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By Herbert Clark Hoover, Lou Henry Hoover

QUESTIONS as to the methods of smelting ores and of obtaining metals I discussed in Book IX. Following this, I should explain in what manner the precious metals are parted from the base metals, or on the other hand the base metals from the precious'. Frequently two metals, occasionally more than two, are melted out of one ore, because in nature generally there is some amount of gold in silver and in copper, and some silver in gold, copper, lead, and iron ; likewise some copper in gold, silver, lead, id iron, and some lead in silver ; and lastly, some iron in copper2. But I will begin with gold. Gold is parted from silver, or likewise the latter from the former, whether it be mixed by nature or by art, by means of aqua valens3, and by powders which consist of almost the same things as this aqua. In order to preserve the sequence, I will first speak of the ingredients of which this aqua is made, then of the method of making it, then of the manner in which gold is parted from silver or silver from gold. Almost all these ingredients contain vitriol or alum, which, by themselves, but much more when joined with saltpetre, are powerful to part silver from gold. As to the other things that are added to them, they cannot individually by their own strength and nature separate those metals, but joined they are very powerful. Since there are many combinations, I will set out a few. In the first, the use of which is common and general, there is one libra of vitriol and as much salt, added to a third of a libra of spring water. The second contains two librae of vitriol, one of salt-petre, and as much spring or river water by weight as will pass away whilst the vitriol is being reduced to powder by the fire. The third consists of four librae of vitriol, two and a half librae of saltpetre, half a libra of alum, and one and a half librae of spring water. The fourth consists of two librae of vitriol, as many librae of saltpetre, one quarter of a libra of alum, and three-quarters of a Mbra of spring water. The fifth is composed of one libra of saltpetre,

Jan 1, 1950

By Earl Ingerson

BORE surfaces of used guns commonly show a pattern of cracks in various degrees of development. It has been suggested that these cracks may aid erosion by providing channelways for the gases, eventually leading to the tearing out of blocks of metal. Under the general studies of gun erosion conducted at the Geophysical Laboratory it appeared desirable to consider this factor, and to determine the resistance to surface cracking offered by gun steel and by various other materials that might be used in the bores of guns. METHOD AND APPARATUS In order to make such a determination it is necessary to have (I) an arrangement in which the surface to be studied can be subjected to conditions similar to those in a gun with respect to temperature, pressure (developed by explosion gases), composition of the gases and length of time the surface is exposed to the gases; and (2) a specimen that can be examined readily after any number of shots, and then fired again, if necessary. The first of these conditions can be met by using an explosion vessel designed by H. S. Roberts of the Geophysical Laboratory. Fig I shows a cross section of the apparatus. The "gun" G from which the charge is fired is made from the receiver of a caliber 0.30 army rifle, M1903, and the charges are prepared in caliber 0.30 cartridge cases. The test specimen S is held in place by a cone-shaped plug P and by a steel ,bridge B which is bolted to the outside of the explosion vessel on either side of the section shown. The plug, in turn, is held in place by a screw collar C. Maximum pressure is controlled by a brass rupture disk R. Part of the explosion gases flow past the two flat areas on S. st the two flat areas on S. Temperature and composition of gases, and the time before the rupture disk breaks, can be controlled by amount and kind of powder used, and pressure can be controlled by using rupture disks of different thickness. While the explosion vessel used was not designed so that temperature and pressure could be measured, in other vessels of closely similar size and shape containing proportionate charges of the same kind of powder as that used for standard testing procedure, values of 2700°K and 5000 psi were obtained. Since the orifices past the flat areas on the plug are small compared to the rupture disk hole (1:16), most of the gas goes out through the rupture disk when it breaks. The amount that goes by the plug depends on (I) the pressure attained before the rupture disk breaks and (2) the time it takes for this pressure to be built UP. The second condition (examination at will after any firing) is met by using for specimens short rods that have flat areas ground on opposite sides. These flat

