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Edward Halse, Puerto Berrio, Colombia, S. A. (communication to the Secretary): I have read with much pleasure the interesting and valuable paper by Mr. Kunz, and hope that the following brief notes, gathered a few years ago, while a resident in Mexico City, may help to elucidate the subjcct: Turquoise.—This was known to the Aztecs as Xihuitl. Santiago Ramirez states that they found it in the Cerro Xicohtzonc, close to Atzcapatzalco, a suburb of the City of Mexico (compare page 59). Opal.—This was known to the ancient Mexicans, for they named it mezcuitlatt (compare page 63). Jade.—Under this was iucluded a third mineral, prehnite, not mentioned by Mr. Kunz. According to James D. Dana, part of the "jade " of China is prehnite; and Humboldt informs us, in his work on New Spain, that the same species of jade is known in some parts of Mexico as mahagua (majagua ?). The same writer says, in his Views of the Cordilleras, that the Aztec name Tecpatl included flint, hornstone, and green jade; and finally, in his Travels in South America," he discusses the nature of the ancient amazon-stones, and declares them to have been made out of a jade resembling " compact feldspar," one of the constituents of the gabbro verde di Corsica. IIence those stones were probably composed of nephrite. According to Humboldt, the form given to them most frequently is that of the Babylomian cylinder, longitudinally perforated, and loaded with inscriptions and figures. They were also cut by the natives into very thin plates, perforated at the center, suspended by a thread, and worn as amulets. According to the historian Clavijero, the specific name given by the Aztecs to the nephritic stone (jadeite) was Quitzalitztli,

Jan 1, 1902

By R. W. Nelson

The theoretical basis is presented for energy dissipation methods of measuring permeability in saturated heterogeneous media. Analysis starts with the equation for single-phase flow in heterogeneous porous media which is a first-order partial differential equation in the unknown permeability. This equation is reduced to a system of characteristic equations useful in deriving a differential expression for the permeability as a function of the known potential distribution. For steady flow systems the expression is integrable, giving the permeability integral for direct calculation of the distribution along successive streamlines. The boundary condition in permeability is presented and includes a discussion of the special requirement to assure uniqueness. Theoretical results and necessary computations are incorporated into two general computer programs capable of determining the permeability distribution in two- and three-dimensional steady flow systems. Results are then presented for an energy dissipation analysis using the methods and soltware to determine a field permeability thickness distribution. INTRODUCTION Theoretical work leading to the description of fluid flow in heterogeneous porous media has developed slowly and somewhat sporadically, although the areas of engineering applications predominantly involve flow in nonhomogeneous media. The lack of accurate and economical methods for measuring field permeability distributions has been a major limitation to realistic description of natural flow systems. The economical measurement of permeability using energy dissipation methods may overcome this limitation. Among other things, any permeability measurement method involves consideration of energy dissipation; as used here, "energy dissipation method" denotes the following general approach. The areal energy distribution is measured on an existing flow system in porous media. Then through appropriate analysis of the dissipation of energy in the flow system, the permeability distribution is determined throughout the region using the minimum boundary conditions required to assure a mathematically unique result. This paper presents the theoretical basis for such a method, as well as the techniques and computer software needed to carry out the analysis. The method and techniques are then used in a preliminary field application. EQUATIONS DESCRIBING FLOW IN HETEROGENEOUS MEDLA Heterogeneous as used here implies differing in kind, having unlike quantities or possessing different characteristics. Accordingly, a heterogeneous porous medium has unlike quantities or differing characteristics at different locations. More precisely, if a porous medium is heterogeneous with respect to some property, then that property is functionally dependent on the spatial location. (Media properties are considered here as macroscopic.) Specifically considering permeability k,** then k = G(x, y, z) ,............(1) or the permeability is a scalar function G of the location (x, y, z). Spatial variation of several other properties, of which porosity, dispersivity and medium compressibility are but a few, is implied by the broad title of heterogeneous porous media. The term will be used hereafter to imply only heterogeneity with respect to permeability. The porous medium is considered isotropic as implied by G being only a scalar function. Anisotropy

