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By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By R. W. Ludt, C. C. DeWitt

The use of froth flotation for the separation of minerals has become one of the most important of ore dressing processes. Its particular adaptability to the enrichment of low grade ores has made the process an important factor in the national economy. The methods have been extended to the recovery of a great number of minerals. Among the few minerals which have resisted efforts toward industrial flotation is chrysocolla, a hydrated partly colloidal copper silicate. Chrysocolla, being a product of natural oxidation, has been found to occur in small quantities with many ores which are recovered by flotation methods. In present practice, these small quantities of copper silicate pass off with the tailings and are lost. The advantages to be gained by a satisfactory process for the recovery of chrysocolla is apparent. Any application of principles which points a way toward the satisfactory industrial flotation process for copper silicate would be of advantage. This paper presents an attack on this problem. Two methods for the recovery of chrysocolla have been developed by the United States Bureau of Mines.1,2 They have been successful on a laboratory scale but have been seriously restricted in industrial application by critical requirements in the procedure. In one of the Bureau of Mines methods,' the ore is activated with sodium or hydrogen sulphide in an aqueous solution at a pH of 4. Amy1 xanthate is then used as a collector with pine oil as a frother in the flotation process. An excess of sulphide acts as a depressant and the state of optimum conditions is difficult to control industrially. In the second Bureau of Mines method,2 soap is used as the collector at a pH of between 8 and 9. The diffi- culties with this process are that soap is not a specific collector, that heavy metal or alkaline earth ions cause the formation of insoluble soaps, and that a more acid solution causes the formation of a free acid which does not act as a collector for chrysocolla. The problem of recovering chrysocolla by flotation involves the selection of a suitable collector. The collector molecule must be composed of an active polar group that has an attraction for chrysocolla, and of a hydrocarbon chain. Certain dyes have been shown to have an attraction for certain minerals. Suida3 found that hydrated silicates are colored by basic dyes. Dittler4 showed that chrysocolla, among other colloidal minerals of acid reaction, preferentially takes up such basic dyes as fuchsin B, methylene blue, and methyl green. Endell5 gave information to show that the colloidal material in clay may be determined by its selective adsorption of fuchsin. A simple experiment, likewise, illustrates the difference in the adsorptive power of chrysocolla and of silica for the basic triphenyl methane dyes. When a mixture of chrysocolla and silica is immersed in a very dilute dye solution, less than 5 ppm, the chryso-colla is rapidly dyed and the silica is dyed more slowly. The difference is substantial but one of degree. Dean2 showed that the dyes, crystal violet and toluidine blue, are taken up by quartz in an adsorption type process. The difference in the adsorptive power, however, offers the means by which a new collector may act. To form such a collector, a hydrocarbon chain must be attached to the dye molecule. This involves a process of organic synthesis. Butyl, hexyl, and octyl hydrocarbon chains were selected for substitution in the malachite green molecule. For the purpose of identification, the alkyl-substituted dyes formed are called: butyl-malachite green; hexyl- malachite green; and octyl-malachite green. An outline of the procedure for their synthesis is given in the appendix. It is generally recognized in the preparation of this type of dye that the chemical structure of some of the dye molecules varies. However, a uniform formula is attributed to the dye. Such a procedure has been followed in specifying the structure of these alkyl-substi-tuted malachite green dyes. The structure is given on the basis of their properties as an homologous series of dyes, on their method of preparation, and on the purity of intermediates used. Structure of substituted alkyl malachite green is: C6H4 N(CH3)2 p-R C6H4 CH C6H4 N(CH)2 Procedure The flotation cell is a Bureau of Mines 100-g, batch unit provided with an air inlet at the bottom above which is a variable speed agitator. The agi-