Jan 1, 1947

By J. C. Melrose

The contact angle is one of the boundary conditions for the differential equation specilying the configuration of fluid-fluid interfaces. Hence, applying knowledge concerning the wettability of a solid surface to problems of fluid distribution in porous solids, it is important to consider the complexity of the geometrical shapes of the individual, interconnected pores. As an approach to this problem, the ideal soil model introduced by soil physicists is discussed in detail. This model predicts that the pore structure of typical porous solids will lead to hysteresis effects in capillary pressure, even if a zero value of the contact angle is maintained. The model is generalized to situations in which the contact angle takes on values between zero and 40 degrees. For the imbibition branch of the capillary- pressure function, the model predicts a considerable departme ftom the usually assumed cos 0 relationship. In fact, according to the model, it is possible that a displaced wetting phase will not be able to reimbibe, even when the contact angle does not exhibit hysteresis. INTRODUCTION The subject of capillarity in porous media has long been of interest in many branches of engineering and applied science. The earlier investigators were those concerned with the physics of soils. 1-5 More recently, petroleum engineers and others dealing with the problems of petroleum production from reservoir rock have given much attention to the subject.6-10 Also, important additions to the literature of capillarity have been contributed from the field of chemical engineering.11-12 These attest to the wide range of industrial applications in which capillary phenomena play a role. The present paper is concerned with the role which wettability plays in capillary action in porous media. As is well known, capillary-rise (or capillary pressure) phenomena have frequently been interpreted with the aid of a model employing the concept of a cylindrical capillary tube. This approach has enjoyed a certain degree of success in correlating experimental results.13 The generalization of this model, however, to situations which involve varying wettability, has not been established and, in fact, is likely to be unsuccessful. In this paper another approach to this problem will be discussed. A considerable literature relating to this approach exists in the field of soil science, where it is referred to as the ideal soil model. Certain features of this model have also been discussed by Purcel114 in relation to variable wettability. The application of this model, however, to studying the role of wettability in capillary phenomena has not previously been attempted in detail. In the present paper, additional features of the model are introduced. These features are critical in determining the quantitative behavior of the model. GENERAL FEATURES OF CAPILLARY HYDROSTATICS BASIC PRINCIPLES When the interstices of a typical porous solid are occupied by two or more immiscible fluid phases, the fluids are microscopically commingled. Hence, fluid-fluid interfaces are found within a certain fraction of the pore openings. The fundamental equation of capillarity specifies the configuration of these fluid-fluid interfaces. This is known as the Laplace equation, when derived from mechanics, and as the Gibbs-Kelvin equation when derived thermodynamically.15 Given two fluid phases, a and ß, in hydrostatic equilibrium, the Laplace equation states that the respective fluid pressures in regions close to the interface are related by Here oaß is the surface or interfacial tension and rl and r2 are the principal radii of curvature of the surface or interface. The pressure difference, Pa-Pß, is the capillary pressure, PC. As Buff15 has shown, Eq. 1 states the condition for hydrostatic equilibrium within the two-phase confluent region, which is referred to as the interface. It thus can

Jan 1, 1966

By Gilbert Soler

Producers of alloy steels recognize the importance of chemical composition in relation to the hot-working properties and the typical surface defects found in their product. Each analysis of steel has its own peculiar characteristics. Under conditions of standard mill practice each analysis is susceptible to certain types of defects. Mill practice must be varied to obtain the best combination of surface and internal quality in the product. Chemical composition influences the cast structure and crystallization characteristics of the ingot. It also determines the rate of heating and cooling, the plastic hot-working range, and the phase structure of the steel at various temperatures. as well as the tendency toward scale formation and decarburization. This paper endeavors to emphasize the manner in which chemical composition affects the various properties of steel, and to indicate the relative importance of these factors in relation to the hot-working properties and surface characteristics of killed steel. The influence of chemical composition may be outlined as follows: I. Effect on the cast structure of steel, including: A. State of deoxidation, and type of inclusions. B. Gas content of steel. C. Freezing point and melting point of steel. D. Crystallization characteristics and segregation. 11. Effect on the hot-working properties and surface characteristics of steel, including: A. Plastic hot-working range. B. Phase structures at hot-working temperatures. C. Rate of heating. D. Cooling characteristics. E. Scale formation. F. Surface decarburization. EFferect of Chemical Composition on Cast Structure of Steel State of Deoxidation and Type of Inclu-sions.—The state of deoxidation is limited by the final chemical analysis desired in the finished product, and is controlled primarily by carbon, manganese, silicon, and aluminum, and to a lesser degree by chromium, titanium, vanadium, or other deoxidizing elements. The degree of deoxidation affects the density of the cast structure and broadly classifies the steel as killed, semikilled, or rimming. This in turn manifests itself in surface characteristics. The manner and extent of deoxidation also controls the amount, type, and distribution of nonmetallic inclusions formed. The equilibrium of manganese, silicon and aluminum with the slags and pouring refractories with which the metal comes in contact is important, especially in regard to inclusions of fire-clay origin. Some surface Seams and hot-working difficulties can be traced to nonmetallic inclusions.

