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By L. F. Mondolfo, B. E. Sundquist

The undercooling associated with the nucleation of the secondary phase from the liquid by the solid primary phase was studied in sixty binary alloys by means of a hot-stage microscope. It was found that in a system of a and ß, a usually nucleates ß at low undercoolings, but ß does not nucleate a, except possibly at undercoolings approaching homogeneous nucleation. This behavior can be explained in terms of relative interfacial energies and shows that crystallographic disregistry is only a minor factor in heterogeneous nucleation from metallic liquids. PREVIOUS experimental work1-6 on nucleation of solids from liquids has shown that normally nucleation is heterogeneous, and that small solid particles present in the liquid are responsible for the nucleation. These experiments and the theory that has evolved from them have made apparent that there is a "characteristic undercooling" associated with the nucleation of the solid from a given liquid by a given impurity. Little is known, however, about the chemical and structural relationships between the nucleating agent and nucleated solid that control the effectiveness of the nucleating agent in catalyzing the nucleation, as measured by the required undercooling. A review of the literature has yielded seventeen undercoolingsL-6 for the nucleation of solid from liquid metals by "known" nucleating agents. All values come from experiments in which the metal studied was divided into a number of particles (10 to 300 pin diam.) much larger than the number of extraneous impurity particles so as to obtain a large number of particles free of foreign nucleating catalysts. Known nucleating agents are then introduced by coating the droplets with particles or a thin film of the catalyst. Six of the seventeen undercooling values referred to cases where, for various reasons, the identity of the nucleating species was not at all certain. Another six cases involved nucleating agents with a crystal structure that was not known. Four other cases involved undercoolings listed as greater than or equal to undercoolings which were very likely those for homogeneous nucleation. One investigation3 involved adding to droplets powdered oxides, carbides, and so forth that were doubtlessly covered with adsorbed oxide or nitride films. The highly variable nature of these films resulted in highly variable undercooling (as was also found in preliminary work in this investigation). It is apparent that the information on heterogeneous nucleation in liquid metals is too limited to give rise to any definite conclusions on the nature of the catalytic process. With these problems in mind a new method was

Jan 1, 1962

By N. M. Levine

This work defines and systematizes the physical factors of the problem of leaching and demonstrates for the first time the utility of macropore volume, micropore volume, specific surface, pore size distribution and permeability as parameters of leaching based on a study of the recovery of uranium from the Top Black member of Chattanooga Shale.

Jan 1, 1962

By Reed J. Irvine

One normally does not find sudden and dramatic changes in the investment climate, barring the unexpected outbreak of-wars or revolutions. Asia has seen a fair amount of military action and revolt during the past year, not all of it unexpected There was the fighting in Laos, which resulted in the as yet unconcluded negotiations which will probably lead to the establishment of a neutralist regime. In April of 1961 another revolution occurred in South Korea, and the elected government was replaced by a military dictatorship.. Communist guerrilla activity in South Vietnam was stepped up, and uncertainty about the future of that area increased. Relations between Pakistan and Afghanistan became more strained, and while no fighting has broken out, diplomatic relations between the two countries were broken off. India was both the victim of further incursions of her territory by communist China and the perpetrator of the forcible seizure of territory from Portugal. Indonesia has been making preparations for an armed attack on the Dutch in New Guinea.

Jan 1, 1962

By A. R. Taylor

This report describes the design, construction, and operation of a low temperature adiabatic calorimeter for measuring heat capacities of solids or liquids from 60° to 300° K. A brief discussion of the basic theory involved in chemical thermodynamics and the problems involved in obtaining accurate experimental data is presented. The operation of the calorimeter was tested by measuring the heat capacity of a sample of benzoic acid obtained from the National Bureau of Standards over a temperature range of 60° to 300° K. The measured heat capacity values of the benzoic acid compared favorably with similar values obtained by the Bureau of Standards, the maximum deviation being 0.5 percent. THEORY A brief discussion of the basic theory involved in chemical thermodynamics will illustrate the applications of heat capacity data and the problems involved in obtaining accurate experimental data.

