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By R. F. Mehl, B. Lustman

The formation of intermediate phase layers in cementation processes has been subjected to extensive qualitative investigation though to relatively little quantitative study; this work has recently been fully summarized by F. N. Rhines.' It is necessary here only to cnumerate the general conclusions drawn concerning the kinetic laws governing the growth of intermediate layers and to state what is known concerning the structural changes accompanying the generation of phase layers. I. When the intermediate phase is protective in type—i.e., when its density is less than that of the base metal, so that a continuous coating is formed and maintained—the isothermal growth of the phase follows a simple parabolic equation: X2 = kt [i] where X is the thickness of the alloy layer, k thc reaction rate constant, and t the time. The applicability of this equation to diffusion processes is tested by plotting the square of the thickness versus time, or by plotting the thickness versus the square root of time; the resultant achievement of a straight line in such a plot has been considered sufficient proof of the validity of this equation. Exceptions have been found where liquid phases are involved in the reaction, where the diffusion layer is cracked,2 and where thin semimetallic oxide and sulphide coatings are formed on metals.$ In the first two cases the thickness increases linearly with time, and in the latter it is a logarithmic function of time. 2. The rate of thickening varics with temperature according to the Arrhenius equation: k = Ae-Q/RT [2] where k is the parabolic rate constant of Eq. I, or some other rate-descriptive function, A is the action constant, e the base of natural logarithms, Q the heat of activation, R the gas constant, and T absolute temperature. This equation has been found to be generally valid except when transformations occur during reaction in either the base metal or in the reaction layer; in such instances Eq. 2 is still applicable with different values for the constants A and Q above and below the transformation temperature. 3. Ali phases that are stable at the temperature at which diffusion occurs will appear in the interdiffusion of two components. In some cases certain of the phases may be too thin to be observed and identified easily. Nonequilibrium phases have never been noted in thick reaction layers; i.e., layers of a thickness that may be discerned microscopically. The relative thickness of each phase in a diffusion layer is proportional to the concentration gradient and to the rate of diffusion in that phase.4 The reaction layers tend to have a

Jan 1, 1942

By Niander A. Cerqueira, Afonso G. Azevedo, Mairyanne S. Souza, Victor B. Souza, Victor T. Bartolazzi, Igor W. D. C. Pereira, Rondinelli C. Ribeiro

The common glass machining process used in the market of Brazil’s civil construction generates tons of waste through the folder of that waste disposal out by the water used during machining. After drying the product is intended for landfill representing a great environmental liabilities since these deposited glass waste in the environment have a decomposition time greater than four thousand years due to its high chemical and mechanical resistance. Aiming to give a destination that addresses this waste disposal problem in the environment, much has been studied in an attempt to incorporate them into the mix cement to partially replace the sand. In this work it was decided to carry out specific studies using common traits comparing the stroke with sand with a dash with partial replacement of 30% of the sand for the glass machining residue was analyzed resistance compressive resulting in a potential good product.

Mar 1, 2017

By B. Mishra

This paper presents a rock mechanics investigation of the time-dependent behavior of the rock immediately surrounding the excavation in a hypothetical one-entry coal mine based on the geology of the Illinois coalfields Research in the area of time-dependency is almost nonexistent and, therefore, this research was performed to make inroads into this neglected research area. Numerical analysis of a typical one-entry coal mine in an Illinois basin was performed using the commercial finite difference program FLAC3D. The immediate roof of the coal entry was assumed to be a shale formation. Shale in other formations has shown a tendency to creep with time. Therefore, in this study the authors modeled the shale in the roof using time-dependent characteristics. The input properties were taken from laboratory creep tests performed on shale. Model runs were performed at different stages, mimicking the progressive excavation of the entry. The model results showed that stresses in the roof attained the limit of yielding. Using Mohr-Coulomb failure criteria, potential zones of failure were also predicted. The results showed that the current computational capacities are sufficient to explore this previously uncharted territory of ground control.

