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By A. J. Ardell, O. D. Sherby

The elevated-temperature steady-state creep behavior of polycrystalline a Zr was studied in vacuo under constant tensile stress. The experiments were conducted from 660° to 845°C over the stress range 870 to 5400 psi. The steady-state creep rate, is, of a Zr was found to be related to the applied stress, a, and temperature, T, by the equation where C is a constant. Two interpretations of the data are considered, each requiring different values of the parameters ß, Q, and . It is shown that this formula can be derived using Gilman's phenomeno logical equation relating dislocation velocity to the shear stress for the case where dislocation mobility is limited by the nucleation of kink motion. From the fundamental dependence of strain rate on dislocation velocity and the density of mobile dislocations, the factor exp(ßo) can be related to the stress dependence of the dislocation density, and Q to the energy of kink formation. The two interpretations considered are as follows: Case I—the parameters are adjusted so that the equation above describes the data over the entire range of stress and temperature, implying that creep is controlled exclusively by dislocation glide; Case IIthe parameters are adjusted to allow for the possibility that creep is diffusion-controlled at high stresses but glide-controlled at low stresses. For both cases the values of the parameters are within the spread permitted by the data. Factors favorable to the observation of the unusual stress -dependence of i, for a Zr are discussed and it is shown that the anomalously rapid rates of self-diffusion and the low modulus on the principal glide system are primarily responsible for the anomalous creep behavior. Metal-lograflhic observations are presented and discussed with reference to the overall creep behavior. PREVIOUS investigations of the creep behavior of a Zr have been conducted from room temperature to about 500C The results of these investigations are primarily of engineering significance because of the variety of conditions under which they were carried out, and the low testing temperatures employed. Little information is available concerning the fundamental nature of the elevated-temperature creep behavior of a Zr. This investigation of the creep behavior of a Zr above half the melting temperature (the melting temperature, T,, of a Zr is estimated to be about 1860"K was initiated because there are two significant anomalies of the physical properties of a Zr: a) the rate of self-diffusion in polycrystalline a Zr is anomalously rapid: b) both Young's modulus for polycrystalline a Zr and the shear modylus as-sociated with the prismatic slip system { 1010)( 1120) (the principal slip system in a Zr 7) have anomalously large temperature variations The importance of these quantities to the understanding of creep behavior has been demonstrated, and it was hoped that this investigation would provide a critical test of the predictions based upon the analysis of creep data for other pure metals. However, as the investigation progressed it became increasingly clear that the unusual creep behavior of a Zr could not be analyzed in a conventional manner. 1) EXPERIMENTAL EQUIPMENT AND PROCEDURES Two grades of zirconium, designated A and B, were used in this investigation. The analyses, as supplied by the vendors, are presented in Table I. Material A, with a nominal purity of 99.84 pct, was supplied by the Wah Chang Corp. in the form of cold-rolled sheet from which specimens were machined without further fabrication. Material B, with a nominal purity of 99.95 pct, was purchased from the Nuclear Materials and Equipment Corp. in the form of iodide crystal bar.

Jan 1, 1968

By J. R. Schneider

INTRODUCTION Landowners in Texas for many years have freely granted, reserved and leased "oil, gas and other minerals" or interests therein. In recent years we have witnessed much litigation concerning what sub- stances should be included as "other minerals" within the phrase "oil, gas and other minerals," and this question has received the attention of numerous legal scholars. At the South Texas Uranium Seminar held in Corpus Christi, Texas, in September, 1978, Mr. William R. Dodson presented a paper dealing with this very subject and entitled "Uranium - Mineral or Surface? Who Owns It?" In his paper, Mr. Dodson reported on two recent Texas Supreme Court decisions, Acker v. a, 464 S.W.2d 348 (Tex. 1971) and Reed v. Wylie, 554 S.W.2d 169 (Tex. 1977). which held that the particular substance in question in each case is not a mineral within the phrase "oil, gas and other minerals" if substantial quantities of the substance lie so near the surface that production will entail the stripping away and substantial destruction of the surface. Since that time another chapter has been written in the Texas saga of "When is a Mineral not a Mineral?" and it is the intent of this paper to present an update of the Texas law. A review of the early Texas cases so ably covered by Mr. Dodson in his paper will not be repeated, except as is necessary to illustrate the evolution of the legal doc- trine which has been so aptly named "The Surface Destruction Test". BACKGROUND In order to appreciate the genesis of the problem, one must consider that oil and gas production commenced in Texas many years ago, Spindletop came in in 1901. As oil and gas became more valuable, land- owners with considerable frequency sold interest in the oil, gas and mineral estates in their lands, and reserved interest in the oil, gas and mineral estates in their lands when they disposed of their property. Due to the oil and gas background, and perhaps be- cause oil and gas was paramount in the minds of the parties, the traditional language employed in these grants and reservations was "oil, gas and other minerals" or variations thereof. There are literally hundreds of instruments employing this language constituting a link in the chains of title to thous- ands of acres of Texas land. In addition, there are thousands of acres of Texas land held by oil, gas and mineral leases, the primary terms of which have been perpetuated by production, containing similar language in their granting clauses. The severance of the mineral estate from the surface estate results in two separate and distinct estates, each having all of the incidents and attributes of an estate in land. with the surface estate being the serviant estate, and the mineral estate being the dominant estate and having certain easements in the surface estate to explore. produce and remove the minerals. Harris v. Currie. 176 S.W.2d 302, 305 (Tex. 1943). As observed by the court in the Harris case, this is because a grant or reservation of minerals would be wholly worthless if the grantee or reservor co~lld rwt enter upon the land in order to explore for and extract the minerals granted or reserved. Although the Texas law has recognized that an oil and gas lessee has the right to use so much of the surface as is reasonably necessary to produce the minerals. Warren Petroleum Corporation v. Monzingo, 304 S.W.2d 362, 363 (Tex. 1957), recent decisions of the Court have qualified this doctrine. In Getty Oil Company v. Jones. 470 S.W.2d 618 (Tex. 1971). Getty's pumpine, units were interfering with ones self-propelled sprinkler system utilized for irrigating the premises, and Jones sought to require Getty to install the-pumping units in cellars so that the sprinkler system could pass over them. In an effort to accommodate both the surface estate and the mineral estate, the court held (page 622) "...where there is an existing use by the surface owner which would otherwise be precluded or impaired, and where under the established practices in the industry there are alternatives available to the lessee whereby the minerals can be recovered, the rules of reasonable usage of the surface may require the adoption of an alternative by the lessee". Bearing in mind that the "reasonable use doctrine" grew up in the oil and gas industry involving sub- stances which can be produced by methods that do not destroy or deplete the surface estate, the question presented is whether the Texas courts will extend this doctrine to situations where claimants of "other minerals" seek to produce shallow deposits of iron ore, coal, lignite and uranium by surface mining methods which do destroy or deplete the surface estate? The surface destruction test has answered this question in the negative, at least as to iron. coal and lignite. However, the multitude of mineral estates in Texas which have been created by a grant. reservation or lease of "oil, gas and other minerals" will, doubtlessly, continue to fuel the fires of litigation. EARLY TEXAS DECISIONS In view of the evolution of the Surface Destruc- tion Test, an exhaustive review of the early Texas

