Search Documents

By M. N. Shetty, A. C. D. Chaklader

RECENTLY, it has been demonstrated that a considerable densification and interparticle bonding can be achieved if a pressure is applied to a powder compact while the material of the compact is undergoing either a decomposition reaction' or a polymorphic transformation.' The term "reactive hot pressing" has been coined to identify this process in which a phase change is combined with pressure to achieve interparticle bonding. This process is based on a principle which postulates that there is an enhanced reactivity and mobility of the molecular species at the phase-transformation temperature and this effect is utilized for interparticle bonding in powder compacts. This note summarizes the results obtained in an attempt to utilize this technique to produce ceramic-metal composites. In this case, a decomposition reaction of a compound (which after decomposition yielded an oxide) was used to achieve interparticle bonding in ceramic-metal composites. The reactive hot pressing was carried out in a Phillips induction heating unit, using either a graphite or a high-temperature steel die which functioned as both the susceptor and the hot-pressing component. The die was heated to the desired temperature in a helium atmosphere. All cermets produced by this technique were based on alumina as the ceramic phase. Different metal phases such as iron, copper, and chromium were used to study the effect of varying the metal phase on the properties of the composite. a Mono-hydrate (Boehmite) was mixed with different proportions of metal powders (-325 mesh) in dry condition in a mortar and pestle. No special precautions were taken for proper mixing. The mixtures were then compacted into a cylindrical form having an approximate dimension of 1 cm in diameter and 1 cm in height. For this compaction an ordinary

Jan 1, 1965

By E. H. Jr. Dix

THE use of magnesium as an alloying element in aluminum alloys has been limited, in general, to comparatively small quantities. In duralumin-type, strong-aluminum alloys, magnesium is present to the extent of ½ to ¾ per cent. and various grades of Magnalite and the "Y" alloy of the National Physical Laboratory of England contain up to 1 1/2 per cent. In this country small quantities of aluminum alloy sheet containing 4 per cent. magnesium are produced commercially. All commercial aluminum contains sufficient silicon to convert a portion of the magnesium added to the compound Mg2Si. It is well known that the solubility of both magnesium and magnesium-silicide decrease with decrease in temperature. It is, therefore, impossible to separate the age-hardening effect of the magnesium-silicide from that of magnesium, except by the use of aluminum of such high purity that the silicon content is negligible. The present paper is the fifth1, 2,3,4 of a series from the laboratories of the Aluminum Co. of America reporting the results of investigations of the equilibrium relations in aluminum-rich alloys made from the high purity aluminum manufactured by this company .5

Jan 1, 1929

Jan 1, 1965

By J. B. Cheatham, M. D. Biggs

This paper presents a systematic method for determining the forces on a simplified roller bit. The kinematics of an actual roller bit drilling in rock is complex; nevertheless, it is desirable to obtain an accurate analytical model.. As a preliminary study, the roller bit is represented here by a simple two-dimensional bit and the rock by a Coulomb plastic material. Results from previous work, plus additional assumptions, are incorporated into a computer program to determine the forces required to move the bit in a specified manner. Example problems are worked by use of this program. By studying similar drilling problems and by supporting laboratory work, one could eventually obtain an accurate analytical model for drilling by an actual roller bit. This could lead to the compilation of a catalog of results that, in turn, would allow selection of the optimum drill bit for any given situation. INTRODUCTION