Jan 1, 1941

By E. Miller, R. Geffken, K. L. Komarek

The thermodynamzc properties oJ liquid Cd-Sb alloys were investigated using the cell arrangement measurments were obtained every 2°C at a heating and cooling rate of 12°C per hr and at equilibrium every 2O0C frorn 500°C down through the stable liquidus. The S-shaped asCd US composition curve was used in the cotnposition regzon near Cd,Sb, to calculate a tempeerture-dependent inleraction coefficient from quasichemical theory. Rapid changes in a scd were observed at a transition temperature varying from 400" to 465°C depending on con/kosition. It could not be determined if the changes in aScd were discontinuous, but tlze composition dependeke of the magnitude of the change is indicative of a second-order phase transformation in the liquid. The values of the experimental changes in ASCd are in agreement with calculations from the slope of the transition temperature, using the concept that a second-ovdev phase transition occurs in liquid Cd-Sb alloys. II is suggested that the transformalion is associated with the formation of Cd4Sb3 molecules in the liquid. ThE structure of liquid alloys is the subject of many investigations. X-ray, resistivity, and thermody-namic data have been interpreted as indicating varying degrees of short-range order in the liquid in alloy systems forming inter metallic compounds. In general, the melting process is not a transition from an ordered to a completely disordered state, but some degree of order is retained in the liquid. Maximum ordering in the liquid state occurs close to the melting temperature of the compound and the arrangement of atoms becomes more random at higher temperatures. Of special interest in this respect is the Cd-Sb system. It is one of the few metallic systems which form both stable and metastable compounds when liquid alloys are cooled at normal rates. The stable system exhibits an intermetallic compound, CdSb, melting at 459"c.l A second compound, CdrSbs, has also been reported,' melting close to this temperature. The metastable system has one compound, CdsSbz, melting at 420"c.I Resistivity measurements on liquid Cd-Sb alloys close to the liquidus temperatures have been interpreted in terms of a complex ordering behavior which changes rapidly with increasing temperature.3 The resistivity-composition curve is characterized by two maxima corresponding in composition to CdSb and CdsSbz. The resistivity-temperature plots show sharp breaks for alloys in the composition range of 45 to 70 at. pct Cd on cooling through a transition temperature close to the stable liquidus. Fisher and phillips4 investigated the influence of temperature and composition on the viscosity of liquid CdSb alloys. The viscosity of some alloys increases sharply on supercooling below the stable liquidus. A maximum in the viscosity-composition curve occurs at the composition CdSb. The thermodynamic properties of liquid Cd-Sb alloys have been investigated by Seltz and ~e~itt' and Elliott and chipmane by the electromotive-force method and their results are in good agreement. However, these investigations were carried out at temperatures well above the liquidus temperatures of the alloys, and the temperature coefficients of the electromotive force, dE/dT, were obtained from experimental points for each alloy at a few temperatures considerably above the liquidus temperature. Scheil and ~aach' investigated the thermodynamic properties of this system by the dew point method in the temperature range from about 100°C above the stable liquidus down into the supercooled liquid region. They reported several anomalies, i.e., the activity of a melt on heating differed from that on cooling, and the activity increased sharply in the limited temperature interval immediately above the liquidus temperature of the stable alloy, followed by a sudden decrease below the liquidus. Values obtained on heating and cooling were not in agreement. A reinvesti-gation of a few alloys by Scheil and Kalkuhl' by the electromotive-force method failed to confirm these observations. The authors concluded that the anomalies were due to inhomogeneities in the starting alloys and they discarded their previous results. The present investigation was undertaken in order to obtain thermodynamic data close to the liquidus temperature and in the supercooled region where the anomalies were originally reported, employing the electro motive-force method. This method is quite precise and will most easily permit observations of small changes in activity and partial molar entropy with temperature. Measurements were taken every few degrees so that the dE/dT values could be calculated over the entire temperature range and small changes in the thermodynamic properties close to the liquidus temperature could be observed. I) EXPERIMENTAL PROCEDURE Specimens were prepared from 99.999+ pct Cd and Sb (Cominco). Surface oxide was removed by scraping and then melting the metals under vacuum and filtering through Pyrex wool. Appropriate amounts of the metals were weighed on an analytical balance to k0.1 mg, sealed in double Pyrex capsules under vacuum,