Jan 1, 1950

By M. J. Sinnott, H. B. Probst

AN extensive survey of the factors which affect austenite grain growth has already been made.' These factors are temperature, time at temperature, rate of heating, initial grain size, hot-working, alloy content, ofheating,initialand rate of cooling from the liquidus-solidus temperature. In the present work, a vacuum-melted temperature.electrolytic iron was used and the variables studies were temperature, time at temperature, and prior ferrite grain size. Other factors were maintained constant. The iron used in this study was vacuum-melted electrolytic iron of nominal composition of impurities of 0.07 wt pct. It was supplied as a ½ in. round cold-drawn bar. This iron was tested in three conditions: as-received, annealed 6 hr at 1200°F, and annealed 6 hr at 1600°F. Samples were ? in. disks cut from the bar. The prior anneals were carried out in vacuum and the isothermal treatments were carried out in vacuum-sealed Vycor tubing. The thermal etch technique was employed to determine the austenite grain size. Prior to sealing the test specimens, one surface of the sample was polished metallographically. This surface, after heating, was examined to determine the austenite grain size, since the austenite boundaries are revealed by thermal etching. This is essentially the only technique available for measuring the austenite grain size of low carbon steels or pure irons without altering the composition. It has been shown to yield results that are in agreement with other methods used for determining austenite grain sizes.' The specimen size was quite large compared to the grain size measured, so inhibition of growth due to size effects is probably negligible. After vacuum sealing, each sample was placed into a furnace at temperature and at the completion of the run was quenched into a mercury bath. The growth temperatures used were 1700°, 1800°, 1900°, and 2000°F controlled to -~10"F. Growth times were varied from 10 to 240 hr. The long times were used in order to eliminate the nucleation and growth effects occurring during the initial transformation. Time was measured from the introduction of the capsule into the hot furnace to the time of quench. Grain-size measurements were made with the use of a grain-size eyepiece of a microscope. By determining the number of grains per square millimeter at X100 and taking the square root of the reciprocal of this number, the average linear dimension of the grains was determined. Figs. 1 and 2 are plots of these data as a function of time and temperature for the various conditions investigated. The variation of D, the linear dimension of the grains, was assumed to follow the equation3 D = A tn. The curves of Fig. 1 were obtained from the data by the use of the least-squares method of analysis. Fig. 1 is for the growth of the as-received stock and Fig. 2 is for growth after prior treatments. Differentiating the foregoing equation gives an expression for the rate of growth dD/dt = G = nAtn-1 = nD/t. Both D and G as functions of t are given in Table I. It should be noted that G is a function of time; the growth rate is rapid at early stages and decreases with increasing time. Since increasing temperature increases the growth rate, it has been common practice to use the empirical relationship G = Go e-Q/RT to relate temperature to growth rate. The growth rate customarily has been taken at constant values of D on the basis that the rate of growth is related to the boundary surface tension and this is measured by the curvature of the boundary. At constant D values, the growth rate is a function of time and temperature. The growth rate can be related however to temperature at constant time, and this has the advantage that under these conditions the growth rate is a function only of temperature. Obviously the Q values, activation energies, obtained for each assumption will not be the same and the question of which is the more correct is a moot one, since the assumed exponential relationship in either case has no particular theoretical significance. By plotting G, at constant grain size, vs 1/T, the activation energy over the temperature range of 1800" to 2000°F is found to vary from 30,000 cal per mol at the smaller grain sizes to 50,000 cal per mol at the larger grain sizes. The 1700°F data do not correlate with the data at higher temperatures. The activation energies for the 1200" and 1600°F prior annealed materials were calculated as 50,000 and 62,000 cal per mol, respectively, using the reciprocal time to a given grain size as a measure of the growth rate. Plotting G, at constant times, vs 1/T yields an activation energy of 12,300 cal per mol for the tem-

Jan 1, 1956

By H. Becke, D. Stolnitz, D. Flatley, W. Kern

Extensive solid solubilities of CdTe (zincblende-type struckre) and InTe (B37 type) in each of the rock salt-type compounds, PbTe and SnTe, have been observed. Partial phase diagrams have been determined by thermal analysis and X-ray metallography. The limiting mol fraction. X,, of the solute in the rock salt-type a phase and the corresponding eutectic temperatures, T,, are: (PbTe)l-x(CdTe)x: X,- 0.2, T, =866°C; (PbTe),-,(lnTe),: X, - 0.35, T, = 646"C; (SnTe),-,(CdTe),:X,- 0.11, T, = 784 "C; (SnTe),-,(lnTe),: X,-0.53, T, = 630°C. The lattice parameters of the a phase decrease linearly with X, even in (PbTe),-,(CdTe),, where a, (CdTe) = 6.481A > %(PbTe) = 6.459A. This is taken as proof that the cadmium atom enters an octahedral interstice of the tellurium atom sublattice; i.e., the formation of the a phase entails the direct replacement of lead by cadmium. The a, us X curve extrapolates to 6.16A at X = 1, in agreement with the value predicted for an ionic crystal of CdTe; it is also consistent with the reported lattice parameter It is well-established that the compositions of intrinsic semiconducting and semimetallic compounds conform to normal valence rules.1"5 The apparent exceptions can be explained by taking account of anion-anion covalences, as in CdSb, or of multiple cation valences, as in In Te.'This empirical generalization is the basis of the chemical approach to semiconductors2 by which the properties of an intrinsic semiconductor are rationalized in terms of the ionic-covalent bonds necessary to saturate the valence-electron complement of the anion sublattice. A fundamental shortcoming of this approach is its disregard of long-range crystal interactions. It cannot, accordingly, deal with the phenomenon of charge conduction except through the use of ad hoc postulates. As an example, a crystal of CdTe would, in the valence-bond picture: be described in terms of electron pairs, each with the same discrete energy, localized between every cadmium and tellurium atom. This is, of course, contrary to the Pauli of the high-pressure rock-salt form of CdTe, corrected for decompression from 36 kbar. The free energy of formation of the a phase of pure CdTe at room temperature is calculated from the phase diagram to be +10 kcal per g-atom, in accmd with the value calculated from the transformation pressure. The standard enthalpy is +13 kcal per g-atom, and the standard entropy is +9 eu. The latter value implies the formation of extra classical particles, such as vacancies, interstitials, or nondegenerate charge carriers, but these alternatives are not consistent with the semiconducting properties and the densities of the a phase. The extrapolated values of the lattice parameters of (PbTe),-,(lnTe), and Spectively, for the rock salt-type modification of InTe. The corresponding interatomic separation is intermediate between monovalent and trivalent indium. The qualitative implications of the results are considered from the viewpoints of both valence-band theory and energy-band theory. principle, and is corrected by methods of molecular-orbital theory in which bonds are replaced by bands of molecular orbitals whose energies, E, depend upon a crystal-momentum vector, k.7 Each band is derived from a linear combination of atomic orbitals with two electrons required to saturate each molecular orbital in the band. In a crystal of N atoms containing z atoms in its primitive unit cell, there are 2 N/z states per band which lie in a region of k space bound by the Brillouin zone. In an intrinsic semiconductor, the bands can be grouped into valence bands which are normally filled and conduction bands which are normally empty. If the highest valence band and the lowest conduction band overlap anywhere within the Brillouin zone, the material is rendered semimetallic. The quantity defines the effective mass, m*, of an electron in a conduction band (or of a hole, i.e., an electron deficiency, in the valence band) and leads directly to the concept of charge mobility through the relation \x = et/m*, where e is the electron charge and t is the lattice relaxation time.

