alloy has a large exothermic (?H700° K = -2700 cal per g-atom6) enthalpy of formation, favoring ordering and making the hypothetical molecular association not unreasonable. The possible existence of such solidlike arrays, or of a high degree of order that occurs preferentially at a specific composition in a liquid alloy, might also be revealed by thermodynamic behavior somewhat analogous to that in highly ordered solid alloy phases. The latter often exist over wide composition ranges, within which the highest degree of order occurs at the ideal composition for which the atomic fractions are equal to the fractions of sites which are "right" for each kind of atom. On departing from the ideal composition, the excess atoms occupy "wrong" positions, raising the internal energy and making it progressively easier for additional atoms to occupy "wrong" positions. Thus, on either side of the ideal composition, there should be a pronounced rise in the entropy and enthalpy, which would be shown particularly by the change in the relative partial molar enthalpies, ?Hi, since they depend strongly on d?H/dx. In the one case where accurate measurements have been made, the solid AuCu ordered phase, the structure becomes much less ordered as the composition deviates from the ideal, and relative partial molar enthalpies change sharply as shown by the data6 given in Table I. This suggests the possibility of finding similar pronounced changes in the relative partial molar enthalpies of gold and tin in liquid alloys near the composition AuSn if the postulated solidlike ar-

Jan 1, 1967

By A. Weiss, W. A. Coster

The search for ore is characterized by a great variety of uncertainties, each of which can be resolved by obtaining information at a cost. Three exploration stages may be distinguished in which information can be obtained, based on inherently different cost structure: 1) the reconnaissance or scanning stage, 2) the examination or screening stage and 3) the project stage. This exploration sequence would roughly coincide with replies to questions as to: where, how, why and how much. As complete information in each stage is too costly to acquire, we must assess the probability that adequate information will be furnished by a limited amount of effort and attempt to maximize the expected value of ore to be found for a given exploration expenditure. Several problems are discussed relative to the mathematical formulation and possible computer procedures for determining the optimum allocation of a total exploration effort. Based on the available literature possible solutions to this problem are indicated. When scanning through published literature on mineral exploration, it seems at first that there is little room for substantial and systematic improvements in the efficiency with which the problem of discovery of new ore deposits is presently being handled by large organizations active in exploration. It appears equally difficult to offer something relevantly new which could generate a break-through in exploration thinking and cause a marked improvement in the ratio of successful undertakings to the total exploration projects started. On the other hand, a number of experts in recent years have urged that the problems in prospecting be analyzed in a more skillful and sophisticated manner than in the past. Their thesis is based mainly on the premise that the cost of finding mineral deposits will increase with increasing technical difficulties. In present large-scale exploration ventures, especially in those regions where outcrops and immediately visible geologic evidence are scarce, older methods of prospecting are increasingly being replaced by more indirect and systematic geophysical and geochemical methods with more emphasis on correct statistical design of exploration patterns. It is perhaps the oil industry which has made the greatest strides in developing statistically, well justified patterns in its search for oil; possibly because oil seepages, as indicators of the presence of oil, left off at an earlier point in time than did outcrops as indicators of base metals. Among the pioneers in the field of statistics and operations research, as applied to mineral exploration, the excellent works of Allais, Slichter, Koop-man, Mickey, de Guhnin, Krumbein, Griffith, Sichel, Krige, de Wijs, and Matheron may be mentioned. It should, however, be pointed out that three subjects of basic importance to the allocation of exploration efforts have so far received only scant attention in published literature, even by the aforementioned authors. In the first place, a more precise definition of the object of the search, i.e., a minimum-size orebody, seems to be outstanding. Secondly, a decision model is not a widely-discussed subject. Thirdly, no concentrated attempt so far seems to have been made to establish probabilities of the occurrence of economic deposits on a regional scale and to arrive at a slightly more accurate knowledge of the probability laws governing the deposition of ore. It is not the purpose of this paper to create new order in the complexity of uncertainties in which our decision processes in exploration necessarily have to be conducted. Rather, we intend to highlight some of the outstanding, hitherto unmapped territory, where diligent compilation and a utilization of present and historic data may statistically improve our chances of success. We hope that the contribution of this paper will lie in bringing allocation problems into better focus and in increasing the mineral industry's realization of the magnitude of the factors involved. THE MINIMUM-SIZE OREBODY The concept of target specifications for what constitute a minimum-size orebody in exploration is a rather variable one and depends to some extent on

