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By J. B. Dyess

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 form the various oxide-sulphide films studied. The comparative resistances afforded by (1) 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 T= MX10 8 2D X 96,494 X 103 (a) 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 Angström 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 values2 of t for cuprous and cupric oxides (12.36 and 6.39, respectively) were used in the present work.

Jan 1, 1939

By R. Raring, W. J. Harris, J. A. Rinebolt

The effects of additions of alloying elements on the true-stress, true-strain characteristics of 0.30 pct C, 1.00 pct Mn, 0.30 pct Si pearlitic steel were studied. The alloying elements investigated were C, Mn, Si, P, The alloys are compared on the basis of fracture stress, fracture strain, energy to fracture, rate of strain hardening, strain hardening exponent, height of the flow curve, and lower yield point. IN the past, nearly all studies of the effects of alloying elements on the tensile properties of metals have compared the conventional engineering parameters, namely, tensile strength, yield strength, elongation, and reduction of area. Recently, however, the true-stress, true-strain method of recording results from the tension test has been used; Lacy and Gensamer,' Hollomon," and French and Hibbard- are used this method to study the effects of composition on strength and ductility of metals. In this paper, the effects of certain alloying elements on true-stress, true-strain curves of steels with nearly constant grain size and pearlite spacing are presented. The notation employed in this paper is given in Table I. Since the definitions of stress and strain and the analytical geometry of the stress-strain curve have been explained previously, for example by Gensamer,' they will not be reviewed here. However, the method used for the determination of energy to fracture, E,, requires mention. These energy values were calculated on the assumption that the flow curve followed the idealized equation:' corresponds to the specific energy absorption to that strain value. There is justification for preferring the use of eq 1 for the determination of the energy to a particular strain rather than the area under the experimental stress-strain curve, since Gensamer showed that the use of the Bridgman correctione for stress at the neck of a tensile specimen brought the corrected experimental curve nearer to the idealized power-law curve than to the uncorrected experimental curve. However, it should be noted that the difference between the areas under the idealized curve and the experimental curve is not great for strain of less than 1.0, as can be seen from Fig. 1. In this figure, the true-stress, true-strain curve for a 0.01 pct C, 1.00 pct Mn steel is plotted through the experimental data points. From the value of a,, from this curve and the value of n as determined by the Inm-

Jan 1, 1952

Executive SCOTT TURNER, Chairman FREDERICK M. BECKET JOHN A. MATHEWS H. A. GUESS WILLIAM WRAITH Finance HENRY KRUMB, Chairman PAUL D. MERICA ROBERT E. TALLY Admissions JOHN M. LovEJOY, Chairman GEORGE D. BARRON ERLE V. DAVELER WILLIAM H. BASSETT W. D. B. MOTTER, JR. Alternates HENRY B. FERNALD F. JULIUS Polls AMOR F. KEENE

Jan 1, 1932

Jan 1, 1968

Jan 1, 1970

By F. H. McDowell

The increasing interest in the subject of electrical separation warrants the addition to what has already been written of a few lines covering the practical workings of the Tilly Foster mill under the direction of Mr. E. S. Moffat, General Manager. Since my last paper was presented to the Institute, Mr. S. P. Tomkins, the superintendent, has had thrust upon him for solution several problems complicated by the introduction of new conditions. 1. The richer portion of the lean ore dump, and that nearest the railroad track, having been worked up in 1890, the handling of the balance, including a largely increased amount of rock, could only be accomplished at an increased cost. 2. The tailings had accumulated close about the mill to such an extent that arrangements had to be perfected to move them further away.