Jan 1, 1968

By Hsun Hu, B. B. Ruth

The rates of migration of high-angle boundaries in zone-refined aluminum crystals rolled 20 to 70 pct in the (110)[i12/ orientation were studied. Following a recovery anneal at an appropriate temperature to stabilize the polygonized structure, boundary migration rates of artificially nucleated grains were measwed isothermally at several temperatures. Results indicate that the rate of boundary migration depends strongly on the amount of deformation and on the cell size of the polygonized matrix, and is related to the driving free energy by a power function. The degree of anisotropy in growth 0.f the re crystallized grains nn&apos;th preferred mientation is independent of deformation; the migration rates of the fast-moving and the slow-moping boundary segments of a gowing grain differ by as much as one order of magnitude. The actir\ation energy fm a grain boundary migration, although nearly the same for both the fast-moving and the slow-moving boundaries for a given deformalion, decreases from 45 to 30 kcal per mole with an increase in deformation from 20 to 70 pct reduction. Re crstallization by the growth of the artificially nucleated grains results in preferred orientation. The Percentuge of&apos; grains favorably oriented for growth increases with increasing deformation. None of these grains corresponds to the ideal Kronberg-Wilson orientation relationship. The observed growth aniso-tropy is discussed in terms of boundary structure. The boundary velocity as a function of the cell inter -facial area, or the driving free energy, is discussed in the light of current theories of boundary migration. It is well established that recrystallization with re-orientation occurs by the migration of high-angle boundaries of strain-free grains. The driving force for this process is provided by the free energy stored in the metal during deformation. A quantitative study of the effect of varying driving force on grain boundary migration in deformed metals has not been possible heretofore, primarily because of: 1) concurrent recovery steadily decreasing the available driving free energy for boundary migration, &apos;-3 and 2) in-homogeneity of strain in the deformed metal.4 Aust and Rutter3 studied grain boundary migration in striated single crystals of zone-refined lead. Although the driving free energy in such crystals remains unaltered during annealing, this method does not provide a range of driving free energies over which measurements of grain boundary migration can be made. In the present investigation, the rates of migration of high-angle boundaries in deformed aluminum zone- refined single crystals were studied at various temperatures, after deformation ranging from 20 to 70 pct reduction by rolling at -78°C in the (ll0)[i12] orientation. The boundary migration rates along different crystallographic directions were determined under steady-state conditions, i.e., in the absence of competing recovery processes or impingement of recrystallized grains growing into the deformed single crystal matrix. Simultaneous recovery was eliminated by suitable anneals prior to the boundary migration measurements. The recrystallized grains, which grew a ni so tropically into the homogeneously polygonized matrix, developed flat boundary segments during early stages of growth. These boundary segments subsequently migrated along a direction approximately normal to the boundary plane into the matrix rystal. Increasing deformation over the range employed was estimated to increase the driving free energy for boundary migration by about five times. The kinetics of the boundary migration process, examined under these conditions, indicate that the boundary velocity is greatly affected by a small change of the driving free energy in the matrix crystals. These results were examined in the light of the current theories of grain boundary migration. EXPERIMENTAL PROCEDURES Single crystal strips (9 by 1 by 0.125 in.) of zone-refined aluminum, were seed-grown by the Bridgman method in a high-purity graphite mold (<lo ppm ash) at 1 in. per hr. Precautions were taken to minimize contamination of the metal during crystal preparation and subsequent handling. Spectrographic analysis of the metallic impurities in the grown crystals is Qven in Table I. The crystals were rolled in the (110)[112] orientation at -78°C to various reductions in thickness, ranging from 20 to 70 pct, in 10 pct increments. The desired reduction was achieved by many rolling passes, each being no more than 0.002 in. To minimize surface friction, the crystal was rolled between two thin layers of teflon. For those crystals rolled more than 40 pct, it was necessary to remove the disturbed surface layers by electropolishing at -5" to -10°C at an intermediate stage of rolling. The edges of deformed crystals were removed by a jeweler&apos;s saw while submerged in alcohol at -78° C to obtain samples of about ? by i in. The distorted metal at the cut edges and the surface layers were then removed by electropolishing, with removal of a minimum of 0.004 in. from each surface. The thickness of the crystals prior to rolling was chosen so that the final thickness was 0.025 in. for all samples. These deformed single crystals were each prean-nealed for 1 hr at an appropriate temperature in the range of 130" to 280°C, depending upon the amount of deformation. The purpose of this preannealing was to

Jan 1, 1970

By H. S. Price, R. L. Reed, J. E. Warren

The behavior of the reverse-combustion process in a linear adiabatic system is theoretically investigated by means of an idealized physical model. T his model is described by a pair of non-linear equations involving heat and mass transfer which are coupled by a concentration-dependent reaction-rate function of the Ar-rhenius type. The differential equations governing the quasi steady-state temperature and concentration distributions are approximately solved by using either physical or mathematical simplifications. It is shown that the reverse -combustion process can be mechanistically described by simple physical models whose behavior equations can be solved formally. It is further demonstrated that the derived reverse-combustion equations can be solved numerically within the error limits for the experimental data. The theoretically predicted peak temperature-flux-velocity relationship exhibits reasonable agreement with experimental data obtained from Athabasca tar sand. The principal contribution of this work lies in its usefulness as a starting point for developing a more comprehensive theory. A description of the vaporization-coking process must be obtained; then, the theory must be extended to three dimensions to include geometrical effects and heat losses. INTRODUCTION In another paper,&apos;" he physical processes visualized as occurring during reverse combustion have been described. In this paper, the extent to which an elementary theory can account for experimental observations is determined. Theoretical results that can be used to estimate some of the behavior characteristics of importance to this process are also presented. Since it is not possible to include all the features of the combustion mechanism of which we are currently aware, the mathematical formulation refers to the highly idealized system developed herein. This simplified physical model is based on the simultaneous transfer of mass and heat accompanied by a chemical reaction: it is described mathematically by a pair of coupled, nonlinear differential equations. Similar sets of equations have been studied extensively in the field of flame propagation; an excellent review of these investigations has been published by Evans.1 FORMULATION OF THE PROBLEM It will be recalled that the experiments are performed with a thin-walled cylindrical tube that is uniformly packed with sand and oil. The system is maintained substantially adiabatic by means of heat supplied externally in such a way that the radial temperature gradient in any plane normal to the axis of the tube approaches zero. Initially, the tube is at ambient temperature, except at one end where it is rapidly heated to a predetermined temperature. When the prescribed temperature is achieved, air is caused to flow into the cold end of the tube. As the oxygen in the air stream contacts the hot oil, a localized exothermic reaction takes place. The generated heat is conducted and convected away from the reaction zone so that definite temperature and concentration profiles are rapidly established and move uniformly in a direction opposite to that of the air flow (Fig. 1). As a consequence of this mode of oxidation, all of the oxygen in the air is consumed; then, the remaining nitrogen and the gaseous combustion products sweep out all vaporized hydrocarbons and leave an immobile hydrocarbon-coke on the sand.

