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By E. Gregory, A. Coucoulas

Carbm dioxide, which exists metastably as a constantly subliming molecular solid in a normal room-temperature environment, has been shown to exhibit many microstructural features which are similar to those observed in metals and ceramics at temperatures approaching their melting points. An examinution has been made of some of the factors affecting a brittleness condition known as "smzdiness" which occurs in solid carbon dioxide. It has been shown to be highly dependent on manufacturing and storage conditions and is thought to be a marked intergranu-lay brittleness which results from a combination of excessive grain growth and a concentration of gas-filled pores at the grain boundaries. In the course of an investigation carried out to explain certain physical and mechanical properties of solid carbon dioxide, observations were made of the microstructure and fragmentation of samples after fabrication and storage under varying conditions. Many similarities between the structures of solid carbon dioxide observed under ambient conditions and those existing in metal and ceramic systems at temperatures approaching their melting points have been observed. There are, however, important differences between solid carbon dioxide and the common metallic and ionic solids which result primarily from the differences in the nature of the bonding forces. Despite these differences, the relative ease with which certain microscopic observations can be carried out, may make solid carbon dioxide a useful material model for the physical metallurgist and the ceramist. It could also prove a valuable material for educational purposes where it is required to illustrate grain phenomena which normally can only be seen with the aid of a high-temperature microscope, and after prolonged chemical or thermal etching.

Jan 1, 1963

By P. Duwez, C. B. Jordan

The phenomenon of the change of volume of pressed powder compacts upon sintering is well known in the field of powder metallurgy. Depending upon the metal or metals involved and the pressure used in forming, a compact may, in the course of time of sintering at a given temperature, expand mono-tonically, contract monotonically, or first show a volume change of one sign followed by a change of the opposite sign. It is clearly desirable to have accurate knowledge of the magnitude and sign of the change in dimensions to be expected in any given case, both from the point of view of direct usefulness in the fabrication of parts by powder metallurgy, and from the longer range viewpoint of elucidating the fundamental mechanism of metallic sintering. The present study was therefore undertaken as a first step in acquiring systematic and reasonably quantitative knowledge of the change in density of metal powder compacts during sintering. For practical reasons, copper was selected as the material to be studied first, and its densification followed as a function of temperature and time of sintering in hydrogen and in vacuum. Experimental Procedure The copper powder used was that designated by the manufacturer (Metals Disintegrating Co., Elizabeth, N. J.) as MD-151. This powder was sifted through Tyler standard screens to separate the fraction having particle size range between 200 mesh and 325 mesh, and this fraction was used in all the subsequent work. Compacts weighing about 10 g were then pressed in a 1 in. diam round die, using a pressure of 20,000 psi throughout. Sintering was carried out in commercially built electric furnaces in which the resistance windings are so disposed as to produce a nearly uniform temperature along the axis of the furnace for a length of about 18 in. centrally located. In order to be able to sinter in a controlled atmosphere, a 2 in. stainless steel tubing was inserted in the furnace. Each end of the tube was cooled by a water jacket about 7 in. long, and closed with a rubber stopper. The hydrogen used for one series of specimens was purified as described in Ref. 1. For the other set, a pressure of about 0.5 mm Hg was maintained during sintering by a Welch Duo-Seal Pump. The specimens were heated on square trays made of stainless steel. In placing specimens in the trays, a thin even layer of powdered aluminum oxide was first sprinkled on the bottom of the tray. A copper guard disk about half the thickness of the specimen was then placed in the tray and covered with a second layer of alumina. The actual specimen was then set on the guard disk, and a final coat of alumina sprinkled over the specimen. This technique was evolved for sintering the specimens in such a way as to reduce the influence of unknown extraneous factors to a minimum. If the specimen is placed directly on the tray and sintered, it is found that the resulting shape is that of a frustum of a cone, rather than a section of a right circular cylinder, since friction with the tray prevents the bottom of the specimen from contracting at the same rate as the top. In the arrangement used in these experiments, the guard disk provided a support which shrank at the same rate as the specimen, and the alumina powder reduced to a minimum friction between guard disk and tray, and between specimen and guard disk. The procedure followed in sintering consisted of bringing the furnace to the required temperature, and then inserting the specimen into the central heated portion of the furnace tube in one of the two atmospheres used. At the end of the heating period, the specimen was cooled by bringing it into a portion of the furnace surrounded by a water jacket. These manipulations were carried out without opening the furnace, by means of rods which were attached to the trays and operated through a sliding seal in the rubber stopper. The progress of densification of the copper compacts was studied at 1300, 1400, 1500, 1600, 1700, and 1800°F. At each of these temperatures, a specimen was allowed to sinter for each of the following time intervals: M, 1, 2, 4, 8, 16, 32, and 64 hr. The thickness and diameter of each specimen were measured with micrometers before and after sintering, and each was weighed on an analytical balance after sintering. Results The techniques described in the preceding section were found to give satisfactory results. The specimens were not detectibly warped after sintering, and were usually of uniform diameter (that is, truly round) to within 0.001 in., a very few showing a variation in diameter of ±0.002 in. All specimens were found to have the same diameter