Jan 1, 1970

By R. F. Hinds

A pressurizing system was designed and built to apply a radial pressure of 5.000 psi to rock samples. Samples of the Bradford, Weir and Kirkwood sandstones were subjected to radial pressures parallel and perpendicular to the bedding in the system and the changes in conductivity, porosity and permeability were deter-mined. Asymptotic decreases in conductivity, porosity and Klinkenberg permeability were observed over the 0- to 3,500-psi range. From these data, the increase of formation factor over the same range was calculated. The cementation exponent expressed in the Archie equation was found to increase with pressu,re. The rate of change varied from formation to formation. Only small differences were observed for samples taken parallel to the bedding as comnared to those taken perpendicular to it except for the Bradford sand. Above 3,500 psi the data are not good enough to tell if the properties continue to fall-off asymptotically or in a different manner. A possible explanation for the probable litnit of the asymptotic rate around 3,500 to 4,500 psi is that this represents the maximum pressure which the formations have unrdergone during their geological life as a result of burial. INTRODUCTION For many years measurements have been made in the laboratory of the properties of oil-bearing sandstones with little consideration being given to whether these properties had been changed when the samples were moved from their original position in the ground to the laboratory. Relatively little has been reported in the literature on the effect of pressure on the properties of sandstones. The changes in permeability for eight typical consolidated oil-bearing sandstone samples with overburden pressure (0- to 15,000-psi range) was presented by Fatt and Davis' in graphical form. In 1953 Fatt' also reported the relationship between porosity and overburden pressure for four typical consolidated oil-bearing sandstone samples (0- to 5,000-psi range). Fatt later described the changes of formation factor and porosity of 20 typical oil-bearing sandstone samples with overburden pressure changes (0- to 5,000-psi range) giving the values of the coefficients and exponents in the Archie' equation, and the more general Winsauer equation', where C, k and m are empirical constants, F is the formation factor, and + is the porosity. During the experiments of this investigation the core was contained in a neoprene rubber sleeve as shown in Fig. 1. It was held between two steel end members which were mounted in a steel cylinder. The unassembled pressure cylinder with its component parts is shown in Fig. 2. The core was insulated from the two steel end members by a Teflon sleeve with a small hole in the

By Mario L. Villa

Argentina's oil production continues in its upward trend. The year 1940 closed with an important increase over 1939; that is, 1,996,371 bbl., or 10.72 per cent. The Government oil fields (Y.P.F.) are responsible for these results, as their total output was 12,474,655 bbl., which compared with the 10,222, 533 bbl. produced in 1939 represent an increase of 2,252,122 bbl., or 22.03 per cent. Fields operated by private companies yielded 8,134,882 bbl., against 8,390,633 bbl. in 1939, a decrease of 255,751 bbl. (3.04 per cent). To the total of 20,609,538 bbl. produced in 1940 in Argentina, the Comodoro Rivadavia field contributed 14,976,222 bbl.; Plaza Huincul, 1,275,814 bbl.; the Province of Salta, 1,845,1977 bbl. and the Province of Mendoza, 2,51I,475 bbl. Table 3 compares the output of companies working in Comodoro Rivadavia. The total increase of 186,819 bbl. (1.26 per cent) registered in the Comodoro Kivadavia area is due only to an intensification of development programs in the known

Jan 1, 1941

By Mario L. Villa

Argentina's oil production continues in its upward trend. The year 1940 closed with an important increase over 1939; that is, 1,996,371 bbl., or 10.72 per cent. The Government oil fields (Y.P.F.) are responsible for these results, as their total output was 12,474,655 bbl., which compared with the 10,222, 533 bbl. produced in 1939 represent an increase of 2,252,122 bbl., or 22.03 per cent. Fields operated by private companies yielded 8,134,882 bbl., against 8,390,633 bbl. in 1939, a decrease of 255,751 bbl. (3.04 per cent). To the total of 20,609,538 bbl. produced in 1940 in Argentina, the Comodoro Rivadavia field contributed 14,976,222 bbl.; Plaza Huincul, 1,275,814 bbl.; the Province of Salta, 1,845,1977 bbl. and the Province of Mendoza, 2,51I,475 bbl. Table 3 compares the output of companies working in Comodoro Rivadavia. The total increase of 186,819 bbl. (1.26 per cent) registered in the Comodoro Kivadavia area is due only to an intensification of development programs in the known