By J. L. LeBlanc, R. L. Lewis

This study presents an analysis of annular backpressure variations associated with controlled gas kicks and their pronounced effect on casing .strings and exposed under lying formations. A mathematical model describing the volumetric behavior of an extraneous gas as it is transported from reservoir to .surface conditions under changing temperatures and pressures has been programmed in a Kingston FORTRAN II language for digital computer analysis. The gases under investigation typify Gulf Coast reservoir gases within a 0.6 to 0.7 .specific gravity range. The program output has been substantiated by actual field cases. of gas kicks encountered in Gulf Coart we1l.s. The development of empirical equations for calculating suitable gamy deviation factors for unique temperatures and pressures was incorporated in the program to provide realistic solution.. An output listing of annular backpressures and corresponding equivalent fluid densities resulting at a predetermined critical depth (casing setting depth) and total depth for selected .stages of circulation is provided in a chronological .sequence. Additional information including reservoir pressure and temperature, kill rnrid density, produced gas or surface volume of the expanded gas intro vion, drill pipe and annular volumes can he obtained from the model. This paper illustrates that a precise knowledge of the volumetric behavior of extraneous gases in annular flow and its effect on equivalent fluid densities at a critical depth is significant and should receive .serious consideration in controlling threatened blowouts and in the design of drilling programs. Surface pressures in excess of formation limitations are a threat to zones of lost circula/ion and are potentially injurious to productive intervals. A knowledge of annular backpressure and equivalent fluid density profiles for probable gas kicks aids in a technological accomplishment of drilling programs and provides a .sale tolerance in the event a threatened blowout is encountered. Introduction Drilling operations are frequently interrupted when the drill bit penetrates permeable gas sands with reservoir CtfuJ manuscript was received in Society of Petroleum Engineers ofice Am. 1 1967. Revised manuscript received JuIy 7. 1968. Paper (SPE 1860) kae presented at SPE 42nd Annual Fall Meeting held in Houston. Tex., Oct 1-4, 1967. @ Copyright 1968 American Institute of Mining, Metallurgical, and Petroleum Engineem, Inc. pressures greater than that exerted by the drilling fluid. The differential pressures resulting permit an extraneous influx of gas into the wellbore. A suspension in drilling progress is necessary to restore fluid equilibrium throughout the system. Whether formation gas kicks originate unintentionally or by design, the prospect of a threatened or actual blowout exists and a method assuring a safe and effective well control procedure must be observed. A significant contribution to well control technology was advanced by Records et a1.l in 1962. Using the concept of transmitting a constant equivalent formation pressure at the point of intrusion, Records et al. introduced a calculation technique providing the annular backpressures encountered in a well control environment as a func tion of the volumetric behavior of a 0.6 specific gravity natural gas. In essence, the procedure outlined an annular backpressure schedule in terms of fluid volume circulated at different stages of a well control operation. A number of other publications2-&apos; proposing various techniques for controlling gas intrusions in a wellbore achieve pressure control essentially through maintenance of a constant bottom-hole pressure by surface choke adjustments. The subsequent pressure effects induced in the annulus unfortunately receive little emphasis. Due to the tedious and repetitive nature of annular backpressure computations, a theoretical solution by digital computer is introduced for predicting annular backpressure and equivalent fluid density profiles associated with controlled gas kicks. We point out the effects of volumetric behavior of extraneous gases in annular flow and related field phenomena on equivalent fluid densities at a critical depth. The investigation indicated that equivalent fluid densities at a critical depth are of significance and should receive consideration in the control of threatened blowouts and in the design of drilling programs. Theoretical Considerations The mechanism of vertical gas flow through an annulus is governed by the PVT properties of the fluid, the pressure distribution within the system, the fluid flow rates and the geometry of flow. Due to the numerous variables involved in this type of problem, certain assumptions were imposed in deriving the mathematical model and in establishing the solutions. Two gases, characterized by specific gravities of 0.6 and 0.7, were selected to typify Gulf Coast reservoir fluids. The gas intrustion entered the wellbore as an immiscible &apos;References given at end of paper. JOURNAL OF PETROLEUM TECHNOLOGY

