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By Rizo-Pairón Alfonso, A. M. Gaudin

PREVIOUS studies of activation in flotation have directed attention to the action of the activator on the mineral to be floated rather than to the relationship of the activator to the collector The latter phase of the problem, however, seems to have definite scientific, if not also practical, interest In the investigation reported in this paper, experiments were carried out, largely with quartz as subject, barium as activator, and oleate as collector The results obtained indicate that a I I ratio of collector ion to activator ion gives optimum results, and that a 2 I ratio almost fails to achieve activation and flotation Yet, a 2 I ratio would have been expected on stoichiometric grounds, had the coating been a normal salt of the activator ion with the collector ion, since barium is a divalent cation and oleate a monovalent anion To interpret and rationalize the observations, considerations of the crystal chemistry of quartz are helpful The point of view to which these considerations lead may be of general applicability to systems involving suspensions of solids in liquids, they confirm that an adsorbed coating is inescapable APPARATUS AND SUPPLIES The experimental work consisted in barium-ion abstraction tests, hydrogen-ion and hydroxyl-ion abstraction tests, flotation tests, and determinations of the surface of the crushed quartz The flotation machine was built according to the design of D W McGlashan It consists of a drill press in which the bit has been replaced by a stainless-steel impellor surrounding a stainless-steel stator, as in the Fagergren laboratory machine The air intake is controlled by a valve, and the cell consists of a beaker The quartz was obtained from vein quartz stored in large chunks It was first crushed to 20 mesh, then sized on a 28-mesh screen The 20 to 28-mesh size alone was retained for use This size was freed of coarse iron by passage through a Ball-Norton magnetic separator, bleached with boiling hydrochloric acid to remove residual abraded iron, washed with distilled water until the washings were thoroughly free of ferrous, ferric, and excess hydrogen ion, and stored in covered Pyrex beakers under water until used The barium was used as barium chloride, Baker's analyzed C P The oleate was used as sodium oleate It was prepared from sodium hydroxide, Baker's analyzed C P , and oleic acid purified by R R de Arellano3 in the laboratories at the Massachusetts Institute of Technology The purification procedure was elaborated from the recent researches of Brown and Shinowara 2 It consisted in (I) saponification of olive oil with potassium

Jan 1, 1942

By Ralph Hultgren, Bernard York, David W. Mitchell

It is a well-known fact that magnesium-alloy castings are apt to be coarse grained if the melt is not superheated several hundred degrees above the melting point before casting. (The casting temperature varies according to the shape of the mold. A typical casting temperature is perhaps 1400°F.) British practice is to heat to 900°C. (1650°°F.) for 15 min., cool rapidly to casting temperature, and cast.1 In Germany superheating is carried out at 850° to 900°C. (1560° to 1650°F.) depending on the amount of scrap used. It is stated that further refinement will be obtained by prolonging the period of superheating or by increasing the superheat temperature to 950°C. (1740°F.).2 In the United States superheating is carried out at i600° to 1700°F. (871° to 927°C.), perhaps even higher in some places. It is stated that superheating effects are found as low as 1500°F. (816°C.), but several hours are required.3 These commercial treatments lead to grain sizes in sand castings that may vary from 4 to 8 grains per sq. mm.§ in heavy sections and from 60 to l00 in 3-in sections to perhaps 380 in thin sections. It is also generally known that the refining effect of superheating is lost if the melt is held for some time at lower temperatures before casting. Aside from these very qualitative statements, there is little to be found in the literature as to the effect of temperature and time of superheat on the final grain size. Because of the uncertainty of these factors, the Office of Production Research and Development of the War Production Board placed a research contract with the University of California, supervised by the War Metallurgy Committee. This research, which was done under the "Restricted" Project NRC-550, is the basis of this paper, which has been released for publication by the O.P.R.D. The material studied was an alloy prepared from carbothermic magnesium. The temperatures required for grain refinement proved to be widely different from those used in practice, as described in the statements in the first paragraph. This difference is attributed to the fact that the magnesium in the specimens was of carbothermic origin instead of the electrolytic magnesium in common use. MATERIALS AND METHODS The magnesium alloy studied was one of the most popular sand-casting alloys, with a nominal composition of 9 per cent aluminum, 2 per cent zinc, and 0.r per cent (minimum) manganese and the balance magnesium. This is designated

