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By A. F. Crawley

The density and viscosity of 1iquid thallium have been measured by absolute methods to temperatures of about 200° and 150°C, respectively, above the melting point. These new data reported, especially density data, do not closely confirm previous work. Density p, in g per cu Cm, is shown to vary linearly with temperaluve t, in °C, according to the equation p = 11.658 - 1.439 X l0-3t. The viscosity data obey the well-known Andrade equation nv1/3 = A exp C/vT , the constants A and C for thallium having values of 2.19 x A and 79.648, respectively. This paper reports some new data for the density and viscosity .of liquid thallium. Measurements of these fundamental physical properties were undertaken as part of a continuing research program at the Mines Branch, Department of Energy, Mines and Resources, Ottawa. Canada. A literature search has revealed that data are so scarce that there could not be a consensus on the true values of the density and viscosity of liquid thallium. To be more specific, there exists only one set of viscosity data' and only two acceptable sets of density data,273 one of which is limited in scope.3 In Liquid Metals Handbook,3 another density study is reported but indications of impurities in the thallium render the results suspect. In this situation, further careful experimentation was required to realize the true density and viscosity of thallium. EXPERIMENTAL METHODS Density. Densities were determined using a graphite pycnometer. The technique and its accuracy have been discussed in earlier papers.4'5 It is considered that experimental data can be obtained which are accurate within +0.05 pct, all sources of random and systematic errors having been evaluated. Density results for thallium were identical whether measured under an atmosphere of argon or a vacuum of 5 x 10-6 torr and, for the most part, the argon atmosphere was used. Viscosity. Viscosity measurements were made in an oscillational viscosimeter by an absolute method—the liquid metal being held in a closed graphite cylinder. Design and operation of the apparatus, constructed in this laboratory, have previously been discussed.6 For thallium, runs were made under a vacuum of about 2 x 10-6 torr. To evaluate viscosity coefficients from the various experimental parameters, the mathematical analysis of Roscoe7 was used. Measurements of the necessary parameters and the accuracy of these measurements have also been discussed.6 The cylinder dimensions were corrected for the anisotropic expansion of graphite, as discussed for density measurements.4,5 It is well-known that thallium oxidizes rapidly and hence a newly machined surface quickly tarnishes in air. The oxide film, however. is nonadherent and is easily removed by rubbing or by solution in water. Hence, immediately before use, both density and viscosity charges were immersed in water, wiped dry, and quickly transferred to the apparatus which was then rapidly evacuated. Specimens removed after determinations were only slightly tarnished and there was no other evidence that tarnishing affected the results. For example, the sharpness of the specimen edges from the containing vessels indicated complete filling by the liquid metal. Thallium of 99.999 pct purity was used in this investigation. Because of its high toxicity care was exercised in handling this material. For example, the melting procedure to prepare machinable ingots was carried out in an open, well-ventilated area, while protective gloves were always worn when handling the solid metal. RESULTS AND DISCUSSION Density. Measurements were made over a tempera-ture range of about 200°C above the melting point. The results are listed in Table I and plotted in Fig. 1. From the graph it is evident that the relation between density and temperature is linear. Such a relation has been observed before in this program for other metals and alloys475 and elsewhere by other workers. A least-squares analysis of experimental data gives the equation: pT1 = 11.658 - 1.439 x 10-3t where p = density in g per cu cm and t = temperature in "C. In Fig. 1, together with the present results, the data of Schneider and Heymer2 in the corresponding temperature range have also been plotted. Evidently, the two sets of data do not agree well, the results of Schneider and Heymer being about 0.6 pct higher. Viscosity. Viscosity data were obtained from the melting point, 303.5°C, up to 457.5"C. The data are listed in Table I and in Fig. 2 the plot of these results demonstrates a smooth curvilinear relation between

Jan 1, 1969

By W. J. Romanow

RECENT papers by Williams, Sherwood, and Boothby,1 Seybolt et al.2 Heikes; and Roberts4 attest to the increasing importance of the hexagonal ferromagnetic compound MnBi. Since the magnetic properties of MnBi crystals are highly anisotropic, it is useful and necessary to have appropriate aids for determining their orientations—a (00.1) standard stereographic projection and a corresponding table of crystallographic angles for this structure. The tables of crystallographic angles for the hexagonal system available in the literature5 are computed for c/a ratios greater than that of MnBi and cannot satisfactorily be used to find the crystallographic angles of MnBi. A table of angles between the crystallographic planes (HK.L) and (hk.1) was calculated for MnBi from the formula0 F=are cos Hh+Kk+ 1/2(Hk+hK) + 3/4 (a/c)2Ll/v(H2 + K2 + HK + 3/4 (a/c)2L2) (h2+ k2+hk + 3/4 (a/c)2l2) on an IBM Type 650 Magnetic Drum Data Processing machine. The lattice constants used are listed in Table I and are those determined by Willis and Rooksby7 at 20°C. More recently published values obtained by both X-ray and neutron diffraction"' show no difference from these significant to the calculation. From the crystallographic angles between the basal plane (00.1) and the general plane (hk.1) in Table I, an (00.1) standard stereographic projection was made for MnBi which is shown in Fig. 1. Acknowledgments The author wishes to thank R. G. Treuting and J. N. Hobstetter for their technical assistance, and Miss D. P. Booth for programing the IBM machine for the calculations. He appreciates the opportunity to read the paper of B. W. Roberts of General Electric Co. prior to its publication. References 1H. J. Williams, R. C. Sherwood, and 0. L. Boothby: Bulletin Amer. Physical Soc., 1956 vol. 1, p. 132. 2 A. U. Seybolt, H. Hangen, B. W. Roberts, and P. Yurcisin: AIME Trans., 1956, vol. 206, p. 605: Journal oF Metals, May 1956. 3R. R. Heikes: Physical Review, 1955, vol. 99, p. 446. .B. W. Roberts: A Neutron Diffraction Study of the Structures of Manganese B.W.Roberts:ANeutronDiffractionBismuthide, Physical. Review, 1956, vol. 104, p. 607. 5 A. Taylor and S. Leber: AIME Trans., 1954, vol. 200, p. 190; JouRNal of Metals February 1954. « C. S. Barrett: Structure of Metals, 2nd Ed., p. 635. McGraw-Hill Book Co. New York and London, 1952. 7B. T. M. Willis and H. P. Rooksby: Proceedings Physical Soc., London, 1954, vol. 67B, p. 290.