Jan 1, 1963

By D. S. Choi, R. Stefanko

There are a number of complex factors that influence the effectiveness of anchorage to maintain tension in rock bolts. However, a plastic analysis of the anchorage site employing certain simplifying assumptions with application of the Mohr-Coulomb criterion appears to explain the observed phenomena. Such an analysis has been made and a correlation sought with field and laboratory tests. Field tests were made in an anthracite mine in eastern Pennsylvania and included pull tests and long-term tests of a variety of anchorage devices in two basic lengths, 30 and 42 in. in two widely differing seams. Performance is reviewed for wedge, expansion shell, and resin anchorage. Laboratory tests duplicated many of the field conditions but in addition compared the performance of shells with normal and reversed serrations. This performance was compared with the predicted results from the plastic analysis. One of the major problems in conducting long-term underground tests is the selection of suitable instrumentation. All installed bolts were fitted with spherical and hardened washers to insure the best possible torque wrench readings. In addition, commercially available load cells were used. Finally, the performance of a specially developed strain-gage-equipped ring cell is viewed. Rock bolting as a method of support continues to increase with applications in many other industries in addition to mining. Nevertheless, with nearly 55,000,000 roof bolts installed in coal mines alone last year, this remains as the single greatest use. While bolts have frequently supported ground where conventional timbering could not, there are relatively few design criteria; and trial-and-error procedures prevail. Furthermore, there has been a lag in development of suitable instrumentation that is simple to install and read out, sensitive, durable, reliable, safe, and economical in evaluating the effectiveness of a bolt over long periods of time. Therefore, the pull test continues to be the most popular method of evaluating the applicability of a certain type of roof bolt under specific installation conditions. At The Pennsylvania State University in the Dept. of Mining, research has been conducted for a number of years to measure bleed off in carefully controlled laboratory experiments as well as in underground investigations."-' Unfortunately, most of the instrumentation developed has been primarily suitable only for research purposes, not possessing all of the aforementioned characteristics desirable for routine underground use. Other groups also have met with restricted success. Therefore, while relatively crude, the torque wrench continues to remain as the most widely used load measuring device. While both field and laboratory tests continue to be con- ducted, analytical analyses are attempted to discover the more important design parameters in order that more efficient anchorage might be devised. Bolts are being used for a greater variety of purposes in mining. Suspending wire sideframe belt conveyors from roof bolts is a common application. The suspension of a monorail transportation system presents yet another. One such system has just been installed in a recently reopened anthracite mine and is presently being evaluated under production conditions. Preliminary studies revealed that a considerable cost reduction was possible by suspending the monorail on bolts anchored in the top. The monorail was to be installed under two widely differing conditions—a competent sandstone above the Buck Mountain seam and a softer shale top above the Skidmore. The type of anchorage device, length of bolt, and long-term performance, consistent with economy and safety, had to be established for the installation once the decision was made to suspend the system on rock bolts. This paper describes some of the testing procedures leading to a final selection. Theoretical Analysis of Expansion Shell Anchorage A detailed look at an expansion shell assembly might shed some light on the factors involved in the design of a suitable shell, Fig. 1. When a bolt is rotated, the tapered plug is forced downward, expanding the leaves laterally to grip the sides of the hole. Two friction surfaces are present: (1) the interface of the plug and leaf and (2) the interface between leaf and rock. The relationships of these friction planes, geometry of expansion shell, and properties of the rock are important in the design of an expansion shell. Therefore, an analysis assuming the rock to behave as a rigid plastic material with its yield governed by the Mohr-Coulomb criterion was made." Furthermore, the effect of friction between the leaf and rock produced by serrations was analyzed.