Jan 1, 1893

By W. H. Smith

IN the course of an investigation on chromium containing minor amounts of alloying elements, the information herein has been obtained on the crys-tallographic orientations resulting from arc melting, rolling, and annealing. The chromium used in this investigation was electrolytic flake obtained from the Electro Metallurgical Co. This material was heated for 20 hr at 1600°C in hydrogen with a dew point of about — 100°C. The oxygen and nitrogen content of the chromium after this treatment was 0.0003 pct 0 and 0.005 pct N. Five pounds of this chromium were arc melted in a water-cooled copper crucible. After arc melting, the oxygen and nitrogen contents were 0.002 and 0.025 pet, respectively. A section of this ingot is shown in Fig. 1. By means of a back-reflection Laue technique, the crystal habit of the cast ingot was determined. As expected, it was found that the [loo] was approximately the axis of the columnar grains. In this respect, chromium behaves like other body-centered-cubic metals in that a cubic axis is normal to the cold surface of the mold. A slab cut from this ingot was rolled at 600°C as follows: four 30 pct reductions were made with intermediate anneals at 1200°C for 15 min. Rolling was done with the [loo] of the columnar grains in the rolling direction. Following the final anneal, an 80 pct reduction was taken at 600 °C. The final sheet thickness was ten mils. By polishing and etching, the thickness was reduced to four mils and the grain orientation determined by the transmission Laue method using molybdenum radiation with a zirconium filter. Fig. 2 is the (110) pole figure for this material with the ideal (100) [011] and (111) [112] orientations indicated. The orientation is typical of most cold rolled body-centered-cubic metals having the [llO] of the grains approximately in the rolling direction and the (100) planes approximately in the plane of the rolled sheet. There is also evidence of some 10) [1 orientation. The grain orientation of sheet rolled 40 and 80 pct in the same direction as before at 600°C followed by recrystallization at 12000 C for 15 min was determined by a back-reflection Laue technique. A random texture was found in both cases. This 1200°C 15 min anneal was found to give complete recrystallization and some grain growth.

Jan 1, 1956

Official Program

Jan 8, 1950

By Ta M. Li

How will phosphate producers in southeastern Idaho fare with growing governmental regulations and environmentalism of the late 1970's? With a similarity that is reminiscent of the battles between the coal industry and environmental-conservation groups earlier in the decade, Idaho's future growth and a nation's need for phosphate fertilizer products remain uncertain. The catalyst that brought the issue to the forefront was the preparation of an Environmental Impact Statement (EIS) addressing the development of phosphate resources in southeastern Idaho. Although the final EIS was published in August 1977, resolution of rational and orderly growth in this potentially vital region remains stifled as Secretary of the Interior Cecil Andrus virtually "sits" on it.

Jan 1, 1978

Jan 1, 1966

Jan 1, 1967

Jan 1, 1960

By O. D. Gonzalez

ThIS communication presents the results of a determination of the permeabilities of hydrogen and deuterium in a iron from 360° to 560°C. Recently Heu-mann and primas' have given values of the diffusivity and solubility in a iron of the two isotopes from which the permeability can be calculated. The work reported in the present communication, however, is a direct measurement of the rate of permeation of the isotopes through an identical iron specimen under the same conditions, so that systematic errors can be minimized in the calculation of the ratio of the permeabilities—the value which is usually of main importance in establishing limits for isotopic differences in diffusive processes. Experimentally the procedure used was the usual one: a steady-state flow of gas produced by a pressure difference across an iron membrane was observed as the pressure rise with time in a previously evacuated, calibrated volume connected to the outlet side of the membrane, while a constant pressure of gas was maintained on the opposite inlet side. The membrane was a cylindrical tube 9.38 cm long, 0.730 cm inside diam, 0.187 cm wall thickness, fabricated of 99.95 pct vacuum-melted National Research Corp. iron (less than 0.003 pct C). One end was sealed by a heliarc-welded iron (99.95 pctj lid of 0.147 cm thickness; the other end of the tube was welded to a 304 stainless-steel tube (0.318 cm ID and 0.318 cm wall) which connects to a vacuum system and to the calibrated volume including a dibutylphthalate manometer. The temperature of the iron membrane was maintained constant to ±0.l°C and was measured with an iron-constantan thermocouple which was calibrated against a standard Pt/Pt-Rh thermocouple: the temperature variation along the length of the membrane did not exceed ±0.5°C. Hydrogen was allowed to pass through the membrane assembly for 72 hr at 615°C before permeability measurements were begun. The system was tested at temperature before and after the experiments by a substitution of helium for hydrogen in the inlet side; under these conditions the pressure rise observed in the outlet side was negligible at all times. The gases used for the permeability measurements were 99.95 pct Matheson prepurified H2 and 99.7 pct D2 (0.3 pct HD) from the Isomet Corp. The gases were dried with liquid N2 before use. In Fig. 1 the logarithms of observed flows, jt, for a pressure difference of 73.4 cm Hg are plotted against T-1 Each point in Fig. 1 represents the slope determined by a least-square evaluation of a plot of the pressure in the outlet side of the membrane against time, including at least two separate sets of observations. Each point in the figure has an uncertainty of ±0.6 pct arising from the experimental uncertainty in the pressure and time measurements. The standard deviation of the observed pressures from the straight lines in all cases is less than the experimental precision of the measurements. The observed flow, jt, includes a small but not negligible flow through the stainless-steel connection.