Jan 1, 1958

By R. G. Davies

WeERTMANI has shown that the high temperature steady state creep rate, i, in lead and indium-base alloys obeys an equation of the form where AH is the activation energy, o the applied stress, n the stress exponent, and R and T have their usual meanings. He observed a variation in n from 4.5 for pure metals to 3 for concentrated alloys, which he interpreted as due to Change in creep mechanism from the climb of dislocations in pure metals to a micro-creep mechanism in the alloys. The Cottrell-Jaswon microcreep mechanism of the moving dislocation taking its impurity atmosphere with it was considered to be the most likely process, although short-range order and the segregation of solute atoms to a stacking fault will also give a stress exponent of 3. Steady state creep has been investigated in a Au - 27 at. pct Cu alloy at temperatures above 1/2 TIM where TIM the absolute melting temperature. As the oxidation resistance of this alloy is excellent all tests were carried out in air with a furnace built to give a temperature variation of less than 1°C along the 60 mm gage length. A lever-arm arrangement applied the stress with a load being adjusted between each creep test to maintain a constant stress. As each test produced less than 0.5 pct creep strain, the variation in stress during the test was negligible. The creep strain was measured by a transducer at the end of one of the alloy-steel grips, with the out of balance potential being finally recorded on a variable speed chart recorder. A typical creep curve is shown in Fig. 1. The results, Fig. 2, confirm that n is nearer to 3 than to 4.5; the creep mechanism could be any of those given above. The activation energy, AH, which is independent of stress, is consistent with a diffusion controlled process; the activation energies for the self-diffusion of gold and for the diffusion of gold into Copper are both -45 kcal per ml., There is now considerable evidence, that, when the steady state creep is dependent upon diffusion, irrespective of the actual creep mechanism, the activation energy is independent of the stress. The author would like to acknowledge the financial assistance provided by the International Atomic Energy Agency, Vienna, and the Argentine Atomic Energy Commission.

Jan 1, 1962

By Leonard B. Gulbransen, John R. Lewis, W. Martin Fassell, J. Hugh Hamilton

T. E. Leontis (The Dow Chemical Co., Midland, Mich.)—This paper is of particular interest to me because of my own work with F. N. Rhines on the oxidation of magnesium and magnesium alloys a few years ago. The authors are to be complimented on their development of an accurate and reproducible technique for measuring ignition temperatures and on their comprehensive study of the many variables that affect the ignition temperature of magnesium. It is indeed gratifying to see that they have obtained a good correlation between ignition temperatures and the oxidation rates reported by us. The correlation is valid not only with composition within one alloy system but also between alloy systems; that is, alloying elements which effect the greatest increase in oxidation rate also produce the greatest decrease in ignition temperature. There are a few points upon which I would like to comment. In attempting to correlate ignition-temperature data, one must be sure that the same definition of this quantity is used by all investigators. It does not appear to me that such is the case in the authors' comparison of their data with the theoretically calculated values of Eyring and Zwolinski. The equation derived by these investigators defines the ignition temperature, To, as the temperature at the gadoxide interface, whereas the present authors use the metal temperature as the criterion for ignition. The contradiction in the effect of oxide-scale thickness on ignition temperature between the predictions of the Eyring-Zwolinski equation and the observations reported in this paper indicate that some variable has not been taken into consideration. Could that be the geometry and size of the specimen? There is a marked difference in the type of specimen used in this investigation and that used in our work which formed the basis of Eyring and Zwol-inski's theoretical treatment. Another factor which plays an important role in ignition is the vapor pressure or the rate of vaporization. Combustion can safely be assumed to take place in the vapor phase by the reaction between vaporized magnesium and oxygen. Thus, a more accurate theoretical analysis may be made on the basis of the rate of vaporization which may be the controlling rate of the process. The effect of a large number of alloying elements on the ignition temperature has been reported in this paper, but beryllium was not included. Practical experience dictates that beryllium markedly decreases the burning tendency of magnesium. I was wondering if the authors plan to study the effect of beryllium in their future work. The authors predict that concentrations of sulphur dioxide in the furnace atmosphere greater than 5.8 pct would be expected to increase the ignition temperature to values still higher than those they measured. I would like to mention that large concentrations of sulphur dioxide markedly increase the rate of combustion of magnesium once ignition has started. Although it has been shown in the paper that the ignition temperature of magnesium in oxygen increases with increasing sulphur dioxide content up to about 1 to 2 pct, in practice relatively low-melting commercial cast alloys (AZ63A and AZ92A) are being continuously heat treated at temperatures just below the melting point in air containing 0.5 to 0.75 pct SO*. In regard to the change in color of the oxide scale observed on magnesium and magnesium alloys just prior to ignition, I would like to mention that in our work alloying elements were found to color the usually white magnesium oxide even though ignition did not occur. For example, the oxide formed on Mg-A1 alloys was gray, increasing in intensity with aluminum content in the alloy. Finally, I might suggest that the authors indicate their source of the value of 0.8 g per cc for the density of MgO as it is formed on magnesium upon oxidation at elevated temperatures. W. M. Fassell, Jr. (authors' reply)—The comments by Dr. Leontis are very excellent ones and I will attempt to answer them in order. First, the problem of ignition of magnesium is a rather difficult one since many factors are involved. Concerning the comparison of the To in the Eyring-Zwolinski equation, eq 4, with the experimentally determined values, it will be noted that the calculated and experimental values of the ignition temperature in Table I are not self-consistent. In the case of the 1.78 pct A1-Mg alloy the calculated value is 49°C below the experimental value; for the 3.81 pct A1-Mg alloy, 122°C below the experimental value; for Mg with 5x10-' cm film, 19°C above the experimental value; for Mg with 2x10-I cm film, 28 °C below the experimental value. Thus, if it were merely a matter of difference of location of temperature measurement the calculated ignition temperature would always be below the experimental value, the difference being due to the thermal gradient through the oxide film. The possibility of a thermal gradient in the magnesium metal must be considered. From Carslaw and Jaeger,'Y t can be shown that the maximum temperature gradient that could exist between the oxide-metal interface and the center of the sample is of the order of O.Ol°C. The geometry and size of the specimen could certainly have some effect on the ignition temperature. The equation for ignition that has been proposed in reference 14 is of the following type containing terms to account for this and other factors: M dT AHv(T) =Cp--------------\-J(.T—TB) + ZAHl-M A dx where AH is the heat of reaction, v(T) is the velocity of the reaction at temperature, Cp is the heat capacity of sample, M is the mass of sample, A is the area of sample, t is time, J is the total coefficient of heat transfer outward from the reaction zone, TR is the temperature of the bath or furnace, and AH,, is the heat associated with any phase change involved. Prior to the instant of ignition, the vapor pressure of magnesium is of no special significance. After ignition, neither eq 4 nor the above equation is applicable. The actual combination of magnesium cannot safely be assumed to take place in the vapor phase. While experimental data is lacking to support a hypothesis that ignition does or does not occur in the vapor phase, some observation on the pressure ignition experiments may be of interest. At high oxygen pressures, once ignition has occurred, the reaction of magnesium with oxygen approaches near explosive violence, the entire sample being consumed in probably less than 1 sec. At atmospheric pressure it usually requires 15 to 20 sec. Thus it appears that the oxygen concentration becomes the rate determining factor. Further, if burning magnesium is observed through darkened glass (Lincoln Super-visibility Shade No. 12) the magnesium sample is very much hotter than the "smoke" and the outline of the sample is retained perfectly. No "flame" is visible above the metal. No work was done on Mg-Be alloys. We do, however, intend to study this problem in the near future.