Jan 1, 1969

By R. F. Hehemann, R. H. Goodenow

Thermal arrest, hot-stage microscopy, and transtnission electron microscopy techniques have been employed to study the transformations in low-carbon iron and Fe-9 pct Ni alloys. In continuous cooling experiments, each alloy transforms at an essentially constant temperature for cooling rates below the critical rate required for martensite formation. However, high-tenzperature transformation in pure iron takes place by a different mechanism than that in the 9 pct Ni alloys. Pure iron exhibits an equi-a a structure with a low and random dislocation density while the 9 pct Ni alloy exhibits a cell or lathlike substructure analogous to that of low-carbon martensite. This same substructure characterizes upper bainite in higher-carbon inaterials. UNTIL relatively recently, diffusionless transformations have been considered to take place by the same mechanism and have been termed mar-tensitic transformations.l-3 The most characteristic feature2 of this mode of transformation is the shape change produced by a shear deformation and growth of the product phase frequently occurs at an extremely high velocity approaching that of an elastic wave.4'5 A different mechanism of diffusionless transformation was recognized first in Cu-Ga and other copper-base alloys.6,7 From the absence of surface tilting in these alloys, it has been concluded that transformation is not accomplished by the cooperative shear displacements that occur in mar-tensitic reactions. Transformation presumably takes place by the rapid movement of an incoherent interface which is capable of propagating across parent grain boundaries. Although the transformation is diffusionless in the macroscopic sense, advancement of these interfaces is accomplished by an atom by atom rearrangement. Transformations of this type therefore require thermal activation and are generally operative only at high temperature. Although requiring short-range diffusion at the interface, propagation still occurs so rapidly that the reaction cannot be suppressed with normal cooling rates.7 The resulting microstructures exhibit large, irregular-shaped regions of the product phase, which are essentially free of crystallographic features. Consequently, these reactions have been termed massive transformations. Transformation by the massive mechanism has been reported to occur in ferrous systems involving pure iron and binary alloys of iron with nickel, chromium, and silicon by Gilbert and owen.' The Fe-Ni system is of special interest in that the massive transformation was observed in alloys with less than 15 pct Ni while alloys having more than about 28 pct Ni transformed by the conventional mar-tensitic mechanism. By employing cooling rates substantially higher than those used by Gilbert and Owen, Swanson and Parr have been able to suppress the massive transformation in alloys with 0 to 10 pct Ni9 and produce martensite as revealed by surface relief. The massive transformation in the alloys having less than 15 pct Ni was identified by the lack of surface relief and an irregular rather than clearly acicular microstructure.' Speich and Swann, using thin-foil electron microscopy, identified three distinctly different structures10 in quenched binary Fe-Ni alloys. From 0 to 4 pct Ni the structure consisted of blocky grains of a with a low and random dislocation density. Alloys with 4 to 25 pct Ni exhibited a cell structure with a high dislocation density; and at greater than 25 pct Ni the structure consisted of internally twinned plates. The structural change at approximately 4 pct Ni suggests that alloys with low nickel content transform by a different mechanism than those with intermediate nickel contents and the transition from the cellular to the internally twinned structures at approximately 25 pct Ni is analogous to the transition from needles to internally twinned plates that occurs over a narrow range of carbon contents in Fe-C martensites.11,12 Conventional bainitic and martensitic modes of austenite decomposition operate in ternary Fe-C-Ni alloys having less than 10 pct Ni. This investigation was conducted in order to explore the conditions under which the massive, bainitic, and martensitic transformations occur and the relationships between these modes of decomposition.

Jan 1, 1965

By John I. Yellott

SINCE the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate procducer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. LIQUID FUELS COMPETE WITH COAL As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal- burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an