Jan 1, 1950

By Carle R. Hayward

This work was first undertaken in the metallurgical laboratory of the Massachusetts Institute of Technology in 1907 by L. A. Dickinson, E. Phelps, and V. S. Rood, under the author's direction. They attempted to determine the diagram for the system Cu2S-MiS, but several inexplicable results were obtained. The following year, P. H. Mayer with Mr. Dickinson carried on some experiments with nickel sulphide and found that the molten material slowly lost sulphur until it reached a composition corresponding to the compound Ni3S2, established by Bornemann.l At this point the composition remained stable. The freezing points of the mixtures gradually fell off with the loss of sulphur. Since the above facts seemed to explain the erratic results obtained in the first experiments, Mr. Mayer with F. Jaeger attempted in 1910 to establish a correct equilibrium diagram for the Cu2S-Ni3S2 series. They prepared pure Cu2S and Ni3S2 and determined the cooling curves for various mixtures. The fusions were made in a platinum resistance furnace and the temperatures were measured with a platinum-iridium thermocouple connected with a Sullivan galvanometer. The curve was established for mixtures containing more than 40 per cent. Cu2S, but they were unable to determine certainly the direction of the curve beyond that point. Nothing further was attempted with this series until the present year, when the work was carried to a successful conclusion with the assistance of A. Butts, Jr., and E. H. Weil. The results of this work are given in the following pages. Preparation of Cu2S.—A piece of cathode' copper from the Buffalo plant of the Calumet & Hecla Co. was cut into shavings by a shaper and converted into sulphide by heating in boiling sulphur. A porcelain casserole was used for the purpose, the heat being furnished by a Bunsen burner. It was found that after boiling in the sulphur for an hour the copper shavings were completely converted into sulphide. The liquid sulphur was then poured off, leaving the solid sulphide in the casserole in

Jan 1, 1915

By Sir James Kitson

By the courtesy of the President and Council of the American Institute of Mining Engineers, I have been invited to take the chair and open the proceedings of this congress. It is a graceful compliment to those members of the Iron and Steel Institute who are your honored guests at this moment—an acknowledgment of high consid-

Jan 1, 1891

By Alfred James

Some months since, in the Johannesburg gold-fields of South Africa, the attention of the author was directed to certain statements to the effect that the gold-contents of foul or extremely dilute cyanide-solutions could not be effectively precipitated in practice by the usual zinc-method. Such statements caused all the greater surprise, because it is well known that this difficulty is not encountered in other wellknown districts, as, for example, in New Zealand, where solutions containing less than 0.05 per cent. of KCy are regularly reduced in practice to below 1 grain of gold per ton, while in Mexico and the United States almost equally satisfactory precipitations are not uncommon. As a result of these representations, however, the author visited several plants at work in the Transvaal, and noted that while at some few mines the precipitation was really excellent, at others the effluent, after treatment, was much too high in bullion-contents. An investigation into the causes of these unsatisfactory results disclosed the fact that more attention to the close packing of the zinc-shavings in the extractor-compartments tended to improve the results, even with the most dilute solutions. The function of the zinc being one of surface, it stands to reason that a compartment well filled with zinc would be more effective than a half-filled one. Moreover, the quality of the zinc was inferior. This should be in long, tough, thin, light threads; light enough to ignite readily, and tough enough not to disintegrate easily into a slime. The coarse shavings too frequently employed appear to give the reverse of the best practice ; they are brittle, contain less surface, and take up more room. It is almost impossible to pack a compartment properly