Jan 1, 1964

By E. G. Woods, A. G. Comer

A mathematical model is presented and solved for determinution of the saturation distribution and pressure in a radial gas-storage reservoir. The model consists basically of two parts: (I) the growing gas-bubble core, and (2) the surrounding aquifer. Since the total pressure at the injection well is a function of the two-phase flow in the gas bubble and the unsteady single-phase flow in the aquifer, the resistance to flow in both zones was taken into consideration. The assumptions involved for both the radial equivalent of the Buckley-Leverett two-phase-flow equation and the injection-pressure equation are as follows: (I) the geometry is radial, (2) the gas bubble is free to expand or contract, (3) compression or expansion of the gas within the bubble may occur at the beginning of a time step, (4) the fluids are immiscible, (5) water is incompressible within the gas-storage region whereas it is compressible outside of this region, (6) a stable gas-water interface exists and (7) gas injection occurs at a constant rate or a series of constant rates. The mathematical model was solved numerically using an IBM 650 computer. A comparison is presented between the predicted results of the model, the results assuming steady-state flow and the actual initial injection-pressure history of an operating reservoir. Using the initial field pressure for a basis, the average deviation between the predicted pressure and the actual field pressure was less than 4.3 per cent. INTRODUCTION Underground storage of natural gas in abandoned oil fields, in abandoned coal mines, in caverns and in aquifers has had varying degrees of success. The lack of these first three facilities in the vicinity of most major gas marketing areas is leading more and more to storage in virgin aquifers. For the most part, this storage in aquifers has led to the study upon which this paper is based. Several excellent papers have been published discussing the problems involved in the underground storage of natural gas; however, to these writers' knowledge, none of them considered the two-phase flow of fluids in the gas bubble and the fact that the gas bubble will grow or shrink in size depending upon the injection and withdrawal history of the reservoir. Not only will both of these factors influence the required injection pressure, but also they will have a definite bearing upon the amount of water production occurring upon withdrawal from the storage area. To solve this problem on an IBM 650 computer, several simplifying assumptions were made. Only the drainage portion of the relative-permeability curve was considered, thereby neglecting any hysteresis effects introduced during an imbibition cycle. The quantity of gas withdrawn during the period of the field study was only a small percentage of the total gas in place; therefore, this assumption is justified. For the problem studied in this case, the combined effects of capillarity and gravity were assumed to be negligible. This assumption becomes less valid as the formation thickness or the average pore diameter increases markedly. The justification of these assumptions should be studied in each case. THEORY This mathematical model for the prediction of saturation distribution and pressure for a radial gas-storage aquifer is based upon the equations for radial two-phase fluid flow'.' and for radial, unsteady-state, single-phase fluid flow.' The two-phase flow is considered to take place in a "core" whose radius is equal to the maximum radius that the gas zone will attain, as indicated in Fig. 1. The injection-withdrawal history is approximated by a series of constant flow rates. Within the "core", gas is assumed to behave as a semi-compressible fluid; that is, the gas is assumed to have a constant density based on the average gas-zone pressure for the flow period. Between each constant-rate time increment, the gas density is allowed to change. This involves an iterative solution of the pressure equation. The liquid phase in this zone is considered to be incompressible, whereas it behaves as a compressible liquid outside of this region. The equations of incompressible flow in the "core" may be written for the gas phase