Jan 1, 1968

Preheating Feature of Leyner Oil Furnace for Heating Drill Steel The No. 3 Leyner oil-burning furnace, used for heating drill steel, is now made with a preheating chamber. By this addition it is claimed that the heating capacity and, effeciency of the furnace are increased about 50 per cent. This preheater is a section which fits between the body and cover of the furnace of the old design. It may be attached to an old furnace by simply changing a few bolts. Referring to the illustration, it will be seen that the lower chamber is used for the final heating and the upper one for preheating. The type of burner now furnished with this furnace is suitable for either high- or low-pressure air. It hats merely to be throttled for high pressures and when this is done, it, is as efficient as burners designed especially for high pressures and eliminates the noise common to such burners. This furnace burns petroleum or any of its oils, such a, gasoline, kerosene, distillate, etc. Oil heating has many advantages. The steel cannot be injured by absorbing injurious elements such as sulphur, phosphorus or other impurities which :ire present in nearly all coals, nor from unequal heating since the flame imparts a uniform temperature; further, o lie steel is in full view of the operator at all times.

Jan 3, 1916

By W. C. Leslie

W. C. Leslie (Edgar C. Bain Laboratory for Funda mental Research)—This investigation, with its com bination of high-purity metal, calorimetry, and metallography, will serve as a model for annealing studies for a long time to come. The evidence for a competition between recovery and recrystalliza-tion is particularly convincing. The demonstration of edge-nucleated recrystallization was so clear that it may obscure the necessity for other types of "nucleation" sites; otherwise, single crystals of aluminum could not be recrystallized after cold work. At least three types of sites have been found to operate in iron: 1) high-angle boundaries, probably in the same manner as in aluminum, 2) matrix sites, 3) inclusions or second-phase particles. In each instance, the cells developed during cold work and perfected during recovery are the "nucle for recrystallization. Observations by ourselves and others of the dislocation structure of cold-worked metals and of the structural changes that occur during annealing have led us to doubt the validity of the basic assumption of the Lucke-Detert theory, and of the modification developed by Gordon and Vandermeer, that during recrystallization of a metal containing foreign elements in solid solution a high-angle boundary is ad vancing into a cold-worked matrix having a random distribution of solute atoms. We contend that an es sential part of the cold-working and annealing of solid solution alloys is the trapping of solute atoms by the low-energy "wells" afforded by individual dislocations and by dislocation arrays. If cells are formed during cold work, the cell walls are stabilized by this concentration of solute atoms. Thus, solutes inhibit recrystallization not only by decreas-ing the rate of high-angle boundary migration, but also by preventing the formation of high-angle boundaries by subgrain growth or coalescence, i.e., solutes can inhibit both "nucleation" and growth. In addition to stabilizing the dislocation Structure, the solute-dislocation interactions may produce clusters of solute atoms which are not as readily assimilated into the recrystallized grains as are individual solute atoms. There is an additional complication. The dislocation structure formed upon cold working a dilute solid solution may not be the same as that formed during cold working of the pure solvent metal. The solute can either enhance or minimize the formation of cells during cold working. Both effects have been observed in binary alloys of iron. The annealing process is inextricably connected with the mechanisms of strain hardening and solid solution hardening. Although the correlation between experimental boundary migration rates and the predictions made from the theoretical equations are impressive, it should be mentioned that in at least four other instances (Pb-Ag and pb-Au,15, Fe-Mn,16, Fe-Mo)17 the agreement was rather poor. In brief, while it is probable that the migration of high-angle boundaries is held back by solutes in the manner described, this is only a partial explanation of the total effect of solutes upon recrystallization of cold-worked alloys. Paul Gordon and R. A. Vandermeer (author's reply)— The authors first wish to thank Dr. Leslie for his compliments of this work. It is perhaps worth pointing out that some of Dr. Leslie's remarks are directed toward subject matter covered in two earlier papers in our work.18,19 We agree with Dr. Leslie's main contention that the exact nature of the metal structure in the vicinity of a boundary should have an effect on the boundary migration. The theory of Lucke and Detert does not take such detail into account, nor does it account for orientation effects on the migration rates. We assume that since our data checks the theory so well, the effects of detailed structure are statistically averaged out by the polycrystalline techniques used just as are the effects of orientation factors.

