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By E. P. Hindes

The total amount of oil produced in the state of Oklahoma during the year 1928 was 242,286,400 bbl., as compared to 273,372,650 bbl. in 1927; 177,650,000 bbl. in 1926; and 167,900,000 bbl. in 1925. The year 1928 ranks second to 1927 in which more oil was produced in the state than in any previous year. The large in in 1927 and 1928 was due principally to the development of the Greater Seminole district. The decrease of approximately 31,000,000 bbl. in the 1928 production as compared with the production in 1927, was caused by a drop of nearly 8,500,000 bbl. in the Seminole district production and a more or less normal decline in the production of practically all the other older and more settled fields. During 1928 approximately 1800 producing wells were drilled in Oklahoma, which yielded during the year approximately 90,000,000 bbl. of oil. The average initial production of these wells was 850 bbl. per day, and the average daily production per well for the year was 137 bbl. The average daily production per well of the total number of wells producing in 1928 was 10.9 bbl., which is a 13.5 per cent. decrease from the 1927 average of 12.6 barrels. At the close of 1928 a total of 95,400 producing wells had been drilled in the state, and approximately 61,000 were still producing. The grand total amount of oil produced in the state from the time the first well was drilled up to and including 1928 was 2,553,000,000 bbl. The production in 1928 was 9.5 per cent. of the total oil produced in the state. Texas led all other states in 1928, with a production of 251,835,200 bbl. Oklahoma was second with 242,286,400 bbl., and California was third with 231,982,600 barrels. Fields outside Greater. Seminole District Practically all the old settled fields in Oklahoma experienced a normal and expected decline during the year 1928. The fields showing the most, pronounced decline as compared to 1927 were: Burbank, which dropped from 15,230,400 to 11,939, 150 bbl.; Tonkawa, from 7,692,000 to 4,952,900 bbl.; Garber, from 5,056,300 to 3,139,400 bbl., and Wewoka, from 6,188,-800 to 2,450,400 bbl. There were no new extensions, discoveries of

Jan 1, 1929

By AIME AIME

THE Fall Meetings of the Institute of Metals Division and of the Iron and Steel Division were held in Cleveland from Tuesday, Oct. 20, to Thursday, Oct. 22, as a part of the National Metal Congress. The registration at the technical sessions was something over 450 and the attendance at the joint dinner of the two Divisions on Wednesday evening taxed the capacity of the dining room. The president of the British Institute of Metals, W. R. Barclay, consulting metallurgist to the Mond Nickel Co., Ltd.; of London, was in attendance at several of the technical sessions and was one of the after-dinner speakers at the banquet. He commented on the desirability of greater international amity and cooperation in these troubled times and of the role that technical societies, such as the A. I. M. E. and his own British Institute of Metals, can and indeed are playing in bringing this to pass, with their membership and contacts reaching to all parts of the world. He also referred to the new reciprocal membership arrangements in effect between the A.I.M.E. and the British Institute of Metals.

Jan 1, 1936

By D. K. Deardorff, H. Kato

THE transformation temperature of hafnium from hcp to bcc is 1750° + 20 °C in contrast to previously published values by Duwez and fast2 which are believed inaccurate. The Bureau of Mines determined this value by measuring the temperatures at which a sudden decrease was observed in the electrical resistance of hafnium alloys containing up to 18 at. pct Zr, and then extrapolating the temperatures to 0 pct Zr. Duwez1 previously reported a transformation temperature of 1310°C, obtained by use of a rapid-cooling thermal-analysis technique. Later, Fast2 published a much higher value of 1950° 100°C based upon: a) his own determination of 1690°C for the beginning of the transformation range for hafnium containing 5.7 at. pct Zr, and b) his belief that lattice parameters reported3 for Duwez' hafnium indicated i contained 19 at. pct Zr and that the 1310°C value should be associated with that composition. Russell4 subsequently stated that Duwez and Fast probably were reporting their lattice parameters in different units and reassigned a value of 6.0 at. pct Zr to Duwez' hafnium. If this assumption were true, Duwez' hafnium was of approximately the same purity as Fast's, but his transformation value was considerably lower. The reason for this divergence is not known. Fast's value for hafnium containing 5.7 at. pct Zr agrees well with our data. McGeary5 determined a transformation value of 1660°C by metallographic examination of heat-treated specimens, but the zirconium content of his hafnium was not definitely established. The specimens used in this investigation were 1/8-in.-diam rods 6 1/2 in. long, fabricated by hot-swaging bars cut from arc-melted buttons. These buttons were melted from crystal bar hafnium and crystal bar zirconium. The chief impurity in the hafnium