Jan 1, 1945

By W. D, D. W. Mounce, W. M. Rust

The almost universal acceptance of electrical logging by the petroleum industry calls for a critical examination of the physical bases of the common methods. This is particularly needed for the natural potential log. The conventional explanations are based on the phenomena of electrofiltration and electro-osmosis. However, experimental data show that they fail to give a basis that is quantitatively sound. Moreover, they lead to interpretations of details of electrical logs that are erroneous. It was found experimentally that when a plug of shale is placed in a chain of dissimilar electrolytes, a current flow results. Experiments on oil-well cores and fluids similar to those existing in wells show that potentials are set up which are in reasonable agreement with those encountered in electrical logging. Doubtless other sources of potential are important but this explanation not only accounts for much of the potential but also clarifies some fairly familiar examples of misinterpretations. Introduction The extraordinary value of electrical well logging as a tool for petroleum engineers and geologists is now so uni- versally recognized that it is not necessary to point out the ways in which it can be useful. It is sufficient to mention only the saving that has resulted from the elimination of much coring that would have been necessary under former practices and the considerable additions to reserves resulting from the discovery of sands missed in coring. Paradoxically, the very remarkable success that has resulted from the application of electrical logging to correlation and completion problems has cost some of its most consistent users dearly.' The fact that some operators have placed unwarranted faith in erroneous interpretations of electrical logs does not reduce the value of the logs. It should, however, make one pause long enough to ask why experienced users should be misled. The answer to this question is not hard to find. In nearly every case, the fault has been oversimplification. This is illustrated very aptly by the familiar interpretation and theory of the natural potential log. Recording and Interpreting Logs The natural potential log is extremely simple to record precisely enough for all present-day uses. One needs only an electrode, a cable to lower the electrode through the drilling mud, a recording meter and a surface ground connection. The electrode can be elaborate but need not be. A simple brass rod 2 in, in diameter and 2 or 3 in. long is quite satisfactory. The cable need not be particularly well insulated, nor need it have a very low resistance. The recorder can be a vacuum-tube 1 References are at the end of the paper.

Jan 1, 1944

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.' 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' 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.9'10 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 C. H. Stewart, R. A. Fagin

A two-dimensional, three-phasereservoir simulator was programmed for a large memory digital computer. It was designed to provide a practical solution to describing the complex physical relation between the natural forces and the physical properties of a heterogeneous reservoir when subjected to a specific set of conditions. A reservoir study is briefly described to illustrate application of the model. A full volumetric account of three phases (oil, gas and water) is performed simultaneously throughout an integration net representing the reservoir. Absence of one or two of the phases is treated as a special case of the more general situation. Expansion (or contraction) of all phases, including rock expansion, is performed so that the pressure calculation is the general unsteady-state case. To account for the large variations of subsurface elevation encountered in some reseruoirs, and to allow for segregation of the various phases, a gravity head term is included in the basic drive potential. Appropriate fluid and rock properties are used in polynominal surface form (functions of pressure and/or depth) or they can be entered as space variables at each position of the integration net. An unsteady-state water influx calculation, based on the method of van Everdingen and Hurst, l was connected to the boundary of the matrix to simulate aquifers of various sizes. In addition to reservoir calculations, three-phase fluid flow from the producing depth to the wellhead, including provisions for gas lift, was incorporated in the simulator. A workover routine was also built which can automatically switch to a different set of production relations when a gas-oil ratio or water fraction reaches a limit; or it can shut-in the well if prescribed. INTRODUCTION This paper describes a reservoir engineering mathematical simulator used to represent the complex interaction of natural forces and physical properties of a reservoir during natural depletion or with various injection schemes. The simulator, which was programmed for a large memory digital computer, is a two-dimensional calculation which handles three mobile fluid phases simultaneously (oil, gas and water). Basic requisites for the method are individual well production and pressure data, hydrocarbon fluid properties, geological data (producing depth and net sand), capillary pressure data, relative permeability data and permeability and porosity information. Matching the past performance of a combination drive reservoir often has yielded information concerning continuity and the validity of basic data. Detailed predictions of future performance can be made for continuation of current depletion methods (natural depletion) as well as for various types of recovery by gas or water injection. Combination injection cases and pattern studies can also be performed. Workover programs, gas lift and different types of artificial lift programs have been investigated using a technique similar to that described by Kern and Nicholson2 except that conditions of pressure and saturation at the block within which the well is located are used rather than average reservoir conditions. Drilling additional wells to optimize profit was explored, both as to number and location, by placing wells at different spots within the reservoir matrix. Special depletion processes can be examined, such as upstructure drainage and lateral (or strike) waterfloods in thin oil columns. In one case the mathematics of the simulator were modified to calculate the displacement in the vertical plane rather than in the horizontal plane. In this manner specific reservoir problems can be studied, such as coning of gas and/or water around production points, fingering along permeable stringers or, more generally, frontal advances in a heterogeneous section.

Jan 1, 1967

By A. W. Hale

IN a work published in 1838, De Morgan, the author of the article on "Probabilities,' in the Encyclopedia Metropolitana, says " The method of least squares is not yet introduced into the affairs of common life,….that many things which are demonstrable only by the higher branches of mathematics are looked upon as useless." And he mentions an instance in which "a method was suggested for estimating the relative importance of boroughs, by considering their population and contributions to the revenue com-