Jan 1, 1963

By Walter O. Snelling

Discussion of the paper of WALTER 0. SNELLING, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 100, April, 1915, pp. 695 to 704. A. C. McLAUGHLIN, San Francisco, Cal.-It seems to me that Mr. Snelling's work, if it is what it appears to be, is one of the most important contributions to petroleum technology that has been brought out iii the last 25 years. If his end products are what they seem to be, he has made a discovery, which, in my judgment, will revolutionize the petroleum industry. As to industrially carrying out these processes I do not think there is the slightest difficulty, for I have had some work recently where crude oils were handled successfully at a temperature of 750°F. and pressure of 750 lb. per square inch. WILLIAM A. WILLIAMS, San Francisco, Cal.-What metal did you use, Mr. McLaughlin? - A. C. McLAUGHLIN.-Ordinary seamless tubing, extra strong. WILLIAM A. WILLIAMS.-Tests were made in Dr. Rittman's experimental plant at Pittsburgh, upon samples of residuum furnished by Mr. Bell, the residuum being the remainder of the crude oil after the lighter fractions had been removed. After the material had been run through Dr. Rittman's plant, yields of from 43 to 58 per cent. of material, boiling under 150°C. were obtained. The distillate had a peculiar odor, due to the presence of benzene, toluene, and other unsaturated hydrocarbons. W. N. BEST, New York, N. Y.-What is the difference between the Rittman and the Snelling process or system? WILLIAM A. WILLIAMs.-The fundamental difference is that reactions take place under relatively higher temperatures and pressures and with none of the oil present in its original or liquid state, while the reactions secured by Mr. Snelling and other investigators have been from the liquids in the presence of some vapors. Under such conditions as Mr. Snelling operates, the temperatures and pressures used are limited and the flexibility in the control of these variables is extremely limited when compared with the Rittman process.