Jan 1, 1969

By Ravindra M. Nadkarni, Milton E. Wadsworth

The kinetics of cetnentation of copper with iron were observed to follow first-order kinetics and increase with speed of agitation to a limiting value. Maximum rates agree closely with theoretical values based upon a model of aqueous solution diffusion through a litniting boundary film. Back reaction kinetics are shown both theoretically and experimentally to be independent of ferrous iron concentration in solution. The inlportance of attnospheres of air, oxygen, nitrogen, and hydrogen was studied and the results have been correlated with several impovtant oxidation processes involving metallic iron and copper. The kinetics of the reaction of ferric ion with metallic iron were found to be slow in the absence of metallic copper and essentially proportional to the surface area of metallic copper present in the system. THE precipitation of copper on iron is classic as an example of a relatively ancient art applied successfully for centuries with little fundamental understanding of the important parameters involved. There is some indication that the process has been a commercial means to produce copper since the sixteenth century.&apos; The amount of fundamental work on the cementation of copper with iron is not great. Wartman and Roberson2 carried out a series of detailed copper cementation experiments using natural and synthetic mine water. The following were presented as the three principal reactions: Reaction [I] is the desired cementation reaction and accordingly 0.88 lb of iron would produce 1 lb of copper. In actual practice iron consumption would more normally fall in the range of 1.5 to 2.5 lb per lb of copper. Wartman and Roberson attributed the excess consumption of iron to Reactions [2] and [3]. They found that Reactions [I] and [2] proceeded at approximately the same velocity while Reaction [3] was much slower and would be diminished by controlling the contact time. It was also pointed out that increased agitation is beneficial in removing hydrogen bubbles and barren layers of solution at the iron surface as well as removing contaminants resulting from the hydrolysis of iron. Episkoposyan3 and Episkoposyan and Kakovskii4 studied copper and silver cementation on rotating iron disks in chloride solutions. The kinetics based upon a diffusion model were first order and varied linearly with surface area and with angular velocity raised to the one-half power according to the Levich equation. The experimental activation energy for both copper and silver was approximately 3 kcal per per mole. Excess iron consumption was found to increase with temperature. The rate of cementation first increased with increasing acidity and then diminished at high acid concentrations. sutolov5 has presented an excellent review of the Leach-Precipitation-Flotation (LPF) process including a discussion of copper cementation from an electrochemical point of view although few experimental results were presented. From voltage considerations he predicted that cementation should not be influenced by the concentration of ferrous iron in solution. He considered several secondary reactions including Reactions [2] and [3] and pointed out the importance of oxidation of ferrous iron to ferric with oxygen. In addition it was suggested that Reaction [2] was enhanced by the dissolution of metallic copper by ferric iron which in turn consumed excess iron by the cementation reaction, Eq.[1]. Cementation of copper on metals other than iron has been studied by several investigators but, as in the case of iron, the amount of fundamental work is not extensive. Bashkova and kovalenko6 and Bashkova7 studied the cementation of copper on indium from copper and indium sulfate solutions. The rate was found to be first order and to increase with acidity. This was associated with a decrease in potential (EIn — ECu) and the simultaneous reduction of hydrogen ions at low pH. The rate of cementation also decreased with increasing indium concentrations which was postulated to be due to the decrease in the rate of diffusion of the ions in solution. Below 97°C the experimental activation energy was found to have the unusually low value of 2 kcal per mole and was attributed to diffusional control. Above 97°C the rate increased suddenly and was explained as a change in the rate-controlling step to a chemical reaction. In Part I of this study Nadkarni et a1 .1 have reported on preliminary results obtained in a laboratory study of the kinetics of the cementation process. The rate was found to be first order, proportional to the surface area of the iron, and to increase with speed of stirring until a maximum rate was observed. At low stirring speeds the deposit was spongy and adherent. At medium speeds the copper peeled off in bright strips and at high speeds finely divided copper was produced and continually removed from the surface. The amount of excess iron consumed increased with speed of stirring and with temperature. The average experimental activation energy combining results from several types of iron was 5.8 + 1.6 kcal per mole suggesting diffusional control through a limiting boundary film. Traditionally copper cementation has been carried out over the centuries in gravity-fed launders of various design containing scrap iron. More recently rotating drum precipitators and activated launders8&apos;10 have been used. In the latter, copper-bearing solutions are