Jan 1, 1881

By J. E. Hilliard

Isobaric sections of the eutectoid region of the iron-carbon phase diagram have been exgerimentally determined at 35, 50, and 65 kb. The phase boundaries were located by metallographic analysis of specimens quenched after equilibriatwn at known temperatures and pressures. With increasing pres -sure a pronounced decrease in the solubility of FesC in austenite was observed together with a depression of the eutectoid temperature. These two effects resulted in a shift of the eutectoid composition toward a lower carbon content; at 65 kb the eutectoid was at less than 0.2 wt pct C. These results are in qualitative agreement with thermodynamic calculations. It has also been shown by calculations that Fe3C in contact with saturated austenite will be stable with respect to both graphite and diamond formation at all pressures above -3.5 kb. 1 HE investigation described in this article was part of a more general study of the effect of high pressure on transformations in Fe-C alloys. Thermodynamic calculations and exploratory runs made in 1959 at the start of the program indicated an appreciable change with pressure in the phase equilibria of Fe-C alloys. However, the calculations were not considered reliable enought to provide the quantitative information required for the interpretation of the effect of pressure on the kinetics of transformations. An experimental investigation was therefore made to determine a series of isobaric sections of the eutectoid region of the phase diagram at pressures up to 65 kb. EXPERIMENTAL PROCEDURE Materials. Seven alloys with analyzed carbon contents of 0.10, 0.20, 0.38, 0.60, 0.77, 0.93, and 1.20 wt pct C were prepared from Ferrovac" iron and high-purity graphite induction melted in magnesia crucibles under argon. The ingots were hot worked and swaged down to 0.19-in.-diam rod which was then centerless ground to a final diameter of 0.125 in. Samples for chemical and spectrographic analyses were taken from each end of the rods. The prin- cipal impurities were found to be Ni, Al, Co, and Si which were present in amounts up to 0.03, 0.02, 0.01, and 0.01 wt pct, respectively. Specimens were prepared by slicing the ground rods into pills 0.06-in. thick which were silver plated to reduce decarburization during the equilibration. Silver was chosen for this purpose because of its very low solubility for carbon and its mutual immisicibility with iron. High-Pressure Apparatus. The high-pressure runs were carried out in the "Belt" apparatus.' As shown in Fig. 1, this consisted of a cylindrical cell compressed between two Carboloy punches loaded by a uniaxle press. Radial support to the cell was given by the "belt" which was a Carboloy die heavily prestressed by a series of steel binding rings. Laminated gaskets of lava and metal separated the punches from the inner surface of the "belt". A cross-section of the high-pressure cell is shown in Fig. 2. Two specimen pills were located inside a resistance heater of 0.20-in.-diam Nichrome tubing. The ends of the tube were sealed with alumina and lava pills tamped in place after the

Jan 1, 1963

By H. M. St. John

THE melting department is the heart of the foundry. From it clean metal flows to the molding floor, in the right quantity, at the right time and at a sufficiently low cost-or, if not, the foundry fails to thrive. Since it is our purpose here to discuss present-day melting practice in the foundry, it may be well at the start to emphasize the wide differences in foundries and the conditions under which they must operate in order to reach the goal stated in the first paragraph. In every foundry, large or small, jobbing or captive, the same factors must be dealt with but they are of varying consequence and must be dealt with in varying ways in different foundries. Particularly in the nonferrous industry, there is so wide a variation in the composition of alloys used and in the character of castings made that no one type of furnace, nor any one method of operation, can be expected to produce the best results at all times. The present discussion will not attempt to include all nonferrous metals. It is intended to cover only the copper-base alloys in which copper is the dominant element, most of which are commonly known as brass or bronze. The discussion is further limited to the melting of these copper-base alloys for use in sand-casting foundries. Die-casting plants, the brass-rolling mills and certain other metal industries have melting problems peculiar to those industries, which will not be considered here. The following considerations are elemental in all foundries and are listed in what is believed to be the relative order of their present-day importance: I. The melting department must meet the foundry's requirement for dean, fluid metal, of specified composition and purity, at a temperature suitable for the work the foundry has in hand. This is the prime consideration in any foundry, at any time, anywhere. 2. Working conditions surrounding the melting furnaces and attending their use must be good. 3. The cost of molten metal at the mold must be as low as possible. 4. The operating characteristics of the furnaces must be sufficiently flexible, to meet normal variations in foundry requirements. 5. The operation and maintenance of the melting equipment must not require more skill and experience than is available in the particular foundry in question. METAL QUALITY It is not a function of the melting furnace to refine or improve the quality of the metal but simply to melt it without impairing its quality. Good practice requires, therefore, that care must be taken to supply the melting department with metal of inherently good quality, assured by specification or otherwise, having all the properties necessary to produce the castings desired. An alloy contains a number of primary elements, which must be present in definite proportions if the castings made from it are to have the desired properties. If the castings are made to a customer's specification, this will state the range within which these principal elements (for example, copper, tin, lead and zinc) are permitted to vary.