Jan 1, 1971

By A. E. Bibb, F. W. Kunz

A platelet form of zirconium hydride was found in zirconium and ZY-1 wt pct U single crystals containing hydvogen in the range of 50 to 100 ppm. The habit planes for the hydride plateletg in the zirconium crystals were found to be {1012}, {1121}, and (1122) while the habit planes in the ZY-1 wt pct U crystals were {1121), {1123}, and (1.231). With the exception of the {1231} plane, these have been identified as the twin planes in zirconium. The different effect of hydridc on the mechanical puoperlies of zirconium at high and low strain rates has been explained in terms of the defornzation mechanism and the habit planes of the hydride. ZIRCONIUM and zirconium-base alloys are considered for many nuclear reactor applications, where the pick-up of hydrogen is a distinct possibility, if not an unavoidable occurrence. An excellent example of this is the absorption of hydrogen by zirconium and its alloys during aqueous corrosion, where as much as 30 pct of the hydrogen produced by the corrosion reaction is picked up by the metal. Under the proper conditions, the absorbed hydrogen would precipitate as zirconium hydride and consequently alter the mechanical and physical properties of the zirconium-base alloys. The knowledge obtained from a study of the crystallographic aspects of the hydride precipitation is necessary for the interpretation of the observed changes in the mechanical and physical properties. The deleterious effect of hydrogen on zirconium-base materials is not always observed in normal slow tensile loadings at or above room temperature, but becomes immediately obvious under impact loading, where the energy absorbed decreases with increasing hydrogen content,' and in notched specimens where triaxial loadings are attained.2 This effect is of serious consequence in the applications of Zr where shock loads or high strain rates are experienced. The purpose of this investigation was to determine the crystallographic planes of the Zr and Zr-1 wt pct U matrices upon which zirconium hydride will precipitate and to correlate these with the observed mechanical property data. PROCEDURE Crystal Growth—Single crystals of Zr and Zr-1 wt pct U alloy were used in this investigation. The Zr crystals were made from sponge that had a typical analysis as shown in Table I. Large grains were grown in this material by rapid cooling an arc-melted charge in a button furnace. This operation undoubtedly lowered the volatile impurity concentration below those listed in Table I. Back-reflection Laue patterns of these large grains showed the presence of considerable substructure and lattice distortion within each grain. It was found that an 18-day anneal in an argon atmosphere at 840°C (a high a heat-treatment) followed by furnace cooling, resulted in the further growth of the large grains and removed the detectable substructure ana lattice distortion. Equiaxed crystals with a cube edge of approximately 1/4 in. were produced in this manner. Large crystals of Zircaloy-2 (1.5 wt pct Sn, 0.15 wt pct Fe, 0.1 wt pct Cr, 0.05 wt pct Ni) also were produced by this technique but the large amount of substructure formed could not be removed by annealing. The Zr-1 wt pct U solid solution crystals were produced from an alloy rod consisting of Westing-house-Foote hafnium-free crystal bar zirconium and depleted uranium. The chemical analysis of the alloy is also given in Table I. Three-inch sections were cut from an 0.120-in.-diameter alloy rod and tapered to a fine point on each end. The samples were sealed in evacuated Vycor tubes, homogenized for 5 hr at 1000°C in the ß-phase field, and slowly lowered in a gradient furnace into the a phase (800°C), annealed for 60 hr at this temperature to produce grain growth and furnace cooled. This technique produced large grains approximately 1/2 to 3/4 in. long over the entire cross section of the rod, which were free of observable substructure. Metallographic examination up to X1000 did not show the existence of any second phase in these grains. Crystal Orientation—All crystals were abraded on fine emery paper to produce two flat surfaces 90 deg to each other. The crystals were analyzed by the standard Back-Reflection Laue technique to obtain the crystal orientation with respect to the abraded surfaces. The Back-Reflection Laue Photograms of all crystals used were clear and sharp indicating that the crystals were free from any substructure that could be detected by these means. Hydriding—Only samples containing four to five grains were used for hydriding. Samples that exhibited fine grained patches were discarded. The samples were hydrided using the following technique. After etching in 48 vol. pct HNO3, 48 vol. pct H2O, and 4 vol. pct HF (48 pct) solution, the specimens

Jan 1, 1961

By G. C. Fryburg, H. M. Murphy

ThE rates of oxidation of metals are usually obtained by heating the metal specimens in furnaces. Such a procedure is satisfactory for most metals. However, there are several metals that oxidize according to the reaction.