Jan 1, 1898

By L. P. (Les) Haldane

Building a small underground coal mine is a risky endeavor, especially in the recent economic environment. ARCO's Mt. Gunnison No. 1 Mine, located in western Colorado, was designed and built as a small expandable speculation mine with initial production to be sold on the spot market, so it was very important to minimize capital exposure. This mine, operated by West Elk Coal Company, a subsidiary of Anaconda Minerals, was successfully built under budget at $35 million, and has been operating successfully since completion of construction in late 1982. The initial planning phase of a project is extremely important for testing the economic and technical feasibility of a proposal. The construction phase, by contrast, carries with it significant cost and quality risks which can relate to long-term economic and operating problems and therefore directly affect the viability of the project. This paper discusses several different aspects of the cost overrun risk involved in building an underground coal mine, and how attempts were made to minimize these risks during construction of the Mt. Gunnison Mine. Good people, construction planning, and execution are essential factors in assuring a quality, cost-effective project, with corresponding risk minimization during the construction phase and long term favorable implications for the operating phase.

Jan 1, 1985

By D. E. Etter, J. E. Selle

HIGH-PURITY cerium metals, supplied as 99.9 pct pure, by various suppliers, vary widely in melting points and in the shapes of the differential thermal-analysis curves obtained as the samples are heated. A definite correlation is noted between the melting point, amount of premelting, and the number of inclusions present in the material. Briefly, the DTA apparatus, previously de-

Jan 1, 1964

By George H. Ashley

It has been said that the Pittsburgh bed is the most valuable single mineral deposit yet known to man. The figures in Table 1 are presented in substantiation of that claim. Production and Value In order that the figures of Table 1 may have any weight, a statement must be made to show how they were arrived at. Because, to the writer's knowledge, no accurate separate figures ever have been kept of the production and value of the Pittsburgh coal bed, the states will be considered separately. Pennsylvania Accurate figures are obtainable for Pennsylvania for recent years because recent reports of the Pellnsylvania Department of Mines show the production from each mine and the bed worked at each mine. For recent years, therefore, it is only necessary to list the mines working in the Pittsburgh bed and add up their production. The value was obtained by treating each county separately, applying the average price for the county to the production of Pittsburgh coal in that county. Unfortunately for great accuracy, while production figures for individual mines are available for many years, the name of the bed being

Jan 1, 1938

By George H. Ashley

It has been said that the Pittsburgh bed is the most valuable single mineral deposit yet known to man. The figures in Table 1 are presented in substantiation of that claim. Production and Value In order that the figures of Table 1 may have any weight, a statement must be made to show how they were arrived at. Because, to the writer's knowledge, no accurate separate figures ever have been kept of the production and value of the Pittsburgh coal bed, the states will be considered separately. Pennsylvania Accurate figures are obtainable for Pennsylvania for recent years because recent reports of the Pellnsylvania Department of Mines show the production from each mine and the bed worked at each mine. For recent years, therefore, it is only necessary to list the mines working in the Pittsburgh bed and add up their production. The value was obtained by treating each county separately, applying the average price for the county to the production of Pittsburgh coal in that county. Unfortunately for great accuracy, while production figures for individual mines are available for many years, the name of the bed being

Jan 1, 1938

By H. R. Thresh, A. F. Crawley, D. W. G. White

The densities of liquid tin, lead, and Sn-Pb alloys have been measured over a range of temperature above the liquidus. In all cases, data can be adequately represented by an equation of the type p = a + bT. For pure tin, the values of a and b are, respectively, 7.139 and 7.125 x 10-4, and for pure lead, 11.060 and 12.220 x 10-4. At constant temperature, molar volumes in the Sn-Pb system vary linearly with composition. DURING the course of a long-term program at the Department of Energy, Mines and Resources, Ottawa, Canada, the densities of liquid tin, lead, and Pb-Sn alloys were studied. The work reported herein draws on two sets of results independently achieved by Thresh, on the one hand, and by Crawley and White, on the other. EXPERIMENT The method and apparatus were originated by Thresh and have been described in detail in Mines Branch reports.172 In operation, the 14 cu cm graphite pycnometer is put in the furnace as shown in Fig. 1 after a machined charge has been placed inside the pycnometer and the lid screwed down. The dimensions of the charge are such that, upon melting, a small excess of liquid metal is discharged through the capillary hole to displace the weighted float above. When the pycnometer has been equilibrated at the experimental temperature, the