Jan 1, 1946

By G. H. Kesler, J. E. Oberele, C. E. Dryden, J. H. Oxley

Heat-transfer rates were measured in a model of a multifilament vapor-deposition bulb fo the preparation of high-purzty metals. Local transfer coefficients for heat transfer frow the filaments to the circuates process stream were determined as a functiol of gas flow rates and bulb, inlet, and filament, geowzetvies. These results a-e then convertted to n mass-t7,ansfer basis to provide a method of correlating vapor-deposition rates and to predict the performance of commercial urzits. The firm1 cor?,elating equation for mass transfer was found to be- wheve k, is the mass-transfer coefficient; D, is bze gas difficsivity : P is the system pressure; R is the gas constant; T is the gas temperature; Df, DB, and Di ave tlze diameters of the filament, bulb, and inlet, respectively; k is the gas conductivity; C, is the specific heat of the gas, M is the wzolecular zleight of the gas; Npr . N,,, NRe a7'e the Prandtl, Schmidt, and Reynolds numbem of the system, respectively; LB is the height of the bulb; and SB and Sf are the total suyiace area of the bulb and filaments, respectively. ONE of the more conventional methods of preparing very high-purity metals is the vapor deposition of the metal upon heated filaments. The reactions which can be employed in such a process generally fall into two classes: 1) Pyrolysis of a volatile metal compound. Generally because of their instabilities, metal iodides are used; however, other metal halides and hydrides have been employed. These processes are frequently carried out under vacuum conditions, and the filaments are maintained at high temperatures. 2) Hydrogen reduction of a volatile metal compound. A metal chloride is normally the preferred feed for these processes, but other halides are sometimes used under special conditions. These hydro- gen-reduction processes are usually operated at atmospheric pressure. Many of the current processes for the production of semiconductor materials are actually vapor-deposition processes. However, the vapor-deposition process itself is relatively old, and almost all metals can be prepared in a state of very high purity by the use of vapor-deposition techniques. Loonam has recently given an excellent review of the iodide process for metal deposition,' and Owen has started some detailed studies with a carbonyl system.' A more general treatment of all vapor-deposition processes has been outlined by Powell, Campbell, and Gonser.3 Despite the fact that vapor-deposition techniques have been employed since 1890, there is a surprising lack of fundamental information regarding the transport characteristics of even the simplest deposition system, the heated filament. The purpose of the investigation described in this paper was to extend some of the earlier data obtained at Battelle to predict deposition rates and the uniformity of deposition in large-diameter, multifilament deposition bulbs under forced convection conditions.4'5 A number of other investigators have already presented a simplified treatment of the deposition process under non-flow conditions, i.e., pure diffusion.6"9 To obtain information on the transport characteristics of a deposition bulb, a model of a typical plant deposition unit was constructed, and local heat-transfer coefficients from the filaments to a circulating air stream were determined under various conditions of air-flow rates and bulb, inlet, and filament geometries. These results were then converted to a mass-transfer basis, and consequently provided a method to correlate experimental vapor-deposition rates and to design commercial deposition units. EXPERIMENTAL WORK Description of Model. The apparatus which was used in this work was a scaled model of one type of deposition bulb. It was constructed of Lucite and was easily altered to give several combinations of diameter of bulb liner, inlet size and location, number of filaments, and outlet geometry. The model is shown in Figs. 1 and 2. The bulb shell was made octagonal for convenience in construction and observation, and the bulb liners were cylindrical. Air, introduced through one of several different jet inlets, was used as the test fluid in these model studies. Filaments for deposition of metal were simulated by metal rods 1/4-in. in diam. Two of the rods could be heated by passing electrical current through them ¦ while the remaining rods could not be heated. This procedure minimized the amount of heat which was

Jan 1, 1962

By J. H. Richards, G. Derge, W. Peifer

A WIDE Variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware, They have been related to hydrogen largely by circumstantiat evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British committee on the Heterogeneity of Steel Ingots,' and current approaches to the problem were reviewed in a recent symposium of the AIME.I2 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principal object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem, The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow in However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross-section large enough to develop cracks, Yet small enough for convenient handling and sampling. Rails were also selected because they arc made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitat~s early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion, (2) Vacuum extraction (without melting), (3) Total combustion.

Jan 1, 1949

By G. Derge, W. Peifer, J. H. Richards

A WIDE Variety of metallurgical defects in steel have commonly been attributed to the presence of excessive amounts of hydrogen. These defects include flakes in rails and forgings, cracks in welds, and blisters in enameled ware, They have been related to hydrogen largely by circumstantiat evidence because the proper sampling and analysis of steel for hydrogen has been known to be difficult and because no general agreement has existed with regard to the relative suitability and accuracy of available methods. The need for a direct approach to these problems has been widely recognized. This general situation has been well described in the publications of the British committee on the Heterogeneity of Steel Ingots,' and current approaches to the problem were reviewed in a recent symposium of the AIME.I2 The plans described by the present authors at that meeting have now matured satisfactorily and will form the basis of this paper. The principal object of this paper will be to describe the methods of sampling and analysis which have been developed and to illustrate the usefulness and limitations of these methods by citing their application to a specific problem, The first problem selected for investigation was the behavior of hydrogen in rail steel. This was chosen because the occurrence of shatter cracks in rails has received a great deal of study over a long period of time. The defect can be controlled by the expensive procedure of slow in However, it may be hoped that a better understanding of the factors influencing the hydrogen content of rails will lead to a more efficient control of this problem. Rails provide a good starting point for a more general study of hydrogen in steel because they provide a cross-section large enough to develop cracks, Yet small enough for convenient handling and sampling. Rails were also selected because they arc made from plain carbon steel and it was felt that the initial work should not be complicated by the effects introduced by alloying elements. The considerations which determined the original planning of this study should be reviewed. The inherently complex nature of most hydrogen problems requires that a large amount of data must be collected for any particular case. This in turn means that any analytical procedure should be as rapid and simple as possible. The same objective of speed is indicated by the fact that it may finally become desirable to use hydrogen analysis in process control. It is also known that hydrogen is highly fugitive and that any procedure which facilitat~s early analysis of the sample without prolonged or irregular storage has distinct advantages. The most important previously reported methods of analysis may be classified into three general groups: (I) Vacuum fusion, (2) Vacuum extraction (without melting), (3) Total combustion.