Jan 1, 1952

By C. S. Giggins, F. S. Pettit

The oxidation properties of Ni-Cr alloys with fine grains, coarse grains, and deformed surface layers have been studied at temperatures of 900" and 1100°C in 0.1 atm of oxygen. The oxidation rates of alloys containing between 10 and 30 wt pct Cr have been found to be dependent upon the grain size of the alloy. Finegrained alloys had smaller oxidation rates than coarsegvained alloys because of the selective oxidation of chromium at alloy grain boundaries. In this compositional range alloys with deformed surface layers behaved similar to fine-grained alloys due to recrys-tallization of the deformed surface layer. In the preceding paper1 it was found that during the oxidation of Ni-Cr alloys, the volume fraction of precipitated Cr2O3 could be greater at alloy grain boundaries than at other areas of the alloy surface. In the case of alloys with chromium concentrations equal to or greater than 30 pct,* the volume fraction of Cr2O3 *AIL compositions are given as weight percent unless specified otherwise. precipitated at grain boundaries and within grains on the alloy surface both exceeded the critical amount required for lateral growth of the Cr2O3 particles and the surfaces of these alloys were completely covered with a continuous, external layer of Cr203 during oxidation. However, in the case of alloys with chromium concentrations between approximately 5 to 30 pct, the volume fraction of precipitated Cr2O3 exceeded the critical value required for external scale formation only at grain boundaries.but not within the interior of the grains. Consequently, the surfaces of these alloys had external scales of Cr3O3 over the grain boundaries but internal Cr2O3 subscales with external scales of NiO away from the grain boundaries. Under these latter conditions, it was found that chromium could diffuse laterally in the alloy from those areas covered with an external layer of Cr2O3, i.e., grain boundaries, to areas where the Cr2O3 was present as a subscale. This diffusion of chromium resulted in an increase in the volume fraction of Cr2O3 precipitated in the sub-scale zone and continuous layers of Cr2O3 could be formed at the subscale front in these regions. For the alloys used in the previous studies,' continuous layers of Cr2O3 were formed on Ni-20Cr alloys in the subscale regions after approximately 30 hr of oxidation at 900°C. For shorter periods of oxidation, the Cr2O3 layer was semicontinuous with the continuous portion at the subscale front emanating from points where the Cr2O3 had been formed as an external scale over alloy grain boundaries. Some lateral growth of a Cr2O3 layer in the subscale region was observed on Ni-15Cr and even Ni-10Cr alloys but this layer was never continuous after 30 hr of oxidation. These results indicate that the selective oxidation of chromium in Ni-Cr alloys with chromium contents between 5 to 30 pct may be dependent upon the grain size of the alloy. Fine-grained specimens in this compositional range should have a larger fraction of the surface covered with external Cr2O3 than coarsegrained specimens and the subscale areas required to be sealed via lateral diffusion of chromium should be smaller. It is therefore to be expected that a continuous layer of Cr2O3 can be formed on alloys in this compositional range after short periods of oxidation providing the alloy grain-size is sufficiently small. bo studieS2,3 have established that the oxidation behavior of alloys can be significantly influenced by pretreatments which produce mechanically deformed surfaces. It has been found that deformed surfaces usually promote the selective oxidation of elements in alloys and it is believed that these effects are due to rapid diffusion of elements in the deformed layer. In view of the previous results,' which showed that alloy grain boundaries may play an important role in the selective oxidation of chromium in Ni-Cr alloys, deformed surfaces may promote the selective oxidation of elements in alloys as a result of the numerous grain boundaries formed on the alloy surfaces via recrys-tallization during heating to the oxidation temperature. The purpose of the present studies was to determine the effect of alloy grain size and surface deformation on the selective oxidation of chromium in Ni-Cr alloys at temperatures of 900" and 1100°C in 0.1 atm of oxygen. EXPERIMENTAL The average grain diameter of the alloys used in the previous studies1 was not less than 0.04 mm and alloys with compositions between 5 and 30 pct chromium had average grain diameters between 0.04 and 0.14 mm. Since the oxidation kinetics were already available for these relatively coarse-grained alloys, it was desirable to use these same alloys in the present studies. The surfaces of the alloys listed in Table I of the previous paper were deformed by using a Model F S.S. White Industrial Airbrasive Unit, which delivered a controlled mixture of 25 µ Al2O3 particles in a stream of dry air at high velocity against the surface of a specimen. The amount of surface deformation produced by this treatment was not determined but a re-crystallized layer about 15 µ thick was formed upon annealing deformed specimens. The grain size at the surface of the specimens was reduced to an average grain diameter of 0.01 mm by annealing the deformed specimens, i.e., grit-blasted,