Jan 1, 1916

By D. S. Bloom

RECENTLY a report has been published on an investigation of the MO-RU system by E. Raub.' In this report it is stated that below approximately 1200°C the system consists of two terminal solid-solution phases and the intervening two-phase field; at 1200°C and above, an intermetallic compound labeled Mo,Ru, makes an appearance. Along with some other little known systems in which it was considered possible for a u phase to form, the Mo-Ru system had been under investigation in this laboratory. Since molybdenum and ruthenium have very high melting points and also since ruthenium is expensive, the investigation was confined to X-ray diffraction by sintered powder compacts. The compositions which were studied were (in atomic percentages): 75 Mo-25 Ru, 67 Mo-33 Ru, 50 Mo-50 Ru, and 25 Mo-75 Ru. All compacts were made from the pure powders, and no chemical analyses were attempted. Each compact weighed about 5 g. All annealing was done in evacuated Vycor capsules, and even though the capsules completely collapsed at 1250°C, they still admitted no air. The results of this investigation in general corroborate the work of Raub. Up to 1150°C the two terminal solutions and the intervening two-phase field were found, and at 1200°C and above an intermetallic compound was found. However, the composition limits of the compound were estimated to lie close to 70 atomic pct Mo rather than 62.5 atomic pct Mo as Raub had reported. At least the X-ray diffraction results indicated that the 75 atomic pct Mo specimen consisted of the molybdenum solid solution plus the compound, while the 67 atomic pct Mo specimen consisted of the ruthenium solid solution plus the compound and the equiatomic composition contained only very little of the compound. The most interesting observation, however, was that the diffraction pattern of the compound was similar to that of the well known u phases, except that unusually large lattice constants were indicated. The d-values, or interplanar spacings, of the diffraction lines (as produced by filtered copper KCX radiation) of the compound are given in Table I, as determined from specimens annealed at 1250°C for 9 hr and then quenched in water. Also shown are the lines of the Mn-Mo u phase as given by Decker, Waterstrat, and Kasper,' the lines of the Fe-Mo a as given by Goldschmidt," and the lines of the Mo-Ru phase multiplied by constants in order to make comparison with the Mn-Mo and Fe-Mo patterns easier. These results indicate that the compound in the Mo-Ru system is apparently isomorphous with the other o- compounds. The rather large lattice constants of the Mo-Ru a phase are acceptable in view of the comparatively large size of the constituent atoms. The data in Table I for the Mo-Ru compound check quite well with those given by Raub, not shown here, though there are some discrepancies between the two sets of data in the estimated intensities of a few lines. Although very little is known at present about this u phase, there are some things which may be pointed out, mainly in comparison with other better known u phases. Even though molybdenum and ruthenium are in the same columns in the Table of Elements as chromium and iron, respectively, the Mo-Ru u phase contains much more molybdenum than ruthenium, while the Cr-Fe u phase centers around or very nearly around the equiatomic composition; furthermore, the Mo-Ru u is stable only above approximately 1200°C, but the Cr-Fe u is stable only below about 825 °C. With respect to its being unstable below 1200°C, the Mo-Ru u is similar to the other binary molybdenum u phases in the Co-Mo and Fe-Mo systems. Similar to the latter two systems, the Mo-Ru u apparently exists over a rather narrow composition range, whereas the Cr-Fe u at lower temperatures is stable over a much wider composition range. The Mo-Ru u thus is closer to the other molybdenum u phases than to the Cr-Fe cr phase. The most striking feature of the Mo-Ru u phase, however, is the absence of any of the transition elements of the First Long Period.