Jan 1, 1949

By T. W. Guy

THE increased moisture due to water¬spraying for coal dust control is of interest even for mines from which the coal is to be wet-washed before screening, because in many cases wet coal dust materially decreases the loading efficiency of men an equipment at the faces. It also causes serious increase in the normal wear and deterioration of all equipment with which it comes in contact. It is important to the consumer if it increases his as-receive moisture. No attempt will be made in this paper t cover the entire subject of water-spraying of coal for dust control. It will be confine to discussion and data on (r) percentages c dust in bituminous coals, (2) moisture increases due to spraying for dust control in mines or plants by methods which have proven satisfactory for periods of one to five or more years, and (3) a few suggestions for research. SIZE AND PERCENTAGE OF COAL DUST The U. S. Bureau of Mines1 classifies a coal dust all bituminous coal passing 20-mesh sieve (0.0328 in. square opening; The percentage of such dust to be found is ROM coal, of course, varies widely wit. the characteristics of the seam, and with the methods used in the mining and in the preparation of the coal. ROM screen analyses of 12 U. S. coals selected at random from personal files given in Table I show: A few other screen analyses examined indicating 40 pct or more of 2o-mesh X o dust in 3/8 in. X o-sizes were not included because of uncertainty that they were representative. The number of results in Table I is not sufficient to give a reliable estimate of the average, or of the range to be expected, but it indicates that in every case the coal dust is a relatively large percentage of the total ROM coal, and, of course, a progressively larger percentage of resultants as the larger sizes are separated for marketing.

Jan 1, 1948

By C. C. Harris

The characteristics of some common size distribution equations are critically discussed. A generalized form of several well-known size distribution equations is obtained from a differential equation describing statistical distributions. The equation contains three parameters and can describe the major features of size distributions in the fine and the coarse size regions. A graphical method for its implementation is provided. The application of this and other equations to sets of data are compared both for the quality of fit and from a comminution kinetics viewpoint. If a narrow size range of a brittle material is broken sufficiently to obliterate the feed sizes, but not so severely that excessive secondary breakage occurs, a plot of cumulative fraction by weight undersize (Y) vs. sieve size (X) on a log log grid (sometimes called the Gates-Gaudin-Schuhmann plot)1-3 gives a straight line of slope ~ 1 over much of its range. On closer inspection, deviations in the extreme coarse range covering perhaps 10 to 30% of the total sample may be apparent (frequently, a change in slope from ~ 1 to a value different from unity) together with over-all slight irregular departures from a smooth line. One model of breakage postulates that the same fracture pattern persists throughout all size ranges.4 The fracture pattern is characterized by the slope of the line on a log log grid. Accordingly, a distribution of sizes broken in the manner specified earlier is expected to produce a size distribution having the same slope as that of a broken narrow size range. Additionally, the slight irregularities mentioned above should even out in the summation process, giving a smooth straight line of slope ~1 on a log log plot. This idealized state of affairs does not, however, describe the distribution of a multi-event process such as that for a tumbling mill product. On the average, these curves (plotted again log log) tend to have a slope in the fine region different from and usually less than unity,5 while the coarse size region curves with increasing slope for cases of mild reduction, and with decreasing slope when moderate or severe size reduction has occurred. In addition, there are usually slight irregular deviations from a smooth curve. Most curves display two distinct regions — fine and coarse — and a few curves show one or more intermediate regions. Feed size studies6,7 show an effect which theory is required to explain. For the same material, mill loading and other operating conditions, and the same time of grinding, plotting the dimensionless ratios Y vs. X/(feed size) does not reduce the size distribution data to the same curve. Y vs. X does not correlate the coarse region, but it can provide a crude correlation of the fine region which improves as size diminishes and as grinding time increases. The size distribution in the coarse region is somewhat more dependent on the feed size than is the distribution in the fine region wherein the degree of dependence diminishes as time proceeds; the distribution of sizes in the fine region are determined largely by the nature of the material and the comminution conditions. A comprehensive model of comminution must recognize that several different patterns or modes of breakage can occur in a mill; 5,8,9 that there can be some selection in that some size ranges are broken more than others; and that, while some particles may be the product of a single fracture event, or may even remain unbroken, others result from multiple rebreak-age. Thus, breakage in a tumbling mill is more complex than the Schuhmann4 model admits in that several different types of comminution micro-events* occur rather than just one type, and these events, though different in size scale, are of the same overall pattern as that which is visualized by the model. The concept of an average comminution micro-event has, therefore, a mathematical rather than a physical connotation, at least for tumbling milling. Equations with which to describe particle size distributions have been sought for over half a century.10-13 No equation presently in general use was first derived from an analysis of the statistical mechanics of breakage; whatever theoretical basis the existing