Jan 1, 1970

By R. K. Datta

Eluropium -activated yttrium vanadate, excited by short- and long-wavelength ultraviolet radiations, shows enzission lines near 6100A, the principal ones correspondirzg to transitions of EU+3 ions from 5Do to the F2 energy level. The ~neclmlallistns of absorption and etnissiorz of this phosphor have been empirically studied. The absorption is caused by two separate processes in the matrix. The phosphor YVO4:Eu and tlie matrix YVO, haue essentially the same resectance spectra in the region 2500 to 4000if. There are two broat ah~o?~ption bands: natnely, around 2600 and 3600A regions. Whet? compared with the reflectance spectra of the constituent oxides, namely, Y2O3, V205, Eu2 03, the absorption bands of the tnatvix and the phosphor in the short- and long-wavelength ultraviolet regions can be interpreted as due to charge-transfer processes involving i) Y-O and ii) 17-0, respecti~~ely. The excitation spectrum' of the phosphor has two broad bands with peaks at about 2600 and 3600A regions. U can be postulated that enevgy absorbed under short- crud long-wavelength ultraziolet excitatzon, respectzcely, by Y-0 and V-O parts of the niatrix is transferred by radcatio~zless process to EU+3 ions. Thzs postulate can empirically be proved on the basis of the spectra of the systems (YVO4,-YPO4,):Eu. PO? ~ons do not have' any appreciable absorption in the short or long uv regions. When P0't3 ions are substitlited for v0i3 ions in YVO,:Eu phosphors, the absorption and excitation in the lo~zg uv region are gradually reduced. Ailoreover, the £«+3 emission under 3650A excitation is decreased zuitlz increase in PO^ content, lt~lzereas the emission under 253711 excitation remains esserztially constant with as IILUCIL as 60 mole pct of YPO, in YVO,:En. EUROPIUM-activated yttrium vanadate (YV04:Eu) is a well-known phosptor.'-3 When excited by cathode rays, 2537, or 3650A radiations, YV04:Eu emits typical narrow-band spectrum of EU'3 fluorescence in the region of 5900 to 7100A, a very strong maximum occurring at about 6190A. This emission is considered to be due to 5Do — 7F2 transition of excite: EU*3 in 4f state. Moreover, the emission under 3650A excitation increases with temperature markedly. Because of these properties, YV04:Eu phosphor finds wide application in industries, namely, in color television tube, laser, and high-pressure mercury-vapor lamps. It is the purpose of this paper 1) to present the empirical study of the mechanism of absorption and excitation of YV04:Eu phosphor by ultraviolet radiation, and 2) to offer an explanation for the process of emission. It should be mentioned that a theoretical discussion on the mechanism of absorption in terms of the crystal or ligand field theory is beyond the scope of this paper. Empirical studies presented here are based primarily on spectroscopic and crystal-chemical investigations. EXPERIMENTAL i) Preparation of Materials. The synthesis of vanadate phosphorinvolves preparation of (Yi-.tEuj^Oj, blending the mixed oxide with an oxidic compound of vanadium, such as V205 or NH4V03, and firing the mixture at about 1000°C for several hours when YVO4:Eu forms as a primary phase. (Y1-xEux)203 compositions are prepared by coprecipitation of oxalates, and igniting them at about 1000°C. The vanadium compound is added in excess of the stoichiometric proportion for fluxing purposes. The charge is cooled, ground, and the excess of vanadium is removed by a hot wash (-80°C) of alkali or ammonia. Y(VP)04:Eu samples are prepared by mixing (Yi-xEux)203 with stoichio-metric proportions of (NH4)2HP04 and the vanadium compound. The mixtures are prefired at 700" to 800°C for 1 or 2 hr, then ground and refired at 1150°C. The firings of the phosphors are done in silica crucibles, and the homogeneity of the final products checked by X-ray diffraction analysis. ii) Spectroscopic Measurements. Diffuse reflectance sqectra of the samples within the range 2500 to 7000A are obtained by using CaF2 as standard in Cary Recording Spectrophotometer, Model No. 14. The emission spectra from phosphor plaques, excited under different ultraviolet sources, are obtained by a direct-recording spectroradiometer4 adapted with a grating monochromator with nearly constant dispersion. Maximym sensitivity in the spectral region from 2500 to 7000A is obtained with a quartz-windowed, S-20 response p$otomultiplier. The total' band pass is kept about 30A. The spectra are calibrated against the light from a standard tungsten filament lamp reflected from a magnesium-oxide plaque. Brightness data given throughout this report $re measured from the height of the main peak (6190A) of the emission spectra. The excitation spectra are measured using sodium salicy-late as standard. RESULTS AND DISCUSSION The diffuse reflectance spectra of both pure and activated YV04, along with their constituent components, are shown in Fig. 1. YVO4 shows two broad absorption bands, namely, around 2500 and 3600A, respectively. Since there is little difference between the reflectance spectraoof YVO4 and YVO,:Eu in the uv region (2500 to 4000A), it can be postulated that excitation of the phosphor is mainly due to absorption by the matrix, i.e., YVO4. The question, now, is whether the matrix (Yv04) is excited as a whole, or different components are responsible for the two absorption bands. The characteristic absorption spectra of molecular ions involving transition metal ions, both in aqueous solutions and in crystals, are due to electronic transi-