Jan 1, 1962

By D. Bienstock

As part of the development of the hot-carbonate scrubbing process by the Bureau of Mines, the corrosion rates of steel in boiling solutions of potassium carbonate saturated with carbon dioxide and hydrogen sulfide were determined, and the effectiveness of various inhibitors was evaluated by Bureau researchers. The highly corrosive solution of carbonate saturated with carbon dioxide can be inhibited with a 0.2-percent concentration of either potassium chromate or sodium metavanadate. Solutions of carbonate saturated with carbon dioxide and hydrogen sulfide are mildly corrosive, 0.01 inch per year. Complete absence of corrosion is obtained with 0.2 percent sodium metavanadate or 0.15 percent vanadium pentoxide. Oxidizing inhibitors such as potassium chromate are destroyed in the alkaline sulfide mixture, N-alkyl trimethylene diamines, at a concentration of 0.1 percent, lower the corrosion rate to about 0.005. Sodium metasilicate, at a concentration of 0.6 percent, completely inhibits the corrosion but may deposit free silica in the system. Commercial cladding materials such as the epoxy coatings also prevent corrosion.

Jan 1, 1962

By K. T. Aust

The occurrence of annealing twins in high-purity aluminum resulted in the formation of grain boundaries having orientation relationships which correspond to a high density of coincidence sites. The results provide support for the coincidence site model and indicate that large-angle coincidence boundaries have lower free energies than large-angle noncoincidence boundaries. Observations are presented concerning the coherent structure of twin interfaces in aluminum and the importance of inter-facial energy in preferred orientation. RECENT experiments1 have shown that when an annealing twin is formed during grain boundary migration in zone-refined lead, a large-angle random boundary is replaced at the growth front by a large-angle coincidence site boundary. The coincidence site orientation relationships obtained by twinning were of the type considered by Kronberg and Wilson,2 Frank,3 and Dunn.4 On the basis of the theory of annealing twins advanced by Fullman and Fisher,5 these observations indicate that the energy of a coincidence site boundary is less than the energy of a random boundary by an amount which exceeds the energy of the coherent twin boundary. This energy difference between the coincidence and random boundaries must be at least about 5 pct since the ratio of twin boundary energy to grain boundary energy in zone-refined lead is 0.05 * .014.6 Fullman7 has found that the twin boundary energy in aluminum is about 21 i 5 pct that of a large-angle grain boundary. A twin boundary energy as large as this would be expected to exclude the formation of many coincidence site grain boundaries, especially those which have a relatively low density of coin- cidence sites. Therefore, if the coincidence site model is a useful interpretation of certain large-angle boundaries, then it would be predicted that only coincidence boundaries which separate adjacent crystals with a relatively high density of coincidence sites may be obtained as a result of twinning in aluminum. The present experiments provided a means of testing this prediction since annealing twins occurred during the growth of recrystallized grains into striated, melt-grown single crystals of zone-refined aluminum. EXPERJMENTAL PROCEDURE A striated single crystal of zone-refined aluminum, about 1 cm sq and 37 cm in length, was obtained during zone melting of aluminum of 99.996 wt pct starting purity in a graphite boat under helium atmosphere.8 A molten zone of 2 to 3 cm in length, which was maintained by induction heating. was passed along the length of the bar for eleven passes at a rate of 0.9 mm per min. An additional final pass was given at a rate of 0.2 mm per min. The center portion of the zone-melted bar was characterized by an electrical resistivity ratio between room temperature and 4.2° K of 8000 to 9000. Single crystals of 1 to 2 cm in length were removed from the center section of the zone-refined bar and electrolytic ally polished in a 2:l solution of methyl alcohol and concentrated nitric acid. The specimens were then chemically polished in Alcoa R-5 solution. X-ray analysis of the single crystals indicated the presence of striations or lineage substructure having misorientations as high as 2 deg. New, recrystallized grains were introduced into each striated crystal by the technique of artificial nucleation and growth, previously described.9 During the growth of the recrystallized grains at 300' to 600°C in argon, it was sometimes found that a

Jan 1, 1962

By John H. Lichtblau

There are three parties to the oil imports controversy: the domestic oil producers, whose side has just been ably summarized by Mr. Jameson; the oil importers; and the public. Domestic producers and importers are both motivated by economic self-interests, that is by their natural and legitimate desire for profit maximization, in their respective positions. Thus, domestic producers, rightly, regard every barrel of imported crude oil (with the exception of some specialty crudes) as a displacement of a barrel of their own crude. Hence, the lower the import Level the better they like it. Conversely, U .S. refiners whose plants are located at the seaboard or at certain inland waterways generally welcome a higher level of imports because refiner profits are based primarily on the spread between the crude oil price and the refined products price, since crude oil represents by far the refiner?s largest cost factor. The relatively low cost of foreign oil means therefore higher profits to those refiners able to process such oil, This applies particularly to integrated companies whose own domestic oil production is insufficient, to meet their refinery requirements but who have developed ample low-cost foreign oil supplies.