Jan 1, 1960

By C. J. Frosch, J. A. May, H. G. White, C. D. Thurmond

Gallium phosphide epitaxial layers were grown from the vapor phase on undoped single-crystal galliurn arsenide substrates in silica tubes by an open-tube wet-hydrogen process. The epitaxial layers were grown over a range of water pressures at three substrate temperatures. Excess donor concentrations were determined by surface barvier capacitance measurelrzents without removing the layers from the substrates. The excess dmlor concentration, ND-NA, is fo~ind to vary approxilnately inversely with the pressure of water added to the hydrogen carrier gas. This is the relationship that would be expected for singly ionized silicon donors on gallium sites in extrinsic galliunz phosphide, with the silicon coming from the SiO generated by the reaction of hydrogen with the silica tube. An increase in the partial pressure of water in the hydrogen stream decreases the SiO pressure. The results indicate that ni, the intrinsic hole and electrmt concentration for gallium phosphide at the three substrate temperatures, is smaller than the concentration estimated from available data for the density of states effective masses and the energy gap. Mass-spectrographic measurements confirm that the dono?, introduced into gallium phosphide is silicon. The equilibrium concentrations of silicon in vapor-flown gallium Phosphide have been estimated from available thernzodynamic information that includes the solubility measurements of silicon in gallium phosphide in equilibrium with a gallium-rich liquid phase. Satisfactory agreement with the measured silicon concentrations is obtained. FROSCH1 has described an open-tube process for growing single-crystal Gap from the vapor phase by a GazO transport mechanism. The method depends upon the reaction of H20 in an H2 carrier gas with a heated source of polycrystalline Gap which provides the necessary vapor species. When the temperature of these vapor species is lowered, super saturation occurs and single-crystal Gap will deposit on a suitable substrate. Unintentionally doped single crystals of Gap grown by the wet H2 process in silica tubes are n type. Evidence is presented to show that the donor introduced is silicon, and that a qua si-equilibrium model accounts for the inverse dependence of the donor concentration on the water partial pressure and predicts the magnitude of the donor concentrations. Ainslie et al. experimentally showed a similar inverse relationship between the carrier density and oxygen pressure for GaAs. Emission-spectrographic analyses showed a decrease in the silicon concentration with increasing oxygen overpressure for GaAs. Cochran and Foster suggested the theoretical possibility of suppressing silicon contamination by using Ga20 generated by the reaction of gallium with water vapor. 1) EXPERIMENTAL The apparatus and procedures are essentially the same as those described by Frosch.' The apparatus consists of a 25-mm-ID SiO2 tube extending through a controlled high-temperature flat zone for the location of the polycrystalline Gap source and a downstream temperature gradient falling at a rate of about 14°C per cm. The latter provides the region of super saturation for the location of the single-crystal substrate. The partial pressure of water in the inflowing hydrogen stream, pA2, O was controlled by mixing me-tered proportions of dry H2 with H2 saturated with H2O vapor at 0°C. The total gas flows were about 200 cu cm per min in all experiments. The Gap sources were prepared by pulverizing boat-grown polycrystalline ingots to pass a 20-mesh sieve. The substrates were cut from an undoped single-crystal boat-grown GaAs ingot purchased from Monsanto. This ingot had a carrier concentration of about 1015 atoms per cu cm, a resistivity of about 5 ohm-cm, and a mobility of about 5000 sq cm per v sec at 25°C. Substrates with dimensions of 1 by 1 by 5 x lo-' cm were employed. The growth faces were chemically polished (111) arsenic faces. Epitaxial layers, at least 7.5 x 10-3 cm thick, were grown,. This required from 1 to 24 hr depending upon the Pii2Q values and the temperatures. In all of the runs, the source temperatures were 50°C higher than the substrate temperatures. Samples were prepared

Jan 1, 1968

By K. C. Lau

INTRODUCTION The design of engineering structures such as mine openings in and foundations on rock requires a knowledge of the constitutive laws governing the behaviour of discontinuous and layered rock masses. At the present time there are two main approaches for predicting the stress distributions and displacements in such engineering structures. In one method, the whole of the rock mass is discretized. The behaviour of the components of the rock mass, that is, the joints and the intact rock are modelled using analytical techniques such as the finite or boundary element methods. Typically the intact rock is modelled as a linear elastic material bounded by non-linear discontinuities. An alternative method of analysis is to describe the load-deformation properties of the jointed, layered or even reinforced rock mass in terms of smeared or equivalent homogeneous material properties. Such equivalent material properties may then be used to compute the stress distributions around openings and in foundations using standard methods of analysis such as the finite or boundary element techniques. Once the stresses have been obtained for the equivalent material, the stresses in the individual constituent layers or discontinuities may then be determined. Each approach to the problem has particular advantages. The first method is more likely to yield results which more closely represent the behaviour of the rock mass, since the behavioural responses of both the joints and intact rock are modelled. However, for many large or complicated geologic structures such an approach can become unweildy and uneconomical. In such cases, the equivalent