Jan 1, 1941

By E. H. Boswell, E. M. Cushing

The Mississippi embayment east of the Mississippi River is part of a vast geologic and hydrologic province. The abundance of water available is largely responsible for the agricultural history of the area and is perhaps the key factor in the rapidly accelerating trend toward industrialization. The multiple artesian aquifer systems that underlie the region and the alluvial aquifer along the Mississippi River are virtually undeveloped sources of fresh water in that they are yielding only a fraction of the water available. The potential yield of the 12 aquifer systems is estimated to be about 25,000 mgd (million gpd) of which only about 600 mgd is presently being withdrawn. The amount of water in storage in these systems is about 1600 trillion gal. Ground water having a dissolved-solids content of less than 500 ppm is generally available at depths of less than 1000 ft, and water having a dissolved-solids content of less than 1000 ppm is available in some places to depths of more than 3000 ft. Iron is the most common troublesome chemical constituent in the ground water. Water in varying amounts is also available from streams within the region. The amount of water which originates within the region and which leaves it as streamflow during a year averages about 50 million acre-ft (about 45,000 mgd). An additional 375 million acre-ft (about 340,000 mgd), which originated outside the region, leaves the region as streamflow during an average year. Some streams have considerable flow during periods of no precipitation and the water during these periods generally has a low dissolved-solids content. Large quantities of water from streams and waterbearing sands (aquifers) are available in the Mississippi embayment east of the Mississippi River. Most of the region is underlain by aquifer systems that will yield large quantities of water to wells, making ground water the most readily available source of fresh water. About 90% of the water used in the region is obtained from wells. Streams have been used primarily to dispose of, and dilute, wastes that have been dumped into them. The Mississippi, Ohio and Tennessee rivers, and the lower parts of the Tombigee and Yazoo rivers also serve as a means of transportation. This nominally water-rich region receives from 48 to 56 in. of precipitation in average years and is crossed by several large rivers. The largest, the Mississippi River, is the western boundary of the region discussed in this paper. The economy of the region is basically agricultural, but industry has become increasingly important since World War 11. The diversification and mechanization of agriculture have resulted in a surplus of manpower, most of which is being absorbed by the expansion of industry. Further industrial expansion probably will occur because of the available manpower, natural resources and economical transportation. Increasing demands on available water supplies will be made and the future economic growth of the region will be largely dependent upon wise utilization and management of the water resources.

Jan 1, 1969

Large deposits of manganiferous iron ores, representing several million tons of metallic manganese, occur in the United States. The Minnesota deposits of such ore are of outstanding importance because of their size, state of development, ease of mining and proximity to the Great Lakes, which permits water transportation to steel centers. In view of the fact that our steel industry requires large quantities of manganese, for which no satisfactory substitute has been found, and because our reserves of ferro-grade ore are comparatively small, the development of methods that will make our large deposits of manganiferous iron ores available as a source of ferromanganese is an important problem. Realizing the importance of this problem, some years ago the North Central Station of the U. S. Bureau of Mines and the Minnesota School of Mines Experiment Station undertook jointly the development of methods for recovering the .manganese content of manganiferous iron ores in a form suitable for the production of ferromanganese, the 80 per cent. alloy indispensable in producing steel. Two types of manganiferous iron ores have been described in previous reports.' The brown ores are higher in iron and lower in manganese than the black ores; the black ores are more siliceous but contain less phosphorus. The utilization of the iron content of the brown ores in the production of steel appears to furnish the best basis for their treatment. The method of attack has been to work out modifications in iron and steel practice so as to recover manganese in the form of slag comparable to ferro-grade ores. The greater part of the experimental work has been conducted with a 6-ton blast furnace and a 1/2-ton basic open hearth. This paper is devoted mainly to open-hearth tests in which high-phosphorus spiegel