Jan 1, 1962

By Henning E. Soderberg

Yesterday, air pollution was somebody else's problem -- today, it is everybody's problem. The coal industry with thermal coal drying, is aware of their problem and the necessity of doing an acceptable job; however, there is much to be said as to how good a job is required and what performance limits should be set up. American Air Filter Company has been one of the pioneers in the solution of the thermal coal dryer dust problems, Because of high moisture content, products of combustion and occasional temperature surges, only wet collection has been considered as the practical approach. Our first installation goes back some 12 years with a total to date of 29 Individual wet collectors, each, fabricated of suitable corrosion-resistant material, at 14 operating plants. To eliminate a potential air pollution problem, a performance requirement of not more than approximately one-quarter (1/4) grains per cubic foot in the dust collector discharge was used. In nearly all installations, operating performance surpassed requirements, but discharge stacks were not entirely free of discoloration. However, plant nuisance and air pollution complaints were eliminated. This satisfactory performance was accomplished by medium priced wet dust collectors operating at a 4-6" W.G. pressure drop with cater drain requirements of about 1 gallon of drain water per 1000 cubic feet of air exhausted.

Jan 1, 1962

By R. W. Fountain, John Chipman

The solubility of nitrogen in Fe-B alloys (0.001 to 0.91 pet B) is determined by the Sieverts' technique for temperatures of 950° to 1150°C. The activity coefficient of nitrogen is decreased by boron. The three-phase equilibrium between ? iron, BN, and gas is established and also the four-phase equilibrium between iron, BN, Fe2B, and gas. The above equilibria are calculated for a iron. The relation of these data to hardenability and strain aging of boron-treated steels is discussed. BORON additions are known to enhanbe the hardenability of heat-treatable steels and to assist in the control of strain aging in sheet steel for deep drawing. The increase in hardenability is explained by the theory that adsorption of boron on austenite grain boundaries reduces their free energy and thus retards ferrite and upper bainite nucleation.l,2 Digges and Reinhart3 have shown that the full effectiveness of boron in commercial steels is achieved only when strong nitride formers such as titanium and zirconium are also present. The influence of nitrogen on eliminating the boron contribution to hardenability was also demonstrated by Shyne and Morgan.4 These workers prepared Ni-Mo steels containing either nitrogen or boron or nitrogen plus boron. The nitrogen-plus-boron steels showed the lowest hardenability which was attributed to the presence of stable nucleating particles, presumably nitride. Morgan and Shyne5-7 have shown that boron in the amount of 0.007 pet will completely eliminate strain aging due to nitrogen in low-carbon, open-hearth steels. In addition, by proper control of the boron additions, a rimming steel can be produced. Since the effectiveness of boron on hardenability and eliminating strain aging is influenced by the amount and distribution of the nitrogen in the steel, the present study was. undertaken to determine the influence of boron on the solubility of nitrogen in iron. EXPERIMENTAL PROCEDURE The solubility of nitrogen in Fe-B alloys was measured by the method of Sieverts, which consists of determining the amount of gas dissolved by the metal in a constant volume system. The apparatus employed in this investigation and the experimental details have beendescribed previously.B AMcLeodgage was added to the apparatus to allow measurements at very low pressures. The alloys were melted at reduced pressure in a basic-lined induction furnace using electrolytic iron and ferroboron. Ferroboron was added after the primary deoxidation of the iron with carbon. Since it was difficult to attain a constant low level of oxygen by this procedure, silicon was added after the carbon deoxidation and prior to the ferr obor on addition. The alloys were castas 2-in. sq ingots, heated in argon at 1050loC, and forged to 1/4-in. plate. After forging, 1116 in. was machined from each side of the plate to remove any possible contamination, and it was then cold-rolled to 0.010-in. sheet. The sheet was cut into approximately 1/4-in. squares and pickled in an inhibited H2SO4 solution to ensure a clean surface. In the case of the boron alloys, a hydrogen treatment could not be used for surface cleaning because boron losses resulted. The composition of the alloys is given in Table I. For a solubility determination, a 75-g sample was inserted in a quartz tube and sealed in place in the apparatus. The entire system was evacuated at room temperature and leak tested for 24 hr. If no leaks were observed, the system was heated to the temperature of measurement and again leak tested for 24 hr. If no leaks were detected, the hot volume and solubility determinations were begun. The hot volume was determined at a constant temperature for each run by admitting successive amounts of argon and recording pressure vs volume, which, in all cases, resulted in a straightline relationship. The argon was then removed and the procedure repeated with nitrogen. Successive additions were made until the desired nitrogen content of the metal and equilibrium pressure of the system were obtained. The

