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By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By A. A. Jr. Smith, J. S. Smart

The controlled amounts of phosphorus, arsenic, sulphur or selenium found in commercial coppers perform a variety of highly useful functions. Indeed, a large segment of modern copper technology is essentially dependent upon the presence of one or more of these elements. Consequently, the literature contains many references to their effects but the scope is broad and has been only partly covered. New data are presented herewith directed toward a better understanding of the basic behavior of these elements in copper, with particular emphasis on the composition range o to 0.05 per cent. These data are a part of a general program of research on the effects of impurities on the properties of oxygen-bearing and oxygen-free copper, other portions of which have been reported previously. Schematically, the behavior of individual elements is determined from measurements of conductivity and softening temperature,'v2 and the binary alloys employed are synthesized from high-purity copper in order to eliminate interference from the effects of extraneous impurities. Alloys of selected composition were first prepared in the oxygen-free form by continuously casting the melts in the form of %-in. diameter rod. Oxygen was added subsequently to portions of the alloys, either by remelting or by diffusion at 8jo°C. from a surface scale. Test wires wcre drawn one B. and S. number per pass, using four 30-min. 600°C. anneals at 0.3125, 0.257, 0.204 and 0.162 in., and a final cold reduction of 75 per cent to 0.081 in. Oxygen-bearing slugs made by remelting nere hot-rolled to 4ia in.. drawn to 0.162 in., annealed for 30 min. at 6o0°C. and cold-drawn 75 per cent to 0.081 inch. The alloys containing phosphorus, having been compounded very early in the program, were prepared in the form of 3i6-in. rod, and processed to wire with only the last three intermediate anneals listed above, all of these having been conducted in commercial nitrogen. In addition, the conductivity anneals on these alloys were also performed in the same atmosphere, and the small amount of oxygen present as an impurity in the gas resulted in some loss of accuracy at temperatures of 700' to 8o0°C., as will be shown later. Subsequently, the anneals for all oxygen-free alloys were conducted in hydrogen to prevent oxidation, and purified nitrogen was employed only for oxygen-bearing samples. All conductivity anneals wcre of one hour duration followed by a rapid quench in 10 per cent HZSO*. Effect of Phosphorus The widespread use of phosphorus as a deoxidant has resulted in universal appreci-

Jan 1, 1946

By K. D. Jacob

IN the decreasing order of the tonnages involved, the uses of phosphates can be grouped conveniently into three general classes, namely, fertilizer; chemicals for military, industrial, and technical purposes; and mineral feed for livestock. The quantity of phosphate used as fertilizer, principally in the form of superphosphate, has always exceeded by far that used for all other purposes, though in recent years a marked increase has occurred in its consumption for the other two general classes of uses. Prior to the present century large quantities of superphosphate, as well as a considerable portion of the production of phosphorus chemicals, score made from bone materials which were plentiful and cheap in some areas and which could be more easily processed than phosphate rock for the manufacture of chemicals. Today, however phosphate rock has almost completely displaced bone as a raw material for the manufacture of chemically processed phosphates in nearly all countries of the world.

Jan 1, 1944

By E. T. Turkdogan

The activities of SiO2, FeO, and Fe2O3 are calculated from previous experimental data on the activity of oxygen in Fe-Si-O melts at 1550°C. Using the oxide-activity data, the free energy of formation of fayalite from its oxides is evaluated for 1550°C. A number of investigators1-4 contributed to the study of the state of oxidation of iron in SiO,-FeO-Fe,O3 melts and the phase equilibria in the system Fe-Si-O. In a more detailed study, Schuhmann and Ensio5 and Michal and Schuhmann% easured the state of equilibrium in the SiO,-FeO-Fe,O3 melts saturated with y-iron or silica or both under low-oxygen potentials and within the temperature range 1250" to 1350°C. Similar measurements were also made by Turkdogan and Bills7,' over wide ranges of composition and oxygen potentials at 1550"C. Using the experimental data on the oxygen activities in the ternary system, Schuhmann' calculated the activities of silica and ferrous oxide in Si0,-FeO-Fe2O3 melts for 1350°C. Adequate knowledge on the activities of the constituent oxides of melts is essential in the study of reaction-equilibria and reaction-kinetics in oxide-melts. With this in view, the activities of oxides in SiO2-FeO-Fe2O3 melts at 1550°C are computed using the experimental data of Turkdogan and Bills7'8 on the oxygen activities in these melts.