Jan 1, 1984

By John W. Cahn, David A. Karlyn, Morris Cohen

The massive B(bcc) — am (fcc) transformation in Cu-Zn alloys has been studied isothermally by pulse-heating the retained ß phase from room temperature to the reaction temperatures. The transformation is found to occur only in the single-phase a region of the equilibrium diagram. The massive growth rate is of the order of 1 cm per sec and is constant at each temperature, usually after a delay time of some milliseconds. The delay time depends on the reaction temperature in C-curve fashion, while the growth rate increases monotonically with temperature over the single-phase range. The absence of isothermal massive transformation in the two-phase region does not arise from slow growth rates at such temperatures, but because the reaction cannot get started there. It is proposed that the massive transjormation initiates at small preexisting a particles which have rejected zinc into the surrounding 0 matrix. Only within the single-phase region can these particles consume the excess zinc during diffusion-controlled growth and thereby accelerate to the steady-state massive growth rate. The onset of massive growth marks the end of the delay time, and the growth rate then becomes interface-controlled. These isothermal transformation characteristics explain why the usual composition range for massive-kinetic studies by quenching is so limited. The same principles can be extended to more complex alloy systems by recognizing that the single-phase region in which the massive transformation can occur may not be stable with respect to phases not participating in the reaction. MASSWE transformations are now recognized as a regular class of solid-state reactions involving no compositional change (like martensitic transformations) and no shear displacements (unlike martensitic transformations). The name was first coined by Greninger1 in 1939 to describe the coarse grains of fcc a solid solution generated via a fast reaction from the parent bcc 0 solid solution in Cu-A1 alloys. However, some 9 years earlier, phillips2 had already described a similar transformation in the Cu-Zn system. The fact that the massive a formed as a single phase during drastic quenching from the 0 region of the equilibrium diagram signified that compositional changes were precluded. and the reaction was presumed to take place as in a one-component polymorphic transition by nucleation and growth. Phillips also observed that the occurrence of the massive transformation in the Cu-Zn system was extremely sensitive to alloy composition. For example. in a Cu-37.3 at. pct Zn alloy. the ß — am (am = massive transformation product) reaction was found to predominate and was not suppressed by iced-brine quenching from the 0 region. whereas at compositions greater than 38.3 at. pct Zn the massive reaction did not appear at all. Knowledge concerning massive transformations has bee11 substantially enhanced over the years by Massalski and his coworkers; an excellent summary of his papers and the current understanding of this type of reaction has been published recently by Barrett and ~assalski." he massive transformation product grows in roughly nodular form. often with irregular boundaries but sometimes with almost planar interfaces. The latter may have simple crys-tallographic indices relative to the 0 matrix. or the indices may be complex just as in the case of mar-tensites.'1 Little is known about the existence of orientation relationships between the massive and parent phases. A striking feature of massive transformations is that the massive units start almost exclusively at grain boundaries of the parent phase and frequently propagate on a broad front across matrix grains and grain boundaries of various orientations. Because of the rapid growth rate, it is thought that the interface motion is controlled. not by long-range diffusion. but by thermally activated atom jumps across the transformation boundary.

Jan 1, 1970

By Henry Drinker

The Institute has lost a valued member by the death of Eckley B. Coxe, Jr. He bore the name of one who was largely instrumental in founding the Institute, and to whose support and guidance as active member, Vice-President, and President, the Institute owes. much. Eckley B. Coxe, Jr., was the nephew of the late Eckley B. Coxe. He held a large interest in the coal estates owned and developed by his family, and he was thus naturally led to take a continuing interest in mining matters, and for years and up to the time of his death was a full member of the Institute. He died at his residence, Drifton, Pa., on Sept. 20 last, aged 44. He was a member of the class of '93 of the University of Pennsylvania,. of which great institution he was a devoted alumnus. His educational and charitable activities were numerous, but his chief life-work and interest was in archeological investigation and research in Egypt, carried on through the Museum of the University of Pennsylvania of which Museum he was President. The discoveries made by the various expeditions financed and directed by him, and the notable publications issued by his direction and at his expense, chronicling the results, are among the most important researches ever made of buried Egypt. Mr. Coxe was a member of the International Historical Society and of many educational and charitable organizations. By his will, among other bequests, he left $500,000 to the Museum of the University of Pennsylvania and $100,000 to the University, the income of the latter fund to be applied to increasing the salaries of the professors of the Institution. He also left $100,000 to the Children's Hospital of Philadelphia, of which he was a manager, and in addition thereto $10,000 of which the income is to be applied in providing Christmas presents for .the child patients, and in providing an annual dinner for the patients and attendants of the hospital. He bequeathed $50,000 to Leonard Hall, an associate mission of the Episcopal Church, at South Bethlehem, Pa., $25,000 to the Epileptic Hospital and Colony Farm (Philadelphia) ; $50,000 to the Philadelphia Orthopaedic Hospital and Infirmary for Nervous Diseases; $15,000 to the United Charities of Hazleton, Pa., the income to be applied to the salaries of nurses; and $25,000 to the Mining and Mechanical Institute of the Anthracite Coal Region of Pennsylvania, founded by his uncle, Eckley B. Coxe, and of which Eckley B. Coxe, Jr., was an active trustee up to the time of his death. This Institute is known as one of the best preparatory schools for technical education in Pennsylvania, and is mainly devoted to extending an opportunity for education by day and night schools to the boys and young men of the Anthracite Region. Its principal is an alumnus of Lehigh University; it has an able local Board of Trustees, and an Advisory Board consisting of the Provost of the University of Pennsylvania, the President of Lafayette College, and the President of Lehigh University, all three of which institutions have established prize scholarships in the institute. Mr. Coxe carne of a distinguished ancestry, the record of which is fully given in the biographical notice of his uncle, Eckley B. Coxe, by Dr. R. W. Raymond, in Vol. XXV of the Transactions.`