Jan 1, 1968

By Tasuku Fuwa, John Chipman

Equilibrium data on the reactions of gases with carbon and oxygen dissolved in liquid iron are reviewed and correlated. A source of error in oxygen analysis of graphitic samples is exposed. New experimental data on the oxygen content of high -carbon iron in equilibrium with carbon monoxide indicate that the activity coefficient of oxygen is decreased by additions of carbon. The carbon-oxygen product decreases slightly with increasing carbon content. In recent years a number of investigations have been reported dealing with the equilibria between carbon and oxygen in liquid iron and gases containing carbon oxides. The laboratory study of these reactions dates back to 1931 with the publication of a paper by Vacher and Hamilton' on "The Carbon-Oxygen Equilibrium in Liquid Iron". The principal object of this study was to obtain data on the reaction shown by Eq. [3] below; their data and others by vacherZ permit evaluation of the other equilibrium constants as well. Subsequent studies have been reported by Matoba, Phragmen and Kalling and by Marshall and Chipman.5 The equilibria may be expressed by the following three equations: C + CO,= 2CO;Kl = Pc° [1] 0-+CO = CO,;K2=-P co, "0.PCO c + O = CO; K3 = In the equilibrium constants, ac and a0 are taken as equal to [% C] and [% 0] respectively in the infinitely dilute solution. At finite concentrations an activity coefficient is introduced such that ac =fc [%C], and so forth. It is to be noted that these equations represent only two independent relations, the third being derivable from any two. Richardson and Dennis have determined the conditions of equilibrium in reaction [I] at temperatures of 1560" to 1760°C. Their results have been confirmed by Rist and chipman7 who have shown how the data may be extended to cover the entire range of liquid compositions at temperatures from the eutectic up to 1760°C. An approximate confirmation has been reported by Fuwa and chipman.' These investigations also established the activity coefficient of carbon which was shown to increase rather rapidly with increasing concentration. For the very dilute solutions the value of Kl is expressed in the equation: log^i = - 7280/T+ 6.65 This equation leads to a value of Kl = 430 at 1540° C in excellent agreement with the average value of Marshall and Chipman.5 It is shown as line 1 in Fig. 1 together with the experimental observations. In the case of reaction [2] the direct experimental results can be supplemented by observations on the corresponding reaction with hydrogen, namely reaction [4]:

Jan 1, 1961

By V. B. Tare, H. Schmalzried

The use of solid electrolytes for determining kinetic paraneters at elevated tevnperatures is pointed out. The reaction rate constant k1 of the phase-boundary reaction during oxidution of iron to wiistite by CO2-CO gas mixtures has been deternined between 850 nnd 975C, using ZrOz(+CaO) as an electrolyte. Values are between 1.4 x 10-a and 5.2 x 10 ole per sq ctn atm. The tzain difficulty is due to mixed potentials arising from side reactions at the electrolyte inteyface. In a number of papers the calcium-doped zirconia electrolyte has been used for the determination of thermodynamic data from measured differences in oxygen activities (or potentials) between two electrodes. The purpose of this note is to suggest the use of this solid electrolyte for kinetic measurements as well. The principle can be seen from Fig. 1. A thin and compact phase II (electron conductor) is fixed on a plate of gas-tight, polished ZrO2(+CaO) (I), which separates two compartments with different oxygen potential. p, is a constant reference pressure of oxygen (1 atm). The electromotive force of this galvanic cell is given by E = RT5 In pep, and pe is the oxygen partial pressure at the interface electrolytephase 11. If phase I1 is in equilibrium with the surrounding gas phase, p, = DR. If pg changes sud- denly to a value pi, p, and therefore the electromotive force, E, change as a function of time according to the phase-boundary reaction rate at the gas phase I1 interface and the transport processes inside phase 11. It is assumed that local equilibrium is established at the boundary electrolytephase 11, that the gas phase shows no concentration gradients, and that the con-

Jan 1, 1967

By W. A. Selvig

BY plotting fixed carbon against British thermal units of coals free from mineral matter, and ranging in rank from anthracite to lignite, it is found that the coals of higher rank, from anthracite to the higher rank of the high-volatile bituminous coals, inclusive, can be separated into groups according to their degree of metamorphism by reference to their fixed carbon. Such charts show also that the coals lower in rank can be best separated into groups with respect to B.t.u., especially when plotted on the moist basis, that is, coal containing its natural bed moisture. A tentative scheme for coal classification was presented at the October, 1932, meeting of the Technical Committee on Scientific Classification, of the American Standards Association Sectional Com-mittee on Coal Classification. This scheme was sponsored by Sub-committee IV on Tentative Classification of Coals, under the chairmanship of W. T. Thom, Jr. It proposed the grouping of coals according to rank by reference to fixed carbon and B.t.u., on the basis of coal containing its natural bed moisture but free from mineral matter. This scheme proposed classifying coals into four broad classes: (1) anthracitic, (2) bituminous, (3) subbituminous, (4) lignitic.. The anthracitic class was divided into three groups designated as meta-anthracite, normal anthracite, and semianthracite. The bituminous class also was divided into three groups, low volatile, medium volatile, and high volatile. The high-volatile group was further subdivided into four subgroups according to moisture content, as follows: (1) less than 5 per cent, (2) 5 to 10 per cent, (3) 10 to 15 per cent, and (4) 15 per cent and more. The subbituminous class was divided into two groups, group, 1 including subbituminous coals having calorific values of 10,500 B.t.u. or more, and group 2 including those with less than 10,500 B.t.u. , The lignitic class of coal was divided into two groups both below 8,000.B.t.u., the one group consisting of consolidated and the other of unconsolidated