Jan 1, 1962

By Edward H. Bzirdick

THE territory under particular consideration in this article comprises portions of La Plata and Montezuma Counties, situated in the southwestern corner of Colorado, and around the base of the La Plata Mountains. (See Fig. 1.) In southeastern Utah and northeastern Arizona there are several mountain systems whose origin and structure are practically identical with the La Platas so that ore occurrences found in the latter can be hopefully looked for in the former. With this assumption, there is an area around the laccolithic ranges which offers promise for a successful exploration for gold ores. Ore occurrences of the Silverton, Telluride, Rico, or Ouray Districts will not be discussed, although in these areas the Mesozoic sediments are more or less involved within the ore-bearing complex. These have been intensively studied and developed. The idea is to set forth what my mining experience has been within the largely unaltered . Mesozoic horizon which remains around the extreme bases of the La Plazas. This, until recent years, has been almost entirely neglected by prospectors and operators and, so far as similar territory in Utah and Arizona is concerned, so remains.

Jan 1, 1934

By J. S. Browning

The pegmatites of the Kings Mountain-Lincolnton, N. C., area constitute the largest known domestic reserve of beryl and spodumene. The reserve is estimated to contain 90 million tons of pegmatic material with 1,280,000 tons of recoverable Li2O (lithia) as spodumene.1 The pegmatites also contain 0.4 to 0.5 pct beryl disseminated throughout the orebodies. The pegmatites may contain a potential reserve of 240,000 tons beryl, equivalent to approximately 34,000 tons of BeO. Different flotation methods for separating beryl from feldspar or quartz, or both, have been developed by various investigators.2,3,4,5,6,7 On the other hand, published information is limited on concentration of spodumene-beryl ores. As the response of beryl and spodumene to flotation is essentially the same, a successful separation of the two minerals depends upon use of a selective depressant or a selective collector for one of the minerals.

Jan 7, 1961

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By A. B. Parsons

LECTURE, it appears, is a discourse that is supposed to be instructive. I am quite sure that you will derive no instruction from what I have to say. I will be satisfied if my remarks provoke thought along one or two mental paths that have not been traveled so fre¬quently as to be devoid of interest. I have no particular message apropos of professional engineers or professional engineering, and any conclusions that I may seem to reach will be purely tentative and incidental. Probably at times you have wondered, in a casual way at least, why so many people who are not, never have been, and never will be engineers, want to use the title. For example, I recently received a communication from a life insurance broker or salesman, whose chaste letterhead bore the legend "Estate Engineer." He was perfectly serious about it, as is also the expert accountant who assumes the imposing name of cost-analysis engineer. Dozens of equally amazing titles might be cited. Then there is that class of individuals who have been engineers, in the true sense of the word; who have gone into some other kind of occupation; but who cling tenaciously to the name engineer, usually prefixing some word or other which at once gives them away by telling what their work really is. For example, we have such pseudomorphs as the management engineer, and the sales engineer. It is quite evident that engineer is a word to conjure with. Evidently both the man who appro¬priates the designation without any justification and the ex-engineer who persists in calling himself an engineer even after he has abandoned engineer-