Jan 1, 1946

By K. A. Slagle

Hydraulic analysis of the wellbore has become increasingly inzportant for designing cementing operations and selecting equipment, materials and techniques to complenzent modern well-c-ompletion practices. Non-Newtonian fluid technology has advanced beyond the point where former empirical methods of analysis adequately define the hydraulic system and fluid properties. In view of these factors, this paper describes a series of rheological calculations which have been found practical, through field usage, for assistance in selecting a cementing program. A relatively simple laboratory method using standard viscometric equipment is suggested for determination of the rheological properties of slurries, and clrrta are presented on some of the more common cementitrg conzposition.A. A criterion for divergence from laminar-flow characteristics has been proposed. Usefulness of the calculations is indicated by examples of cementing operations where they have been used. INTRODUCTION With the changing aspects of well-completion practices during the past few years, it has been increasingly important to have a relatively simple method of analyzing the flow conditions existing in the well during cementing operations. This is particularly true in view of the improved economics toward which most of the changes have been directed. Rheological characteristics of slurries used for cementing should be a major consideration in the trend toward smaller casing sizes, either single or multiple strings. Receiving increased attention is the practice advocated in 1948 by Howard and Clark' of attaining turbulent flow with the fluids circulated during a primary cementing operation. While there may still be a difference of opinion concerning this technique, most available information indicates that superior primary-cementing results are generally obtained when high displacement rates are employed. Fluid properties of the slurry to be used must be available, as well as calculation methods, to determine what flow rates should be attained and the probable consequences in terms of frictional pressure and horsepower utilization. It would certainly be inappropriate to attempt high displacement velocities if sufficient pressure might be developed to create lost circulation. Since cementing slurries are non-Newtonian fluids, it is not possible to define their rheological or fluid properties by the single factor of viscosity and then make calculations for the quantities just described. Because the shear stress-shear rate ratio is not constant: it becomes necessary to establish at least two parameters for adequate fluid-flow calculations. It is not the purpose of this paper to delve into the mathematical development of non-Newtonian technology, nor to discuss the arbitrary classification system under which a single fluid may resemble two or three different classes depending upon experimental conditions. Rather, the intention is to present a useful series of calculations based on a concept applicable to both Newtonian fluids and to the preponderance of non-Newtonian fluids encountered in the oil-producing industry. Development of this approach was begun some 32 years ago,' and has most recently been brought to fruition by Metzner and his co-workers at the U. of Deleware. Some non-Newtonian fluids encountered in the petroleum industry, other than cementing slurries, have also had the benefit of this method of analysis."' The two parameters required to define the fluid are usually denoted by the symbols n' and K' and, for the purposes of this discussion, are called "flow behavior index" and "consistency index", respectively. These two slurry properties permit calculation of the Reynolds' number and the "critical" velocity, or the velocity at which departure from laminar flow begins. EXPERIMENTAL DETERMINATIONS The two principal instruments used for rheological studies are the pipeline (capillary-tube) viscometer and the rotational viscometer. When conveniently possible, a capillary-tube viscometer (where the pressure drop and flow rate of the material can be measured) is the better method for rigorous determination of the flow behavior index and consistency index for non-Newtonian fluids. With pressure-drop data at various flow rates, it is then possible to prepare a logarithmic plot of shear rate as the abscissa-shear stress as the ordinate. For fluids which do not exhibit time-dependency, these data will usually produce a straight line. The flow behavior index n' represents the slope of this line, while the consistency index K' becomes the intercept of this line at unity shear rate in accordance with the mathematical derivations associated with this concept of rheology. Due to the difficulties anticipated in maintaining a uniform, pumpable cement slurry for the time interval required to obtain measurements from the pipe viscometer, the n' and K' data reported herein were obtained using a direct-indicating rotational viscometer (Fig. 2). The

By Arthur Phillips, E. N. Skinner

DURING the course of an experimental program concerned with the hydrogen embrittlement of copper containing oxygen in concentrations within the solubility limits it became necessary to make a critical appraisal of the literature dealing with the solubility relationships of oxygen and solid copper. The latest determinations, and perhaps the only data obtained on "spectroscopically" pure copper, are those of Rhines and Mathewson1 who reported that the solid solubility increases from 0.007 per cent oxygen at 600°C. to about 0.015 per cent at 1050°C. Hanson, Marryat and Ford2 had previously placed the solubility limit at less than 0.009 per cent oxygen at 1000°C. and Allen and Street3 had suggested, on the basis of an unpublished research by T. Hewitt, not over 0.005 per cent oxygen at 500°C. In the introductory stages of the investigation indirect evidence accumulated to suggest that the solubility limits were significantly lower than those previously reported. For this reason it was deemed essential to clarify this point before proceeding with a program intended to establish a quantitative relationship between hydrogen embrittlement and oxygen concentrations positively known to be within the solid solution range. Furthermore, the increasing production and the highly selective applications of the commercial "oxygen-free" coppers inevitably direct attention to the practical necessity for exact knowledge regarding the effects of minute concentrations of the elements ordinarily found in the high-purity coppers now available. Of these elements oxygen occupies a unique position, not only by virtue of its specific effects on copper but more particularly in view of its important reactive tendencies toward the other impurities with which it is associated. Rhines and Mathewson considered several methods for measuring the solubility of oxygen and finally adopted the simple plan of saturating the specimens, obtained from redeposited cathode copper, by heating at the desired temperature in air. After the removal of surface oxide by mechanical and chemical means, the oxygen content was determined in the underlying metal. In general, this process of saturation, with a few modifications, was followed by the present writers. Although the procedure is direct and has obvious advantages, its effectiveness, unfortunately, is reduced by an excessive scaling of the copper, particularly at the higher temperatures. After saturation treatments above 900°C. the writers found that the specimens, necessarily rather thin in the original condition, consisted largely of scale and yielded too little metal for a satisfactory analytical sample. Furthermore, great difficulty was experienced in effecting complete removal of the scale. Needless to say, it is necessary to exercise extraordinary care in the preparation of the surface of the analytical sample in order to eliminate submicroscopic fragments of cuprous oxide which ordinarily are lodged in the crevasses and