By J. D. Verhoeven

In the past 15 years a considerable amount of experimental and theoretical work has been done concerning the onset of convection in liquids as a result of interm1 density gradients. This work, which has been doue in many different fields, is reviewed here and extended slightly to give a rrlore quantitative understanding to the probletrz of conzection in liquid metal dlffusion experinletzts. In liquid metal systems the capillary reservoir technique is currently used, almost exclusively, to measure diffusion coefficients. In this technique it is necessary that the liquid be stagnant in order to avoid mixing by means of convection currents. Convective mixing may result from: 1) convection produced as a result of the initial immersion of the capillary; 2) convection produced in the region of the capillary mouth as the result of the stirring frequency used to avoid solute buildup in the reservoir near the capillary mouth; 3) convection produced during solidification as a result of the volume change; and 4) convection produced as a result of local density differences within the liquid in the capillary. The first three types of convection have been discussed elsewhere1-a and are only mentioned for completeness here. This work is concerned only with the fourth type of convection. Local density differences will arise within the liquid as a result of either a temperature gradient or a concentration gradient. It is usually, but not always, recognized by those employing the capillary reservoir technique that the top of the capillary should be kept slightly hotter than the bottom and that the light element should be made to migrate downward in order to avoid convection. In the past 15 years a considerable amount of work, both theoretical and experimental, has been done in a number of different fields which bear on this problem. This work is reviewed here and extended slightly in an effort to give a more quantitative understanding of the convective motion produced in vertical capillaries by local density differences. The Stokes-Navier equations for an incompressible fluid of constant viscosity in a gravitational field may be written as: %L + (v?)v = - ?£ + Wv - g£ [1] where F is the velocity, t the time, P the pressure, p the density, v the kinematic viscosity, g the gravitational acceleration, and k a unit vector in the vertical direction. A successful diffusion experiment requires the liquid to be motionless, and under this condition Eq. [I] becomes: where a is the thermal expansion coefficient [a =-(l/po)(dp/d)], a' is a solute expansion coefficient [a' = -(l/po)(dp/d)], and the solute is taken as that component which makes a' a positive number. Combining with Eq. [3] the following restriction is obtained: Since there is no fixed relation between VT and VC in a binary diffusion experiment, Eq. [5] shows that the condition of fluid motionlessness requires both the temperature gradient and the concentration gradient to be vertically directed. Given this condition of a density gradient in the vertical direction only, it is obvious that, as this vertical density gradient increases from negative to positive values, the motionless liquid will eventually become unstable and convective movement will begin. The classical treatment of this type of instability problem was given by aleih' in 1916 for the case of a thin fluid film of infinite horizontal extent; and a very comprehensive text has recently been written on the subject by handrasekhar.' It is found that convective motion does not begin until a dimensionless number involving the density gradient exceeds a certain critical value. This dimensionless number is generally referred to as the Rayleigh number, R, and it is equal to the product of the Prandtl and Grashof numbers. For the sake of clarity a distinction will be made between two types of free convection produced by internal density gradients. In the first case a density gradient is present in the vertical direction only, and, since the convection begins only after a critical gradient is attained, this case will be called threshold convection. In the second case a horizontal density gradient is present and in this case a finite convection velocity is produced by a finite density gradient so that it will be termed thresholdless convection. Some experimentalists have performed diffusion experiments using capillaries which were placed in a horizontal or inclined position in order to avoid convection. These positions do put the small capillary dimension in the vertical direction and, consequently, they would be less prone to threshold convection than the vertical position. However, if the diffusion process produced a density variation, as it usually does, it would not be theoretically possible to avoid thresh-

Jan 1, 1969

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By J. B. Dyess, H. A. Miley

Tarnish films on some of the common metals (particularly on copper and silver) have been of much scientific and commercial concern for a long time, but before the development of the electrical method1 of measuring film thicknesses there was no satisfactory quantitative approach by which to study the separate parts of these complex films. This method has been adapted to the measurement of duplex (cuprous-cupric) oxide films on copper.2 In the present work it has been used to measure tarnish films on copper when they were mixtures of cuprous oxide and cuprous sulphide, and also when they contained cuprous oxide, cupric oxide and cuprous sulphide, each component part being measured at a different potential value. Oxide-coated copper specimens, prepared by heating copper in air at chosen temperatures for given periods, were exposed to moist hydrogen sulphide in air to forml the various oxide-sulphide films studied. The comparative resistances afforded by (I) different thicknesses of oxide films, and also (2) equal thicknesses of oxide and sulphide films, against severe attacks of hydrogen sulphide were measured. The electrical method requires that the time be observed for the cathodic reduction of each part of the film substance, and these respective time values multiplied by the constant current give the corresponding quantities of electricity expended. Then each millicoulomb per square centimeter represents a film thickness of M X 108____ 2DX 96,494 X 103 where M is weight of oxide (or sulphide) giving one gram-atom of oxygen (or sulphur) for cathodic reduction, D is density of the oxide (or sulphide) and t is the thickness in Angstrom units per millicoulomb per square centimeter. The value of t for cuprous sulphide (cubical) is 14.27, and is obtained by substituting 5.78 for D and 159.20 for M in equation a. Previous values hf t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By Donald T. Hawkins, Ralph Hultgren

The lorsion effusion method has been used to measure the vapor pressure of lead over pure lead and eight Pb-Sn alloys ranging from 9.1 to 87.9 at. pct Pb in the temperature range 950° to 1125°K. The resulting ?H°y 298 = 46,630 ± 200 cal per g-atow for pure lead is in excellent agreement with previous work. Deriued ?Gph values for the alloys were smoothed and correlated with previous heat of formation data to obtain entropies for the liquid alloys. values for the tin component were calculated by Gibbs-Duhem integmtion. Surfhce depletion of these liquid alloys was found to be absent, as shown by the fact that the measured pressure remained substantially constant with time in contrast with previous measurements on iron-rich solid Fe-Mn alloys. The activities and Gibbs (free) energies of the liquid Pb-Sn system are not well known although the heats of formation have been accurately determined by K1eppa.l Vapor pressure determinations of the activity of lead by Voronin and Evseev2 disagree with those of Predel.3 Elliott and chipman4 measured activities by the electromotive -force technique in the ternary Pb-Sn-Cd system. From the resulting values of the activity of cadmium, they were able to calculate the activities of lead and tin for the binary Pb-Sn system at the compositions xsn = 0.33 and 0.67. Atarashiya, Uta, Shimoji, and Niwa5 determined the activity of tin from Hz-H2O equilibrium measurements, but their results are subject to question due to uncertainty in the final state of their samples. To resolve these differences, measurements of the activity of lead were made using a torsion-effusion apparatus. Among other advantages, this apparatus rapidly detects errors caused by surface depletion, which tends to reduce the apparent vapor pressure of the more volatile component. If the measured torques remain nearly constant with time, only bulk depletion is occurring. This contrasts with the rapid decrease in torque found in solid Fe-Mn alloys at high temperatures and low manganese contents.6 EXPERIMENTAL 99.999+ pct Pb was obtained from the American Smelting and Refining Co. and 99.999 pct Sn from Vulcan Detinning Co. Eight Pb-Sn alloys were prepared by melting together weighed amounts of the pure metals in evacuated Pyrex tubes and quenching the melts in water. Loss of weight in preparation was less than 0.02 pct in all cases. The effusion cells were made from high-purity, nonporous graphite. Graphite was chosen because of its resistance to reaction with lead and tin and because it can be accurately machined with precision orifices. Two cells were used with overall dimensions as shown in Fig. 1. The orifices of cells 1 and 2 were, respectively, 1 and 1.5 mm in diam.