Jan 1, 1933

By M. E. Wadsworth, I. B. Cutler, R. W. Bartlett

The oxidation kinetics of ZrC was studied between 450" and 580°C in oxygen pressures from 6.5 x 10-to 1 atm using a ther mogravimetric apparatus and sized powder samples. Two parallel rate controlling processes were observed. A surface reaction occurring at the ZrC-ZrO2 phase boundary accounted for most of the oxidation and had an activation enthalpy of 46 kcal per mole. The other process, believed to be diffusion of oxygen into the ZrC lattice partially replacing carbon, had an activation enthalpy of 53 kcal per mole. The enthalpy for chemisorption of O2 on ZrC was determined to be —13 kcal per mole. Water vapor in the presence of oxygen accelerated the surface reaction rate. THERE has been little reporting of formal rate studies or attempts to ascertain the mechanism of oxidation of carbides. MacDonald and Ransley1 studied the oxidation of titanium carbide which has the same structure as zirconium carbide, fcc. They observed an initial increase in rate with increasing temperature followed by a rapid decrease through a rate minimum and a subsequent second increase at higher temperatures. The discontinuity in the rate rise was attributed to a phase change in the oxide which changed the rate determining step from the surface reaction at the carbide-oxide interface to diffusion through the oxide layer. Samsonov and Golybera 2 studied titanium carbide and reported that during the initial period of oxidation a dense film of Tic-TiO was formed followed by the formation of less adhering layers of higher oxides. The purpose of this investigation was to study the kinetics of oxidation of zirconium carbide and to attempt to gain some knowledge of the mechanism by which oxidation occurs. EXPERIMENTAL PROCEDURE Measurement of the weight gain associated with the oxidation of ZrC was used to determine oxidation rates. The principal experimental parameters were surface area, temperature, and oxygen pressure. Although moderately sized crystals of ZrC can be grown by the Van Arkel method, the only commercially available ZrC is a powder. In using powders, the surface area must be controlled either by fabricating the powder into a sintered pellet with a measurable surface area, relatively fixed during oxidation, or by using sized unconsolidated powder and applying appropriate geometric considerations to the shape of the grains to correct for their diminishing surface areas as they oxidize. Both techniques involve some difficulties. pellets of binder-free zirconium carbide can be made by hot pressing, but it is difficult to obtain densities greater than 90 pct of

Jan 1, 1963

By Gordon H. Geiger, J. Bruce Wagner

Electrical conductavity and therrnoelectvic nzeasuretnents on synthetic hematite slabs with 0.01 to 0.90 at. pet Ti and with 0.30 at. pet Ca were made. Additions of titanium and of calcium both increased the electronic conductivity with titanium yielding greater n-type behavior and calciurn p-type behavior. Reduction studies of hematite to magnetite in CO-CO2 atmospheres between 600° and 900°C initially exhibited linear kinetics. These linear rates were increased by additions of titanium and decreased by calcium. IN recent years many studies have been reported in the literature on the kinetics of the reduction of hematite and magnetite to iron. In addition, Hansen and Josephl and Schenck and Schultz2 have reported studies on the reduction of hematite to magnetite, the first step in total reduction to iron. In order to evaluate the results of the studies of over-all reduction in terms of the actual mechanism of the reaction and to define further the important factors in the rate- controlling mechanism of the magnetic roasting reaction, the following experiments were undertaken. Specimens of undoped hematite and hematite containing titanium or calcium in solution as doping agents were reduced to magnetite in CO-CO2 mixtures. In addition, electrical-conductivity measurements were correlated with the reduction kinetics using concepts of defect solid-state chemistry. EXPERIMENTAL Fisher certified Fe2O3 powder was used to make specimens for both the electrical and kinetic studies (see Table I for analysis). Doping with titanium and calcium was accomplished by adding TiO2 and CaO powders to the Fe2O3 powder. The powders were mixed in a Waring blender for minimum times of 1/2 hr. Satisfactory blending was achieved based on comparison of analyses of individual specimens af- ter reduction. The specimens were formed in a steel die using opposed punches with a rectangular opening 10.0 by 40.0 mm. The Fe2O3-TiO, platelets were pressed cold at 16,000 psi. They were sintered for approximately 16 hr at 1075°C in air, in accordance with information in the literature3, 4 on the time and temperature needed to obtain solution of the titanium in the hematite. The Fe2O3-CaO mixtures were first cold-pressed at 20,000 psi and sintered for 3 hr at 1225°C to insure solution of CaO. This material was then ground to -325 mesh in a 6-in. ball mill and the resulting powder was used to make platelets in the same manner as above. The sintered platelets were usually between 1/16 and 1/8 in. thick. They were ground on a carborundum wheel and polished on 2/0 paper. Typical dimensions of the kinetic-study specimens were 1.6 by 0.8 by 0.05 cm, and a typical weight was 0.3 g. Conductivity and thermoelectric specimens were approximately the same size, but were subjected to further sintering in order to ensure maximum densification. Finally, all specimens were measured to the nearest 0.0005 in. and weighed on a Mettler H-15 balance to the nearest 0.0001 g and the density calculated. The average density of the specimens used for the reduction studies was 4.87 g per cc, or 7.1 pet total porosity. The standard deviation ranged from 0.14 to 0.063 g per cc within a composition group. In the present study, the apparent surface area as measured with a micrometer was taken as the true surface area. The chemical analyses for calcium and for titanium within a group showed maximum variations of 50.04 pet from the average values used in Figs. 9 and 11. In order to suspend the specimen from the balance for the kinetic studies, a hole, 0.03 in. in