Jan 1, 1941

By William L. Fink, H. R. Freche

The constitution of the aluminum-cobalt alloys has been the subject of relatively few investigations. Brunckl analyzed the residue which remained after treating the 17 per cent cobalt alloy with dilute hydrochloric acid. The results of the analyses indicated the existence of a compound Co3Al13. Guillet2 published a liquidus for the aluminum-cobalt system which contained two maxima corresponding to CoA16 and CoAl2 and two eutectic points at 30 and 74 per cent Co. The most extensive investigation of the system was carried out by Gwyer13 whose results are summarized in Fig. 1. It will be noted that at the aluminum end there is a suppressed eutectic at 644' C. By extrapolation of the duration of the eutectic arrest to zero, the composition of the compound was placed at Co3Al13. Another thermal arrest was noted at 550" C., which Gwyer attributed to a peritectic reaction. The present investigation of the aluminum end of the aluminum-cobalt system is the eleventh of a series dealing with the constitution of aluminum-rich alloys prepared from electrolytically refined a1uminum.l Preparation of Alloys.—The alloys used in this work were all prepared from electrolytically refined aluminum, the analysis of which is shown in Table 1. In preparing some of the alloys, metallic cobalt (98 to 99 per cent) was used either directly or in the form of an intermediate alloy, the composition of which is given in Table 1. In order to obtain alloys of higher purity, cobalt was introduced into some of the alloys by means of chemically pure cobaltous chloride which was readily reduced by the aluminum. A small electric furnace with nickel-chromium heating elements was used in the preparation of the alloys. Chemical Analysis.—An analysis sample from each melt was chill-cast in the form of a plate 3/16 in. thick. In all cases the casting temperature was well above the liquidus. Cobalt was determined electrolytically in all alloys containing more than 0.05 per cent cobalt and by the nitroso-

Jan 1, 1932

By L. A. Weitzenkamp, N. M. Bashara

A study of the electrical conductivity of gold films less than 200 in thickness indicates a negative temperature coefficient of resistance and a thermal actiuatlon energy of less than 0.25 ev. The films consist of discrete metal islands of linear dimensions from a few angstroms to 1000A. Films were able to withstand applied fields up to 60,000 v per cm before breakdown occurred. A model for the conduction mechanism is proposed which involtes a Potential barrier due to work junction, irriage forces , and an electrostatic potential arising from separating an electron from a neutral island leaving behind a positively charged metal island. Activation energies of less than 0.25 ev ave consistent with this model, which includes a tunneling andor Thermal mechanism for conduction between the separate metal islands. An apparent satuvation effect in conductivity at high fields is observed experimentally. The saturation effect may be explained by the influence of the electrostatic contribution to the potential barriers for the transition through several islands adjacent to the original island which was activated to give up an electron. The proposed model gives Poor quantitative agyeement for the intermal electrical field between islands. ThIS paper will relate the structure of discontinuous metal films to the electrical properties and will emphasize the following topics: 1) the relation of the conduction mechanism to particle size and a comparison of particle size from electrical measurements with electron-microscope studies; 2) the saturation of the conductivity at high electric fields; and finally, 3) a comparison between the external field applied and the apparent field between particles. che- latter comparison points to a need for a modification in the model for the conduction mechanism first proposed by orter' and expanded by Neugebauer and webb2 which will be dealt with in the discussion. The paper is based on results on gold films on glass microscope slides. The clms were vacuum-evaporated and were about lOOA thick, thickness being measured by interferometry. It has been observed that metal films of this thickness do not exhibit bulk metallic conduction. Films thinner than some critical thiclmess, depending upon substrate temperature and other factors, have conductivities which increase with increasing temperature with thermal activation energies of less than 0.25 ev. Electron-microscope studies3 have shown that these films consist of discrete metal islands having linear dimnsions from a few angstroms to approximately 1000A. When the metal is being vacuum-deposited on the substrate, islands on the order of a few angstroms appear first. As the deposition continues the islands may tend to agglomerate into larger particles and may eventually grow together into a continuous film,3''' In our tests the conductivity of the gold films was found to be about ten orders of magnitude less than the bulk conductivity of gold. When oxygen was introduced into the test chamber the conductivity decreased by a factor of about one-third. This can be related to an increase in work function for gold caused by adsorption of oxygen, as reported by Oullet and Rideal.s Exposure to an atmosphere of water vapor caused an increase in conductivity by a factor of 2 or 3 when a low field was applied. When the films were exposed to water vapor under a high field the conductivity increased by as much as two orders of magnitude. The activation energies measured were much less than the work function for gold, 0.25 ev or less, with the smaller activation energies observed for thicker films. It will be shown that the activation energy is a function of particle size and spacing. In general the model for the potential between metal islands would include the effective work function, the image force, the applied field, and an electrostatic term. The electrostatic contribution arises from the potential required to separate an electron from a conducting sphere. According to Neugebauer and webb2 the maximum potential due to the field and the electrostatic term only is