Jan 1, 1962

By H. A. Stoess

The Minerals Industry makes heavy demands for and on its Material Handling equipment. It also gives progressive management the opportunity for considerable savings, ad consequently increased profits. In some cases, cost of Materials Handling amounts to 40°/o of the total cost of the ultimate product. Handling costs are hidden in overhead, indirect labor, excessive maintenance, productive workers performing handling tasks, and, a great many more. Even though Materials Handling is the oldest occupation of mankind, it is only within the past twenty years that it has emerged as a specialized field. While this industry has made full use of all types of mechanical and vibratory conveyors, pneumatic conveyors in their proper application can be a distinct asset. me use of pneumatic conveyors by this industry however is limited- to a certain extent by the particle size of your products through the various phases of manufacture, as well as their bulk density. However, with increasing knowledge of the fluidization of dry materials, their use is becoming more wide spread.

Jan 1, 1962

By T H. Clark, R P. Doig, V. A. Saull, R B. Butler

Terrestrial heat flow has been determined for four boreholes in the Montreal area. The mean value of the results (uncorrected for glacial effects) is 0.790 ± 0.053 x 10-6 cal/ cm2/sec (95 per cent confidence limits). Thermal gradients were determined using a thermistor probe and d-c bridge, and also by a new method using a probe-contained phase-shift oscillator, the output frequency of the oscillator being a function of probe temperature. Thermal conductivity determinations were made on core from the boreholes, using a divided bar apparatus. INTRODUCTION T HIS paper concerns the terrestrial heat flow in the St. Lawrence lowland of Quebec, as determined from measurements on four of the numerous boreholes drilled in this region for gas and oil. The work has been supported by Geological Survey of Canada Re-search Grant 3-58, awarded to T. H. Clark and V. A. Saull. This sup-port is hereby gratefully acknowledged.

Jan 1, 1962

By A. A. Cochran

Methods of preparing small heats of steel containing radioisotopes were developed, and the techniques of stripping film autoradiography were used to detect and study the carbide and sulfide phases in titanium-bearing steels. Metallography had revealed areas of titanium sulfide and ferrite or pearlite adjacent to areas of titanium carbide and ferrite, and unidentified, irregular phases at the boundaries between these two areas. Sulfur 35 was used to deter-mine the extent of the titanium sulfide inclusions, and carbon 14 was used to delineate the titanium carbide phase. Individual radioactive areas were located with a resolution of approximately 10 microns. A general background exposure that was not correlated with microscopically visible phases was observed in the carbon 14 autoradiographs. The evidence from both sulfur 35 autoradiographs and carbon 14 autoradiographs indicated that the unidentified inclusions were sulfides rather than carbides. INTRODUCTION The use of radioisotopes to facilitate the work at the Rolla Metallurgy Research Center was expanded in fiscal year 1959 when the Bureau of Mines authorized the installation of an intermediate-level radioactivity laboratory. Before this time, sealed cobalt 60 sources had been employed for radiography, but no tracer work was done. The primary objective of the first experiments conducted in the new laboratory was to supplement physical metallurgy investigations of selected problems in steel research.