Jan 1, 1969

By Leo Tarasov

MAGNETIC torque studies of ferromagnetic single crystals have been carried out in a number of laboratories during the last decade1,2 and some work has been reported on polycrystalline material showing preferred orientation. Goss3 used the method extensively in developing electrical sheet with desirable magnetic properties, but he used it as a control rather than as a means of studying the texture. Bozorth4 made a quantitative correlation of a torque curve he obtained from some cold-rolled iron with the texture as determined from X-rays, but did not extend his studies beyond the one specimen. Other studies, which have been reported from time to time 1.5 have also been incomplete in the sense that no effort was made to study a whole series of samples, differing only in degree of cold reduction, or in the annealing temperature, in order to ascertain the effect of such treatments on the texture as revealed by torque measurements. It is the purpose of this investigation to make such a study, mainly in order to see how useful the method can be made when used under favorable circumstances and to find what kind of a correlation can be expected between magnetic and X-ray studies of texture. Before proceeding further, it is desirable to say a little about single crystals, so as to make clear the concepts involved in magnetic torque measurements.

Jan 1, 1939

By F. Louis Grammer

The rapid advances on the mechanical side of blast-furnace practice have not always been accompanied by a proper appreciation of the metallurgical requirements. This is illustrated occasionally by the improper use of automatic barrow chargingdevices and bins (introduced at the expense of accuracy in weight), with ores of irregular composition or ores that have been poorly graded. The 100-ft. blast-furnace has not always been advantageous, and in many instances the increase in the number of tuyeres, from 8 or 12 to 20, has resulted in decreased output. The data pertaining to this division of blast-furnace practice are now sufficiently complete to allow inferences to be made. The use of fine ores has indicated the manner in which large outputs could be obtained, as it has emphasized the fact that intimacy of contact. between gases and ore, and coke and air, were more important than the time of exposnre. It was reasonable to suppose that if more points of contact were made between the air and the coke, their union would occur in a shorter period of time, and the coke would be burned more rapidly in the same-sized hearth, and an increased output thereby obtained. In consequence of this theory, many furnace men upon relining a furnace increased the number of tuyeres from 8 or 12 to 20, or even more, frequently with unfortunate results. If the number of tuyeres in an old furnace is

Jan 1, 1904

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By M. B. Bever, A. M. Reti, A. K. Jena

The results of this investigation show that in the system SnTe-PbTe l) the solid solutions have small exothermic heats of formation relative to the binary compounds, 2) solid-solution hardening is almost absent, 3) the tin and lead atoms are .randomly distributed on the sublattice occupied by them and do not undergo an ordering transition during a thermal treatment designed to promote such a transition, and 4) the lattice parameter changes linearly with composition. These findings suggest that the solid solutions of tin telluride and lead telluride approach ideal behavior. THE binary compounds SnTe and PbTe form a continuous series of solid solutions.' Information on several physical properties of these solid-solution alloys has been published.1"3 In the work reported here, the heats of formation, microhardness, and lattice parameters of these alloys have been measured and the possibility of an order-disorder transition has been investigated. Order-disorder transitions occur in some solid solutions of binary compounds. In the system Bi2Te3-BizSes, for example, the electropositive bismuth atoms and the electronegative tellurium and selenium atoms always occupy separate layers. In the disordered alloy Bi2Te2Se, the tellurium and selenium atoms are randomly distributed on the layers occupied by them, while in the ordered alloy they occupy distinct layers.4 The NaC1-type (Bl) structure of SnTe-PbTe alloys consists of two sublattices, one of which is occupied by the electropositive tin and lead atoms and the other by the electronegative tellurium atoms; any ordering would be expected to occur in the sublattice occupied by the tin and lead atoms. PREPARATION OF SPECIMENS Polycrystalline specimens of PbTe and Sn1-xPbxTe (x = 0.25, 0.50, and 0.75) were prepared by melting stoichiometric amounts of lead (99.999 pct), tin (99.98 pct), and tellurium (99.999 pct) in evacuated and sealed Vycor tubes. Because of the deviation of tin telluride from the stoichiometric composition5 this compound was prepared by melting 49.8 at. pct Sn and 50.2 pct Te. The tubes containing the melts were quenched into water; the solidified ingots were removed from the tubes and annealed for 2 weeks in vacuum (PbTe approximately 100°C below its melting point, the three alloys 100°C below their solidus tem-