Jan 12, 1916

By Gerald Edmunds

THE liquidus line on the phase diagram for temperature versus composition of a binary alloy system, representing the boundary between the homogeneous melt and the heterogeneous melt plus solid, besides showing the minimum casting temperature, is useful in determining eutectic compositions and the presence of phase changes such as peritectic transformations and intermetallic compound formation. The liquidus often is determined by the cooling curves of thermal analysis, but supercooling frequently occurs, so that the temperature values are low. An alternative method, the one employed here, consists of determining the com- position of samples of the melts from heterogeneous alloys that are at equilibrium. With meticulous attention to fundamentals, this method is capable of yielding values limited in precision only by the temperature control and measurement and analyses. APPARATUS By starting, on the one hand, with a supersaturated solution and allowing the excess solute to precipitate, and on the other hand with an undersaturated solution and allowing more of the solute to be dissolved, both processes being carried out at the same temperature, equilibrium may be said to have been approached from both directions; that is, from above and from below. If the analyses show the solutions to contain the same fraction of solute when equilibrium has been approached from above and from below, one is assured that equilibrium has been reached in both determinations. In order to carry out such determinations, it is necessary to have equipment for obtaining and maintaining the proper temperatures; for holding the melt, measuring its temperature, and stirring, sampling and analyzing it. The present work required temperatures from 420° to 900°C. The equipment consisted of: A furnace, which was a vertical alundum tube, 1 ¾ in. diameter inside and 18 in. long, wound with Nichrome resistance wire, surrounded by a 3-in. i.d. alundum tube wound for 5 in. of length near each end, for compensation of end losses. This muffle was contained in an iron shell with Transite end plates, the intervening space being packed with Sil-O-Cel. The outside dimensions of the furnace were 12 in. in diameter by 18 ½ in. in height. Heating current was supplied by three independent variable-voltage transformers (Variac), one connected to each end compensator winding and manually controlled, and one connected to the main winding through a series resistance of 5 ohms. This resistance was short-circuited for

Jan 1, 1944

By David W. Mitchell

WHILE pure magnesium does not corrode rapidly the presence of even very small quantities of certain other metals accelerates corrosion remarkably. Because magnesium is such an electropositive metal (E° = +2.34 volts)' the presence of substances that permit galvanic activity is extremely undesirable. It is stated that as little as 0.017 pct of iron in magnesium causes a marked increase in the corrosion rate.2 Magnesium and its alloys are commonly melted in iron or steel pots; consequently the commercial metal has the opportunity to pick up iron if it has that tendency. Quantitative data on the solubility of iron in magnesium are of practical as well as of academic interest. Some magnesium alloy castings tend to have large grain size unless suitable treatment is given to the liquid metal just prior to casting. One method of grain refinement consists of "superheating" the metal just prior to casting. "Superheating" is heating to a temperature 100 to 200°C above the casting temperature and holding for a short period of time. Superheated metal has a much finer grain than unsuperheated metal. A satisfactory explanation of this phenomenon has not been forthcoming. One hypothesis attributes the grain refinement in the superheated metal to precipitation of some phase that is miscible at the temperature of superheat but not miscible just below the casting temperature and which is thought to provide nucleating centers for crystallization. This phase, if the foregoing hypothesis is correct, would probably be a metal or an intermetallic compound. Of the metals likely to be found in magnesium alloys, iron is one of the most likely candidates for the role of grain refiner for iron occurs in small quantities in all commercial magnesium and magnesium alloys. A. Beck' states that magnesium, in either the liquid or the solid state, cannot dissolve iron and that iron exists as a finely divided suspension which does not settle out because of its extreme fineness. Beck also presents a micrograph showing a large iron dendrite in magnesium but does not comment on the crystallization of iron from a solution supposed to contain none. It is doubtful that dendrite formation from suspended iron would be possible. This suspension theory is the basis of patents4 covering the removal of iron from magnesium by allowing the iron particles to act as nuclei for the formation of primary magnesium crystals which can be separated by segregation. Also covered by patents is the removal of iron by the addition of another metal to form an intermetallic compound with the iron which, because of its increased particle size, is able to settle out of the molten metal. Here, too, quantitative information on the extent of iron solubility in liquid magnesium is of more than theoretical interest. M. Hansen,5 in his critical collection of the data on binary alloys, states that iron is not soluble in liquid magnesium. W. R. D. Jones6 who studied the physical properties of low iron magnesium alloys observed a

Jan 1, 1948

By H. J. Rose, J. J. S. Sebastian

When coal is stored under ordinary conditions, progressive changes take place in its chemical and physical properties. These changes are largely caused by the reaction of atmospheric oxygen with the coal substance. Although this "oxidation" or "weathering" occurs slowly in the case of high-rank coals, it is nevertheless a matter of considerable importance, since even a small amount of oxidation may affect the value of coal for carbonization purposes. Coal storage is a necessity at all carbonizing plants. In normal times there are about 5,000,000 tons in storage at by-product coke ovens and gas retorts in the United States, as compared with an annual throughput of about 75,000,000 tons. In other words, the average coal reserve at such plants is slightly less than one month's supply. However, owing to the cost of storage and recovery, coal is usually left in stockpile for as long a time as the management thinks advisable. Storage for six to eight months is common practice and is, in fact, a necessity at certain plants which obtain their coal by water routes that are closed during winter months. Modern by-product coke ovens operate continuously, and they are not cooled down from the time that they arc put into operation until they are shut down for rebuilding—perhaps 20 years later. This continuous operation is imposed by silica-brick construction and high operating temperatures. It is therefore obvious that coke plants must at all times maintain an adequate supply of stored coal, in order to prevent a failure in supply from any cause whatever. Thus when strikes or other emergencies threaten, abnormally large coal stocks are accumulated and held at coke and gas plants. Many of these plants have been forced, at some time or other, to use coal that has been stored for several years. Such coal may fail to coke at all, or it may produce a dirty appearing, weak coke of reduced value. The yields of salable by-products may also be distinctly lowered. However, it must not be assumed that slight oxidation or heat effects are always injurious. Certain high-volatile coals produce a stronger, blockier

Jan 1, 1930

By W. C. Kelly, E. J. Essene, A. M. Affifi

Occurrences and associations of natural tellurides are constrained by the relative fugacities of Te, in specific mineralizing environments. Some are rare (e.g., FeTe2) and others absent (e.g. MoTe , ZnTe) m nature because high f-Te2/f-S2 ratios are rare or unattainable , whereas others (e. g . , Ag2Te,HgTe) require lower ratios and are common. Complex and seemingly chaotic sulfide-telluride associations are, in fact, highly systematic and depend both on temperature and fugacity ratios. Some older sulfides act as buffers via reactions such as PbS + Te2 = PbTe + S2, thereby affecting the deposition and paragenesis of younger tellurides and the combined or uncombined mode of occurrence of precious metals. Thermochemical calculations of telluride-sulfide-oxide equilibria can have pragmatic value. The thermochemical approach tells us little about the Te "source", but is beginning to unravel the systematics of telluride mineralogy and controls at the precipitational end of the line.