Jan 1, 1962

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962

By R. J. Allio, C. H. Randall

An automatic system for the quantitative analysis of microstrulcture has been developed. The method is based upon a statistical model of microstructure and employs phase intercept fractions as fundamental random variables. Structure-sensitive properties can be related explicitly to parameters derived from the distribution of phase intercept fractions in a matevial. THE properties of mechanical dispersions and of multiphase alloys art: intimately related to the amount, distribution, and intrinsic properties of the dispersed material. In many instances, the amount and distribution of the dispersed substances have greater influence on the over-all system properties than do the properties of the dispersed substance-Such properties as average particle size, particle size distribution, homogeneity of dispersion, volume per cent of dispersed phase, and mean free path between dispersed particles thus become critical in any evaluation of the properties of a dispersion. Unfortunately, techniques for evaluating quantitatively the microstructural characteristics of dis~ersions rapidly and accurately have not been available. If necessary, qualitative or semiquantitative devices can be utilized. Some such devices are based merely upon comparison of the specimens in question with arbitrary standards. Other techniques involve superposition of grids and tabulation of particles observed in different portions of the grid. Still other methods based upon lineal analysis entail counting lines or points at random upon the specimen to be examined; the number of intersections of the line with a given phase, the proportion of line or number of points which are covered by given phase are variously recorded. The mathematical basis for most of the techniques of quantitative metallography have been amply reviewed in the literature.'l2 without exctption, however, the standard techniques for quantitative metallography are either imprecise or are exceedingly tedious to apply. For example, tranverse integrating stage for rapid manual areal fraction measurement has been designed by Smith.3 Howerer, as in the case of any device based upon visual eslimation, operator bias may cause appreciable error. Various flying spot devices, on the other hand register particle size distributions in 2-dimensions, from which it is difficult to derive other properties of the dispersion. Thus, e.g., the 3-dimensional distribution cannot be inferred unless certain rather broad assumptions are made concerning the randomness of distribution and geometrical configuration of dispersed phase. Many limitations to the application of quantitative structural analysis can be overcome by the use of the microdensitometer, which is essentially an automated areal analysis device. Data obtained in the form of a distribution of phase intercept values are

Jan 1, 1962

By D. W. Rudd, D. W. Vose, S. Johnson

The permeability of Mo-0.5 pel Ti to hydrogen was investigated over a limited range of temperature and pressuire (709° to 1100°C, 1.i and 2.0 atm). The resulting permeability, p, is found to obey the The experimental data justifies the permeation mechanism as a diffusion contl-olled pnssage of Ilvdrogen atoms through the metal barrier. 1 HE permeability of metals to hydrogen has been investigated by a number of workers and their published results have been tabulated by Barrer' up to 1951. Since most of the work on the permeability has been accomplished prior to this date, the compilation is fairly complete. Mathematical discussion of the permeability process has been reported by Barrer, smithells, and more recently by zener. From these efforts several facts are observed. First, the permeability of metals to diatomic gases involves the passage through the metal of individual atoms of the permeating gas. This is evidenced by the fact that the rate of permeation is directly proportional to the square root of the gas pressure. Second, the gas permeates the lattice of the metal and not along grain boundaries. It was shown by Smithells and Ransley that the rate of permeation through single-crystal iron was the same after the iron had been recrystallized into several smaller crystals. Third, it has been observed that the rate of permeation is inversely proportional to the thickness of the metal membrane. Johnson and Larose5 verified these phenomena by measurirlg the permeation of oxygen through silver foils of various thicknesses. Similar findings were noted by Lombard6 for the system H-Ni and by Lewkonja and Baukloh7 for H-Fe. Finally, it has been determined that for a gas to permeate a metal, activated adsorption of the gas on the metal must take place. Rare gases are not adsorbed by metals, and attempts to measure permeabilities of these gases have proved futile. ~~der' found negative results on the permeability of iron to argon. Also, Baukloh and Kayser found nickel impervious to helium, neon, argon, and krypton. From what was stated above concerning the dependence of the rate on the reciprocal thickness of the metal barrier, it is seen that although adsorption is a very important process, at least in determining whether permeation will or will not ensue, it is not the rate determining process for the common metals. A case in which adsorption is of sufficient inlportance to cause abnormal behavior has been noted in the case of Inconel-hydrogen and various stainless steels.'' APPARATUS The apparatus used in this study is shown in Fig. 1. The membrane is a thin disc (A), but is an integral part of an entire membrane assembly. The entire unit is one piece, being machined from a solid ingot of metal stock. When finished, the membrane assembly is about 5 in. long. Two membrane assemblies were made; the dimensions of the membranes are given in Table I. The wall thickness is large compared to the thickness of the membrane, being on the average in the ratio of 13 to 1. There exists in this design the possibility that some gas may diffuse around the corner section of the membrane where it joins the walls of the membrane assembly, If such an effect is present, it is of a small order of magnitude, as evidenced by the agreement of the values of permeability between the two membranes under the same temperature and pressure. A thermocouple well (B) is drilled to the vicinity of the membrane. The entire membrane assembly is then encased in an Inconel jacket and mounted in a resistance furnace. The interior of the jacket is connected to an auxiliary vacuum pump and is always kept evacuated so that the membrane assembly will suffer no oxidation at the temperatures at which measurements are taken. The advantages of this configuration are: 1) there are no welds about the membrane itself, so that the chance of welding material diffusing into the membrane at elevated temperatures is remote. 2) It is possible to maintain the membrane at a constant temperature. Since the resulting permeation rate is very dependent upon temperature, it is advisable to be as free as possible from all temperature gradients. 3) It is possible to obtain reproducible results using different specimens. The only disadvantage to this configuration is the welds (at C) in the hot zone. The welding of molybdenum to the degree of per-