Jan 1, 1969

VARYING in thickness and in number from place to place, coal seams in the Canadian Rockies also range in pitch from nearly horizontal to vertical, sometimes with overturns. Over the entire coal-bearing area there are considerable differences of rank in coals of the same geological age, and there are marked differences in ash content and washability characteristics. Correlation of seams at mining operations within a few miles of each other has often proved impossible. These factors influence mining methods, and, of course, production results. The oldest coal formations of western Canada are of Lower Cretaceous age, as the carboniferous sediments are marine and contain no coal. Coal is also present in formations of Upper Cretaceous and Tertiary ages. The rank of coal varies from semianthracite in some operations in the Kootenay and Luscar formations of the Lower Cretaceous in the Rockies to lignite in the Tertiary fields of the Saskatchewan prairies. Fig. 1 shows the general extent of the formations.

Jan 8, 1954

By J. Chipman, M. N. Dastur

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

Jan 1, 1950

By F. M. d’Heurle

Films of molybdenum have been prepared by sputtering onto oxidized silicon substrates. The resistivity. lattice parameter, orientation, and grain size were studied as a function of substrate temperature and substrate bias. Under normal sputtering conditions, the resistivity of the films was found to be quite high (600 x 10 ohm-crn). However, with the use of the negative substrate bias of 100 v and a substrate temperature of 350°C, films weve produced with a resistivity of ahout twice that of bulk molybdenum. The lattice parameters measured in a direction nornzal to the surface of the films weve found to be gveatev than the bulk value. This was interpreted as being at least partly due to the presence of compressive stresses. The effects of annealing in an Ar-H atmosphere were studied in terms of diffraction line width, lattice parameter, and resistivity. BECAUSE of its relatively low bulk resistivity (5.6 x 106 ohm-cm)' molybdenum is potentially interesting as a thin-film conductor in integrated circuits. An additional feature which makes it attractive for this purpose is its low coefficient of expansion (5.6 x KT6 per "c),' which is fairly well matched to that of silicon (3.2 x 10 per c). It is possible to deposit molybdenum films by evaporation but generally films produced in this manner have a high resistivity. In order to achieve resistivities close to bulk value, Holmwood and Glang found it necessary to operate in a vacuum of about 107 Torr and to maintain the substrates at 600 C during film deposition. Sputtered molybdenum films have been examined by Belser et a1.7 and, recently, by Glang et al.' This paper describes the results of an attempt to extend some of that work and examine the effects of annealing and getter sputtering on the physical and structural properties of the films produced. SPUTTERING APPARATUS AND PROCEDURE The apparatus used for most of the film sputtering work described here consisted of two "fingers" serving as anode and cathode, respectively, which were mounted within an 18-in.-diam glass chamber. A liquid nitrogen-trapped 6-in. diffusion-pump system was used to achieve a vacuum of about 1 x 107 Torr within the chamber prior to sputtering. The essential features of the equipment are shown in Fig. 1. Cathode and anode fingers are stainless-steel tubes isolated from the top and bottom plates by Teflon collars. In order to limit the discharge to the space between anode and cathode, each finger is surrounded by an aluminum hield, at ground potential, having an internal diameter 18 in. larger than the outside diameter of the finger. The cathode and anode fingers are 6 and 4 in. in diam, respectively. A 116-in.-thick sheet of molybdenum is brazed with a 10 pct Pd, 58 pct Ag, 32 pct Cu alloy to a copper disc which is mounted by means of screws and a large 0 ring onto the lower end of the cathode finger. The disc is cooled during sputtering by water circulation inside the finger. The use of several feet of plastic tubing for the water input and outputg reduces leakage to ground to less than 1 ma when the cathode potential is raised to 5 kv. The upper end of the anode finger is terminated by a brazed-on copper block. A variety of specimen holders can be easily mounted on the upper face of this block. Substrate heating or cooling is achieved by use of an appropriate unit attached to the lower face of the same block. Heating is achieved by means of cartridge-type heaters and cooling by copper coils fed with forming gas under pressure. The inner chamber of the specimen finger constitutes a small vacuum chamber of its own which is evacuated by an auxiliary mechanical pump in order to limit heating element oxidation and heat transfer by convection currents. An advantage of the finger arrangement is the absence of cooling and heating coils and wires within the main chamber. The stain less-steel shutter is useful to establish a discharge for cleaning the cathode at the beginning of each sputtering run. Water cooling of the shutter reduces heating and the out-gassing of impurities which might condense on the nearby substrates. Unless otherwise specified, the substrates used in these experiments were 1-in.-diam oxidized silicon wafe:s, 0.007 in. thick, having an oxide thickness of 6000A. The substrate holders were large copper discs onto the surface of which a number of molybdenum discs, 116 in. thick and 78 in. in diam, were brazed. The wafers were clamped to the molybdenum discs