Jan 1, 1965

By R. L. Minckler

PETROLEUM industry forecasts are constantly made and revised but are not in the nature of predictions. Particularly in the field of demand, many of the factors are far beyond control by the producing industry. Supply reacts on demand and demand reacts on supply. Competent economists in the oil business forecasted a year ago, on the basis of experience, that demand would now be at a much lower level than it is. This increased demand increased the price of crude oil and products, and in turn those increased prices have brought forth increased supply. A reduction in demand would lead to a reduction in supply. Shortages are now world-wide, and costs of secondary importance, so if there were extra supplies in California they would be moved into what are termed "unnatural markets." For example, Argentina is in the market today for California gasoline; that is an unnatural market because of the greater transportation distances from California to Argentina than from normal sources.

Jan 1, 1947

By R. Maddin, A. Lawley

Single crystal Mo-Re alloys (99.99+ purity), grown by electron bombardment floating zone heating, were deformed in tension at temperatures from -196° to +200°C. At -196oC, Mo-6 pet Re and Mo-20 pct Re alloys deform by slip on systems of the type (101) [1ll]. Above-78oC, the operative slip system is of the type (112) [111], (101) [1ll], or (211) [1ll], depending upon orientation. Mo-39 pct Re alloys deform by twinning and slip at all test temperatures with a (112) [111] type twinning system. Critical resolved shear stress for slip and twinning is calculated as a function of composition and temperature, and the mechanical properties compared with those of less Pure polycrystalline alloys. HEXAGONAL close-packed rhenium, c/a = 1.615, is highly soluble in molybdenum. The bee molybdenum-rich solid solution extends to approximately 42 at. pet Re* at 2500°C,' Fig. 1. Recent work on polycrystalline alloys has shown conclusively that the addition of rhenium to molybdenum improves both the fabricability and the low-temperature ductility.2"5 Similar behavior is observed for W-Re and Cr-Re alloys.5 Initially, Geach and Hughes2 found that the Mo-30 pct Re alloy could be cold rolled to approximately 90 pct reduction before the onset of cracking. The remarkable effect of the rhenium was later confirmed by Jaffee et al. 3-5 with an optimum condition of maximum strength combined with maximum ductility at the Mo-35 pet composition. At higher rhenium contents, the ductility was severely impaired due apparently to the presence of brittle tetragonal s phase, Fig. 1. In the Mo-35 pet Re alloy, at least 110 ppm (parts per million) oxygen could be tolerated before cold workability was reduced. By comparison, the corresponding tolerance figure in unalloyed molybdenum is ~ 10 ppm. The effect of rhenium was considered in terms of: 1) a reduction in oxygen solubility in the lattice; 2) a redistribution of intergranular oxide from grain boundary films to isolated spheres; and 3) the promotion of twinning as a further mode of plastic deformation. Paradoxically, twinning is often associated with brittle fracture in iron and the silicon irons.6'7 Work to date has been restricted to are-melted and powder metallurgy polycrystalline material of ~ 99.9 pet purity. The present investigation was initiated for the purpose of determining the mode and crystallography of plastic deformation of a series of bee Mo-Re alloy single crystals over a wide temperature range from -196o to +200°C. Using high-purity zone-melted material (~ 99.99 + pet purity), the specific role of rhenium in the molybdenum lattice may be understood more fully since effects due to grain boundaries and oxide redistribution will be absent. At the same time, the study provides a comparison of single and polycrystalline deformation behavior. EXPERIMENTAL TECHNIQUES A) Preparation and Purity of Single Crystals. Alloys in the form of either are-cast and swaged or sintered and ground bar, 0.120 in. diam, were obtained from the Chase Brass and Copper Co. Alloy single crystals ~ 8-in. long were grown from the