Jan 1, 1930

By Gaudin. A. M., S. C. Sun

THIS paper presents the results of a study of the relationship of the electrokinetic or zeta potential to flotation phenomena. The relationship is established on the experimental evidence that mineral behavior in flotation and in cataphoresis is generally governed by the chemical properties and amount of the reagents adsorbed at mineral surfaces. Cataphoresis1-5 or electrophoresis is the name given to the movement of a charged particle in a liquid medium under the influence of an applied electric field. Mineral behavior in cataphoresis, as indicated by the magnitude and sign of its ionic charge, can be represented by the term zeta potential. In this paper, the zeta potential represents the difference in potential between the immovable liquid layer attached to the surface of a solid particle and the movable liquid layer in the body of the liquid, and is the result of the tendency of ions on the surface of the particle and within the liquid boundary layer to establish a condition of equilibrium. A high positive zeta potential means that the mineral surface is dominated by cations, a high negative zeta potential indicates domination by anions, and a low zeta potential indicates that the surface is influenced almost equally by cations and anions. In terms of observed quantities the zeta potential is given by the relation [z = 47ruu(300)$ Kx] in which z is the zeta potential expressed in in volts, u the viscosity of the solution in poises, u the velocity of particles in centimeters per second, x the impressed potential gradient in volts per centimeter, and k the dielectric constant of the solution in c.g.s. units. A convenient source for the derivation of the equation is the book by Thomas,6 The term zeta coefficient is an expression coined to denote the difference between the magnitude of the zeta potential of a mineral suspended in solution A, and that of the same mineral suspended in solution B, which consists of solution A and an additional chemical agent, but is at the same pH. For example, the difference between the zeta potential of galena particles in distilled water and that in any chemical solution at the same pH is a zeta coefficient. Or, when the zeta potential of a mineral particle is measured first in distilled water, then in a mixture of water and copper sulphate, and finally in a mix-

Jan 1, 1946

By R. J. Wensley

THE use of small substations for the supplying of 275-volt energy to the locomotive and cutting machines in coal mines is a well-established practice. A few years ago, when labor costs were lower, these substations were located as near to the load as possible, and an operator was provided for each station. This practice has now become so expensive that substations are being located with reference to other mining machinery, such as hoists or pumps, so that one operator can look after both. Some-times the substation is operated by one whose duties make him traverse quite a large area. In such cases the interruption of alternating-current supply may produce a long interruption in the direct current, as the station cannot resume service until this man reaches it. Such interruptions interfere seriously with production and may easily counterbalance the supposed saving gained by such operating methods. The grouping of substations for convenience in operating may also result in excessive copper loss and consequently poor trolley voltage, with its attendant evils of low locomotive speeds and increased locomotive motor maintenance. The speed of the coal-cutting machines will also be reduced. By relieving the substation of its, burden of the operating labor cost, the most economical location, from an electrical standpoint, may be chosen. The matter of machine insurance should also be considered. If an attendant is caring for several kinds of equipment, he cannot watch the machine continually for signs of trouble; therefore, continued overload, phase failure, low alternating-current voltage, bearing trouble, etc. may result. Some partly automatic equipments have been installed; these have protection against low voltage, reverse current, and bearing trouble and are provided with automatic reclosing circuit breakers. This is a step in the right direction but it does not go far enough to give first-class machine insurance.