Jan 1, 1968

By J. W. Leomrd, B. A. Donahue

Results of research are presented examining the extent to which the analytical characteristics of the relatively distinct coal bands from a variety of coal seams can be related to each other. This paper dis-cusses an approach for developing a practical coal petrographic quality control program based on conventional analyses, most of which is part of the standard A.S.T.M. procedure. The work is a final follow-up to Part I of this series which was prepared by the authors as an approach to applying conventional coal petrography to single coal seams. Recent published work by the authors entitled Petrography for Coal Mining and Coal Prepration: Part I dealt with interrelating various chemical and physical properties of coal1 measured using conventional analyses made on distinct petrographic bands taken from single coal seams. Since most coal production facilities process coal from a single coal seam or from very closely related coal seams in the same area,2 emphasis on interrelating the properties within a single seam appeared appropriate. The distinct petrographic bands were analyzed on the assumption that such differentiated data would be more representative of a heterogeneous coal seam than the single analytical value commonly used to characterize each property of an entire seam.34 Effort was directed at demonstrating the extent to which the interrelated chemical and physical properties 5,6 could be developed into nomographs or petrographic standardization graphs. Thus, one analysis, determined on a series of petrographic fractions separated from a single sample, was used to estimate numerous other properties in each fraction by referring to the previously established petrographic standardization graphs. This conventional approach to coal petrography was undertaken as a suggested feasible means by which a few coal analyses could be employed to develope a more penetrating knowledge of the properties of coal from any given seam in order to monitor more extensively its performance at the point of utilization. Such procedures can support development of the type of in- formation commonly sought through automated testing and through the use of computers.7 The broad knowledge which can be developed through these procedures is intended for application in the generation of an analytical profile or broad characterization of coal. These estimates were not intended as replacements for individual coal analytical tests. In this expanded second part of the research program, distinct petrographic bands from nine coal seams in the Central Appalachian Region were physically and chemically analyzed to elucidate the extent to which this concept of conventional petrography could be broadened for application to numerous coal seams. In presenting this second phase of work, the relationships developed are presented individually and not in a connecting series of nomographs or petrographic standardization graphs as in the previous work, thus leaving open the combinations of possibilities to individual interpretation and application. MATERIAL AND EXPERIMENTAL WORK Nine coal seams, representing a wide range of rank, from the Central Appalachian coal fields were used in this study. The distinct petrographic bands from the Kittanning, Pond Creek, Jawbone, Tiller, Poca-hontas No. 3, No. 2 Gas, Eagle, Winifrede, and Pittsburgh coal seams were separated by carefully removing a portion of each band at the face of the seam. The following were determined: ash, sulfur, free swelling index, heating value, bulk specific gravity, volatile matter, Hardgrove Grindability Index, and Gieseler Plastometer measurements. Determinations, where procedures were available, were carried out using ASTM standard procedures.8 Bulk specific gravity was determined using a kerosene volume displacement procedure modified from a method applied by Headlee and McClelland of the West Virginia Geological survey,9 Those bands with a bulk specific gravity greater than 1.60, which is generally above the practical specific gravity cleaning range of bituminous coals, were excluded and no analyses were performed. Much of the initial organization of this second phase of work was developed through the extensive use of a computerized statistical monitoring program (see Ref. 4). However, in order to achieve the closest possible interpretation of results, the final organization of data proceeded mainly from exhaustive trial

Jan 1, 1968

By A. M. Kivari

Operations at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hy-droseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the mallufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. † About 3I30 tons of limestone, 620 tons of clay and I00 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. up to the present time, the ccrporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modihed-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Red- ding, Calif., the total demand being 5,800,000 bbl. of cement. Following are some of the cement require ments of the Shasta Dam specifications: Per Cent Chemical composition: Loss in ignition.......... 2.25 Insoluble residue......... 0.75 SO3.................... 2.25 MgO................... 5.'' Uncombined lime in clinker (CaO)......... I.25 Percentage of iron oxide to alumina ratio....... I.5 Compound composition: Tricalcium silicate (3CaO.SiO2)........... Not more than 35 Dicalcium silicate (zCaO.SiO2)........... Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O3).......... Not more than 7 Tetracalcium aluminofcr- rite (4CaO.Al²O³.Fe²O³) Not more than 20 Fineness: The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1942