Jan 1, 1962

Established as a Division March 24, 1922 John R McMillan, '56, Chairman Claude R Hocott, '55, Past Chairman Thomas C Frick, '56, Vice-Chairman D W Akins, '57, Vice-Chairman Joe B Alford, Executive Secretary 800 Fidelity Union Building Dallas 1, Texas T A Pollard, Treasurer

Jan 1, 1954

(Members are urged to send in for this column any notes of interest concerning themselves or their. fellow-members.) Members and guests who registered at Institute headquarters during the period Nov. 10 to Dec. 10, 1914: H. F. Grondijs, Oruro, Bolivia. E. B. Kirby, St. Louis, Mo. R. W. Shumway, Denver, Colo. W. R. Webster, Philadelphia, Pa. J. N. Houser, Mascot, Tenn. F. S.. Titsworth, Denver, Colo. F. L. Clerc, Denver, Colo. Frank R. Wicks, Butte, Mont. Robert Sticht, Queenstown, Tasmania. C. Q. Schlereth, Denver, Colo. Francis C. Phillips, Pittsburgh, Pa. Robert Hallowell Richards was given a dinner on December 7 at Boston by the corporation, faculty and alumni of Massachusetts Institute of Technology in recognition of his 50 years as a devoted alumnus and teacher and as an expression of the respect and affection in which he is held.

Jan 1, 1915

By WALTER CARROLL

Between cross currents of economic factors and international expediencies the iron and steel industry in 1948 made an outstanding contribution to the general economic picture. Were it not for an unfortunate episode during the month of April involving a temporary shortage of coal, 1948 would have been an all-time record year in output. Exceeded in no previous peacetime year, the production of iron and steel in 1948 totaled some 88,500,000 tons. That it was a worthwhile effort of no small magnitude is evidenced by the fact that in three and one half years following the war, this nation has produced as much steel as in the five years preceding the war. This figure of 88,500,000 tons is 68 per cent greater than that for 1939.

Jan 1, 1949

By H. W. Imholz

Active interest in the North Central Texas area centered in the development of the Palo Pinto limestone-producing zone, near the town of Avoca, in the northeast part of Jones County. This producing horizon was discovered in 1937, in the Iron Mountain Oil Company's well No. 1 Olander, in sec. 196, B.B.B. & C. survey, at 3238 to 3250 ft. During the development of this pool, it was generally referred to as the Avoca pool. As a second pool has been discovered in the same producing zone, also near the town of Avoca, the writer has taken the liberty of changing the name of the original Avoca pool to Avoca-Olander pool. Forty producers had been drilled in the Avoca-Olander pool by the end of 1938; their initial ranged from 28 to 300 bbl. per hour. Stimulus was given to the interest in the development of the Palo Pinto limestone when the Ungren-Frazier No. 1 Griffin, in sec. 199, B.B.B. & C. survey, Jones County, found the limestone from 3225 to 3250 ft., with an initial production of 931 bbl. per day. (This new pool has been given the name of Avoca-Griffin pool, by the writer.) The best well to be completed, up to the present time, is the Bert Fields No. 1 Taylor in sec. 199, B.B.B. & C. survey, which had an initial production of 748 bbl. in 3 hours. The Owen-Snebold No. 1 McKeever in sec. 158, B.B.B. & C. survey, in northwest Shackelford County, added to the interest in the Palo Pinto limestone when it extended the Ivy pool with a well in the Palo Pinto limestone from 3145 to 3183 ft., and was estimated good for 6,000,000 cu. ft. of gas and 6000 bbl. of oil per day. During 1938, Stonewall County obtained its first commercial producer when the Stonewall Oil Co. in No. 1 Parriott discovered the Palo Pinto limestone saturated from 5169 to 5176 ft. and tested 371 bbl. per day. Two new producing horizons were discovered about 2 miles east of the old Noddle Creek pool, Jones County; the first, the Humble Oil & Refining Co. No. 1 Irvin, in sec. 48, block 18, T. & P. R. R. Co. survey, which had saturated limestone from 2550 to 2567 ft. and was good for 100 bbl. per day; the second, in the Humble No. 1 Horton, sec. 40, which