Jan 1, 1985

By Albert Sauveur

(Cleveland Meeting, October, 1912.) ALTHOUGH many metallurgists know that some pearlitic special steels can be made troostitic, martensitic, and even austenitic, without quenching, and, therefore, without exposing them to the dangers of the quenching-bath, the practical significance of such possibility does not seem to have received the attention it deserves. Let us recall briefly the mechanism of the transformation alluded to. In Fig. 1 (after Guillet) is shown the constitutional diagram of nickel-steel that; is, of alloys of iron, carbon, and nickel. Any steel the composition of which falls within the area LPO is pearlitic after slow cooling; any steel the composition of which is represented by a point within the area MLO is martensitic, and any steel within the area MNO is austenitic. Starting with pearlitic steel, then by increasing the carbon-content or the nickel-content, or both, the metal becomes martensitic and eventually austenitic; that is, its composition crosses first the boundary-line LO and then the line M0-and it remains martensitic or austenitic after slow (air) cooling.1 We have inn this way imparted to the metal without quenching it the properties of hardened carbon-steel. In other words, the steel is now self-hardening. Nickel cannot be introduced into solid steel, but by the well-known process of case-hardening it * Professor of Metallurgy and Metalllography in Harvard University. + Assistant in Metallurgy and Metallography in Harvard University. 1 The boundaries between the various zones are not, as a matter of fact, as sharp as indicated in the diagram, because pearlite is not transformed abruptly and in its entirety into martensite when a certain critical composition is attained, nor is martensite suddenly and completely converted into austenite. Greater refinement in the construction of the diagram would undoubtedly result in the introduction of troosto-pearlitic, troostitic, and troosto-martensitic zones between the pearlitic and martensitic areas and-of a martenso-austenitic zone between the martensitic and austenitic areas. Fur the purpose of this note, however, the existence of these transition-conditions may be ignored.

Nov 1, 1912

By P. J. Burkhardt, L. V. Gregor

The oxidation kinetics of single-crystal silicon has been investigated using extremely dry oxygen as the oxidant. Two techniques were used. The first involved a flow system with which incremental thickness measurements were made. This sytem provided an oxygen ambient at atmospheric pressure which had a moisture content of less than 0.1 ppm of water. The second technique involved measuring the change in volume of oxygen with time in a closed system. A temperature range of 900O to 1200 "C and a pressure range of 20 to 760 Tory were covered. Both techniques showed that a simple parabolic rate law holds only at the higher temperatures. At lower temperatures, the data up to 5000Å can be fitted well to a linear-parabolic equation. The two constants in this rate equation are examined in terms of a physical model. The parabolic portion of the low-temperature oxidatLon fits along the high-temperature curve of an Arrhenius plot. The parabolic rate constant for the flow-system technique can be expressed by k = 2 x 10-9 exp (L 31 kcalRT) sq cm per sec. The manostatic technique gave k = 1 x 10-exp (- 23 kcalRT) sq cm per sec. By extending the thickness range to over 104. a rate law of X = At seems to fit all of the data better than the linear-Pavabolic law. Here the exponent n increases from 0.518 at 1150 V to 0.637 at 900°C. PASSIVATION of silicon planar devices through thermal oxidation is of such great importance that considerable effort has been devoted to the study of the process.17 Much of this work involves hydrothermal oxidation, in which H2O is the oxidant: whereby H2 is produced. It has been proposed that the reaction proceeds by the formation of Si-OH groups and hydroxyl diffusion through the film to react with the silicon surface. Thus, the silicon oxide layer probably contains residual hydrogen in some form after oxidation in H2O and it has already been established that hydrogen has a marked effect on the electronic properties of oxide-passivated silicon surfaces. Silicon is oxidized by oxygen at elevated temperatures; but the rate of oxide formation is considerably lower than that for 0." By using dry O2 as the sole oxidant, the presence of residual hydrogen is presumably avoided. At present, the mechanism of thermal oxidation by dry O2 is a matter for conjecture, and the presence of small amounts of H2O was reported to have a marked effect on the rate of oxide formation10 (perhaps on the electronic properties of the surface, as well). Hence, this study of the kinetics of silicon oxide growth in 0, was undertaken: 1) to determine the oxidation rate at atmospheric pressure in a system designed to exclude rigorously all traces of H2O in the ambient 0,; 2) to obtain oxidation-rate data in situ in dry O2 by means of a continuous monitoring of the amount of 0, consumed during oxide growth. These objectives are complementary—the first assesses what effects (if any) are obtained by excluding H2O from the reaction, and the second expands this information while at the same time avoiding the uncertainty inherent in relying upon incremental measurements of oxide growth to furnish kinetic data. EXPERIMENTAL PROCEDURE The conventional silica open tube in a resistance-heated oxidation furnace is subject to sources of trace H2O, even after the input O2 is thoroughly dried and the outlet gas stream is passed through a trap to prevent