Jan 1, 1980

By C. W. Mac Gregor

THE observation of the flow layers, or Lüders' lines, produced in mild steel when it is stressed into the plastic range often provides considerable useful information for the study of the fundamental mechanism of the plastic flow of metals. It is a commonly observed fact that as soon as the upper yield point in a mild-steel tensile-test bar is passed, an unstable condition develops in the equilibrium, the load on the testing machine drops and if the surface of the bar contains a thin mill scale, the latter begins to flake off rapidly along certain "lines." These "lines" are in reality traces of wedge-shaped flow layers and are formed by the inter-section of the surface of slip and the surface of the bar. The average plane of the flow layer itself has been found by various experimenters to be inclined at an angle of approximately 45° to the axis of the test bar. In a body of more complicated shape stressed in possibly a different man-ner, the tangent planes to the flow layers at each point seem in many cases to be inclined at an angle of about 45° to the principal stress direc-tions at the point. As examples of the latter may be mentioned the logarithmic spirals obtained when a rivet hole is punched in a thin plate, or when a tube is subjected to internal pressure only, etc. Hence if the flow layers are observed from an experiment, the shear-stress trajectories -the curves indicating the directions of the maximum shearing stresses in the body-may then be approximately determined. Since the latter curves form an orthogonal family inclined at 45° to the principal stress directions, the family of principal stress trajectories, or the curves indicating the directions of the principal stresses, may be thus obtained. Although the discontinuous type of stress-strain curve at the yield point is commonly observed with test bars of mild steel, more recent experiments have shown that this is by no means the only material exhibiting this interesting phenomenon. A similar effect has been observed in zinc and cadmium crystals, by Becker and Orowan;1 in duralumin and other aluminum alloys, by Dawidenkow, 2 Elm,3 Fell, and others; in copper and copper-alloy crystals, by Elam;5 in brass by Elam;5 in brass wires by deForest;6 in higher carbon steels, tungsten steel, and

Jan 1, 1939

By Charles L. Mantell, Kurt Straler

The hydrogen reduction of Cr2O3 to chromium metal was found to be feasible at very low water-vapor concentrations, corresponding to dew points of -38° to -24°C, over a temperature range of 1130" to 1490°C. Hydrogen reduction under these conditions was predicted by the calculated equilibrium curves which also indicated that CrzOs is reduced directly to chromium without forming the intermediate oxide, CrO. This reduction path was confirmed by X-ray diffraction analysis. The percent reduction of Cr2O3 at each reaction temperature was constant with time, suggesting an inhibiting effect of water vapor. A small increase in the residual water-vapor concentration of a single temperature, 1490°C, strongly retarded the rate of reduction This effect was expressed by an empim'cal equation which indicated a direct relationship between "distance from equilibrium" and the rate of reduction. me effect of temperature over the range of 1130" to 1490°C was expressed in an Arvhenius plot of log rate vs reciprocal absolute temperature. From this curve the apparent enthalpy of activation was found to be 29,600 cal. Based on the hypothesis that the rate of reductiun is contvolled at the oxide-metal interface, an over-all rate equation consistent with the experimental data and the thery of absolute reaction rates was formulated. A simplification of this expression to an Arrhenius equation was justified by the overriding effect of temperature on the rate of reaction for the minimum water-vapor concentration range. MOST of the metals in Subgroup V1 of the periodic table can be prepared commercially by direct reduction of their oxides by hydrogen or carbon monoxide, at temperatures considerably below the melting points of both the metals and their oxides. Chromium is an exception, being generally reduced from its ore, Cr2O3 . FeO, by silicon in an electric arc furnace which operates above the melting point of the Fe-Cr alloy or above the melting point of chro- mium if a chromium oxide be the starting material. In reduction of chromium oxide by hydrogen, either reduction does not occur at all or the rate of reduction is extremely slow. Theoretical considerations based on the high, exothermic, free energy of formation of Cr2O3 compared to the oxides of the other Subgroup VI metals, molybdenum, tungsten, and uranium, would also suggest a slow rate of reaction and a high activation energy. Interest in the direct gaseous reduction of fine-powdered ores in fluidized beds was considered justification for examination of this reaction. In order to develop a basis for a continuing study of the commercial feasibility of the direct gaseous reduction of chromite, a study of the kinetics of the reduction of Cr2O3 with hydrogen was undertaken. To the authors' knowledge no accurate kinetic data for this reaction have been obtained. Neither has an activation energy been determined nor has an attempt been made to establish a mechanism of reaction. LITERATURE Maier10 compared the data of I. Y. Granaat,6 H. von Wartenburg and S. Aoyama, and G. Grube and M. Flad7 with that derived from calorimetric and ther-modynamic properties for the equilibria for the reduction of Cr2O3 with hydrogen. These results, plotted as the log of the equilibrium constant vs absolute temperature for the reduction of Cr2O3 and the intermediate oxide, CrO, to chromium, show agreement between the differently derived data. In both cases the equilibrium constants were extremely low. Maier showed that, over a temperature range of 1000° to 2000°K, Cr2O3 is more readily reducible than CrO. Granat assumed that CrO was preferentially formed from Cr2o3 above 1100°C. Grube and Flad's analysis of their reaction products in the 895" to 1000°C range indicated the coexistence of only Cr2O3 and chromium. The hydrogen reduction of the other Subgroup VI metals, molybdenum, tungsten, and uranium, shows that reduction of the higher oxide proceeds through all of the intermediate oxides before being reduced to the metal. Since evidence pointed to an anomaly in the reduction behavior of Cr2O3, the authors investigated the reduction path of Cr2Os.to chromium. This was done theoretically with more recently available free-energy data and experimentally by X-ray diffraction analysis. This work reinforces Maier's conclusion.