Jan 1, 1939

By H. W. Imholz

Active interest in the North Central Texas area centered in the development of the Palo Pinto limestone-producing zone, near the town of Avoca, in the northeast part of Jones County. This producing horizon was discovered in 1937, in the Iron Mountain Oil Company's well No. 1 Olander, in sec. 196, B.B.B. & C. survey, at 3238 to 3250 ft. During the development of this pool, it was generally referred to as the Avoca pool. As a second pool has been discovered in the same producing zone, also near the town of Avoca, the writer has taken the liberty of changing the name of the original Avoca pool to Avoca-Olander pool. Forty producers had been drilled in the Avoca-Olander pool by the end of 1938; their initial ranged from 28 to 300 bbl. per hour. Stimulus was given to the interest in the development of the Palo Pinto limestone when the Ungren-Frazier No. 1 Griffin, in sec. 199, B.B.B. & C. survey, Jones County, found the limestone from 3225 to 3250 ft., with an initial production of 931 bbl. per day. (This new pool has been given the name of Avoca-Griffin pool, by the writer.) The best well to be completed, up to the present time, is the Bert Fields No. 1 Taylor in sec. 199, B.B.B. & C. survey, which had an initial production of 748 bbl. in 3 hours. The Owen-Snebold No. 1 McKeever in sec. 158, B.B.B. & C. survey, in northwest Shackelford County, added to the interest in the Palo Pinto limestone when it extended the Ivy pool with a well in the Palo Pinto limestone from 3145 to 3183 ft., and was estimated good for 6,000,000 cu. ft. of gas and 6000 bbl. of oil per day. During 1938, Stonewall County obtained its first commercial producer when the Stonewall Oil Co. in No. 1 Parriott discovered the Palo Pinto limestone saturated from 5169 to 5176 ft. and tested 371 bbl. per day. Two new producing horizons were discovered about 2 miles east of the old Noddle Creek pool, Jones County; the first, the Humble Oil & Refining Co. No. 1 Irvin, in sec. 48, block 18, T. & P. R. R. Co. survey, which had saturated limestone from 2550 to 2567 ft. and was good for 100 bbl. per day; the second, in the Humble No. 1 Horton, sec. 40, which

Jan 1, 1939

By Lawrence H. Van Vlack

DISCUSSION, H. L. Burghoff presiding C. S. Smith (University of Chicago, Chicago)—The author is to be congratulated on his valuable contribution to the extremely meager absolute data on interface energies in metallic systems. It is interesting to note that the ratio between a and r iron boundary energies is approximately the same in the quaternary alloy with silicon, carbon, and sulphur as in the binary Cu-Fe alloy. A value for the copper grain boundary energy can be obtained from the author's data, Tables IV and VI, by utilizing the energy ratios of the following pairs of interfaces: copper-sulphide/copper, copper y iron, y iron/y iron, y iron/ copper, and copper/copper. This gives a value of 595 erg per sq cm for the free energy of the copper grain boundary. Despite this circuitous route and the assumption that the y iron boundary is identical in alloys with and without sulphur and does not change between 1105" and 100O°C, this figure is in remarkably close agreement with other values of the copper boundary energy, obtained by equilibration against lead and against the free copper surface. It therefore appears either that impurities do not greatly affect the grain boundary energies or that boundaries in even nominally pure metals are already sufficiently contaminated so that further change has little effect.