Jan 1, 1967

By A. F. Taggart

This paper describes the result of a series of experiments run in the laboratory of the School of Mines, Columbia University, during the winter of 1927-28. It shows that the several operating adjustments of a pneumatic table produce effects in the action of a given coal that may be grouped into two classes, viz.: stroke length, speed and rocker-arm angle, which affect longitudinal travel; air supply and table slope (transverse and longitudinal), which determine transverse travel. The magnitude of the effect of the different adjustments varies. Some of the adjustments affect stratification of the bed, both as respects size and specific gravity of the bed components, as well as direction of travel. Operation of a pneumatic table is fundamentally different from that of a wet table in that the former exerts, through the air supplied, a force on the particles upward away from the deck which is lacking on the wet table while, on the other hand, it lacks the positive control over cross travel that is supplied by the wash and feed water. Apparatus The pneumatic table used is shown in Fig. 1. Deck A is 20 by 12 in. and consists of nainsook supported on slats that register with the riffles. Fig. 2 is a photomicrograph of the nainsook used. It shows that the cotton threads average about 0.13 mm. dia. and the apertures about 0.17 mm. The deck carries 12 riffles consisting of wooden strips, 3/16 in. wide and 1/4 in. high, laid parallel to the feed side of the table. The riffles terminate along a line starting on the feed side at a point 11 in, from the mechanism end and running to the corner formed by the coal side and slate end. Taper starts from a line that runs parallel to their terminal line through the junction of the upper riffle with the mechanism end. The height at the terminal line is about 1/32 in. The deck with its supporting slats is carried on a framework consisting of rails A, sloping end rails B, and adjustable metal strips C, which latter permit variation in transverse slope. This frame is enclosed at the edges by means of heavy canvas, indicated in the sketch by wavy lines, which makes a flexible conduit between the deck and the stationary air chamber,

Jan 1, 1930

By E. Lifshin, R. E. Hanneman

QUANTITATIVE applications of the electron micro-beam probe frequently involve the evaluation of complex mathematical expressions and/or the analysis of large amounts of experimental data. The purpose of this communication is to describe briefly a versatile and useful computer program system that is applicable to analyze rapidly a wide variety of practical microprobe problems. This system consists of a group of ten FORTRAN programs that can be stored on tape, cards, or in the memory disc of the computer. These programs, or links, can be run individually or in any prespecified sequence without interrupting the operation of the computer or without destroying information which is being transfered from one link to another. For the program system described here a GE-235 computer with disc storage was used, so that the DCHAIN method of program linking was employed. Included in the library are programs to: 1) initiate analysis of a new set of data and transfer control between all other programs in any predetermined manner; 2) generate theoretical calibration curves of composition vs relative intensity; 3) generate empirical deviation parameters from least-square fits of experimental calibration data from standards of known composition; 4) convert raw X-ray data to corrected composition; 5) determine inter diffusion coefficients by Matano analysis of con centrat ion -distance data on a uniaxial diffusion couple; 6) determine activation energies and frequency factors of temperature-activated processes such as diffusion; and 7) generate calibration curves for determination of the thickness of thin films using microanalysis. A detailed description of these computer programs and their underlying principles is available on request from the authors."' The first program to generate theoretical calibration curves of corrected relative intensities vs composition uses the Poole and Thomas atomic number correction' and the Philibert absorption factor' with a voltage-dependent mass absorption coefficient for electrons in the alloy. A modified Castaing fluores- cence correction is also used which includes the effects of both Ka and KO radiation and over voltage.' Once the theoretical curves have been calculated in 1 wt pct intervals, these results are least-squares fit to obtain Ziebold deviation parameters' which are stored in COMMON in the computer memory. The net discrepancies between the original theoretical calibration curve and the regenerated curve using the Ziebold parameter are computed. Although this link is explicitly written for K-K fluorescent interactions, it can be applied to K-L, L-K, and L-L interactions as previously disc~ssed."~ Similar programs have also been written to utilize the Wittry fluorescence correction, Birks combined corrections, and various other corrections.' These modified programs have proved to be quite useful for quantitative comparisons of the results of the various theories. The program for conversion of raw X-ray data to corrected composition includes corrections for drift, backround, and instrumental dead time. The corrected intensities are converted to composition by use of the Ziebold equation"2 and parameter obtained from the program system. The results can be obtained for either atom or weight fractions. In addition to accurately computing interdiffusion coefficients the Matano analysis program calculates least-square smoothed values of concentration, concentration gradient, and curvature for each point on the raw input concentration profile. In order to obtain high accuracies a unique method of performing a least-square polynomial fit to incrementally advancing profile segments which overlap is used.' This program has been successfully modified for use in ternary diffusion problems3 and can readily be modified to handle analysis of diffusion profiles which include phase boundary discontinuities. This link is generally applicable to analysis of interdiffusion data obtained by other techniques as well as by the microprobe. The primary function of the next program is to least-squares fit experimental diffusion data to the normal Arrhenius function: D = Doexp(-Q/RT), to obtain values of Do and Q. In addition the probable error and one, two, and three u statistical confidence limits of DO, Q, and log D are evaluated. This program is also directly useful for analysis of any other simple temperature-activated processes including conductivity, and certain deformation and chemical processes. The program to generate calibration curves for film-thickness determination using the microprobe is based on a numerical integration of the equation derived by Cockett and ~avis.' Values of film thickness obtained by this program for copper on various substrates are in good agreement with measurements made by other techniques. Versions of the above program system have been prepared for use with or without a remote teletype connection to the computer for processing on either a real-time or time-share basis. The instrumentation coupling a microprobe to a teletype for automatic data collection and analysis by the presently described program system has been reported elsewhere by the authors.' If teletype equipment is not used to communicate with the computer, standard methods of card reading and tape reading can be used. In either