By A. M. Kivari

Operations at the cement plant of the Permanente Corporation, in the hills about 45 miles south of San Francisco and 12 miles west of San Jose, are interesting to the members because of the adoption of modern hydrometallurgical methods for handling and beneficiating raw materials. Closed-circuit grinding, classification, hy-droseparation, flotation, agitation, and thickening are familiar terms at this cement plant. These methods make it possible to process refractory limestone into suitable materials for the mallufacture of modern cements. Construction of the plant, having originally a design capacity of 7000 bbl. of cement per day, was started in June 1939, and the first clinker was ground on the following Christmas Day. At present the capacity is about 12,000 bbl. of finished cement per 24 hr., most of the production being low-heat cement. † About 3I30 tons of limestone, 620 tons of clay and I00 tons of gypsum are required daily for this output. Occasionally iron oxide is added to the clay to obtain the desired composition. This, together with the gypsum, is purchased from outside sources. up to the present time, the ccrporation has produced low-heat, normal, moderate-heat, moderate-sulphate-resisting, high-early-strength, oil-well, modihed-oil-well, and plastic cements. Most of the present production is for Shasta Dam, near Red- ding, Calif., the total demand being 5,800,000 bbl. of cement. Following are some of the cement require ments of the Shasta Dam specifications: Per Cent Chemical composition: Loss in ignition.......... 2.25 Insoluble residue......... 0.75 SO3.................... 2.25 MgO................... 5.'' Uncombined lime in clinker (CaO)......... I.25 Percentage of iron oxide to alumina ratio....... I.5 Compound composition: Tricalcium silicate (3CaO.SiO2)........... Not more than 35 Dicalcium silicate (zCaO.SiO2)........... Not less than 40 and not more than 65 Tricalcium aluminate (3CaO.Al2O3).......... Not more than 7 Tetracalcium aluminofcr- rite (4CaO.Al²O³.Fe²O³) Not more than 20 Fineness: The average specific surface in the bin sampled shall be not less than 1800 sq. cm. per gram and no individual sample less than 1600 sq. centimeters. Compressive strength: The average compressive strength in pounds per square inch of three mortar cubes composed of one part cement and 2.75 parts fine testing sand, by weight, shall be equal to or greater than the following:

Jan 1, 1942

By Carl L. Shapiro, Jerome and Strauss

This is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I Influence of Body-centered Cubic Elements The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tan. talum) are reviewed individually. Iron-carbon-chromium System.—In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts1 concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.—Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. 2; these results have received general approval. , I ron-carbon-molybdenum System.—In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and ReedI8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-S

Jan 1, 1944

By Jerome and Strauss, Carl L. Shapiro

This is a critical examination of the theory that the amount of carbon necessary to form the iron-carbon (carbide) eutectoid is lowered by the addition of any carbide-forming element. Although this theory has been built up over a long period of years, it appears, in the light of recent published investigations upon the ternary constitutional diagrams of iron with carbon and other alloying elements, to be no longer tenable. A survey of these new results, summarized below, shows that (as is known) some metals lower the carbon content of the iron-carbon (carbide) eutectoid, whereas others raise it, but (as not heretofore clearly set forth) some first move the eutectoid in one direction and then, at higher concentrations, shift it in the opposite direction. Moreover, these differences in behavior exist even among the common alloying metals classed as carbide formers. PART I Influence of Body-centered Cubic Elements The effects of the various body-centered cubic metals (chromium, tungsten, molybdenum, vanadium, columbium and tan. talum) are reviewed individually. Iron-carbon-chromium System.—In the monograph on Alloys of Iron and Chromium, Kinzel and Crafts1 concluded that the carbon content of the eutectoid is lowered by increasing the chromium content. The quantitative influence of chromium on the eutectoid point of iron-carbon alloys was shown by Monypenny2 (Fig. I) and no data have been forthcoming to refute his findings. Iron-carbon-tungsten System.—Gregg,3 in the monograph on Alloys of Iron and Tungsten, accepted the data showing that tungsten decreases the amount of carbon required to form the eutectoid. The influence of tungsten on the eutectoid percentage of carbon as determined by Oberhoffer and Daeves4 is shown in Fig. 2; these results have received general approval. , I ron-carbon-molybdenum System.—In the monograph on Alloys of Iron and Molybdenum, Gregg5 reviewed the work of Guillet,6 Swinden,7 and ReedI8 all showing that molybdenum lowered the carbon content of the eutectoid, whereas Takei9 contradicted this conclusion. Svetchnikoff and Alferova,10 a little later, showed that large additions of molybdenum shift the eutectoid to the right. These last-named investigators found that molybdenum, up to 1.2 per cent, shifts the pearlite point and the point of maximum solubility of cementite in the gamma phase only slightly in the direction of lower carbon content; on the other hand, increasing amounts of molyb-S