Jan 1, 1952

By D. Turnbull, J. H. Hollomon

THERE is a large body of evidence'" indicating that solidification during the liquid-solid transition is usually induced by heterogeneities present in the liquid. By dispersing liquid metals into small droplets, the impurities responsible for catalyzing solidification are isolated within a small number of these droplets. The effect of the foreign body therefore is restricted to a single drop by this technique. Thus upon cooling below the melting temperature, solidification is initiated by homogeneous nucleation in the majority of the droplets that do not contain impurities. In the case of solidification of liquid metals, the activation energy for nucleation is so great that its rate changes by orders of magnitude for a change in temperature of only several degrees centigrade.' Effectively homogeneous nucleation occurs at a critical temperature upon continuous cooling. Thus by microscopic observation of single particles during cooling, a temperature at which the rate of homogeneous nucleation becomes sensible can be determined.3 since at the temperatures at which nucleation occurs in the absence of impurities the rate of crystal growth is extremely rapid, the temperature at which the entire particle solidifies is very nearly the temperature at which the nucleation of the solidification occurs. Thus for liquids that freeze at high temperatures the onset of nucleation can be established by simply observing the temperature at which the marked heat evolution and increase in brightness of the particle occur. For liquids that freeze at lower temperatures the onset of nucleation can be determined by a rumpling and change in shape of the particle resulting from its solidification. The microscopic technique for observing the solidification of small particles has already been described." In earlier papers the nucleation of solidification of pure metals 5,6 and of alloy systems7 showing complete liquid and solid solubility have been described. In the present paper, the observations are extended to a simple eutectic system (Pb-Sn) where the possibility of the formation of two solid phases exists. Metals for the investigation were obtained from the American Smelting and Refining Co. in the form of pure lead and pure tin, 99.8 and 99.9 pct purity, respectively. An ingot of each of the pure metals was made into shot by heating the metals at a temperature about 50 °C in excess of the melting point and pouring the liquid slowly into a container of water at 15°C. Samples of the shotted pure metals were weighed out to make alloys containing 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, 80, and 90 atomic pct Pb. Samples of each alloy were then melted in separate beakers. Each melt was poured through a pyrex funnel into a cylindrical mold (% in. ID). The casting solidified in 10 to 20 sec. The inside of the mold as well as the funnel through which the metal was poured were coated with graphite to eliminate adherence of the metal. Analyses were performed on some of the compositions and are given in Table I. The compositions also were checked for these samples and for those that were not analyzed by determining the spread between the liquidus and the solidus upon melting the small metal particles. These measurements agreed as well with the nominal compositions as the analyses listed above. Results The results of the supercooling experiments for the several alloys are summarized in Table II and plotted on the constitution diagram in Fig. 1. Data for the pure lead and pure tin were taken from earlier investigations. The values for the maximum supercooling of the several alloys are the average of several determinations on a number of drops of each alloy. The maximum value in any determination was within about 2 pct of the average. For the alloys containing from 20 to 60 atomic pct Sn, inclusive, two marked changes of the surface structure were observed upon cooling. At the higher temperature, after the first appearance of the solid phase it continued to grow slowly at a constant temperature and then stopped. At the lower temperature the alteration of surface structure was abrupt. For the alloys containing from 70 to 95 atomic pct Sn, inclusive, an abrupt change in surface structure was observed at a single critical temperature.

Jan 1, 1952

By Edward Steidle

Those who have followed the rapid progress in rock-dusting bituminous-coal mines must admit that opinion crystallized during the year just closed in support of this preventive of coal-dust explosions. Up to 1924 only one mining company in America practiced rock-dusting on a large scale, but during 1924 forty-two companies had adopted this safety measure, and the "boom" is expected to extend over the next two or three years. Alabama is represented by 1 company, Colorado by 3, Illinois by 4, Kentucky by 1, New Mexico by 4, Pennsylvania by 20, Utah by 8, and Wyoming by 1. A total of about 500 miles of entry has been dusted. Illinois leads with 275 miles of dusted entries and Pennsylvania holds second place with about 175 miles. In each case there is a sense of great security, not only on the part of the operator but by the miner as well. It is also interesting to note that during 1924 the compensation rating or inspection bureaus in twelve of our coal-producing states revised their rating schedules so that a credit would be given for rock-dusting. This credit ranges from 10 to 20 cents per $100 payroll. Recent drastic federal and state regulations approved by mine operators made rock-dusting compulsory in bituminous coal mines in Utah, beginning July 1, 1924. Legislative action favorable to rock-dusting may be expected in other states. Colorado has already proposed a change in its laws, and Pennsylvania, Maryland, Washington, and West Virginia are giving the matter consideration. If the rock-dusting problem is handled properly and proves to be entirely successful, no mining man of any standing will delay applying it in his mine. State legislation regarding this matter may or may not solve the problem. At present, the mining companies that are rock-dusting of their own choice are doing it carefully and thoroughly. In Utah, some are doing it conscientiously, trying to get what benefits can be obtained while others are reported to be doing it only to keep within state regulations. In any event, if we are to have new legislation, it is essential that the various states know what they are about and then, if possible, work for uniform regulations.

Jan 1, 1925