Jan 1, 1967

By Edward Hyde

THE HIGH-TEMPERATURE SCALE IN OPTICAL PYROMETRY AT the basis of optical pyrometry lie the theoretical and experimental data of the so-called blackbody. The black body is essentially a theoretical conception, with certain simple properties attributed to it -fundamentally, the property that its radiation at any temperature is a unique function of the temperature and does not involve any other variables. As a theoretical conception, an equation has been developed by Boltzmann connecting the total radiant power with the temperature, and another equation by Planck connecting the distribution of radiant power throughout the spectrum with the temperature. The integral of the latter with respect to wave-length conduces to the former and permits the evaluation of the constant c1 of the Planck equation, ass given in the form. J-= cl?-5 c2 (1) e ? T ? 1 assuming that the constant Q of the Stefan-Boltzmann law E=a(T4-T40) is known. The other constant c2 is arrived at by other methods, which will be discussed later. This equation for the black body lies at the foundation of optical pyrometry. To make the discussion complete, it should be stated that the theoretical black body is quite closely realized by a hollow enclosure with walls at a uniform temperature and radiating through a small orifice. The electrically heated black body, first introduced by Lummer and Kurlbaum, is an essential part of the equipment of a pyrometric research or testing laboratory. Numerous investigations have shown that its radiation conforms to that of the theoretical black body within experimental errors. Hence by operating the electrically heated black body at the melting point of some pure metal for which the temperature of melting has been determined on the vas scale. a standard is obtained for comparison with

Jan 9, 1919

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

By J. M. Flaitz, A. S. Parks

OF the various methods of sampling gas-condensate wells, a method that secures a continuous representative sample of the well stream is desirable. Such a method, consisting of a sampling tube introduced into the well tubing, has proved satisfactory. The method is sufficiently accurate for operating and engineering problems A portable testing apparatus can be used with the sampling tube to obtain data useful in studying the economic and technical aspects of the development and operation of gas-condensate properties. Introduction The recent discovery and development of gas reserves that contain hydrocarbons that condense with reduction of temperature or Pressure, or both, to form a product known as condensate, has brought many new problems to the oil and gas industries. With further discovery of deep, high-pressure fields it is presumable that many more gas fields of this type will be added to the steadily increasing number. Such gas reserves are found either associated with oil as a gas cap or in separate formations. There seems to be no positive correlation between the physical or geological nature of the reservoir, and the chemical composition or phase characteristics of its contents. Knowledge of the chemical make-up and phase behavior of gas-condensate reserves is needed to cope with many problems. A knowledge of the chemical composition and phase characteristics of the reservoir material is necessary to properly design a gasoline or recycling plant, to estimate natural gas and condensate reserves, to enable the operator to study the economic and technical aspects of various methods of operation and development, and to carry Out the plan of operating subsurface and surface lease equipment. This information is often useful in questions of mineral ownership, proration, legal position, and taxation. It is the purpose of this paper to discuss methods used by the writers to determine the chemica1 composition and phase characteristics of the fluids produced from a condensate well. The scope of the paper includes a discussion and description of the method of sampling, the results of tests on the accuracy of the sampling method, a description of a portable testing apparatus used to examine the phase characteristics, typical results of tests on wells from several condensate fields, and some of the applications of these data to production problems. References to previous work on this subject are cited at the end of the paper. The Problem At reservoir conditions of temperature and pressure, the fluids produced from a condensate well exist in a homogeneous vaporous condition. The consequent reduction of temperature and pressure that occurs as this gas enters and flows up the well tube results in condensation of some of the hydrocarbon material to form a liquid. The relative amount of liquid condensed at any point in the flowing system