Jan 1, 1964

By A. C. JR. Boyle

I. INTRODUCTION THE geological field work of the Bully Hill district, upon which this paper is based, was begun July 1, 1908, and covered a period of three months. The time was found too short for a complete report and the district was again visited in the early part of July, 1912,. from which time detailed study of the locality continued until September of the same year. This paper is the result of observations made in the mines in the immediate vicinity of Winthrop, Shasta county, Cal., during these two periods of study. The preparation of this report has been greatly facilitated by various courtesies rendered the writer by D. M. Riordan, President of the Bully Hill Copper Mining & Smelting Co., and by John B. Keating and Herbert R. Hanley, managing officers actively in charge at the mines. The elaboration and further study of the notes and collections were carried on in the laboratories of the Departments of Geology and Mining at Columbia University, and the writer takes pleasure also at this point in expressing his acknowledgments to Profs. James F. Kemp, A. W. Grabau, Charles P. Berkey, and William Campbell, for advice and assistance. In order that one may appreciate at first reading the significance of some of the details which follow, and for the sake of clearness, a brief outline of the geological relationships is here given, together with certain conclusions which have been reached regarding the genesis. of the ores and the gypsum masses. In the Bully Hill mining district an associated series of Triassic lavas and tuffs, chiefly andesites, is preceded as well as followed by sediments. The entire system is tilted so that the original bedding planes dip in general to the southeast. The surrounding region has been greatly disturbed, and in the immediate vicinity of the mines close folding of the later sediments and extreme shearing of the igneous rocks locally is a striking feature. Into the nearly vertical shear zones have been intruded post-Triassic dikes of various rock types in the following order: alaskite-porphyry and andesite-porphyry. Outside the area under consideration diorite dikes are known, but they will not receive attention further than to note that' they, probably, represent a differentiation product of the same magma from which the other two dikes came. In this connection all the dikes have an important bearing on the origin of the ores and of the gypsum found in the mines.

Jan 1, 1914

By J. M. Eldridge, P. Balk

Phosphosilicate glass films were formed, by reacting gaseous P2O5 with SiO2, over a large range of temperature (800° to 1200°C) and gas phase composition (nearly two orders of magnitude of effective P2Ospressure). The film compositions generally corresponded with the liquidus curve, delineating the maximum solubility of the tridymite Phase of SiO 2 in phosphosilicate liquid solution at the temperature of film formation. It is shown that the P2O5 concentration of the phosphosilicate liquid film tends to decrease by reaction with the underlying SiO 2 layer until the liquidus curve is reached. The validity of the thermodynamic argument used in this explanation is supported by the results of a determination of the composition of borosili-cute films, prepared by reacting gaseous B2O3 with SiO2 at different temperatures. The kinetics of phosphosilicate film formation were described by a model predicated on a steady-state diffusion of P2O5 through the film. UNDERSTANDING of the processes leading to formation of phosphosilicate and borosilicate glasses is of great importance for producing passivating layers on FET devices. Passivating films with optimum characteristics are preferably formed in a separate step, independent of the doping of the semiconductor.' The results of an investigation carried out to gain improved insight into the mechanism of glass formation are presented in this paper. It would be expected that application of the known Pz05-Si02 and B 2 O 3-SiO2 phase diagrams should be useful in extending understanding of the glass-forming processes. However, the question of the propriety of treating thermally grown SiO2 in these binary oxide systems by the methods of equilibrium thermodynamics must be considered when this application is attempted. Although Sah et a1.' and Allen et al. 3 investigated the kinetics of formation of phosphosilicate glass (PSG), they failed to adequately relate their diffusion models to the occurrence of experimentally observed phases in the PSG/SiO 2/Si system. Horuichi and yamaguchi4 investigated the diffusion of boron through an oxide layer and described their results in terms of a model similar to that of Sah and coworkers. More recently, Kooi 5 and Snow and Deal6 reported the compositions of PSG films formed by depositing P2 O 5 onto SiO2. These compositions apparently coincide with those at the liquidus curve delineating the maximum solubility of crystalline SiO2 in phosphosilicate liquid solutions. These authors did not discuss the thermodynamic implications of their results on the structure of thermally grown SiO2 films. The structure of thermally grown Sio2 films and that of vitreous silica are generally thought to be quite similar. Since the solubility of a substance depends on its structure, it is relevant that the solubility of vitreous silica in water7 is highly reproducible, like the solubility of thermally grown SiOz in phosphosilicate liquid. Furthermore, the vitreous silica-water system appears to be in true thermodynamic equilibrium (viz., the same solubility value can be approached from both supersaturated and under-saturated solutions). Sosman7 suggested that a type of two-dimensional lattice may form at the silica/solution interface, resulting in the observed solubility behavior that is characteristic of a crystalline solid. An alternative explanation may be that vitreous silica has a microcrystalline grain structure. Other investigators have suggested that vitreous silica has essentially the structure of B cristobalite,' or is composed of microcrystals of p tridymite or cristobalite, or a mixture of both. Presumably the grain size would be sufficiently large to minimize any appreciable contribution of the grain boundaries to the solubility of the crystalline matrix. The present investigation was carried out to clarify the significance of the boundaries in the Pa,-SiO, and B2O3-SiO2 Systems in determining PSG and BSG (borosilicate) film compositions. Furthermore, the kinetic data for PSG film formation were extended, using a wider range of formation parameters than were previously reported. One model describing the kinetics of film formation will be presented that is compatible with the thermodynamics of the Pa5-Si02 system. EXPERIMENTAL PROCEDURE Glass Film Preparation. SiO2 films (1000 to 8000A thick) were obtained by oxidation of silicon substrates in dry O2 at 1100°C. PSG and BSG films were prepared by exposing these layers to gaseous oxides obtained by reacting high-purity POC13 and BBr3, respectively, with O2. A double-columned saturator was used to ensure complete saturation of the N 2 carrier