Jan 1, 1967

By J. A. Herrick Nashua

IN this country steel made in a Siemens furnace or Bessemer converter, is generally tapped into a ladle or shoe, and then drawn through an aperture in its base into the various moulds. In order to regulate the flow of the molten mass a refractory valve is arranged at the aperture. A plumbago nozzle is fixed firmly in this aperture, and a stopper of like material is fitted to it, making a socket valve. In order to raise and depress this stopper at will, a rod is fastened-to it, extending through, the metal and over the brim of the ladle, where it is bent back in a half circle and secured in a slide. This slide plays vertically in a frame, permanently fastened to the outside of the ladle, and is moved by a lever having as a fulcrum a pin fixed in this frame, one end, of the lever being temporarily fixed to the slide, and the other end being moved by hand. Reference being had to the drawing (see Plate 1, Fig. 1), E is the nozzle, D is the stopper, A is the rod, protected as hereinafter described, C is the cast-iron framework, B is the wrought-iron slide, B' is the offset into which the rod, A, enters, and is secured in the usual manner by a key, a. Section J, K, shows the manner of hanging the lever. J is a pin attached to the slide by which the end of the lever raises the slide, B. J is the fulcrum fastened to the frame, C. K (Fig. 1) is a hand-nut fastening the slide, B, to the frame, C, at will. Fig. 2 is a side elevation of ladle, showing the outside working of the parts above described. It is the common practice to protect the rod, A, by a coating of clay and fire-sand, kneaded to the right consistency and applied to the rod, and then thoroughly dried. Just before casting, the plumbago stopper, D, is heated at its extremity to redness separate from the ladle and, at the moment of pouring, is placed in the ladle and slide, and adjusted as well as practicable. Some very serious defects ensue, causing much trouble and vexation as well as actual loss. The fire-clay coating in drying becomes cracked and seamy, and at its best is more or less loose on the rod. The hot metal sometimes cuts

Jan 1, 1879

By D. S. Gleason, D. E. Severson, D. R. Skidmore

Pittsburg and Midway Coal Co. has modified the German Pott-Broche process, on which patents date back to 1927, to produce on a bench scale liquid products by solution hydrogenation of coal. A continuing program of lignite solution-hydro gena-tion experiments is directed toward investigating coal solution reactions, determining favorable conditions for the solution refining of lignite by the Pott-Broche process, and investigating some of the uses for the de-ashed product obtained from lignite The German Pott-Broche process1" on which patents date back to 1927, has been modified by the Pittsburg and Midway Coal Co., a Gulf Oil subsidiary, to produce on a bench scale liquid products by solution -hydrogena-tion of coal." The objectives of the present effort are to investigate coal solution reactions, to determine favorable conditions for the solution refining of lignite by the Pott-Broche process, and to investigate some of the uses for the de-ashed product obtained from lignite. This paper is a summary of results to date in a continuing program of lignite solution-hydrogenation experiments. The coal solution reaction program has several principal aims. The first of these is to determine whether lignite can be successfully dissolved in solvents that might be practical for commercial development. The second object is to determine whether the solvents function after successive cycles of use, recovery, and reuse. It seems necessary to the economics of a potential commercial process that the solvent be recycled. Third, it is desired to learn something about the distribution of the ash constituents between cake and filtrate. The extent of ash removal is important. The nature and quantity of mineral matter passing through the filter may determine end-use marketability. For certain use applications, trace quantities of certain minerals can be objectionable, e.g., titanium and vanadium must be very low in electrode carbon for aluminum production. The Solution Reaction The coal solution Process involves an extremely complex system of chemical reactions. An initial solvent such as anthracene oil is a mixture of hundreds of different compounds with a boiling range of roughly 500" to 750°F at atmospheric pressure. The coal macro-molecule is broken down by thermal decomposition and solvent action into myriads of different compounds, some the same as those comprising the solvent. This similarity in structures opens up the possibility of production and subsequent recovery of solvent. Some solvent is inevitably lost by reaction. Regeneration of solvent was not a problem in the early German Pott-Broche plant. The coal refinery was an integral part of a petroleum refinery complex and replacement solvent was readily available. A coal refinery using lignite, however, might be isolated from other hydrocarbon processing facilities and the regenerability of solvent could be vital to the economic success of the venture. Several structural features of the solvent molecules have been cited as important to the coal solution process.'. The first of these is aromaticity of the material, the second, ability to transfer hydrogen to another molecule, as for example the ability of tetralin to transfer hydrogen and be converted to naphthalene. Finally, the presence of hydroxyl groups on aromatic rings within the molecule, i.e., phenolic character, seems beneficial. Mixtures of pure compounds have been tried by various investigators. Mixtures of o-cresol, a phenolic substance, and tetralin were found to dissolve bituminous coal better than either substance alone.3 This maximum solubility was not found with lignite." Hydrogen contributes to the reaction by hydro-genolysis and by combining with free radicals and molecular "loose ends" to stabilize the compounds formed in coal depolymerization. High boiling point, and correspondingly high molecular weight, seems to be a property which improves solution potential for coal with a given type of compound.' The maceral components of the coal appear to have an important bearing on its ease of solution. The fusain portion is quite inert to solvent action, but the an-thraxylon material dissolves quite readily.3 The hydrogenation reaction can be improved by the use of a catalyst; commercial hydrogenation catalysts having been found effective. Although cost is involved in the use of catalyst and catalyst recovery, the resulting saving in time and perhaps lowered temperature or pressure might justify their use in the solution refining process and decrease the total process costs. Apparatus and Procedure The coal solution runs were made in a 1-gal stainless steel stirred autoclave. The autoclave was provided with thermocouple wells and a transducer to permit continuous recording of temperature and pressure. The autoclave stirrer was magnetically driven, eliminating the leakage inherent with a rotating pressure seal. For runs in which a catalyst was used, the catalyst in the form of beads was placed in a wire mesh container mounted on the stirrer shaft. A control system programmed the heatup and reaction cycle. The permissible heating rate was 5°F per min because of the need to minimize thermal stress in the autoclave body. The temperature was raised at that rate until the reaction temperature was attained and then the temperature was held constant for the desired length of time. The maximum temperature seldom exceeded the average run temperature by more than 15°F.