Mar 1, 2014

By Alexander I. Raitchenko

"Although one takes into account only thermal expansion usually at analysis of convection onset, the essential factors include magnetic and electric fields. If Lorentz-force originating from intercrossed electric and magnetic fields' action is directed downwards its effect strengthens gravitational action, and value of critical Rayleigh number (limit value for convection onset) must decrease; increasing of critical Rayleigh number should be observed in case of Lorentz-force directed upwards. Extent of such an influence is determined by relation of Lorentz-force to hydrostatic head in gravitational field. Competition between electromagnetic force due to nonuniformity of electroconductivity (on account of its temperature dependence) and electromagnetic buoyancy force may have ambiguous effect: both increase or decrease of critical Rayleigh numbers. Proposed conception is applicable to analysis of situations in liquid conductors and conductive gases.IntroductionStatic or dynamic situations in fluid media are determined besides properties of these media by a variety of external influences. However one correlate~ the onset of the convection and its development with influences of the minimum quantity of external causes frequently. Most known and usual factors are the gravitational and temperature fields. The number of processes includes heat generation in media volume, and theoretical analysis in these cases takes into account this interior heating together with boundary temperature conditions. But explanation of many natural and technical events is not complete and cogent within limits of thermo-gravitational terms. The whole complex of acting factors which influence convective processes in techniques and nature is greater in many cases. In particular the action of · electromagnetic nature often has not less importance than gravitation one. Stability or instability of a current layer in the plasma must be determined by non-uniformity of electroconductivity owing to non-uniformity of temperature [1]. The presence of Joule dissipation in the plasma through which the electric current flows stipulates initiation of origin of overheated instability [2]. It is known that electroconductivity of arc in the boundary zone changes sharply with radial distance [3], and this must influence its stability essentially. If the intercrossed electric current and magnetic field begin to act on an electroconductive fluid besides the non-uniform temperature field and the gravity, the conditions for the onset of the convection change radi- . cally: both the temperature field and their solutions have to be changed also. The analysis of equilibrium single-time correlation functions of fluctuations must be employed for situations with enlarged number of factors as this was in case for the Rayleigh-Benard problem where the object is a horizontal layer of liquid. This can be carried out by taking into account the detached forces' correlations [ 4, 5]"

Jan 1, 1999

By F. W. Jessen, N. Lamont

The effect of an existing fracture or joint plane, which may exist in a rock, on the extension of a hydraulically induced fracture through the rock has been investigated in the laboratory. By use of a series of models made from various outcrop rocks, the width and orientation of existing fractures do not alter the extension or direction of the hydraulic fracture. The results, which conform quite well with the Grifith theory of failure, are illustrated by a series of photographs of the various models. INTRODUCTION The process of hydraulic fracturing has been widely used in the oil industry since its introduction in 1948 and has made possible the production of many reservoirs which would have been uneconomical prior to this process. Numerous studies of the mechanics of the process2-h nd of the effects of oriented fractures on recovery'.' have appeared in the literature. The increased recoveries led to attempts to predict the orientation of hydraulic fractures at the wellbore and to the development of methods to control this orientation. Field tests have been devised"." which indicate the validity of theoretical predictions of fracture orientation at the borehole. The direction of extension of hydraulic fractures from the borehole has not received much attention since most studies have predicted, at least implicitly, that a fracture will continue in the same plane unless a change of state of stress in the rock occurs. Since such predictions are based on the assumption of rock homogeneity, the effects of rock heterogeneities are left unknown. Most sedimentary rocks are composed of layers which reflect the changing depositional conditions of geological time. In addition, the more competent rocks frequently are fractured and jointed as the result of structural deformations or tectonic movements. Evidence of such joint systems exists in many surface outcrops, and it can be assumed that similar systems occur in many subsurface rocks, although the individual joints may be rather tightly closed due to overburden forces. This paper investigates the effect that an existing fracture in a rock would have on the direction or orientation of an extending or advancing hydraulic fracture when it intersects the existing fracture. The study was conducted on small rock models under triaxial stress conditions. The results indicate that an existing fracture will have little effect on the hydraulic fracture. THE MODEL STUDY The rock model represents an elemental portion of the earth containing an existing fracture which is located at some distance from a borehole from which hydraulic fracture is being extended. A generalized view of a model is presented in Fig. 1. The models were constructed from cement blocks and natural rocks. The various materials tested and some of the physical properties are listed in Table 1. The rocks were cut into rectangular blocks with dimensions of 11/2 X3Y2 X4 to 8 in. An initial slot was cut into the end face of each block along the longitudinal axis normal to the top face. The slot was filled with plastic aluminum along its outer edge to a depth of 1/16 in. A hole of 3/8-in. diameter was drilled into the sealed slot at the center of the end face to serve as an entry port for the fracturing fluid. Existing fractures of various types were simulated in the models. A "hairline" fracture with essentially zero width was created by cutting the model into two parts with a diamond saw and replacing the two parts together along the cut. A finite-width fracture was created by placing a layer of sand grains between the two faces of the cut just described (see Fig. 12). A large open fracture (similar, perhaps, to a vug) was created by cutting the model in two parts and removing a portion of the downstream block to a depth of % in. See Fig. 13. For a fourth