Jan 1, 1969

By E. H. Dix

All commercial aluminum contains small percentages of copper, iron, and silicon as unavoidable impurities. The purest metal obtainable commercially, special grade high purity ingot, contains a maximum of 0.50 per cent. impurities of which the usual minimum amount of copper is 0.01 per cent.; silicon, 0.12 per cent.; and iron, 0.20 per cent. This grade is too costly for most purposes. The two standard grades, Nos. 1 and 2, containing a minimum of 99.0 and 98.0 per cent. aluminum, respectively, are more generally used. Other grades of secondary aluminum often contain as high as 3 or 4 per cent. of impurities, which include 1 per cent., or more, of zinc. Specifications for high-grade aluminum-casting alloys generally allow a maximum of 1.7 per cent. for total impurities. The S. A. E. Specification No. 33, which is intended to cover alloys made from secondary aluminum ingot, gives the iron maximum as 1.5 per cent. and the maximum for silicon (including manganese and tin) as 0.75 per cent. The effect of even relatively small amounts of impurities on the physical properties of ingot aluminum is shown by the following cornparison of two lots of aluminum, which may be taken as representative of special grade and grade No. 2 ingot, respectively. AnalysEs Special Grade, Gbade No. 2, Per Cent. PeR CBnt. Copper................................. 0.01 0.32 Silicon................................. 0.12 0.32 Iron................................... 0.42 0.82 Aluminum.............................. 99.45 98.54

Jan 1, 1923

By E. H. Dix

All commercial aluminum contains small percentages of copper, iron, and silicon as unavoidable impurities. The purest metal obtainable commercially, special grade high purity ingot, contains a maximum of 0.50 per cent. impurities of which the usual minimum amount of copper is 0.01 per cent.; silicon, 0.12 per cent.; and iron, 0.20 per cent. This grade is too costly for most purposes. The two standard grades, Nos. 1 and 2, containing a minimum of 99.0 and 98.0 per cent. aluminum, respectively, are more generally used. Other grades of secondary aluminum often contain as high as 3 or 4 per cent. of impurities, which include 1 per cent., or more, of zinc. Specifications for high-grade aluminum-casting alloys generally allow a maximum of 1.7 per cent. for total impurities. The S. A. E. Specification No. 33, which is intended to cover alloys made from secondary aluminum ingot, gives the iron maximum as 1.5 per cent. and the maximum for silicon (including manganese and tin) as 0.75 per cent. The effect of even relatively small amounts of impurities on the physical properties of ingot aluminum is shown by the following cornparison of two lots of aluminum, which may be taken as representative of special grade and grade No. 2 ingot, respectively. AnalysEs Special Grade, Gbade No. 2, Per Cent. PeR CBnt. Copper................................. 0.01 0.32 Silicon................................. 0.12 0.32 Iron................................... 0.42 0.82 Aluminum.............................. 99.45 98.54

Jan 1, 1923

William Kelly, Vulcan, Mich.:—In the northern part of Bedford county, Pa., the county immediately south of Huntingdon, the Clinton measures appear along the eastern slope of Tussey mountain near its base. The only iron-ore bed that has been worked is in the upper part of the formation. Along the mountain this seam has a dip of more than 60°. At the outcrop the ore is soft and rich, but with depth it passes often abruptly into an almost pure limestone similar to that described by Dr. Rutledge. The soft ore extends deeper in the cross-gullies than it does under the higher gound between the depressions. The slates adjoining the rich ore have been weathered, but where in juxtaposition to lean ore and limestone they are hard. The alteration of the ore-bed is evidently the result of the conditions of drainage in quite recent geo-