Jan 1, 1959

By C. S. Barrett

THE crystal imperfections known as faults in stacking (stacking disorder) are of importance to both fundamental and applied science and are receiving increasing attention. On the theoretical side there have been recent advances in the analysis of diffraction patterns in terms of stacking faults, and on the experimental side it has been found that certain metals develop a faulted structure on cooling through a phase transformation. Beyond this, little is known of what may be called the physical and mechanical metallurgy of faulting, although there has been no lack of discussion and conjecture as to the presence of faults in metals and the effect of faults on mechanical properties and microstructures. In the close-packed metals the nature of faults can be described very simply. Face-centered cubic (FCC) crystals consist of close-packed layers of atoms, (111) planes, stacked above each other in a definite manner. If one layer is designated as the A layer, the next must be a B or a C layer; that is, every atom of the second layer lies not above the atoms of the A layer, but nestles in the hollows between these, using the hollows designated as the B positions, or the equivalent hollows designated as C. If the sequence of layers is ABCABC...., so that layers three spacings apart are directly over each other, the crystal is FCC; if CBACBA ... it is an FCC crystal that is a twin of the former; if ABAB........or BCBC..it is hexagonal close-packed (HCP). A fault is a break in the sequence, such as ABCABABC .. . which has the effect of inserting an HCP lamella into an FCC crystal. Regularly spaced faults spaced two layers apart would convert an FCC crystal entirely to HCP, or an HCP to FCC. A fault in an FCC crystal is also equivalent to creating an FCC twin of minimum thickness; in fact, the entire crystal would be converted to its twin if faults were introduced regularly. (In HCP crystals, however, twinning does not occur on the basal plane and a fault on this plane is not identical with a thin twin). Faults are one of the possible causes for annealing twins,' for the strain markings that are brought out by etching deformed metal,'," for the altered X ray reflecting power of metal at slip bands that is revealed in X ray reflection micrographs,' for the extinction of Kikuchi lines in electron diffraction patterns, and for the hardening of latent slip planes.' Since other explanations of these effects are also available," there has been no direct proof of faults from deformation; yet it has appeared likely that they would occur. Faults resulting from phase transformations in metals, however, have been clearly revealed by diffraction in cobalt" and lithium. It is to be expected that the faulting tendency is greatest

Jan 1, 1951

By J. Groyecki, M. Markuszewicz, J. Lassota, A. Zawada

The ratio of stable to unstable inclusions was found to ploy an essential role in the process of sccorldar-y recrystatlizalion in Si-Fe. The analysis of the free energy of inclusions in the range of heat-treatment of individual inclusions to be predicted. The effects MnS. ns inslable inclusions. were investigated. TO secure a high induction, the secondary recryslulliztt-lion associated wilh the texture is necessary. To obtain a low core loss an additional refiuing in the solid state is required. It has been found that sulfur can be more easily removed in racunm than in hydrogen and thai this process was hindered by the prescrzce of INCLUSIONS play an essential role in the development of cube-on-edge texture in Si-Fe. Their function consists in restraining the growth of primary grains up to about 900°C and in passing subsequently into solution at higher temperatures. This process is accompanied by the selective growth of secondary grains with (110)[001] orientation. The general effect of inclusions depends on such factors as the type of impurities, their amount. dispersion and stability, the conditions of diffusion in the space of lattice of metal, and the reactions at the metal/gas interface. In recent years, some of these factors were the subject of a special investigation. A positive influence of Mns, siN,' and vN3 has been established. The quantity of impurities4 and their dispersion5 have been found to be of major importance. Attention was called to the vital importance of diffusion and the conditions under which the impurities are removed from metal., It has also been demonstrated that in Fe-Si alloys by the techniques of powder metallurgy a special opportunity exists to obtain the (110)[001] type texture. 6 The aim of this work was to conduct qualitative investigations on the influence of inclusion stability on the development of cube-on-edge texture in a metal containing approximately 3 pct Si. Experiments were carried out on cast alloys and on those manufactured by powder-metallurgy techniques. The results obtained from these experiments were utilized to explain the phenomena involved and to analyze the relationships between stable and unstable inclusions and the magnetic properties of alloys. EXPERIMENTS AND RESULTS The raw materials used in these experiments were the powder of carbonyl iron with the analysis (in pct) 0.044 C, 0.01 Mn, 0.005 Si, 0.009 P, 0.002 S, traces of Cu, 0.06 Ni, 0.0015 Al, 0.03 Cr, 0.02 Mo, 0.01 Ti, 0.002 Co, traces of Pb, and the powder of silicon containing 94.14 Si, 0.003 S, 0.048 C. The powders were ground and mechanically mixed in 100-g batches. and then pressed at 9 tons per sq cm into 74 by 24 by 8 mm blocks. Sintering was carried out at 1100°C for 12 hr in vacuum (2 x lo-' Tr) or in hydrogen. In this instance the material was heated slowly and subjected to prolonged soaking at 350°, 650°, and 750 2C, respectively, to secure reduction of ferro-oxides. This was checked by making measurements of the dew point, which was found to change from -15" to -35°C after reduction. The compacts after sintering were hot-rolled to 2.4 mm, annealed at 800 C, and finally cold-reduced to 0.35 mm with intermediate annealing at 800°C at a gage of about 0.8 mm. Impurities were added in the powdered form and mixed with iron and silicon powders. Sulfur in the elemental state, electrolytic manganese, and pure aluminum oxide were employed. Besides, to obtain a material with low contents of impurities, especially

Jan 1, 1967