Jan 1, 1942

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

By E. S. Bartlett, D. N. Williams

QUANTITATIVE values for the oxidation rate of unalloyed molybdenum in air at temperatures above the melting point (1460°F) of the characteristic oxide are contained in the literature as a result of previous investigations. Lustman' reported values corresponding to 0.36 in. penetration per day (IPD) at 1500 and 1600°F in still air, noting essentially no variation in rate with temperature. Jones, Spretnak, and Speiser' reported values corresponding to 0.14 and 0.13 IPD at 1500 and 1800°F, respectively, in still air, attributing the decreased oxidation rate at higher temperatures to a lesser accumulation of the corrosive molten oxide on the surface at the higher temperature as a result of increased volatilization rate. Harwood3 ecently summarized work in the field, presenting generalized data corresponding to 0.48 to 0.96 IPD at 1800°F and 0.55 to 0.83 IPD at 1700°F in slowly flowing air. In a recent program at Battelle, it became desirable to know more about the characteristic oxidation behavior of molybdenum under varying conditions of temperature and atmosphere. Using oxidation-test apparatus designed for dynamic, continuous recording of weight change during testing,' values for the oxidation rate of molybdenum were obtained at temperatures from 1400 to 2150°F. In addition the effect of air flow on the oxidation rate was studied briefly at temperatures of 1600, 1800, and 2000°F. Exhaust of the contaminated atmosphere from the oxidation chamber was effected by an impeller pump attached to a 3/16-in.-diam opening in the oxidation chamber. The volumetric exhaust rate (cubic feet per hour) was normally maintained slightly in excess of the input rate to avoid condensation of MOO,,' on the sample suspension rod. The entering atmosphere was preheated prior to admission to the oxidation chamber by a 1 1/2-in.-diam cup packed with shredded asbestos. The experimental data are presented in Table I. Comparing conditions 2 and 3 (taking into account the temperature difference) and conditions 8 and 9. shows that in the absence of forced exhaust an atmosphere of moving air results in greater oxidation rate than a stagnant atmosphere. The use of forced exhaust, as shown by comparing conditions 3 and 4 and conditions 14 and 15: resulted in an even greater increase in oxidation rate. By virtue of the size of the atmosphere input and exhaust openings, it was calculated that the exhaust velocity was about 60 times that of the input velocity for essentially equal volumetric flow rates. Because of the proximity (about 3/4 in.) of the exhaust port to the specimen, it is logical to assume that cleansing of the atmosphere immediately surrounding the specimen was accomplished much more efficiently by the exhaust flow than by the input flow at a constant-volumetric flow rate. Also, it can be seen by comparing conditions 4 through 7 and conditions 11 through 13 that increasing the rate of atmosphere flow (by increasing input velocity with a proportional increase in exhaust velocity) above some optimum value has little, if any, further effect on the oxidation rate. These results suggest that there is a maximum oxidation rate for molydenum at a given temperature which is obtained when conditions are maintained such that the partial pressure of MOO3 in the atmosphere surrounding the specimen is at a low value. By controlling the partial pressure of MOO, surrounding the sample, it is possible to control the rate of volatilization of MOO:, from the surface. This, in turn, affects the rate of oxidation, since the thickness of the MOO3 layer determines the amount of oxygen which will be able to reach the reaction surface.' When the liquid oxide layer is less than some critical thickness, i.e., when the volatilization rate is high, enough oxygen is transported to the active surface to permit oxidation to proceed at the maximum rate allowed by the kinetics of the oxidation reaction. However, if the volatilization of MOO,, is suppressed, the thickness of the layer of MOO3 on the surface increases, and the diffusion of oxygen through the oxide layer becomes the rate-controlling step in the oxidation process. The lack of agreement between the present results and those of previous investigators is presumed to be due to differences in removal of the oxidation product (Moo,) from the immediate vicinity of the sample. By comparing conditions 1, 5, 10, 12 and 14, it is seen that when forced exhaust was used the oxidation rate of molybdenum increased with increasing temperature. A rapid increase was observed between 1400 and 1600°F, attributable to the effects

Jan 1, 1959

By H. M. Howe

On commencing the construction of the Orford Company's copper smelting works, at Bergen Point, N. J., I endeavored to convince our President, Mr. W. E. C. Eustis, by actual tests, that at the pressure of from 15 to 18 ounces per square inch, employed by us in smelting, less power was consumed in delivering a unit of blast by a Baker blower than by a fan blower. I attempted to prove this in the following manner: Across the mouth of a No. 5) Baker blower I firmly fastened a board with two round holes, 6 inches in diameter, cut in it. The board was fastened so tightly that no air could escape except through the holes. I then drove the blower at several differerent speeds, observing the pressure at which the air excaped through the two openings for each different speed of the blower, and also indicating the engine, whose only work at that time was to drive the blower. From this I calculated the quantity of power required to deliver, with a Baker blower, sufficient air to keep the pressure at a given point, while it escaped freely through the two six-inch apertures into the open air; or, in other words, to deliver air at a given pressure through these two openings. From the total power so consumed it was, of course, necessary to deduct the power which was required to drive the engine itself. This was ascertained by removing from the engine the belt which drove the blower, and then noting the quantity of power consumed in simply turning the engine over without any

Jan 1, 1882