Jan 1, 1910

By D. Turnbull, J. H. Hollomon, J. C. Fisher

Application of the concepts of nu-cleation and growth to the analysis of experimental transformation data has led to valuable descriptions of phase transformations, an outstanding example being the transformation austenite —* pearlite which has been examined with particular care by Mehl and co-workers.&apos;-5 In addition to the pearlite transformation, the proeutectoid fer-rite and proeutectoid carbide transformations are known to proceed by nucleation and growth. Martensite, on the contrary, until recently was thought to form by a mechanism involving neither nucleation nor growth; however, extension of standard nucleation theory6 suggests that martensite, bain-ite, and the other products of austenite decomposition all grow from nuclei in the parent phase. The theory that martensite forms by nucleation and growth is strongly supported by recent experimental work of Kurdjumov and Maksimova.7 The concepts of nucleatioli and growth have been fruitful also in providing a sound basis for quantitative theoretical treatments of the kinetics of phase transformations. For example, Volmer and Weber8 and Becker and Döring9 developed the theory of nucleation from fundamental considerations to a point where excellent agreement was obtained with the results of experiments on the condensation of supercooled vapors. As a result of their analysis, the kinetics of vapor-liquid transformations now can be predicted. It seems probable that application of the theories of nucleation and growth to a quantitative study of austenite decomposition similarly will clarify the nature of the individual transfor: mations involved, and will enable the calculation of austenite transformation kinetics. In the present paper, the theories of nucleation and growth are applied to the austenite ? martensite transformation in steels. The analysis begins with a discussion of nucleation in single component systems. Martensite appears to be coherent with the parent austenite, hence the nucleation theory is modified to include the effects of elastic distortion. Nucleation in the two component iron-carbon system then is discussed, for most steels are primarily alloys of these two elements. Finally, M. temperatures and martensite transformation curves are calculated for each of several alloy steels of varying carbon and chromium content, and are compared with those determined experimentally by Lyman and Troiano10 and Harris and Cohen.11 Nucleation Theory NUCLEATION IN SINGLE COMPONENT SYSTEMS6,12-14 The work required for reversible formation of a region of phase within the parent a phase is expressed conveniently as the sum of two terms: W1 = Aa, the product of the area of the interface and the interfacial free energy, and W2 = VAf, the product of the volume of the region and the free energy increase per unit volume associated with the transformation. The total work is therefore W = Aa + VAf. When a is more stable than ß, Af is positive and W increases without limit as the volume increases. The transformation a ?ß does not occur. It is nevertheless true that small regions of phase ß enjoy temporary existence here and there in the a. The equilibrium number of ß regions of given size is proportional to exp(— W/kT) per unit volume of a, assuring that larger (ß regions occur with diminishing probability. When a is less stable than ß, Af is negative and W passes through a maximum as V increases. Assuming for simplicity that regions of ß are spherical, as is true when the interfacial tension is isotropic and there are no elastic strains, W = 4r2a + (4/3)*r3Af The maximum value of W is W* = 16iro3/3Af2 [1] for regions with radius r* = -2o/Af. [2] For single component condensed systems it has been shown14 that the steady rate of nucleation of 0 per unit volume of untransformed a is nearly proportional to exp[- (W* + Q)/kT] where Q is the activation energy for the unit processes of adding or removing one atom from an embryo or nucleus. If To is the temperature at which a and ß are in equilibrium, the rate of nucleation is a maximum at a temperature 0 < T < To where (W* + Q)/kT is a minimum. P regions smaller than critical size are called embryos; they tend to grow smaller and disappear, only exceptionally growing larger. Regions equal to or larger than critical size are called nuclei. A critical size nucleus may grow indefinitely large or may shrink back to a, either process decreasing the free energy of the region.

Jan 1, 1950

By F. E. Jaumot, R. L. Smith

Self-diffusion in zinc has been used as an instrument for comparison of the absorption and sectioning techniques as a means of studying diffusion. Single crystal as well as poly-crystal samples were used asanda the temperature range of diffusion extended from 200° to 415°C. For temperatures above 200°C, the data indicate that the results obtained from the absorption technique agree with those obtained from the sectioning technique. The effect on the values of the diffusion coefficient of electroplating vs evaporation as a means of applying the tracer was investigated and no significant difference observed. It was found that an excess or deficiency of tracer did not materially affect the results obtained from the sectioning technique, but invariably caused errors with the absorption technique. NEARLY all self-diffusion experiments and many alloy diffusion experiments have employed radioisotopes as the instrument for following the diffusion. Of the various techniques in which radioisotopes are applicable, the two most widely used are the sectioning and absorption techniques. In the former, the diffusion coefficient is obtained from a curve of log concentration vs the square of the mean penetration depth. In the latter, the diffusion coefficient is calculated from a knowledge of the decrease in activity at the surface after diffusion. In spite of the importance of knowing the reliability of the diffusion data and the widespread use of these two techniques, they had not been directly compared experimentally on the same samples. Thus, such a comparison was worthwhile. The specific system chosen for this comparison was the self-diffusion of zinc, since the metal was readily obtainable in high purity, single crystals were easily grown, and the anisotropic features of the diffusion added an additional factor of interest to the comparison. Self-diffusion in both single and polycrystals was investigated, since the possibility existed that grain boundaries and grain boundary diffusion might produce different effects for the different techniques. Also, the effects of electroplating vs evaporation as a means of applying the radioactive tracer, and the effects of applying an excess or deficiency of tracer material were studied. The general experimental procedures and the mathematical analyses of both techniques have been described previously in some detail, and only those points essential to an understanding of the present work will be discussed here. The mathematical analysis of the sectioning data requires only a knowledge of the solution of Fick&apos;s equation. where C,, is the initial concentration, C is the concentration at depth x, D is the diffusion coefficient, and p is the absorption coefficient of the solvent metal for the radiation from the solute. Having obtained F from the experiment, the value of z can be read from a plot of F vs In z, and D can then be calculated if is known. The necessity of knowing the absorption coefficient causes most of the criticism of the absorption technique. It is very difficult to measure accurately under the conditions existing in the diffusion experiment, but it is absolutely necessary, as will be indicated briefly later. Portions of this problem have been discussed in detail elsewhere." The difficulties involved in the measurement of the absorption coefficient arise from three principle factors: the physical characteristics of the absorber, the geometry, and complex radiation spectra. The first two are heavily dependent upon the third. If