Jan 1, 1968

By Charles L. Mantell, James E. Hoffmann

Mechanical inclusion, electrophoretic deposition, and adsorption were studied as mechanisms for code-position of aluminas present in copper-plating electrolytes as an insoluble disperse phase. Mechanical inclusion was not a significant factor. That codeposi-tzon of aluminas by an electrophoretic mechanism was unlikely was substantiated by measurements of the potential of the aluminas. The alumina content of the deposits was studied as a function of the pH of the bath. These tests in conjunction with sedimentation studies demonstrated the absence of an isoelectric point for the alutninas over the pH range examined. Thiourea in the electrolyte (a substance known to be adsorbed on a copper cathode during electrodeposition) affected the amount of alumina in the electrodeposit. However, no adsorption of thiourea on aluminas in aqueous dispersions was detected. If it were possible to produce a dispersion-hardened alloy of copper and alumina by electrodeposition, an alloy possessing both strength and high conductivity at elevated temperatures might be anticipated. Investigation of the mechanism of codeposition of aluminas with copper was undertaken with the hope that knowledge of the mechanism would aid in the development of such an alloy. The word "codeposit" here does not necessarily imply an electrolytic phenomenon but rather that the materials codepositing, the various aluminas, are transported to and embedded in the electrodeposited copper by some means. Mechanical inclusion in electrodeposition implies a mechanism of codeposition which is wholly mechanical in nature; the only forces acting on a particle are gravity and contact forces. Such a particle is presumed to be electrically inert and incapable of any electrical interaction with electrodes in an electrolytic plating bath. Processes for matrices containing a codeposited phase by electrodeposition from a bath containing a disperse insoluble phase frequently state that code-position is caused by mechanical inclusion.10,2,12 If settling, i.e., gravity, be the controlling mechanism for codeposition of aluminas, then assumptions may be made that 1) the content of alumina in the electrodeposit should be enhanced by increasing the particle size, 2) the geometry of the system, that is, the disposition of the cathode surfaces relative to the di- rection of the falling particles, should affect the alumina content of the electrodeposit, 3) in geometrically identical systems the chemical composition of the electrolyte employed should exercise no effect on the alumina content of the deposit, that is, the alumina content should be the same in all cathode deposits irrespective of bath composition. A bent cathode19 evaluates the clarity of filter effluent in electroplating baths by comparing the roughness of the deposit on the vertical surface with that on the horizontal surface. Two difficulties are inherent in this technique: 1) the current density on the horizontal portion of the cathode would be substantially greater than that on the vertical surface; 2) should the deposit obtained be rough, projections on the vertical face could act as horizontal planes and vitiate the relationship between the vertical and horizontal surfaces. Bath composition should have no substantial effect on the alumina content of the deposit. Two different electrolytic baths were employed. They possessed variant specific conductances and substantially different pH ranges. The experimental tanks were rectangular Pyrex battery jars 6 in. wide by 3 1/4 in. long by 9 3/4 in. deep. The cathodes were stainless steel 316 sheet of 0.030 in. thickness, cut to 7.5 by 1.75 in. and bent at right angles to form an L-shaped cathode whose horizontal surfaces measured 1.75 by 3.0 in. All edges and vertical surfaces were masked with Scotch Elec-troplaters Tape No. 470. The anodes were electrolytic cathode copper 9 in. high by 2.25 in. wide by 0.5 in. thick. To eliminate inordinately high current densities on the projecting edge of the cathode, the anode was masked 1 in. above and below the projected line of intersection of the cathode with the anode. The exposed area of the anode was equal to that of the cathode, providing both with equal average current densities. The agitator in the cell was of Pyrex glass and positioned so its center line was equidistant from cathode and anode, and a plane passed horizontally through the center of the blade would be located equidistant from the bottom of the cathode and the bottom of the deposition tank. The assembled apparatus is depicted in Fig. 1. Hatched areas on anode and cathode represent the area of the electrodes wrapped with electroplaters tape. MATERIALS The chemicals were copper sulfate—CuSO4 • 5H2O— technical powder (Fisher Scientific Co.). Spectro-graphic analysis showed substantial freedom from antimony, arsenic, and iron. Traces of nickel were present.

Jan 1, 1967

By F. W. Bloecher, A. M. Gaudin

Using an adsorption-column technique the partition of dodecylamine between quartz and water has been determined at concentrations ranging from 0.5 to 4000 mg per liter. The adsorption varies as the square root of the concentration. Attachment of dodecylamine to quartz is reversible. The amount adsorbed in a flotation operation giving almost complete recovery is under 5 pct of the amount required for a monolayer.

Jan 4, 1950

By R. Hogg

Sintering is a process in which the pore structure of an agglomerated powder is modified. For many applications, it is desirable to be able to control the pore structure in order to optimize such properties as mechanical strength and reactivity (availability and accessibility of solid surfaces to reactant gases, for example). In general, these properties will be determined by the total porosity and the pore size distribution of the agglomerate. In the work described in this paper, a physically realistic mathematical model for the sintering process has been developed. The model is based on the usual assumption that the pore system in an agglomerate can be treated as a network of interconnecting, cylindrical pores of continuously varying size. It is further assumed that the total pore length is conserved during the course of the sintering process. Using standard expressions for the rate of shrinkage of an individual pore, the model can be used to predict the changes in total porosity and pore size distribution as sintering proceeds. Experimental pore size distributions, obtained by mercury intrusion porosimetry, for the sintering of oxides appear to be in general agreement with the predictions of the model.

Jan 1, 1977

By Evert Hoek

An empirical criterion is presented for use in estimating the strength of heavily jointed or weathered rock masses. This criterion incorporates the intact strength of the rock material and introduces two dimensionless parameters m and s which characterize the behaviour of the interlocking particles in a jointed rock mass. The use of rock mass classification systems for estimating the values of these parameters is discussed. The application of this non-linear failure criterion to the analysis of slopes is illustrated by means of a worked example.

Jan 1, 1983

By W. L. Saunders

When work was begun in September, 1910, on the rock excavation for the foundation of the gigantic dam at Valhalla, N. Y., which is to convert Kensico lake into an important storage reservoir of the Catskill Aqueduct system, one of the first steps taken by the contractor, H. S. Kerbaugh, Inc., was the development of a quarry to supply the stone needed in the

Jan 1, 1915

By Russell A. Carter

Although significant phosphate mining activity has occurred in four western states-Idaho, Montana, Utah, and Wyoming-southeastern Idaho contains the largest, most easily mineable reserves, and mining has focused there. More than half of the western phosphate field&apos;s economic reserves are within a 32 x 96-km (20 x 60-mile) rectangle bounded by Montpelier, Idaho, on the south, Soda Springs on the west, and Grays Lake on the east. A large amount of this land lies within the boundaries of the Caribou National Forest.