Jan 1, 1934

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

In the special number of the magazine Ocl und Kohle (Oct. 22, 1940) dedicated to the petroleum industry of southeastern Europe, there appeared several articles relating to Yugos1avia.t In the first article the author calls attention to the fact that there are two fields in Yugoslavia that have been explored and exploited by more than 100 wells at variable depths during the last 50 years. These are on the Island of Mura, at the confluence of the Mura and the Drave. Additional exploration drilling in various other parts of the country has been without result, but certain ones of these explorations have revealed the existence of gas horizons that have some value, which are being used for industrial purposes. Table I shows the production of oil and gas between the years 1900 and 1939. TaBle —Production of Oil ad Gas in Yugoslavia . n,i Natural Natural Years oil Years Gas, Cu. Years Gas, Cu. Meters Meters T900-1929 10,000 1923 507,000 1934 1,388,000 1930 277 1924 567,000 1935 1,401,000 1931 202 I92S 691,000 I936 1,483,000 t932 289 19261 1.472,000 1937 1,841,000 1933 629 1927! 1,732,000 193s 2,431,000 1934 324 1928 2,515,000 1939 2,628,000 1935 260 1929 4,700,000 1936 137 I93O 5.345,200 1937 463 1931 6,376,153 1938 1,091 1932 1,661,737 1939 1,114 1933 959,574 The number of wells drilled from 1884 to the present time was in the neighborhood of zoo and the total footage drilled was 65,000 m. up to July I940 They may be divided roughly as follows: 12 wells in the region produce natural gas; 134 wells in the two old fields of the Island of Mura and about zo wells for the exploration of the zone of the Flysch, in Bosnia. The depths of 50 of these wells was roo to 200 m.; the depths of 50 wells oil the Island of Mura ran from zoo to 500 m.; of 2 ; wells, 500 to I000 m.; of ro wells from rooo to 2000 meters. The deepest well drilling in Yugoslavia has reached 2000 in. In the Valley of Morave, in the region of Selnica, I00 km. south of Nish, there have been discovered asphalt-bearing limestones, which contain about 15 per cent asphalt and are associated with bituminous clays. Later, at Paclenica, important deposits of natural gas were found. A zone rich in gas and oil seepages runs through Pracec, Miklenska, Bujavica, etc. The author studied these regions from the point of view of stratigraphy and tectonics. The anticlines and gas-bearing domes are concentrated in two zones: the region of the Drave (Island of Mura) and the region of the Save, southeast of zagreb, which contains the gas field in exploitation in the region of Bujavica. A full description of the productive region of the Island of Mura has been given by Egon Bohm, a geologist, in the second article mentioned. This includes a history of the exploration and exploitation that took place under Hungarian rule in this region. The most important exploration was effected between 1884 and 1885 by Stavenov and Stinger, of Vienna. In 1927 work was done in the same region by Anton Raky, a well-known explorer who makes work of this kind his specialty.

Jan 1, 1941

By R. A. Stauffer

The chief ore of lithium is spodumene, a lithium-aluminum silicate containing up to 3 pct lithium. The preparation of lithium salts from spodumene is costly because of the low concentration of the metal and the difficulty of separating it from the other alkali metals present. Dr. Kroll's and Dr. Schlecten's recent paper1 has reviewed various methods proposed for preparation of lithium. It will be seen from this paper that the methods proposed to date have required one or another of the lithium salts as a raw material. The high cost of these salts has been the chief item of expense in the lithium metal produced. This situation has made it interesting to investigate the possibility of producing the metal directly from spodumene. When spodumene is calcined at 1000ºC in the presence of lime, lithium oxide is replaced in the ore as is evidenced by the fact that it may be leached from the reaction mixture with water.2 Free energy calculations suggested that lithium oxide might be reduced with aluminum or silicon and the lithium produced distilled from the reaction mixture by heating-to about 1000ºC in a vacuum. These facts taken together suggested that it might be possible to prepare lithium metal directly from spodumene by heating a mixture of the ore, lime, and a suitable reducing agent in vacuum and distilling off the lithium metal as formed. The Replacement of Li2O in Spodumene A series of experiments were undertaken to determine the ratio of lime to spodumene necessary to free substantially all the lithium oxide Present in the Ore. The spodumene used in these experiments was supplied by Foote Mineral Co. in the form of powder of about 200 mesh' Analysis of the spodumene was as follows: PCT SiO2......................... 62.7 Al2O3........................ 29.9 Li2o......................... 4.9 Na2O........................ 0.89 CaO......................... 0.75 MgO........................ 0.49 K2O......................... 0.44 Lime (cp —200 mesh) was added in various ratios to spodumene and thoroughly mixed in a ball mill. Two hundred gram samples of spodumene-lime mixtures were charged loosely in fireclay crucibles and held at 1000ºC in a gas-fired furnace for 5 hrs. The product in each case was ground to pass 140 mesh and then placed in a thimble in a soxhlet extractor. Extraction with water was carried on for 6 hrs. After this period the extract was reduced in volume by evaporation in order to precipitate dissolved lime and was then filtered and titrated with 1/4 normal hydrochloric acid. After correcting for residual calcium oxide in solution, the alkali present was calculated as lithium oxide. The results of these experiments are shown in Table I and Fig I. At lime-spodumene ratios less than 1.5, the products were invariably fused. At the ratio of 1.5 and above, the product was loosely sintered with little evidence of fusion. When the ratio of lime to spodumene was three, replacement of alkali oxides in the