Jan 1, 1971

President MRS. ROBERT HURSH River Road, Silvermine Norwalk, Conn. First Vice-President MRS. THORNE E. LLOYD 14 Green Hill Road Morristown, N. J. Second Vice-President AIRS. JOHN PAUL DYER Short Hills New Jersey Third Vice-President MRS. FELIX E. WORMSER Acorn Lane Larchmont, N. Y. Fourth Vice-President MRS. JOHN J. LINCOLN Elkhorn, McDowell Co. West Virginia

Jan 1, 1942

By W. L. Mamme, G. Y. Chin

The problem of selection of the active slip systems for a crystal undergoing an arbitrary strain was analyzed by Taylor and by Bishop and Hill in terms of a minimum (internal) and a maximum (external) work criterion, respectively. These two criteria have now been generalized to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (noncrystallographic) pencil glide. The generalized treatment also takes into account the possibility of a Bauschinger effect and of unequal hardening among the shear systems, which were considered in the Bishop and Hill work. Optimization techniques of linear and nonlinear programming are shown to be applicable for the numerical calculation of the minimum or maximum work. In the case of crystallographic shear, the constraint functions are linear and hence the optimal work is obtained as the saddle value of the lagrangian function Wi(y) e minimum and W,(u) + (a) for the maximum, where Wi is the (internal) work, We is the (external) work, Y is the crystallographic shear strain, u is the applied stress, and and are constraints. It is shown that the Lagrangians are functionally the same and the saddle value of one problem is identical to the saddle value of the other, proving that the two analyses are completely equivalent. In the case of pencil glide, although the constraint functions are nonlinear and neither convex nor concave, the equivalence of the optimal values to the saddle value of the Lagrangian (which is again identical for both problems) is still valid. WHEN a crystal deforms plastically by crystallographic shear, five independent shears are generally required to accommodate five independent strain components specifying the deformation. Assuming slip as the only shear mechanism, Taylor1 in 1938 analyzed the deformation in terms of a minimum work criterion. He hypothesized that of all combinations of five slip systems which are capable of accommodating the deformation, the active combination is that one for which the internal work C is a minimum, where 1 TI is the critical resolved shear stress for slip on the 1-th slip system and is the corresponding simple shear. By further assuming equal 72 for all equivalent slip systems and no Bauschinger effect, Taylor re- duced the minimum work problem to one of minimum and applied the analysis to the case of axisym- Metric flow by {111}(110) slip in fcc crystals. However, he did not consider the question of whether the resolved shear stress has in fact attained the critical value for slip on the newly found active systems without exceeding it on the inactive systems. In 1951 Bishop and ill' put forth the maximum work analysis in which slip is again assumed as the only deformation mechanism. In this analysis, the work o1 done in a given strain ij by a stress ujj not violating the yield condition is maximized. In addition, the analysis takes into account the possibility that the critical resolved shear stress for slip may not be equal among the slip systems and that the slip behavior may exhibit the Bauschinger effect. As with Taylor, a single set of slip systems—{111)(110) — was analyzed numerically. It thus appears that the Bishop and Hill treatment is on a more sound physical basis than the Taylor treatment. However, Bishop and Hill showed that where there is equal hardening among all slip systems and when there is no Bauschinger effect, Eq. [11 ] of Ref. 2, as assumed by Taylor, the results of their maximum work analysis are the same as those of Taylor's minimum work analysis. Hence at least under those conditions there is an implication that the Taylor analysis does lead to a critical resolved shear stress for slip on the predicted active systems without violating the yield condition on the inactive systems. Recently, the Taylor analysis was applied for numerical solutions of the axisymmetric flow problem, for slip on {110}(111), {112}(111). {123)(111) systems as well as a mixture of all three sets of svstems."1 Computational techniques based on the optimization theories of linear and nonlinear programming4 were employed in these solutions. The same techniques were employed in the solutions of an axisymmetric flow problem of deformation by slip on (111) (110) systems and twinning on (111)(112) systems5 which had been considered theoretically from a modified Taylor approach. The utilization of these techniques has led to the realization that the solutions of Taylor's minimum work problem imply the solutions of Bishop and Hill's maximum work problem. The two problems turn out to be dual problems in the well known sense of mathematical programming. It is thus the purpose of this paper to first generalize the minimum and maximum work analyses to include crystallographic slip on several sets of slip systems, twinning mixed with slip, and slip by (non-crystallographic) pencil glide, as well as the possibility of a Bauschinger effect and of unequal hardening