Jan 9, 1921

By Herbert H. Kellogg

The chemistry of sulfide roasting is analyzed to show those aspects of performance which Thecan be predicted from considerations of thermodynamic equilibrium. It is concluded that equilibrium calculations can serve as a yardstick for prediction of roaster-gas composition and sulfate formation in the calcine for fluid-bed roasting practice. A method of calculation which combines the equilibrium and stoichiometric factors is outlined, and illustrated by an example from the roasting of Cu-Fe sulfides. ON first examination the roasting of sulfides would not seem to be a process to which equilibrium calculations could be applied to yield results of practical value. The burning of sulfides is an ex-tremely spontaneous reaction, excess air is always used to obtain rapid reaction, and in most traditional roaster designs (hearth roasting) the temperature and gas composition vary widely from point to point in the roaster. These are all conditions which promote a non-equilibrium state in the roasting process. However, the introduction of the fluid-bed roaster1 has brought to roasting practice new conditions of operation, so that equilibrium calculations can be used to predict certain limited aspects of practical operation. The fluid bed is characterized by uniformity of temperature, gas composition, and calcine composition from point to point throughout the bed. These relatively uniform properties of the bed make the meaningful calculation of the equilibrium state of certain reactions in roasting possible. It is the purpose of this paper to analyze roasting from an equilibrium viewpoint, to show where the method may be expected to yield valuable information, where it fails, and to outline methods of calculation. Main Roasting Reaction The reaction MS (s) + 3/2 0, = MO (s) + SO, [I] might well be called the main roasting reaction. It adequately accounts for the well known facts that metal sulfide and air are the main reactants, and metal oxide and SO, the main products. Deviations from this simple stoichiometry will be discussed under side reactions. For all metal sulfides, Reaction 1 is strongly exothermic and the equilibrium position is far to the right. Since the reaction is exothermic, the equilibrium shifts in the right-to-left direction as the temperature is raised. However, at all practical roaster temperatures (between 500" and 1200°C), the amount of this shift is small, and the equilibrium position remains far to the right. The main roasting reaction is essentially irreversible, and the application of equilibrium considerations to this reaction will not be! a fruitful field of investigation. A knowledge of the rate of this reaction. although not the proper subject of this paper, is of great importance to the roasting process. Analysis of the factors which influence this rate shows that: 1) The rate will increase rapidly with increased temperature. 2) The rate will be proportional to the partial pressure of oxygen at the surface of the reacting particle. Because of diffusion effects, the partial pressure of oxygen at the particle surface may be considerably less than in the bulk of the roaster gas. For this reason, intimate contact between gas and solid and high relative velocity between gas and solid, such as can be obtained in a fluid bed or flash roaster, will markedly increase the rate of reaction. 3) The rate will be proportional to the surface area of metal sulfide. Therefore, smaller particle size will permit a more rapid rate per unit of weight. To achieve practical rates of roasting the partial pressure of oxygen in the roaster gases must be maintained at a finite level at all times. Even where the gas-solid contact is very good, as in the fluid-bed roaster, the oxygen content of the gas must not be allowed to drop below some limiting value (perhaps 1 pct), or the rate of the main roasting reaction will become too small for practical operation. Side Reactions in the Gas Phase The gas phase during roasting of metallic sulfides contains the elements oxygen, sulfur, nitrogen, by-

Jan 1, 1957

By A. Raja, C. C. Harris

Apparatus for maintaining constant — but adjustable — pulp level and rate of froth removal are described. The results of preliminary experiments into the effect of scraping speed on the rate of solid and liquid recovery with a semi-batch system are presented. Glass spheres restricted to a narrow size range is the solid under investigation. Graphical methods for estimating the mass of recoverable material and the zero error are given. The semi-batch procedure1 is extensively used in laboratory flotation testing, though the method is subject to variability of moderate severity. Raffinot2 concluded from a statistical study of the difference between replicate tests, that the ptincipal source of errot was the test itself and not sampling or chemical analysis. These differences can be ascribed principally to changes in pulp volume and reagent concentration, and uncontrolled rate and depth of scraping. Semi-batch testing has been criticized1 on these grounds as a means of investigating flotation kinetics. This paper discusses and describes modifications to laboratory flotation equipment which reduce the number of manual operations and lead to improved control. Kinetic studies were the primary reason for developing the apparatus described. It should, however be a useful aid in normal flotation testing. Some preliminary results of experiments are presented.