Jan 1, 1957

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By Arthur C. Simmons

The State of Pennsylvania produces approximately 60 per cent of the total production of Pennsylvania Grade oil, and naturally represents the dominant factor in the area producing that grade. The producing area comprises the states of New York, Pennsylvania, West Virginia, and a small part of Ohio. The importance of this area is too commonly neglected because it produces only 2 per cent of the total amount of crude produced in the United States. It is, of course, unimportant in its percentage of total crude production, but extremely important for its production of lubricating oil. The lubricating fraction from a barrel of Penllsylvania Grade crude oil represents about 22 per cent of the total, whereas the lubricating fraction from the total United States production represents only about 2.5 per cent of the crude oil. The Pennsylvania Grade area produces about 6,000,000 bbl. of lubricants, which is 15 to 20 per cent of the total produced in the United States. All Pennsylvania Grade lubricants are classified as "high-grade," and with a production of 15 to 20 per cent of the total lubricants, it appears probable that the Pennsylvania Grade area accounts for 25 to 50 per cent of the high-grade lubricants produccd in the United States. Production Bradford Field The production figures quoted in Table I apply only to the part of the Bradford held that lies wholly within the state of Pennsylvania; approximately 15 per cent of the Bradford field is in Cattaraugus County, New York, and 10 per cent of the production is obtained from that sector. The Bradford-field production in 1941 was 12,729,900 bbl. as compared with a production in the year 1940 of 12,748,279 bbl., or a reduction of 18,379 bbl. The year 1941 represents the fourth successive year in which production in the Bradford field has declined. All of the production from the Bradford field is obtained by water-flooding methods and increases or decreases in production are due more to economic factors than to any physical limitations of the pool, inasmuch as additional drilling of water-intake and producing wells would increase the total production of the field. It is apparent that increased drilling of oil and water-intake wells does not take place except under stimulps of a favorable price; and while oil prices during 1941 were moderately favorable, they were not sufficient to prevent a mild decline. Too many wells were drilled in the Bradford field in 1937, but this was compensated by subnormal drilling activities in 1938 and 1939 and a large increase in 1940, The increase in 1941 over 1940 was about 7 per cent. The effect of new drilling is becoming less pronounced on a per well basis because more properties yielding less per acre are being drilled than were drilled in former years. Central and Southern Pennsylvania The production in central and southern Pennsylvania amounted to a total of

Jan 1, 1942

By E. T. Turkdogan, L. S. Darken

Calcium ferrite melts were equilibrated with sulfur and oxygen-bearing gases at temperatures within the range 1290°C to 1620°C. The results show that at oxygen partial pressures below 10-4 atm the sulfide-reaction occurs and at higher oxygen pressures the sulfur dissolves in the melt principally as sulfate ion. It is also observed that when the product increases, sulfate ions are converted to pyrosulfate ions and the results permit the evaluation of the pyrosulfate/sulfate ratio. It is shown that the ratio y CaSO,/rCaO increases with decreasing concentration of calcium oxide in calcium ferrite, silicate and aluminate melts. Indications are that oxy-acids, e.g. silica, alumina and ferric oxide, increase yCaS0,. A few experiments were carried out within the sul-tide range and the results are in accord with those obtained by other investigators on aluminate and silicate melts. BECAUSE of the industrial importance and theoretical interest, many investigators have studied the reactions between molten oxides, silicates or alumi-nates, and gases containing oxygen and sulfur. The early work reviewed by Schenckl and studies made by Bardenheuer and Geller2 indicates that solution of gaseous sulfur in an oxide melt resulted in the replacement of the oxide ions by the sulfide ions. Measurements made by Grant and Chipman3 on the equilibrium partition of sulfur between molten iron and complex silicate melts also demonstrated that, for a given temperature and silicate composition, the distribution of sulfur between slag and metal increased with decreasing oxygen content of the metal. Fincham and Richardson4 studied the effects of temperature and partial pressures of sulfur and oxygen on the solubility of sulfur in simple silicate and alumino-silicate melts. They observed that at oxygen partial pressures below about 10-5 atm sulfur in the gas dissolved in the melt as sulfide ions, replacing an equal number of oxide ions of the melt. At oxygen partial pressures higher than 10-3 atm, sulfur entered the melt as sulfate ions. Similar studies were made by St. Pierre and Chipman5 using calcium ferrite and calcium silico-ferrite melts. The experimental data presented in this paper were obtained in this Laboratory about 10 years ago; this is the first formal presentation although a preliminary report was given previously.6 In each of these experiments, a pure synthetic CaO-Fe2O3 melt in a platinum crucible was equilibrated with a gas mixture (SO2-O2, SO,-air, SO2-CO, or SO2-CO2-CO) at a temperature ranging from 1296°to 1620°C. The experimental technique was essentially the same as that reported by Darken and Gurry,7 the main difference being that the atmosphere in the reaction chamber contained sulfur dioxide together with oxygen, or carbon dioxide-carbon monoxide

Jan 1, 1962

By T. E. Leontis

The specific effect of various rare-earth metals on the room- and elevated-temperature properties of magnesium has been evaluated. Alloys containing didymium exhibit the highest tensile and compressive strengths at room and elevated temperatures. All the rare-earth metals increase the creep resistance of extruded magnesium at temperatures in the range of 400° to 600°F, but the degree of enhancement depends on the temperature and on the concentration of the added metal. THE effects of rare-earth metals on the properties of sand-cast magnesium were discussed in some detail in earlier paper by the author.&apos; The present paper deals with the effect of the same alloying elements on the properties of extruded magnesium. This investigation also had as its aim the development of a wrought alloy having a better combination of room-temperature strength and ductility and elevated-temperature strength and creep resistance than is found in magnesium-Mischmetal-manganese alloys, which have been reported earlier.2-5 The only known attempt to study wrought magnesium alloys containing pure cerium instead of Mischmetal was made by Mellor and Ridley.6 They found that in the form of rolled bars there is a definite, optimum cerium content for creep resistance at 200 °C and that the creep resistance of these alloys at 200 °C is significantly Improved by heat treatment at 550" to 580"C. In the present investigation the compositional variation in mechanical properties of the following alloy systems is presented: I—magnesium-Misch-metal. 2—magnesium-cerium-free Mischmetal. 3— magnesium-didymium. 4—magnesium-cerium. 5— magnesium-lanthanum. Alloys containing predominately praseodymium are not included in this series because of the lack of this material. Experimental Procedures The alloying ingredients used in preparing the alloys described herein are the same as those reported in the earlier paper.&apos; Cerium-free Mischmetal is the rare-earth mixture remaining when the cerium is removed from Mischmetal, which contains all the rare-earth metals as they occur naturally in mon-azite sand, the ore from which Mischmetal is produced. Removal of both cerium and lanthanum from Mischmetal leaves what is commonly called "didym-ium," consisting predominantly of neodymium and praseodymium. Although the composition of the particular batch of each metal used may differ somewhat from the analysis presented previously, these differences are not great enough to warrant repeat- ing the specific composition of each material. The electrolytic magnesium used as the starting material in these alloys has the same typical analysis as that given in the earlier paper.&apos; The alloys were prepared in small laboratory melts applying all the necessary precautions for alloying rare-earth metals with magnesium described by Marande.&apos; Most melts were large enough to cast one 3 in. diam billet 10 in. long. In a few cases, particularly the didymium-containing alloys, the lack of sufficient amounts of the rare-earth metal limited the size of the billet to 6 to 8 in. All billets were scalped to a diameter of 2 15/16 in. and faced to a length of 9 ¼ in. as limited by the size of the extrusion container. The alloys were extruded into ½ in. diam rod on a 500-ton direct-extrusion press using a 3 in. container. The details of the extrusion step are: billet preheat, 925°F (2 hr); container temperature, 900°F; die temperature, 900°F; extrusion speed, 10 ft per min; reduction ratio, 36:1; and percent reduction, 97.3. The lower melting point of alloys containing didymium&apos; necessitated reduction of the extrusion speed to 5 ft per min in order to prevent hot shorting during extrusion. Adequate lengths were cropped from both ends of each extruded rod to assure that all the material used for tests was extruded under uniform conditions. Tensile and compressive properties at room temperature are reported in the several conditions of heat treatment. The ASTM designations are used to distinguish these conditions as follows: T5—Direct age at 400°F (16 hr) T4—Heat treat at 950°F (4 hr) for alloys containing didymium T4—Heat treat at 1050°F (4 hr) for all other alloys T6—T4 + age at 400 °F (16 hr) The lower heat-treating temperature for alloys containing didymium is necessitated by the lower melting point of these alloys. All heat treatments were conducted in electrically heated, circulating-air furnaces. A protective atmosphere containing 0.5 to 1.0 pct sulphur dioxide was used for the high temperature heat treatments. Tension and creep specimens 6 Yz in. long and compression specimens 1½ in. long were cut from the extruded rod. A reduced section of ? in. diam was machined on the tension specimens, whereas on the creep specimens a reduced section of 0.450 in. diam