Jan 1, 1962

At the beginning of this year it was my pleasure and responsibility to take over the Presidency of our Institute from Mr A. A. Parish who, as did his predecessors, filled the office with distinction. It is a great privilege to address you as President and it is an occasion for my wife and family, and I am most grateful for your inviting them to the buffet dinner. Our Secretary (Miss Jacka), who processes all Presidents, has told me that there are neither questions nor discussions on Presidential Addresses, and that being so, I felt free to select a controversial topic. The address I have prepared is not strictly true to label; because I intend to include also the effect on agricultural production in Australia if Britain joins the European Economic Community (i.e. the Common Market).Three points of view are1. the European, which is one of equanimity deriving from the initial brilliant success of their scheme,2. the British, which is one of anxiety not to miss the bus, coupled with a commendable wish not to inimically affect existing Commonwealth arrangements,and3. the Australian, which is one of alarm.In England all are drawing their own conclusions on the subject and views range from the extreme desirability, to the extreme undesirability, of the United Kingdom joining.No one in Britain wants Australia, or New Zealand, to...

Jan 1, 1962

By James A. Whelan

The Bureau of Mines sponsored research studies of variables in rotary drilling, done in the Department of Mineral Engineering, University of Minnesota. By studying carefully controlled drilling with good instrumentation, it was hoped to obtain a better understanding of rock failure during drilling and of the stresses in drill bits during drilling. Experimental procedures and equipment are described. From these studies it was concluded that 1. Thrust requirements, other things being equal, are proportional to the total length of cutting edge in the bit. 2. Data from penetrating a wedge into rock under thrust only are not directly applicable to rotary drilling. 3, In rotary drilling the initial wear on a bit greatly decreases penetration rate under any given set of conditions; however, after initial wear the effect of wear on penetration rate is reduced. 4. An increase in rotary speed increases the overall penetration rate but decreases the penetration per revolution. 5. An increase in thrust increases the overall penetration rate and the penetration per revolution. 6, Torque on a drill bit is proportional to both penetration rate and bit diameter. 7. For small-diameter holes full-hole drilling will save both drilling time and energy compared with pilot drilling followed by reaming; for large-diameter holes pilot drilling-reaming is advantageous in both respects,

Jan 1, 1962

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.' The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By W. W. Weller

Thermodynamic values for scandium and its compounds are very sparse. This is evident upon examination of any of the commonly used compilations of thermodynamic data. For example, National Bureau of Standards Circular 5004 lists only four heat of formation values, two free energy of formation values, and four heat-capacity values for scandium compounds. The entropy of crystalline scandium is one of the most fundamental values that has been lacking. This Bureau of Mines paper reports heat-capacity data for scandium metal in the temperature range from 50° to 298° K., together with the entropy value at 298.15° K. derived from these data through application of the third law of thermodynamics.

Jan 1, 1962

By W. D. C. MacKenzie

IT IS almost exactly fifteen years since the discovery of the Leduc oil field and, as this luncheon is part of the Thirteenth Annual Technical Meeting of the Institute's Petroleum and Natural Gas Division, it seems, therefore, a singularly appropriate time to discuss the theme which the program committee has suggested for the occasion -the progress of the Canadian oil industry during the fifteen years since the discovery of the Leduc field. As you will see, I plan to take a few minor liberties with this suggested theme. I shall present ample evidence of growth and progress, but, at the same time, I want to refer to some areas where progress has been anything but conspicuous and to see what can be learned from these areas for the future. The achievements of the Canadian oil industry since the Leduc discovery in 1947 have been substantial, and the public is relatively familiar with the more spectacular developments.

Jan 1, 1962