Jan 1, 1967

By C. van der Poel, R. L. Chuoke P. van Meurs

When an initially planar interface between two im-ttitcihle liquids is displaced at constant rate, U, nor-mat to the front, instability will occur for all rates greater than a critical rate. U, given by provided the Fourier decomposition of the spatial pertmrbcrtiott or deformation of the moving displacetment front contains modes with wavelengths. A, greater than a critical wavelength, given by tit there expressions, p, p and k, with the subscripts I and 2 distinguishing the two 1iquids under consideration, are density, viscosity and effective pemeability coefficients respectively; g is the absolute value of the acceleration due to gravity; and cos (zz') is the direction cosit7e between the vertical carlesian coordinate z' (positive upward) and the z coordinate norma1 to the initially plane macroscopic interface taken positive in the direction from Liquid I to Liquid 2. U is the average volumetric velocity (injected volume of liquid pet. unit time per unit of area normal to Z) and is positive for Liquid I displacing Liquid 2, negative for the reversc displacement and r2 is an effective inter-fucial tension (for displacements between parrallel plates, t0= s the ordinary bulk interfacial tension). further, there is a wavelength of maximum instability given by For natural perturbations, this wavelength will preclotninate and characterize the form of the instability as a quasi-sinusoidal deformation, i.e., viscous fitzgers of peak-to-peak separatiotr, A,,. Comparison of experitient with theory rei'eals tltat these considerations are recsonably valid for displacements in hoth parallel plate chantzels and nnconsoli-clutt'd glass ptnvder packs. These results are. tij particular interest for interpretation of data from laboratory experiments with regard to fielil applica/iotz.s. It is quite possible for A,, although st7zall relative to the large lateral dimension of the reservoir, to rxceed the greatr.st lateral extent of the lahoratory sample or model. If it does, frontal displace- ment occurs in the laboratory experiments, and oil INTRODUCTION Thc puposes of this paper are to present theoretical and experimental evidence for occurrence of macroscopic instabilities in displacement of one viscous fluid by another immiscible with it through a uniform porous medium and to compare available experimental data with some predictions of a theory of instability developed by the first author. The instabilities are referred to as macroscopic in the sense that spatially quasi-sinusoidal, growing fingers of the displacing liquid are formed, the width and peak-to-peak separation (wavelength) of which is large relative to a characteristic length of the particular permeable medium such as grain size. Visual models of two kinds have been used to obtain observations: displacement of oil by water-glycerine solutions through the flow channel formed by closely spaced parallel plates and displacement of oil by water with and without initial interstitial water through unconsolidated glass powder packs, employing the technique of matching indices of refraction. In all cases we have observed macroscopic instabilities or fingers under conditions predicted by the theory to be favorable for their occurrence. The phenomenon discussed here is not the production of streamers due to gross inhomogeneities such as permeability stratification of the porous medium. It is our object to show, on the contrary, that a quantitative prediction of finger spacing is possible in a porous medium known to be macroscopically homogeneous and isotropic throughout. The importance of the phenomenon in its influence on the configuration of oil and water with respect to oil production behavior was noted earlier by Engel-berts and Klinkenberg' who coined the term "viscous fingering". THEORY Necessary and Sufficient Conditions ior Instability anc Initial Kinematics There are several levels of increasing complexity in the theoretical description of instabiIity of fluid displacements in permeable media. Of these, the simplest description, ;tdapted to low permeability systems, is selected for presentation.' More inclusivc tlescriptions are reserved for separate publication.

By L. J. Health

Synthetic rock with predictable porosity and permeability has been Prepared from mixtures of sand, cement and water. Three series of mixes were investigated primarily for the relation between porosity and permeability for certain grain sizes and proportions. Synthetic rock prepared of 65 per cent large grains, 27 per cent small grains and 8 per cent Portland cement, gave measurable results ranging in porosity from 22.5 to 40 per cent and in permeability from 0.1 darcies to 6 darcies. This variation in porosity and permeability was caused by varying the amount of blending water. Drainage-cycle relative permeability characteristics of the synthetic rock were similar to those of natural reservoir rock. INTRODUCTION The fundamental behavior characteristics of fluids flowing through porous media have been described in the literature. Practical application of these flow characteristics to field conditions is too complicated except where assumptions are overly simplified. The use of dimensionally scaled models to simulate oil reservoirs has been described in the literature. 1-3 These and other papers have presented the theoretical and experimental justification for model design. Others have presented elements of model construction and their operation. In most investigations the porous media have consisted of either u ncon soli da ted sand, glass beads, broken glass or plastic-impregnated granular substances—materials in which the flow behavior is not identical to that in natural reservoir rock. The relative permeability curves for unconsoli-dated sands differ from those for consolidated sandstone. The effect of saturation history on relative permeability measurements is discussed by Geffen, et a1.4 Wyga15 has shown quite conclusively that a process of artificial cementation can be used to render un consolidated packs into synthetic sandstones having properties similar to those of natural rock. Many theoretical and experimental studies have been made in attempts to determine the structure and properties of unconsolidated sand, the most notable being by Naar and Wygal.6 Others have theorized and experimented with the fundamental characteristics of reservoir rocks. This study was conducted to determine if some general relationship could be established between the size of sand grains and the porosity and permeability in consolidated binary packs. This paper presents the results obtained by changing some of the factors which affect the porosity and permeability of synthetically prepared sandstone. In addition, drainage relative permeability curves are presented. EXPERIMENTAL PROCEDURE Mixtures of Portland cement with water and aggregate generally are designed to have certain characteristics, but essentially all are planned to be impervious to water or other liquids. Synthetic sandstone simulating oil reservoir rock, however, must be designed to have a given permeability (sometimes several darcies), a porosity which is primarily the effective porosity but quantitatively similar to natural rock, and other characteristics comparable to reservoir rock, such as wettability, pore geometry, tortuosity, etc. Unconsolidated ternary mixtures of spheres gave both a theoretically computed and an experimentally observed minimum porosity of about 25 per cent.7 By using a particle-distribution system, one-size particle packs had reproducible porosities in the reproducible range of 35 to 37 per cent.6 For model reservoir studies of the prototype system, a synthetic rock having a porosity of 25 per cent or less and a permeability of 2 darcies was required. The rock had to be uniform and competent enough to handle. Synthetic sandstone cores were prepared utilizing the technique developed by Wygal.5 Some slight variations in the procedure were incorporated. The sand was sieved through U. S. Standard sieves. A 18-20 sand denotes that the sand passed the Number