Jan 1, 1967

By K. A. Natarajan, I. Iwasaki

With a platinum electrode the Eh-pH response in aqueous systems follows an empirical relation [Eh = E- 0.059 pH](1) where E usually carries a value between 0.8 and 0.9 v. The same potential (E) is observed with a number of other noble metal electrodes in the absence of surface poisoning and of other well-defined redox couples. Many sulfide mineral electrodes also respond in a similar manner in solutions containing their respective ions over wide pH ranges, especially in the alkaline pH region. Such a parallelism between noble metal and sulfide mineral electrodes points to certain implications of their surface conditions, and the flotation and leaching behaviors of sulfide minerals under aerated conditions may be inferred with respect to the foregoing Eh-pH response. Comparison of Sulfide Mineral and Noble Metal Electrodes [Fig. 1] shows the Eh-pH response of pyrite, galena, chalcocite, and pyrrhotite electrodes, reported by Sato, and some experimental points obtained with a platinum electrode in distilled water. [Eq. 1] is seen to be followed by all these electrodes. It is interesting to note that the response of the pyrite electrode as shown is identical to

Jan 1, 1973

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors' knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner' in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation' plots for both horizontal and vertical

Jan 1, 1969

By L. R. Velho, N. A. D. Parlee, J. Gani

THE unsteady-state type of gas-liquid metal diffusion cell1 has found considerable application.2"4 Cells of this general design can function as steady-state cells if allowed to operate long enough to reach steady state. This report tells of some success in the adaption of this type of cell for steady-state work, using the 0-Ag system in which the mass transfer of the gas "species" is basically controlled by diffusion in the liquid. The gas, e.g-., O2, is maintained in the cell tube'-3 at 1 atm pressure, Fig. 1, by buret and sensitive oil manometer. The gas, after diffusing through the stagnant metal, escapes at the annular metal surface around the tube at a lower constant partial pressure, in this case that of O2 in slowly flowing air, 1 atm.

Jan 1, 1970

By R. L. Vaughn, H. R. Cooper

Effective procedures for automating X-ray assaying by use of a computer are described. These methods have advanced the reliability and accuracy of X-ray data, resulting in improved assay measurements for operations and process control. Assaying by X-ray fluorescence has been increasingly used in the mining industry, both for analyzing solid H.R. COOPER and R.L. VAUGHN, Members AIME, are Systems Manager-Process Control and Senior Systems Analyst, respectively, Scientific & Engineering Computer Center, Ken-necott Copper Corp., Salt Lake City, Utah. TP 68B236. Manuscript, Sept. 16, 1968. Discussion of this paper, submitted in duplicate prior to Dec. 15, 1969, will appear in SME Transactions, March 1970, and AIME Transactions, 1970, Vol. 247. samples for smelter, mill, and mine quality control and for continuous stream analysis of mill pulps. The important advantages of X-ray methods in laboratory assaying are reduced analysis cost, and for on-stream analysis, immediate assay information on concentrator streams. Of the numerous reports concerning X-ray analysis in mining operations, one is referenced which can be noted particularly in conjunction with this report.' Continuous X-ray analyzers have been installed at Kennecott and other mining companies for operations guidance and trend information for a number of years. However, complete operational acceptance of X-ray data has been slow, due* to the difficulty in maintaining