Jan 1, 1952

By E. A. Breitenbach

A computer program has been developed to afford rapid and complete quantitative log analysis for exploration and production decisions. The computation consists of automatic selection of tops and bottoms of porous intervals from the digitized data, and then point-by-point calculations within each selected interval. Nearly all log types can be analyzed. This paper presents the calculation techniques found to be appticable to machine evaluation and gives examples of their use. INTRODUCTION As the quantitative interpretation of well logs entails repetitive use of charts and equations, it is natural that digital computer programs would be written. A Universal Log Interpretation Computer Program (ULICP) has been developed to afiord rapid and complete analysis for exploration and production decisions. Application of this program enables the log analyst to: (I) apply rapid quantitative log analysis for exploration and production decisions on either a field, a well or on a single zone basis; (2) apply concepts of interpretation requiring detailed numerical analysis; (3) analyze all porous intervals on each log, rather than a few selected zones, and complete the analysis in less time than previously required. Computations are reported for every digitized point in each zone; (4) use empirical techniques applicable to a given area as an integral part of the computation; (5) experiment with the empirical coefficients and exponents in the interpretation equations to find the best possible solution; and (6) automatically plot both the original and computed data to scales analogous to the field prints. The primary utility of a log interpretation program stems from its ability to do an overwhelming amount of work with very little man-power. If a calculation procedure or thought process can be formalized to the extent that step-by-step logic can be written, a computer program can be developed that follows this logic. The major question is one of economics. A feasibility study of the costs for such a program indicates that digital processing is economical primarily as a means of increasing the productivity of the log analyst. In effect, the probability of missing productive intervals in any well, because of a lack of time to do detailed calculations, is greatly reduced. The nucleus of ULICP is programmed to compute large sections of a suite of logs by selecting zones automatically and then performing all pertinent computations on a data point by data point basis within each zone.&apos;.&apos; An entire suite of logs can be processed in this manner with very little manual intervention. Sufficient programming logic is available so that each log analyst can request computations pertinent to his area. These requests are made by simple additions or deletions of information on the input header cards. Hence, the log analyst is always in complete control of the computation process. The evaluation of a suite of logs requires pre-editing, digitization, computation, presentation of results and interpretation. Work by the log analyst is reqilired only in pre-editing and interpretation. Thus, he is allowed more time for comprehensive interpretation, rather than calculation. For continuity, the discussion of ULICP is organized sequentially: pre-editing, digitization, computation and presentation of results. DISCUSSION PRE-EDITING The extent of pre-editing prior to computation is dependent on the format of the original data. For analog prints, it requires inspection, correlation and editing of the logs, plus the entering of required data an special forms. For digitized data such as magnetic tape field recordings, only the special forms are necessary. The process for analog prints will be given here. The inspection and correlation process involves the selection of sections for digitization and the correlation of the traces to a common depth. To decrease the cost of digitization, traces that exhibit large variations in shale formations can be redrawn to a non-zero baseline. The next step is to enter all pertinent data on the input header cards. The header cards presently used for ULICP are presented as Figs. 1 through 6. Cards 1, 2, 3 and 4 (Fig. 1) are defined as the Main Header Cards. They describe the particular well for output identification and give basic information. Cards 5 through 15 (Figs. 2 through 6) are defined as the Block Header Cards. As such, they define the log types and the interpretation parameters for the block of data immediately following. Cards 1 through 10 are required for every computer run. Cards 11 through 14 pertain only to nuclear logs. Card 11 is required if any nuclear log is supplied, and cards 12 through 14 are required only when gamma-ray, density or neutron log data, respectively, are supplied. Card 15 (Fig. 6) must be supplied when cross-plot calculations are required. Either two- or three-component

Jan 1, 1967

By J. P. Zannaras

Referring to the article by R. J. Charles and P. L. de Bruyn, let us assume that W = weight of glass bar; P = weight of hammer; e = total deformation; E = unit of deformation; K = potential stress energy; E = modulus of elasticity; L = length of the bar; 7, = coefficient of inertia; h = height, ft; V = velocity, fps; and a = cross section area. The portion of kinetic energy which is effective in producing stress energy in a fixed bar struck horizontally is given by the formula [ ]