Jan 1, 1956

By A. H. Larson, R. J. McClincy

The activity of Sb,03 in PbO-Sb,03 slags containing less than 50 mol pct Sb,03 was determined by the inert-gas saturation method at 700°C. In this composition range, the activity gf SbzO3 shows a strong negative deviation from ideality. The activity of PbO in these slags was calculated by application of the Gibbs-Duhem iniegration to the Sb203 activity data. The calculated activity of PbO in slags containing more than 63 mol pct PbO was found to deviate in a positive direction from ideality uthile a negative deviation was found for slags containing less PbO. The standard Gibbs free energies of formation of Sb,03 and PbO. Sb203 have been calculated and compared with existing data in the literature. The activity of Sb203 in PbO-Si0,-Sb203 (PbO/SiO, = 2) slags containing less than 25 mol pct Sb,03 was also determined by the inert-gas saturation method at 700°C. In this composition range, the activity of Sbz03 shows a very large negative deviation from ideality. VERY little experimental work has been published in the past to determine equilibrium data in the oxide systems connected with the refining of lead. These data are of value since impurities such as antimony, arsenic, and tin must be removed from lead and recovered for further treatment. Equilibrium studies on antimony and arsenic systems are also of interest for the design of new processes for lead refining and lead dross treatment. Maier and ~incke' first determined the liquidus curves for the PbO-Sb203 system and identified the compound PbO . Sb203. They found the phase diagram for this system to be two simple eutectics located on either side of the congruent melting compound. They also determined a very limited amount of vapor pressure data for Sb406 abbve PbO-Sba3 melts at 697"~. A second phase diagram investigation on this system was reported by Hennig and Kohlmeyer' who confirmed the existence of the compound PbO . Sb203 as well as the form of the diagram. A disagreement was noticed, however, in that their liquidus temperatures over nearly the entire composition range were higher than those reported by Maier and Hincke. Barthel~ and pelze14 redetermined the liquidus curve at the PbO-rich end of the PbO-Sb@, system and agreed very closely with the results of Maier and Hincke. None of the investigators mentioned above reported any mutual solid solubility in the PbO-SbD3 system. Zunkel and Larson5 have determined the phase diagram for the PbO-rich end of the PbO-Sb203 system by slag-metal equilibrium studies in the Pb-PbO-Sb203 system and by thermal analysis studies in the PbO-Sbz03 system. A maximum solid solubility of 5.6 mol pct Sb203 in PbO was observed at the eutectic temperature of 604°C. Their results for the phase diagram agree favorably with those of Maier and Hincke. The vapor pressure of Sb2O3 in the temperature range from 470" to 800°C has been determined by Hincke, using a modification of the transportation meth~d.~ His results for temperatures below the melting point of Sba3 are the only data reported in the published literature. The predominant vapor species has been shown to be Sb,06 by Norman and staley.? Myzenkov and Klushin,8 using the boiling-point method, have determined the pressure of Sb406 above liquid SbD3 in the temperature range from 715" to 1025°C. The agreement between these two studies is not very close. A portion of the discrepancy lies in the fact that Hincke used silica crucibles, which were attacked by the liquid Sbz03 at high temperatures. This fact does not account, however. for the large difference observed at the melting point. ~aier' gives a brief summary of vapor pressure data for Sb,O, above pure liquid Sbz03 which agree quite well with the data of Myzenkov and Klushin at temperatures near the melting point. This paper describes the determination of Sb2O3 activity data in the PbO-Sb203 and Pb0-Si02-Sb203 (PbO/SiOz = 2) systems by the inert-gas saturation method. These activity data are compared with the data calculated by Zunkel and arson. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade PbO (99.8 pct PbO, 0.14 pct insoluble in CHsCOOH, 0.02 pct not precipitated by HB, 0.1 pct CaO, and 0.08 pct SiOz), Sbf13 (99.6 pct Sb203, 0.004 PC~ C1-, 0.005 PC~ SO;-, 0.15 p~t AS, 0.001 pct Fe, and 0.03 pct other heavy metals such as Pb), and SiOz (chromatographic grade). Apparatus for Vapor Pressure Determinations. The apparatus used in this investigation consisted of a transportation reaction system with two separate gas trains. The argon transporting gas was first mixed with a small amount of hydrogen, metered, and dried by passage through silica gel and anhydrone drying tubes arranged in series. After this preliminary drying, the argon was passed through copper wool at 500°C to convert the residual oxygen to water vapor which was removed by three anhydrone drying tubes. A second stream of argon was metered and dried and then passed around the outside of the alumina reaction tube to flush away the volatile species to pre-

Jan 1, 1970

By P. K. Lucke

One of the interesting features connected with the great continental uplift, which formed the table land of Mexico, is the great depth to which oxidation and secondary enrichment of orebodies occurred. This table land lies at altitudes ranging from 4000 to 7000 ft. (1219 to 2133 m.) above sea level. Several cases could be cited of oxidized zones in copper and lead mines which reached depths of upward of 1500 ft. (457 m.) below the surface, and it is universally admitted that the oxidized zone in a mine is limited by the permanent water level. Mexico, however, like many other countries in which deserts occur, is visited at rare intervals by tremendous floods, which sometimes cause variable water levels over long periods. The following cases bear out the idea, and lead to interesting conclusions of commercial value. My paper demonstrates that carbonates of ores may occur below water level and sulfides above, and I will endeavor to explain the causes of the phenomena in certain specific instances. Case I.—Fig. 1 in this case shows that sulfides of lead remained

Jan 1, 1920