Jan 1, 1970

By R. K. McGeary, B. Lustman

The textures produced in zirconium by cold and hot rolling, and by recrystallization above and below the transformation temperature were determined. Thermal expansivities were measured in the thickness, transverse, and rolling directions of preferentially oriented zirconium and were correlated with the texture scatter in these directions. REVIOUS investigations have indicated that minor differences between hexagonal close-packed metals of similar axial ratio may appear with respect to the textures produced both on cold rolling and on subsequent recrystallization. In the case of magnesium, beryllium, and titanium, metals of axial ratio similar to that of zirconium, the ideal orientations produced by rolling are fundamentally the same, although marked variance is reported in the degree and type of scatter about the mean orientation; in those instances where recrystallization textures were observed, they were reported to be similar to the rolling textures. Measurement of the anisot-ropy of thermal expansion of both rolled and re-crystallized zirconium could not be correlated satisfactorily with the textures reported for the above metals, and therefore a study was made of the preferred orientations produced in zirconium. Reported below are the textures produced in zirconium by cold and hot rolling, and recrystallization above and below the transformation temperature, together with the results of thermal expansion measurements. Determination of Preferred Orientation Two types of zirconium were investigated: 1— "crystal bar" zirconium obtained from the Foote Mineral Co., produced by the thermal decomposition of zirconium tetraiodide, and 2—zirconium ingot obtained from the Bureau of Mines prepared by melting sponge zirconium in a graphite resistor vacuum furnace in a graphite crucible. The major impurities present in the two materials used are listed in Table I. Several of the pole figures were later checked with 0.03 pct hafnium crystal bar material and the results were identical with those to be shown for the 1.5 pct hafnium material. The materials were cold rolled to 0.014 in. in thickness as shown in Table 11. Specimens were cut from the 0.014 in. thick rolled sheets and etched to thicknesses of 0.002 to 0.010 in. Such specimens were used for exposures up to a 50' to 60" angle between the beam and plane of the specimen; for higher angles a wire shape, similar to that described by Bakarian,' was formed on an end of the original 0.014 in. sheet. A fine-bladed abrasive cut-off wheel was used to slot the sheet and to form the cylindrical cross-section. The wire shaped ends were then etched to 0.006 to 0.010 in. in diam. Although absorption of X-rays in the wire-shaped specimens does not vary with angle of rotation, the line width around the diffraction rings was not uniform, because the wire was narrower than the X-ray beam, and this condition caused some uncertainty in the estimation of azimuthal intensities. Furthermore, scanning was not practicable with this type of specimen so that spottiness of the rings due to large grain size was excessive for specimens which had been heated above about 650°C. Nevertheless, satisfactory information could be obtained for high angle exposures from the negatives by the use of both types of specimens. Transmission Laue photograms were taken using unfiltered molybdenum radiation (47.5 kv, 18 ma) and a 0.025 in. pinhole. With the film 8 cm from a 0.005 in. thick specimen exposures of about 30 min were adequate. For specimens with a coarse grain size, a device that scanned about 0.15 sq in. of sheet surface was used. An attempt was made to plot the pole figures by use of an X-ray spectrometer as described by Norton.' However, for the particular technique used, the intensity variations obtained were not considered definite enough to give reliable results, especially for the large grained recrystallized and transformed specimens. This method was therefore abandoned in favor of the standard photographic method. Nine exposures were taken of each specimen: seven exposures with the beam perpendicular to the rolling direction and at 0°, 10°, 20°, 35", 50°, 65", and 80" to the transverse direction, and two exposures with the beam perpendicular to the transverse direction and at 60" and 80" to the rolling direction. Additional exposures were then made where necessary. The intensity variations of the diffraction rings were estimated by eye. It was usually possible to estimate 3 degrees of intensity from the photograms but in some cases 2, 4, or 5 degrees were estimated. Experimental Results The preferred orientation was determined for the following treatments: 1—cold-rolled, 2—low temperature rolled, 3—cold-rolled surface layer, 4— cross-rolled, 5—hot-rolled, 6—recrystallized below the transformation temperature, and 7-—recrystallized above the transformation temperature. I—Cold-Rolled Textures: The slip plane in hexag-