Jan 1, 1944

By W. F. Durfee

The apparatus described in this paper was designed by the writer, in the year 1869, for use in the laboratory of the " American Silver Steel Works," at Bridgeport, Conn., where only the vacuum-pump was erected ; but on two subsequent occasions I have had the combined vacuum-pump and table-blowpipe constructed as represented in the drawings, in which Fig. 1 is a general elevation of the apparatus, the air-chamber being sectioned vertically; Fig. 2, a plan of the air-chamber; Fig. 3, a vertical sectiotnal elevation of the vacuum-pump, the section being on line C L), of Fig. 4, which is a horizontal section on line A B, of Fig. 3. The vacuum-pump is constructed of copper, and consists of a vacuum-chamber, E, supported upon the upper expanded end of a vertical pipe, Q. The vacuum-chamber is provided with four nozzles, C, F, I, D (Fig. 4), two of which are shown in section at A, B (Fig. 3). Passing vertically through the centre of the vacuum-chamber E, is seen the water-supply pipe P, whose lower extremity incloses an internal pipe p, which is supported, and placed in communication with the vacuum-chamber E, by means of the two elliptical nozzles n, n. The upper part of the pipe p is closed by a conical cap, and its lower end is in the same plane with the extremity of the watersupply pipe P, within which it is placed. The relative sizes of the pipes P and p are such that an annular adjutage, one-sixteenth of an inch in thickness, is formed between their lower extremities, through which the water from the supplypipe P passes into the pipe &, drawing any air that may be in the

Jan 1, 1885

By Colin M. Sargent

THE electron diffraction pattern as seen in the electron microscope represents an approximately plane section of the reciprocal lattice. Identifying the zone axis of a diffraction pattern is often laborious for a crystal of low symmetry, especially if several crystal orientations are present. A program has been written in FORTRAN II (Version 2) for the IBM 1620 which will assist in plotting out reciprocal lattice sections. The calculation is performed by choosing a zone axis [uvw] and determining the d spacings and angle between the planes (Ow - v) and (wO - u). (This procedure is varied slightly for zone axes with Miller indices equal to zero.) Cartesian coordinates for the reciprocal lattice points are then calculated for these planes and for (ww— [u + v]). Any reciprocal lattice points within the parallelogram formed by the origin and these three points are then computed. The input and output are best described by use of an example (Monoclinic ZrO2) used in the author's work. Input consists of two cards: 1) The crystal parameters: a, b, c, a, 8, y, e.g., 5.1477, 5.2030, 5.3156, 90.000, 99.380, 90.000. 2) Three numbers, D, E, F, e.g., 5, 3, 3.0710-the first is the limit of the sum (u + v + w) considered; the second limits the absolute value of u, v, and w to (E- 1), e.g., 2, so that zones (221) would be the highest order considered in this example; the third, F, is the required constant, yL. Output is in the format shown in Table I. The reciprocal lattice sections may then be plotted on standard graph paper and compared with the unknown diffraction pattern. (Note that no attempt has been made to deal with systematically absent reflections.) A card deck for the program is available from Colin M. Sargent, ARZ, W-PAFB, Dayton, Ohio, 45433.

Jan 1, 1969

By Richard P. Rothwell

Though coal has been mined in this country for more than a century, no systematic effort was ever successfully made to ascertain the total amount produced. The production of the Cumberland Basin, Md., and the shipments from the anthracite fields of Pennsylvania, have been placed upon record, thanks to the intelligence and foresight of Mr. C. Slack in the former case, and to the late Mr. B. Bannan in the latter. For some of the years between 1822 and 1842, the production of the Richmond Basin was reported by Mr. R. C. Taylor, but since that date till the author undertook this work it was impossible to obtain any statement of the production of this field. A few of the newer fields, such as that of Mt. Diablo, Cal., have been fully reported, and a few of the newer States have also had this service performed by some intelligent private individuals; but no statistics of coal production have ever been collected either by the State or General Government, if we except the returns for the years 1869—70 of the census report. During the year 1875, by great exertions, I succeeded in obtaining, and July 3d, 1875, gave in the Engineering and Mining Journal what, " though not an accurate statement of our coal production," was " by far the most full and reliable that had ever been published." Though that report showed the production of bituminous coal to be 23,630,094 gross tons, or about six million tons more than had ever before been reported, it was in reality two and a half million tons below the actual output. The more full returns I obtained for 1875 gave many figures for 1874