Jan 1, 1966

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By E. C. Stephens

The eastern Washington— Idaho clay region stretches along the northeast margin of the Columbia basin for 150 mil es. The three better known and developed clay areas are Clayton, Wash., (2 miles north of Spokane); Mica, Wash., (10 miles southeast of Spokane); and Moscow-Deary-Bovill, Latah County, Idaho (about 80 to 90 miles southeast of Spokane) see Fig. 1. Clays from the eastern Washington— Idaho clay area have been mined for more than 50 years. At present Mica, Washington deposits are used by the Gladding—McBean & Co. to make a variety of bricks and ceramic products and Latah County, Idaho clays are used by the A. P. Green Fire Brick Co. to make refractories. The Anaconda Co. made an intensive investigation of the clay deposits in the northeastern Washington-!daho area in 1919 to determine the existence of a supply of raw materials from which alumina could be made. The greater part of the work, which included systematic drilling and shaft sinking, was concentrated at Mica, Wash. This was part of a research project carrted on by the Anaconda Metallurgical Research Dept. under the direction of Frederick Laist and F. Frick and it was terminated in 4920. V. D. Perry, Vice President and Chief Geologist for The Anaconda Co., in 1952 assigned the writer to make a preliminary study of clay and other potential sources of alumina ore in the Pacific Northwest with particular emphasis on those deposits which might be of future importance to The Anaconda Co9s. then new aluminurri plant at Columbia Falls, Mont.

Jan 1, 1961

By Walter Fuchs

IT is now generally conceded that coal is the product of deposition and transformation of debris of forests and swamps.29 Ample data are available to illustrate the metamorphosis of biochemical substances through biological action; other data show the progressive regional metamorphism existing in coal beds ;25 and numerous examples of change effected by intrusion of igneous dikes into coal deposits have been established.23 However, often the relative importance of the biological and the geological factor in determining the character of the various natural coals is a debatable question. Since both biological and geological factors are ever present in nature, the problem, at first glance, would appear to resemble certain probability problems: specifically the simultaneous toss of two coins, with the biological factor as heads and the geological as tails. The probability is 2 : I for the combined effect of both factors, as compared to the exclusive effect of either one, if the a priori probability is the same for each factor. This condition can be analyzed by a thermodynamic treatment of data, which may be obtained from a consideration of pertinent biological, chemical, geophysical and geological facts. SYNOPSIS OF BIOLOGICAL AND CHEMICAL FACTS The biosphere is not sterile; i.e., microorganisms are always present. Microorganisms have been established in the ocean deep, under the ice of the polar regions, in the sand of the deserts, and in swamps far below the surface. The various biological media may be acid, neutral, or alkaline, and they may or may not be readily accessible to air. Microorganisms are encountered almost everywhere, except where the temperature is not within the range tolerable by microbial life. Of course, with changing conditions, the type of microorganisms will change. All chemical products of life-proteins, fats, carbohydrates, lignins, waxes, resins may serve as a habitat of microorganisms. In the decomposition of a medium. some microorganisms macerate organic matter mechanically and remove certain constituents for their own nutrition; others decompose a large part of the organic matter but may leave certain constituents undecomposed. Some attack only certain specific ingredients of the organic matter. All of them build up cell substance. The nitrogen content of the medium largely determines the degree of decomposition. Below 1.7 per cent nitrogen, growth of microorganisms and hence decomposition of organic material is retarded; consequently organic material will accumulate.17, 32 Such accumulations of organic material may give coal eventually. Coals differ in type and rank. The nature of the original vegetation and the conditions attending the transformation of the accumulated debris determine the type of coal such as bright, splint, cannel, and algal or boghead coals. Chemical analysis of representative samples of a given type of