Jan 1, 1952

By Frederic L. Kadey

Diatomite is a siliceous, sedimentary rock consisting principally of the fossilized skeletal remains of the diatom, a unicellular aquatic plant related to the algae. Thus, it has-been formed by the induration of diatomaceous ooze, and consists mainly of diatomaceous silica, a form or variety of opal which is first formed in the cell walls of the living diatom. Diatomaceous silica is not generally regarded as a synonym or the equivalent for diatomite, although it has been so used at various times. Accurately, diatomaceous silica is the preferred name for the principal mineral component of which the rock, diatomite, is composed. The terms diatomaceous earth and kieselguhr are used as synonymous with diatomite. The designations tripoli, tripolite, infusorial earth, etc., were used at one time but are now obsolete. With the changing nomenclature, these terms that were at one time correct when proposed and used for generations would be considered incorrect if used today in the light of current knowledge. The designation diatomite is reserved for those accumulations of diatomaceous silica that are of sufficient quality, size, and minability to be considered of potential commercial value. Processed diatomite possesses an unusual particulate structure and chemical stability that lends itself to applications not filled by any other form of silica. Foremost among these applications is its use as a filter aid, which accounts for over half of its current consumption. Its unique diatom structure, low bulk density, high absorptive capacity, high surface area, and relatively low abrasion are attributes responsible for its utility as a functional filler and as an extender in paint, paper, rubber, and in plastics; and as an anti-caking agent; thermal insulating material; catalyst carrier; and chromatographic support; polish, abrasive, and pesticide extender to name a few representative applications. The United States is the principal producing country, although diatomite is found in numerous other locations.

Jan 1, 1975

By W. C. Lilliendahl, G. Meister

Uranium metal with a purity of about 99.9 pct was produced on a large scale by fused salt electrolysis with a material efficiency of about 90 pct. The material efficiency depends mainly on bath composition, electrolysis temperature, electrode smothering, and elutriation during washing of the powder. RESEARCH and development work on fused salt electrolysis carried on by the Westinghouse Lamp Div. Bloomfield, N. J., was done under the Manhattan District Corps of Engineers and later under the Atomic Energy Commission for the commercialization of uranium production for the first atomic pile at the University of Chicago in 1942. From the conception of the atomic bomb project it was recognized that metals with impurity levels having little metallurgical significance would be required. Permissible impurity levels were based on neutron absorption. Of particular significance was boron, which could not be present in amounts exceeding 1 ppm. The electrolytic method as developed in 1930 by Driggs and Lilliendahl,1,2 and later improved, yielded uranium of very low boron and other deleterious impurity content. No other method was capable at that time of producing uranium metal of the required purity.' The low boron content of uranium produced by the electrolytic process resulted from the availability of the reactants which were low in boron content, and from the inherent elimination of boron in the fused salt bath. Since the heart of any electrolytic process is the electrolysis cell, this paper will deal with the development of the original bath composition for the efficient production of uranium from a batch process to one of continuous operation. Emphasis also will be placed on other factors which will affect the material efficiency of the process. With the laboratory cell the material efficiency of uranium powder recovery in the early electrolysis was relatively low, about 35 pct based on the ratio of uranium recovered to uranium added. This early process also had other defects. The electro- lytic bath could not be used continuously. After three runs from a freshly charged crucible, the deposit showed a tendency to slip off the electrode as it was raised from the bath. This condition necessitated pouring the charge every fourth run and preparing a new bath. It was assumed at that time that this condition was caused by the increasing fluoride concentration with each addition of uranium salt, which adected the mobility of the uranium ions. Experimental The electrolysis cells differed in size only. They were of the floating cathode type. The laboratory cells were 21/2 in. ID and 6 in. deep and operated at 30 amp and 5 volts. Production was about 150 g metal powder per 8 hr. The plant cells (5 units) were 9 in. ID x 21 in. deep and operated at 1800 amp at 12 volts. The total production unit was designed to produce 250 lb of uranium powder per 8 hr day. Because of the tendency of uranium fines toward spontaneous combustion, material efficiencies were based only on the recovery of useful coarser metal which could be safely handled. The reported efficiencies are of particular significance only as related to the same group of experimental procedures. At the start of the project no changes were contemplated until previous data could be definitely confirmed. Therefore, the first experiments were with the 50 pct CaCl2-50 pct NaCl mixture. The material efficiency of uranium deposition as a function of the number of electrolyses is shown in Table I. In Table I, the decrease in efficiency at 800°C with number of runs is apparent and confirmed the earlier data. Operating at 900°C enabled the number of runs to be doubled, but before pouring the charge the efficiency of recovery became poor. This test indicated that the improved efficiency might have been caused by an increase in the fluidity of the bath.

Jan 1, 1958

By AIME AIME

The name and address of the school are given first, followed by the length of the regular undergraduate curriculum, the degree granted, types of courses giben, and the name of the man in charge. This covers only work for the first or Bachelor degree in each case. The following abbreviations are used: B. Bachelor Cer. Ceramic. E. Engineer or Engineering Eng. Engineering or Engineer Geol. Geologist, Geological, or Geology M. Mines or Mining Met. Metallurgy or Metallurgical Mng. Mining Pet. Petroleum Ref. Refining S. Science Tech. Technology or Technical

Jan 1, 1939