Jan 1, 1969

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

By D. J. Mack, J. A. Mullendore

MUCH work has been reported in the literature on the separation of individual phases in steels, particularly carbides, for the purpose of structural and chemical analysis. The methods usually involve separation of the particles from the matrix by chemical or electrochemical methods. Another .group of alloys ideally suited for selective removal of one phase is the commercial aluminum bronzes. Al-

Jan 1, 1959

THE second operation in the art of casting, and one of the greatest importance, is that of melting and thoroughly liquefying the materials of which you wish to make your casting. On this operation depends the whole outcome of your intentions and the perfection of your work. Without it, even though you had a great abundance of moulds and vast quantities of bronze, your desires, labor, and expense would all be in vain. In this operation I find on consideration that, in addition to experience, there are three necessities-perhaps indeed four-that must be provided without fail. The first is the furnace or other agent which contains the fire and the metal brought together. The second is the wood or charcoal which is the necessary and proper nutriment of the fire, from whose virtues are derived the greater or lesser forces which, according to their kind, are ready to effect what is required. The third is to have the materials disposed to easy fusion by means of corruption, alloying, or by their own nature. The fourth, as the motivating cause of the whole, could perhaps be listed as the first-this is the ingenuity and good judgment of the worker, together with the bodily exertions not only of himself but also of his helpers in addition. For, besides a certain ordinary caution, it is necessary to pay particular attention, first, to see that the furnaces, machines, ladles, hearths, refineries, and other kinds of instruments or similar vessels be made so as to dispose the metals for melting, and, when melted, that they easily maintain them so. These should also be prepared in such a way that they cannot be injured by the fire, for if they should be damaged the operation would fail. In order to do this, it is first necessary that you arrange the instruments with forethought and action so that the power of the fire can operate. Fire operates on things only when brought together with them in long-continued operation, or when driven by a great force of wind. It burns many things and softens others, but it makes the metals as liquid as water.

Jan 1, 1942

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By Elton A. Youngberg

The Holden mine operated by the Chelan Division of the Howe Sound Co. is on the east slope of the Cascade Range in north central Washington on the south slope of Railroad Creek valley at an elevation of 3500 ft. The mine may be reached by a 40 mile boat trip from the town of Chelan which is at the southern tip of Lake Chelan, to Lucerne at the mouth of Railroad Creek and an 11. mile bus ride up Railroad Creek to Holden. A11 freight and concentrate is moved over this route to Chelan Falls on the Columbia River which is on the railroad four miles below the town of Chelan. The mine is now producing 2000 tons of gold, copper, and zinc ore per day which is treated in the Holden mill. Gold-copper and zinc concentrates are made, the first of which is shipped to Tacoma, Wash., and the latter to Kellogg, Idaho, for smelting. Ore is broken by long-hole blasting using the Noranda system which has been modified to meet local conditions. Until recently, blastholes have been drilled by diamond drills. Now a partial substitution of percussion drill holes, drilled with tungsten carbide insert bits, is being made. Geology The ore body occurs as a replacement deposit in a highly metamorphosed series of sedimentary rocks, mainly gneiss and schists, in a shear zone several hundred feet in width and of undetermined length. Commercial ore has been found in mineable widths of 25 to 100 ft for approximately 2500 ft along its strike. The commercial minerals are chalcopyrite, sphalerite, and gold. During the period of mineralization considerable silicifica-tion took place giving the ore an abrasive drilling characteristic. Following the period of mineralization, numerous dikes were introduced into the ore body. The earlier ones were of granite composition having a width of a few inches up to 80 ft. These were followed by much younger, fine grained basic dikes which usually do not exceed 2 ft in width. Development of Percussion Blasthole Drilling Equipment Test work with the 1½-in. tungsten carbide bit was carried on in development headings for several months early in 1947. The short life of the bits, because of gauge loss caused by the abrasive nature of the rock, prevented its adoption for this use. However fast drilling speed and ability to drill a long uniform hole suggested its use for drilling blastholes in competition with diamond drills as diamond costs were steadily increasing and exper-ienced drillers were difficult to obtain. The 1½-in. bit was the largest available at the time initial test work was started with sectional steel. The 1½-in. hole limited the diameter of the steel thread and coupling which could be used. Type F couplings were first used but because of the small thread section excessive breakage of the steel was experienced. Type H couplings were tried next. In order to use this coupling which is 15/8 in. in outside diameter, it was reduced to 1 3/8 in. giving 1/8 in. clearance between the coupling and the hole. Rod breakage at the thread was substantially reduced but some coupling breakage was experienced, however the overall performance was considered satisfactory (see Fig 1 for illustration of coupling and thread). Early test work with the 1½ in. bit indicated machines of piston diameters larger than 255 in. would cause inserts to loosen or break. It was found however that the additional weight of the sectional steel cushioned the blow enough to prevent bit failures when 3-in. Leyners were used. Rods used with the 1½-in. bits were 7/8 in. q. o. for sectional steel and 1 in. q. o. for all chuck pieces. In May 1948, 2-in. tungsten carbide bits became available and test work was immediately started. The 2-in. hole approximated the AX (1 15/16 in.) diamond drill hole which was being used exclusively for blastholes and permitted their substitution for diamond drill holes in a ring without alteration of pattern, burden, or explosives. The 2-in. bit also gave room in the hole for larger couplings and permitted the use of heavier rods and 3½-in. machines, increasing the