By Klaus Schwerdtfeger

The rules of solution of oxygen from H2O-H2-He gas and of nitrogen from N2-H2 gas in shallow melts of liquid iron were measured at 1610o and 1600o C, respectiuely. Concentration profiles were detemined in the liquid iron. Tire rate data indicate that the solution process is controlled by diffusion in the iron melt. The diffusivities for oxygen and nitrogen in liquid iron, as calculated from the present data, are DFe-o = (12 ± 3) < 10-5 sq cm per sec and DFe-N = 11 ± 2) X 10-5 sq cm per sec at the temperatures employed. AN attempt was made by Shurygin and Kryukl to measure the diffusivity of oxygen in liquid iron. In their experiments a silica disc was rotated in liquid iron containing oxygen, and the rate of formation of liquid iron silicate was measured. Assuming that the rate of dissolution of silica is controlled by diffusion of oxygen in the iron, the oxygen diffusivity was computed from the rate data giving Dfe-0 = 6.1 X 5 sq cm per sec at 1600°C. Although this value seems to be of the right order of magnitude, there is no proof of the correctness of the assumptions involved in the interpretation of these rate data. The oxygen concentration in the iron at the iron-iron silicate interface was taken to be that in equilibrium with the silica-saturated silicate melt. That is, it was assumed that no concentration gradient existed in the liquid silicate. This is a questionable assumption, unless it is proved that the thickness of the silicate layer is very much smaller than that of the diffusion boundary layer in the iron. Furthermore, Shurygin et al.1 used the Levich equation2 to interpret their rate data. This equation was derived for mass transfer between a solid disc and a single-phase liquid. The hydrodynamic and diffusion boundary layers in the iron stirred by a disc, via coupling of the silicate melt, may be appreciably different from those predicted by Levich&apos;s derivations. In the present work the diffusivities of oxygen and nitrogen in liquid iron were measured at 1610" and 1600oC, respectively. EXPERIMENTAL METHOD Iron melts contained in high-purity gas-tight alumina crucibles were reacted with H2O-H2-He gas for the determination of the oxygen diffusivity and with N2-H2 gas for the determination of nitrogen diffusivity. At the end of the reaction period, the samples were quenched in a cold H2-He gas stream at the top of the furnace. Oxygen or nitrogen contents in the iron were determined by chemical analysis. Two different types of diffusion experiments were perforxed. To determine concentration profiles, a few rate measurements were made using 4-cm-deep melts. The solidified samples were sliced into discs and each disc was analyzed for oxygen or nitrogen. In another series of experiments, oxygen or nitrogen was diffused into shallow melts (about 0.5 to 1 cm in depth) and the total sample was analyzed to obtain an average concentration of the diffusate. In most experiments, 4- to 5-mm-ID alumina crucibles were used. Some experiments were also made in smaller (3 mm) and larger (7 mm) diam crucibles. This variation in diameter caused no difference in the reaction rate, within the limits of experimental uncertainty. To promote the establishment of a stable density profile in the melt, all the samples were suspended in the lower end of the hot zone so that the top of the melt was hotter by a few degrees. Molybdenum wire resistance heating was used. The reaction tube of the furnace was a gas-tight recrystal-lized alumina tube. In most experiments the furnace was heated by an ac power supply. To check the possibility of inductive stirring, some experiments were carried out in a dc operated furnace, with essentially the same results. The temperature of the furnace was controlled automatically in the usual manner. The temperature was measured with a Pt/Pt-10 pet Rh thermocouple and is estimated to be accurate within ±5°C. The iron used was prepared by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zir-conia crucible. The main impurities are: Si 0.004 pct P, S <0.002 pct Cr 0.005 pct N 0.001 pct Zr 0.002 pct O 0.003 pct Mn 0.004 pct C 0.002 pct The gas composition was controlled by constant pressure head capillary flowmeters. Oxygen was removed from the gas mixture by passing it through columns of platinized asbestos (450°C) and anhydrone. Selected H2O contents were obtained by passing the purified gas through oxalic acid dihydrate-anhydrous oxalic acid mixtures held at constant temperature in a water bath. Water vapor pressure data for the oxalic acid dihydrate-anhydrous oxalic acid equilibrium were taken from the 1iterature.3 The flow rate used was about 1.5 liters per min. The whole system was checked for tightness at regular intervals.

Jan 1, 1968

By Richard P. Rothwell

THOUGH coal has been mined in this country for more than a century, no systematic effort was ever successfully made to ascertain the total amount produced. The production of the Cumberland Basin, Md., and the shipments from the anthracite fields of Pennsylvania, have been placed upon record, thanks to the intelligence sand foresight of Mr. C. Slack in the former case, and to the late Mr. B. Bannan in the latter. For some of the years between 1822 and 1842, the production of the Richmond Basin was reported by Mr. R. C. Taylor, but since that date till the author undertook this work it was impossible to obtain any statement of the production of this field. A few of the newer fields, such as that of Mt. Diablo, Cal., have been fully reported, and a few of the newer States have also had this service performed by some intelligent private individuals.; but no statistics of coal production have ever been collected either by the State or General Government, if we except the returns for the years 1869-70 of the census report. During the year 1875, by great exertions, I succeeded in obtaining, and July 3d, 1875, gave in the Engineering and Mining Journal what, "though not an accurate statement of our coal production," was " by far the most full and reliable that had ever been published." Though that report showed the production of bituminous coal to be 23,630,094 gross tons, or about six million tons more than had ever before been reported, it was in reality two and a half million tons below the actual output. The more full returns I obtained for 1875 gave many figures for 1874

Jan 1, 1877

By P. Shahinian, J. Weertman

Minimum creep rates of nickel samples were measured in the stress region of 2.5x107 to 2.8xl0 dyne per sq cm and the temperature region of 400° to 1100°C. The creep rate seems to be proportional to (stress) at stresses below 7x10H dyne per sq cm. The activation energy of creep is approximately 65,000 cal per mol. IN a recent theory&apos; of steady-state creep which is based on Mott&apos;s dislocation climb mechanism, the following creep equation was derived for creep in polycrystalline metals (if where K is creep rate, Q the activation energy of self-diffusion, S the entropy of activation of self-diffusion, L&apos; the grain size, L the subgrain size, b the length of the Burgers&apos; vector of a dislocation, u the shear modulus, u the stress, a the critical shear stress, M the density of active Frank-Read sources, v the vibrational frequency of a vacancy, and kT has its usual meaning. This equation predicts a creep rate which depends on the stress through a power law at low stresses. At high stresses the creep rate increases much more rapidly with stress. The theory breaks down for stresses great enough that the inequality holds true. It was the purpose of the present in-

Jan 1, 1957