Jan 1, 1941

THE solid nonmetallic inclusions present to some extent in all commercial steels have been variously designated. In early references they were usually called slag inclusions, and this terminology is still retained to some extent. On the premise that all nonmetallic matter produced in a metallurgical process is slag, this can be justified. We have come to think of slag, however, in a more restricted sense, and calling these particles slag inclusions is further objectionable because it fosters the erroneous concept that they are actually incorporated portions of furnace slag. Rarely is this true. The term sonims (coined from solid nonmetallic impurities) was proposed many years ago but never came into common use. In general, the term non-metallic inclusions seems to be satisfactory and adequate. NATURE AND CONS1lTUTION OF NONMETALLIC INCLUSIONS From the standpoint of origin, inclusions fall naturally into two classes: (1) those occurring as a result of reactions taking place in the body of molten or solidifying metal and (2) those resulting from mechanical incorporation of refractories or other materials with which molten steel comes in contact. The former are by far the more numerous and have been called indigenous, natural, or native inclusions. The latter are by their very nature sporadic in occurrence and have been called exogenous, accidental, adventitious, or foreign inclusions. They are often referred to as the "slag-stringer" type, though here also the material is not likely to be furnace slag. Substances Found in Inclusions. Nonmetallic inclusions are composed principally of oxides and sulfides but carbides and nitrides sometimes play an important role. In the case of indigenous inclusions the reactions by which these particles are precipitated from molten or solidifying steel may be caused by: (1) oxidation such as may occur during refining or during tapping and teeming, (2) deoxidation by added alloys, (3) change

Jan 1, 1964

By Nelson Severinghaus

Mineral fillers have been defined as inert materials that are included in a composition for some useful purpose. Because this definition and the scope of this review are not specific- indeed, exceptions abound-accurate total statistics are unavailable. One source estimates the total production in the United States in 1971 at 5 million tons valued at $200 million, averaging $40.00 per ton. Included are a broad group of minerals-asbestos, barite, bentonite, calcium carbonate, clays, diatomite, feldspar, micas, silica, talc. Additional references will be made to synthetic mineral-derived fillers such as aluminum hydrate, precipitated calcium carbonate, and pyrogenic and precipitated silicas and silicates. A section on related uses at the end of this chapter covers absorbents and filters. Mineral fillers can be included in compounds to accomplish a variety of final results. Hardness, brittleness, impact strength, compressive strength, softening point, fire resistance, surface smoothness, electrical conductivity, and a host of other physical characteristics may be modified by the inclusion of fillers. These effects are the result of properties of the fillers, including chemical activity, hardness, particle size, shape and distribution, surface structure, color, density, and refractive index. To facilitate an overview of the mineral filler industry, this chapter will review the general usage of fillers, the inherent characteristics that intensify their utilization, and similarly their manufactured characteristics. Major using industries will then be examined in detail. Specific information on deposits and processing for industrial minerals will be found in the appropriate commodity chapter. The chart in Table 1, updated from the 3rd edition of Industrial Rocks and Minerals, illustrates the major mineral fillers (both natural and manufactured) and their more important end uses.

Jan 1, 1975