Jan 1, 1949

By Charles M. Rolker

(Read at the Philadelphia Meeting, February, 1878.) THE Mariposa estate, a grant made by the Mexican Government to Juan B. Alvarado, during the time when California was still under the dominion of Mexico, was purchased in 1847 by J. C. Fremont, and the United States patent issued to him in 1856. By sale, or its equivalent, money advanced, the property came into the hands of the Mariposa Company, June 25th, 1863, and through a varied existence of work and temporary inactivity, has as yet been kept as an undivided property, and rests at present with the Mariposa Land and Mining Company of California. I pass over this period of 15 years without giving the history of the ups and downs of the estate, partly because it is familiar to many, and also because I think in such a case this paper would assume too much the character of a narrative. The estate is situated in Mariposa County, California, about 170 miles southeast of San Francisco. It begins in lat. 37° 26’ 38" - north, and long. 119° 55' west, and runs 6 miles north; thence 6 1/2 miles west; thence 5 miles northwesterly towards the Merced River; thence 8 1/2 miles southerly; thence 3 miles easterly; thence 1 mile southerly; thence 2 miles easterly; thence 2 miles southerly; thence 2 miles easterly; thence I mile southerly; thence 2 miles easterly; thence 1 mile northerly, and thence 2 miles easterly to the place of the beginning; embracing 44,387 acres (70 sq. miles) more or less. To describe this vast estate in detail as to its full geology, its numerous quartz veins, its many facilities to exploit them and work them by cheap methods, would lead me further than I intend to go at present, and I will content myself to describe the latest workings of the company and its immediate field of operations. As long ago as 1860 the late Dr. Adelberg advised the running of an adit from the northwestern edge of the estate at Benton Mills on the Merced River. His object was to undercut the deepest workings of the then paying mines on the estate-the Pine Tree and Josephine. Following this advice, the tunnel known as "River Tunnel" was commenced. Its entrance is in S. 5, T. 4, S. R. 17 E. It is run in

Jan 1, 1878

By Aloys H. Wohlrab

THE conditions that govern the selection of a suitable type of detachable bit for the small, isolated mine, for rock work and tunnel contracting and for the large mine are quite dissimilar, therefore intelligent recommendation of a particular make of detachable bit must involve consideration of many factors. Small, isolated mines may find advantageous a detachable bit that a larger mine cannot afford to use, because of more efficient conventional steel sharpening and steel-distribution practice, but a small mine may not be able to adopt the practice of large mines because of necessary capital expenditures for equipment for detachable-bit sharpening and shanking. The perfect detachable bit, suitable for all conditions, has not yet been developed. CONVENTIONAL DRILL BIT IN USE That drilling speed increases as the bit gauge decreases is well known, but since small-hole drilling is the exception rather than the rule the rate of such increase is probably not so generally recognized. Tests carried out by Holman Brothers Limited1 with 7/8 -in. steel show that when bit sizes are reduced from I ½ in., I 3/8 in., and I 3/16 in., to I 3/8 in., I ¼ in., and I 1/8 in., respectively, the volume of the hole is 15 per cent less and the drilling speed 49 per cent higher. Recent tests by the United States Bureau of Mines2,3 in hard, uniform basalt showed that a reduction in average gauge from 2.077 to I.826 in., a difference of 0. 2,5I in., gave an increased drilling speed of 65 per cent. The limits to which a drill hole may be extended depend upon the loss in gauge. Since the conventional bit with 5° and I4° clearances did not possess sufficient reaming edge to permit the smaller gauge changes that were required for small-hole drilling, experiments were made in bit construction with a view to correcting this deficiency. This resulted in the adoption of the full reaming cross bit (having full Carr characteristics) by some mines.4 In order to drill holes having a minimum taper from the collar to the bottom of the hole, full reaming center-hole cross bits with 90° cutting angles, 5° and 14° wing tapers, forged on 7/8-in. quarter-octagon drill rods, are used in the conventional drill-steel practice at Hollinger. In the steel shop close attention is given to the condition of the dies and dollies, which, combined with a rigid inspection of the finished bit, ensures as nearly a perfect bit as can be forged economically. Shop practices and costs have been discussed in earlier papers.5.6 The method by which the radii for the special dies used for forging bits of different gauge diameter are obtained so that the points and reaming edges cut circles of the same diameter has been discussed by Hibbert.7 REQUIREMENTS FOR DETACHABLE BIT FOR HOLLINGER Under these circumstances, it was apparent that it would be difficult to introduce a detachable bit that could successfully compete with the conventional bit already in

Jan 1, 1942

[A Aamodt, H. C., A55 C Sales, Great Lakes Carbon Corp., 18 E. 48th St., New York, N.Y. Aamot, Olav Crone, M29 2126 M4, Galveston, Texas Aaronson, Hubert I., M47 E Prin Res Engr, Ford Motor Co., Met. Dept., Sci. Lab., Engrg. Staff, P. O. Box 2053, Dearborn, Mich. Aase, Glenn D., M54 D Prin Engr, Air Pollution Control Dist., 1480 Mission St., San Francisco 3, Calif. Abbett, W. A., Jr., M56 8629 Beverly St., Duluth 8, Minn. Abbey, Robert G., M56 138 Dartmouth Rd., Bala Cynwyd, Pa. Abbott, A. G., Jr., J52 E Test, Dev Engr, Chrysler Corp. Missile Div., P. O. Box 2628, Detroit 31, Mich. Abbott, Mark L., A58 Rep, General Refractories Co., 208 S. LaSalle St., Chicago, Ill. Abbott, W. K., J58 E Dev Met, Int'l Nickel Co., Inc., 67 Wall St., New York 5, N.Y.]