Nov 1, 1956

By J. W. Clark, C. T. Sims

Wrought chromium-base alloys containing yttrium, cubic monocarbides of the Ti(Zr)C type, and similay alloys containing manganese and rhenium have been melted and fabricated. Strength has been studied by hot hardness and elevated-temperature tensile and rupture measurements, low-temperature ductility by tensile testing, and surface stability by oxidation testing. In additiod, studies have been conducted of the carbide stability, and of aging behavior. The carbide dispersion generates effective elevated-temperature strength, which is further enhanced hv strain-induced precipitation. The dispersion exhibits classical dissolution and aging response. The ductile-to-brittle transition temperature of these alloys is above room temperature. The alloys reported show fairly good oxidation resistance, but nitrogen contamination can cause fortnation of a hard Cr2N layer under the oxide scale. Manganese does not appear to be a promising alloying element in chromium. In the years 1945 to 1950, the metal chromium was considered as a possible base for alloy systems due to its considerably higher melting point than superalloys, its low density, its high thermal conductivity, and its apparent capacity for strengthening. However, this interest in chromium was short-lived. It was found difficult to melt and cast, to be exceptionally sensitive to the effect of minor imperfections, to have a lack of ductility at both room and elevated temperatures, and to be subject to a deleterious effect of alloying elements upon the ductile-to-brittle transition temperature.&apos; Since then, chromium, as a practical alloy base, has remained virtually unstudied. Further, purposeful ignoring of chromium has been promoted by statements that its bcc structure would not allow it to be strengthened to useful values, when compared to the "austenitic" alloys.2 Recently, a new look has been taken at chromium-base alloy systems. Study of the literature will show that chromium, providing some of its disadvantages could be eliminated or minimized, actually has a rather attractive potential as an alloy-system base. Analysis of rather scattered data suggests that chromium is quite capable of being strengthened to high levels. Also, significant strengthening of its two sister elements in Group VI-A, molybdenum and tungsten, has been demonstrated in a number of commercial and exploratory alloys. Chromium should be similar. Since chromium does not readily form a volatile oxide like tungsten or molybdenum, it offers a much higher probability of giving birth to alloy systems with useful oxidation resistance. Concerns about possible high elemental vapor pressure have been mitigated by recent data.3 In addition, the physical properties exhibited by chromium are attractive for application as a high-temperature structural material. For instance, its thermal conductivity varies from 49 to 36 Btu-ft/hr-sq ft-°F over its range of usefulness (which is two to four times higher than most superalloys), its density is about 7.2 g per cc (20 pct less than most nickel-base alloys), its coefficient of thermal expansion varies from 4 to 8 x 10-6 per OF, and it has a relatively high modulus of elasticity, approximately 42 x 10&apos; psi.4 Alloying studies on a chromium base in the past have usually encompassed rather sweeping solid-solution alloy additions for strengthening. This is not consistent with contemporary alloying practice in Group VI-A. For instance, molybdenum, also in Group VI-A, is primarily alloyed for strength improvement by use of heat-treatable carbide dispersions.5 Chromium and molybdenum are similar in their chemical activity and other properties. Thus, strengthening of chromium by carbide dispersions was studied. Chromium-base alloys are plagued with room-temperature brittleness, although high-purity unal-loyed chromium can be made ductile.4,8 Use of yttrium as a scavenger has done much to improve ductility and resistance to nitrogen embrittlement in chromium systems,7 so it was utilized in this program. It has also recently been found8 that small rhenium additions (1 to 5 pct) create improvement in the ductility of Type 218 tungsten wire. This is apparently related to the remarkable effect of rhenium additions near its terminal solid solubility in all Group VI-A metals.9&apos;10 Investigation to establish if dilute concentrations of rhenium would also be effective in chromium appeared to be logical for this program. Since rhenium is too expensive to be practical in alloys for application as structural components, ductility improvements through solid-solution alloying were also sought by substitution of manganese for rhenium; manganese, like rhenium, exists in Group VII of the periodic system. The optimum amount of carbide dispersion for chromium-base alloys was obtained by analogy with molybdenum. Strengthening in molybdenum is achieved by use of Ti-Zr carbide dispersions. A

Jan 1, 1964

By AIME AIME

C. H. BENEDICT, chief metallurgist of the Calumet and Hecla Consolidated Copper Co., has pioneered for nearly half a century. Noted for his ammonia leaching process, lie has Iong been responsible for all Calumet and Hecla mill, concentrator, and reclaination plant flowsheets. His influence has spread far beyond his own organization. lie is dean of Lake Superior metallurgists and has contributed greatly toward raising his specialty-the country over-to an honored profession; not merely an honored profession but a profitable one for industry and the public. The leaching process which he developed in 1912 has, since 1915, produced for Calumet and Hecla 250,000 tons of copper from waste tailings at a cost per pound, in 1929, below five cents. It has yielded profits of $35,000,000. In the war just ended, this process proved the only one adaptable to the recovery of copper from gilding-metal¬clad steel strip, and Calumet and Hecla treated more than 50,000 tons of such scrap for the Government.

Jan 1, 1945

By J. Spotts McDowell

INTRODUCTION The magnitude of the thermal expansion of silica brick, and its inability to withstand rapid temperature changes, present problems of considerable importance in the manufacture of siliceous refractories. In the study represented by the experimental data herein described, these problems are considered from the point of view afforded by the results of recent investigators: Fenner and his associates of the "Geophysical Laboratory, Washington, D. C., who have established the stability relations of the silica minerals, and Endell and co-workers in Berlin, who have studied the changes brought about in the constitution of siliceous refractory materials upon the application of heat. In the process of manufacture, the quartzite from which the brick is made changes in part into cristobalite and tridymite. The attempt is herein made to determine by microscopic methods the degree of transformation in various specimens of test bricks manufactured at slightly varying temperatures of burning, with varying coarseness of grain, and to determine the effect of repeated burning. The effect of variations

Jan 10, 1916