Jan 1, 1970

By Maurice L. Pinel, Thomas T. Read, Thomas A. Wright

THE erroneous, but until recently widely prevalent, belief that iron castings were first made in Europe in the fourteenth century has been adequately refuted in a number of earlier papers;1,11,12 but except for an unpublished metallographic study by the late William Campbell, and a phosphorus analysis by T. A. Wright of the metal of the Han dynasty cast-iron stove described by Laufer,2 nothing was known of either the chemical composition or the metallographic structure of the metal of any ancient iron casting, although data on castings of recent manufacture are abundantly available. The metal of the stove, which had been buried in a grave for at least 15 centuries, was so corroded that it seemed inadvisable to publish the results on it until more and better specimens from other ancient castings could be obtained. During a journey through China, extending from Peking in the north to Canton in the south and Cheng-tu, Ssu-chuan, in the west, in the late summer and autumn of 1936, one of us (T. T. Read) was fortunate enough to obtain, and bring home for study, nine castings, all more than 1000 years old, of which the date of manufacture is precisely known because of inscriptions cast in them, another that lacks a dated inscription, but of which the date, as explained below, can be otherwise established, and a specimen from the largest iron casting ever made," which is also dated. The period covered by this suite of specimens extends from 502 to 1093 A.D. In addition, a sample was obtained from a casting of date unknown, but which was certainly cast before 1000 A.D. and possibly as early as the third century A.D. A detailed description of these specimens is as follows: 1. 502 A.D. A pair (right and left) of recumbent lions (Fig. 1). Base 7 ¼ by 14 3/8 in., height over-all 5 ½ in., weight 26 lb. each. The translation of the inscription on the base is: "Made on the twenty-fourth day of the seventh month of the third year of Ching Ming of Great Wei" (Sept. 11, 502 A.D.).

Jan 1, 1938

By H. Van F. Furman

TO those engaged in the purchase and sale of gold- and silverores, mattes and bullion, the frequent differences in the gold- and silver-contents, as reported by different assayers, is a source of much annoyance and expense. The desirability of uniform methods of assay has long been recognized by certain refiners who specify in their bullion-contracts the method to be adopted in assaying the bullion. One large producer of base bullion employs at each refining-works with whom it has a bullion contract an assayer whose duty it is to see that the bullion is sampled and assayed according to contract-specifications. For the assay of gold- and silver-bullion, standard methods are now generally adopted; the reeult being that differences seldom occur. While we cannot hope for anything near perfection from fireassay methods for ores, mattes and base bullion, as carried out cornmercially, such methods may be made to yield results which answer all commercial requirements, and they will probably be retained for obvious reasons. The object of the present paper is to point out some of the sources of error and to show the importance of more uniform methods of assay and close attention to the details of the work. The sources of error in the assay of ores and mattes are: improper sampling; losses of the precious metals during fusion, scorification and cupellation; imperfect elimination of the base metals on the cupel and imperfect extraction of the silver during the parting in nitric acid. It is not the object of the present paper to enter upon the subject of sampling; but a few remarks may be of value. There has been considerable discussion recently in Colorado upon the frequent differences which occur in the assays of Cripple Creek gold-ores, and these differences have been attributed to various causes. The writer is informed by two of our most prominent smelters that since they have adopted 100-mesh screens (the general practice is 80-mesh) the

Jan 1, 1895

By J. M. Markowitz

The movement of hydrogen in two-phase Zircaloy-2 under the influence of a thermal gradient was studied in specimens of cylindrical geometry. A gross displacement of hydrogen toward the cooler regions of the specimen was observed with consequent copious precipitation of 6-ztrconium (ZrH) there. The kinetics of the diffusion are analyzed and discussed. X HE temperature-gradient redistribution of hydrogen in a-Zircaloy-2 has been treated both theoretically and experimentally Hydrogen moves toward the cold side of the temperature gradient until a steady state has been established; tendency for further hydrogen movement because of temperature differences is nullified by the tendency to move in the reverse direction because of the concentration gradient. The steady state condition is described by the equation in which iV is the concentration of hydrogen at a point in the specimen corresponding to absolute temperature T, R is the gas constant,k is a constant of integration, and Q is a parameter called the heat of transport, characteristic Of the particular system. The value of Q has been determined for hydrogen in Zircaloy-2 by several investigators, using Eq. [11. There is considerable variation in the results, the cause of which has not been resolved; reported values lie in the range 3 to 6 kcal per mole. The physical situation for two-phase thermal migration is much more complex. The -phase boundary for the solubility of hydrogen in Zircaloy-2 ranges from a concentration of 25 ppm at 200°C to a maximum of about 600 ppm at 550°C.4a Thus, if the concentration of hydrogen in Zircaloy-2 is sufficiently great (>600 ppm), the specimen will be entirely two-phase, consisting of a matrix of a-Zircaloy-2 surrounding particles of zirconium hydride. At time zero, with a temperature gradient imposed, the relative amounts of hydride and a-phase in each infinite-simally thin isothermal section of the specimen can be determined from the phase diagram by the lever rule. Moreover, the concentration of hydrogen in the matrix phase varies from point to point, following the a solubility line. Over most of this temperature range (<450°C) 6 phase, Fig. 3, has a constant concentration.5 The diffusion rate toward the cold side should be governed by 1) the slope of the a solubility line and 2) the temperature gradient, The extra complication of two-phase thermal diffusion lies in the fact that migration of hydrogen would leave the a-phase concentration gradient unaffected, since it is fixed at any temperature only by the solubility; gross concentration changes would reflect only the relative amounts of matrix and hydride, which could vary continuously at every point. Migration of hydrogen out of a region would lead to dissolution of hydride, and

Jan 1, 1962