Jan 1, 1961

By A. E. Jenkins, L. A. Baker, N. A. Warner

Rates oj decarburization of levilated Fe-C droplets conlaining 5.5 to 0 pct C have been measured at 1660°C. Gas mixtures of 1, 10, and 100 pct 0, with helium diluenl were used at velocities of 12.5 and 62.5 cm per sec. Rates were independent of carbon concentration in the mell and in good agreement with the calculated rule of oxygen diffusion through the gas boundary layer. The effects of flow rale and total pressure are as predicled and the rates are approxitnalely 2.5 times those with CO2 as oxidant. The mass-transfer correlation used incorporaled the efject of natural convection as well as forced conrection. Graphile spheres are shown to oxidize at the same rate as Fe-C droplets under the same experimental codlions. It is concluded that, for high carbon concentrations in the melt, the rate of- decarburizalion is controlled wholly by the rate of gaseous diffusion. Rate measurements with pure CO, are reported for low carbon concentrations where CO bubbles nucleate within the droplet. Under these circumstances the decarburi-zation decreased with carbon concentration and it is proposed that carbon diffusion is significant in conlrolling the decnvburization rate. In an earlier paper1 decarburization rate measurements were reported for levitated Fe-C alloys at 1660°C but with CO2 as the oxidant. The decarburization rate was found to be independent of carbon concentration in the melt but slightly affected by total pressure. The authors were unable to explain the slight pressure effect but in all other respects the results were consistent with control by diffusion in the gas boundary layer. Subsequent work has been directed at finding the reason for the slight pressure effect and whether the kinetics with oxygen as oxidant parallel those with CO2. Recently Ito and Sano2 have shown that with water vapor-argon atmospheres the decarburization rate is gaseous diffusion controlled until an oxide film appears on the surface. In this work the melts were contained in crucibles. MASS TRANSFER IN THE GAS PHASE In the earlier analysis1 only forced-convection mass transfer was considered. Subsequent recognition of the existence of some free-convection mass transfer explained the observed small effect of total pressure on the decarburization rate. Steinberger and Treybal3 and Kinard, Manning, and Manning4 have developed correlations involving the linear addition of the contribution of radial diffusion, free and forced convection. Steinberger and Treybal&apos;s correlation was chosen as the most applicable to the present work since it correlated most of the data available in the literature and handled the low Reynolds number region exceptionally well. The correlation for (Gr&apos;Sc) < 108 is where Nu&apos; is the Nusselt number for mass transfer based upon the total surface of a sphere in an infinite medium, G&apos; is the mean Grashof number for mass transfer defined by Eq. [2], Sc is the Schmidt number (µ/pDAB)f, Re is the sphere Reynolds number (dpu,pf/µf), p is the viscosity of the gas (poise), p is the density of the gas (g cm-3), Dab is the binary diffusivity for the system A-B (sq cm sec-&apos;), dp is the sphere diameter (cm), u is the approach velocity of the gas (cm sec-I), and subscript f denotes the property value is computed at the film temperature Tf defined by Tf = +1/2(To + Tr) where To is the specimen temperature and T, is the approach gas temperature (oK). Natural convection occurs when inhomogeneities exist in gas density. These may be caused by concentration gradients, temperature gradients, or both. In the present work the temperature gradient between the sphere and the bulk gas was very large and in some cases, for example the runs with pure oxygen, the concentration gradient was also appreciable. The Grashof number defined by Mathers, Madden, and piret5 was used since it took account of both temperature and concentration gradients: where Gr&apos; is the Grashof number for mass transfer (p2fgd3|-yA-yA|/µ2f), Gr is the Grashof number for heat transfer (p2f gd3p|To - T,]/µ2fTf), Pr is the Prandtl number (cpµ/k)f, g is the acceleration due to gravity (cm sec-&apos;f, a is the concentration densification coefficient (1/p)(ap/ayA)T, yA is the mole fraction of component A at the gas-metal interface, yA is the mole fraction of component A in the bulk gas stream, cp is the heat capacity of the gas per unit mass at constant pressure (cal g-I OK-&apos;), and k is the thermal conductivity of the gas (cal cm-&apos; sec-1 OK-1). Mathers et al. tested this combined Grashof number

Jan 1, 1968

By Yves Dardel

The literature concerning the remelting of alunlinum and its alloys is very rich. Unfortunately the majority of the papers on this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges, and the atmosphere of the furnaces bring into the bath during the successive remelt-ings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, or others, if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H², O2, H²O, co², CO, CH,, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of sieverts3 as a function of its partial pressure PH2 in the atmosphere m = K vPH² [I] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Rijntgen and Braun4, RÖntgen and M611er5, Bircum-shaw6 and Winterhagerl have rendered it possible to determine the value of K, when the temperature is less than 1.000°C. One obtains: log K = - 4,702.5T + o 238 [2] Besides its usual significance, the term Ph~ represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is1 when no gas exchange Occurs between the two phases, the Pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary Occurs, the quantity of H² should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature decreases, the internal pressure of H² increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a a depending On the hydro- static pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However1 even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1949

By Charles W. Carter, Alfred H. Bell

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944

By Alfred H. Bell, Charles W. Carter

In 1943, Illinois produced 82,256,000 bbl. of oil, or 5.5 per cent of the total for the United States, and ranked sixth in the nation in oil production. This represents a decline of 23 per cent from 1942, when the total Illinois production was 106,ggo,o~~ bbl. and Illinois ranked fifth. The daily average production for 1943 was approximately 225,000 bbl. Daily averages by months were as follows: Jan......... 238,000 July......... 218,000 Feb......... 240,000 Aug......... 216,000 Mar......... 237,qoo Sept........ 220,ooo Apr......... 230,000 Oct......... 220,000 May....... 221,000 Nov......... 223,000 June......; . 222,000 Dec......... z18,ooo This shows that most of the decline during the year took place between March and May, and that for the last eight months of 1943 production has been essentially steady. This means that there has been enough production from new wells drilled to balance the natural decline of the Older wells. The trends of drilling and production are shown in Fig. I and Table 3.

Jan 1, 1944