Jan 1, 1950

By Edmond S. Miksch

The morphology and growth rate of ice grown in supercooled water are markedly affected by convection of the water. A dendritic ice sheet with water flowing past the dendrite tip exhibits deflection of the dendrite spine toward the upstream direction, accelerated growth of secondary spines on the upstream side, and suppression 01" secondaries on the downstream side. Flow causes a thin disk to become corrugated, the corrugations being parallel to the flow. Flow causes an increase in the growth rate of the ice. IF a small seed of ice is placed in slightly supercooled water, it grows initially as a disk with the axis of the disk parallel to the c axis of the ice crystal.' It appears that growth in the c direction is inhibited, while growth occurs with equal facility in all directions in the basal plane. It appears that growth rate as a function of interface temperature is very nearly equal for all directions similarly oriented relative to the c axis. Subsequent to the discoid growth, branching occurs and dendrites develop. The primary dendrite spines grow parallel to the six equivalent a axes of the crystal. Secondary, and in some cases, tertiary spines also grow in these directions. The highly anisotropic: dendritic growth indicates that there must be some finite difference of growth rate for different directions in the basal plane. These differences must be quite small, however, since if they were large, the discoid mode would not occur. Hence, it was expected that the dendrite growth direction could be deflected from the crystallographic direction by perturbation of the thermal field at the dendrite tip. Experiments were done in which perturbation of the thermal field was accomplished by causing the supercooled water to flow past the dendrite tip. The flow direction was perpendicular to the c axis of the crystal, and was perpendicular to the primary spine of the unperturbed crystal. Supercooled water was supplied by a 15 cm cubical copper box, which was refrigerated and insulated so it could cool water to temperatures down to —2oC, and maintain the temperature constant to O.l°C for the duration of a run. A lucite channel of rectangular cross-section, 12 by 24 mm, was mounted horizontally in the box, with one end open so water could flow into it, and the other end leading out through the wall of the box to a length of tubing leading: to an orifice plate 123 cm below. cnunMn s MIKSCH, MemberAiMe, formerly Research Associate, Research Associate, Fig. l(b)—Vertical section of apparatus A horizontal cross-section is shown in Fig. l(a), and a vertical section is shown in Fig. l(b). Means for observing the ice are shown in Fig. l(a). Collimated light passes through the ice sheet and forms an image on the ground glass screen. A lucite box containing dry air was employed to prevent condensation. Ice of the desired orientation was provided by the seed holder shown in Fig. l(b). This device was made of lucite, and had a reservoir in which ice could be frozen by placing it in a freezer. This reservoir com-unicated with the outside only through a narrow gap between two sheets of lucite. The seed holder (after ice had been washed off its exterior) was immersed in the tank of supercooled water, the narrow gap terminating in a slot in the top of the flow channel. Ice growing through a thin water layer in the gap between the two sheets of lucite was oriented so its c axis was perpendicular to the sheets. This orientation is an application of a growth phenomenon2 which causes ice growing along a smooth solid surface in supercooled water to orient itself so its c axis is normal to the surface. After the ice grew into the channel, further orientation was necessary, since the direction of the a axis

Jan 1, 1970