Jan 1, 1978

By Charles A. Mitke

The Copper Queen mine is composed of seven divisions which are operated through the following shafts: The workings of the different shafts are connected by motor-haulage drifts on the even numbered levels. The general location of the ore-bodies and workings is illustrated by the vertical projection of orebodies of the district as shown in Fig. 1. The Uncle Sam, Southwest, and Czar workings have many connections to the surface through raises and extensive cracks that were caused by moving ground. These divisions are cool and are ventilated entirely by natural means. The Holbrook is ventilated partly by natural and partly by artificial ventilation, while the Spray, Gardner, Lowell, and Sacramento are ventilated entirely by mechanical means. In some of the divisions mentioned above a considerable quantity of air exhausts through shafts of adjoining properties.

Jan 1, 1916

By William P. Blake

In addition to uintaite, the Uintah Mountains contain a deposit, or vein, of the peculiar hydrocarbon mineral, to which I have given the name wurtzilite, * in honor of the chemist, Henry Wurtz, Ph.D., of New York, who, in 1865, described grahamite, and who has added to our knowledge of the composition of the hydrocarbon minerals. Wurtzilite and uintaite are very similar in appearance, but are very different in their physical and chemical properties. Both are black, splendent and shining in fresh fracture; but the wurtzilite has a decided toughness, and a degree of elasticity, especially when warmed, which suggests to some persons a resemblance to caoutchouc. It was at first, at Salt Lake, believed and reported to be a mineral form of India-rubber, and great expectations of its value as a substitute for crude rubber were indulged in. It was, however, found that it would not act like rubber with sulphur; it would not incorporate with it and become "volcanized," and it was very refractory and insoluble in the ordinary solvents of rubber and of uintaite. The elasticity, though unlike the elasticity of rubber, led to the reference of the mineral to the species elaterite, the only name under which an elastic bitumen is described in the mineralogies; and it is so called in the list of the mineral products of Utah, given in the last message of the Governor of the Territory. The name elaterite, as used by Dana, covers at least three differing substances, ranging in specific gravity from 0.905 to 1.223. Two of the varieties are soft and elastic, much like India-rubber, and one is occasionally hard and brittle, imbedded in the softer kinds. All are rare, and comparatively unknown, and not generally represented in mineral collections. One of the varieties referred to here is the subterranean fungus from Derbyshire, described by Lister as early as 1673.

Jan 1, 1890

By Strathmore R. B. Cooke, Iwao Iwasaki, C. S. Chang

PYRRHOTITE has long been considered a gangue mineral to be eliminated as tailing in the treatment of various sulphide ores. However, in recent years the world-wide lack of sulphur resources has called attention to this mineral as a potential source of both sulphur and iron. Its importance as an economic mineral, however, has not been particularly emphasized. For this reason very little is known about its response to flotation, except that it can be depressed easily in alkaline circuit, by long aeration,1,2 addition of oxidizing agents3 or by starch.4 The object of this work was to study the floatability of pyrrhotite. This includes the effect of oxidation by aeration, of copper activation, and of change in pH.

Jan 2, 1954

By Paul R. Wieber, Atam P. Sikri

This paper describes the U. S. Energy Research and Development Administration&apos;s (ERDA) program to develop in situ coal conversion processes, especially gasification. The potential of this technology, the technical directions being explored, and the program strategy to carry the process concepts toward commercialization are emphasized. The geographic location of the U. S. coal resources and a market analysis are described. Commercially successful in situ coal processes could add over a trillion tons of coal to the U. S. coal reserves. The economics of these processes is compared with surface gasification. Independent studies show this process to be 25% cheaper than surface gasification for Western coals. The major projects are briefly described. The Linked Vertical Well process is in the most advanced stage and shows great promise. The last test produced a low-Btu gas averaging 171 Btu per standard cubic foot for average production rates of 8.5 million standard cubic feet per day. The other projects are Packed Bed, Longwall Generator, and Steeply Dipping Beds. Unique factors of the process development are discussed which may lead to commercial processes in the near term. A development strategy is proposed by which this technology could be commercialized before 1985 with potentially lower gas prices and lower environmental impacts, relative to mining plus surface gasification.

Jan 5, 1978

By Alfred Boyles

The experiments described below are a continuation of work on the graphitization of cast iron conducted as part of the program of fundamental research at Battelle Memorial Institute. In previous work it was found that melting in hydrogen increased the amount of eutectic carbide appearing in certain alloys and in others produced marked changes in the size of the graphite flakes. These effects seemed to be closely related to the amount of sulphur and manganese present in the material studied. Iron-carbon-silicon alloys did not respond to hydrogen in the same manner as cast iron and there was no evidence to show that hydrogen was able to stabilize the carbide in such alloys unless additions of sulphur were made. The two alloys examined contained about 2 per cent of silicon. The present paper is concerned with alloys of lower silicon content and describes the structural changes produced by melting in various atmospheres at pressurcs ranging from a partial vacuum up to 300 lb. per sq. inch. Experimental Method The experimental technique was similar to that previously employed, so that direct comparison might be made with earlier work. Alloys were

Jan 1, 1939