By T. D. Tiemann

The purpose of this writing is to make available additional data, not previously published, on the extraction of silica from certain iron ores of Wisconsin and Minnesota and to discuss a possible method of processing. Results of investigations on the extraction of silica from low grade iron ores have been previously presented and discussed in detail in AIME Transactions.1,2 All of the ores investigated are essentially nonmagnetic and consist mainly of hematite, goethite and quartz. Much of the quartz is microcrystalline, particularly in the taconites. The ore from the Cuyuna range contains in addition manganese oxides. Briefly, the method consists in digesting a sample of the ore under pressure in a solution of sodium hy-

Jan 1, 1965

By Nick Katsikaros, A H. Gray

Gold concentrates are produced at many mines by a variety of centrifugal and gravity machines, such as Knelson and Falcon concentrators, however the subsequent recovery of gold is relatively inefficient and subject to security problems. The InLine Leach Reactor (ILR) offers a new method to recover over 95% of gold in concentrates using a simple, secure leaching process. The InLine Leach Reactor is of particular benefit in treating slow or difficult leaching sulphide concentrates and its performance can be reliably predicted from simple laboratory tests. The InLine Leach Reactor is now successfully operating in two gold mines providing benefits of high gold recovery, low operating costs, high security and ease of operation.

Jan 1, 1999

By A. ALLANORE, OLIVEIRA M. DE, D. CICERI, D. P. CHEN

The alkaline hydrothermal processing of K-feldspar rocks in an autoclave can be a pathway to synthesize a potassium fertilizer for tropical soils that is potentially cheaper and more efficient than traditional potash (KCl). When K-feldspar undergoes hydrothermal alteration in the presence of calcium oxide (CaO), it generates a complex mixture of calcium-aluminum-silicate-hydrate (CASH) minerals that incorporate K atoms stochastically in their structure. These atoms are subsequently released, as shown in a test-tube leaching test, indicating a possible uptake by crops. The relationship between the processing temperature and time in the autoclave for the hydrothermal reaction and the resulting mineralogy and elemental release are only partially understood and are investigated in this study. Elucidating that relationship is the key requisite for subsequent techno-economic analysis, and ultimately for the development of a fertilizer that can be considered as a feasible alternative to KCl.

By Hai-Xing Fang, Chao Liu, Tao Zhang, Bing Xie, Hong-Yi Li, Cui Li

"Hongge Ore, a kind of vanadium-titanium magnetite ore containing high content of chromium, is valuable resource for extracting Fe, V and Cr in China. During present processing of the ore, vanadium and chromium were both concentrated in slag, leading to higher content of chromium in the vanadium slag than that of common one in Pan-Steel. Mineral phases and characteristics of spine! crystals, which influenced greatly subsequent roasting process, in the vanadium slag under different cooling conditions were investigated by using XRD and SEM/EDS. Results showed that vanadium slags containing various contents of chromium were composed of spine!, in which V and Cr were both concentrated, olivine and pyroxene. Growth rate of spine ls decreased sharply below 1350°C. The non-isothermal crystallization process could be described by modified Avrami equation and Ozawa equation. Avrami exponent and Ozawa index were calculated and growth mechanism of spine! crystals was discussed.IntroductionVanadium (V) as well as chromium (Cr) is important non-ferrous metal widely used in materials and chemical industries [1, 2]. Especially, both of them are important alloying elements for the production of high alloyed steels to achieve desired physical-chemical and mechanical properties. Vanadium-titanium magnetite ore in Panzhihua-Xichang area (China) is an important raw material for extracting vanadium. During the extracting process, vanadium is firstly reduced into hot metal and then concentrated in slag phase by blowing oxygen into the hot metal in converter [3]. This kind of slag containing 5~20 wt% V20 3 are usually roasted with sodium or calcium salts and then leached to obtain vanadium containing solution and final products. Current vanadium slag obtained from normal vanadium-titanium magnetite ore contains low content of Cr20 3 and chromium extraction is thus ignored. However, chromium content in the vanadium slag would be increased intensively when the Hongge Ore used, which is also important vanadium titanium magnetite in Panzhihua-Xichang area containing 0.2~0.8 wt% Cr203. Therefore, this kind of vanadium slag with high content of chromium would also be important sources for vanadium and chromium extraction. According to previous work [4], both vanadium and chromium could be extracted from vanadium slag with high content of chromium by salt roasting and leaching, which is illustrated in Fig.1."

Jan 1, 2013

By R. A. Cummings

From before the turn of the century until as recently as the 1950s, relatively shallow coal reserves near the margins of the Illinois Basin were extracted by room- and pillar methods. Subsequent development has, in many cases, extended onto ground with high subsidence potential. The same state of affairs exists in many other historical coal mining districts, as well as in Illinois. Pit subsidence in Illinois is particularly common in the towns of Streator, Carterville, and Herrin, although there are others. Pit subsidence is characterized by distinct circular or oval depressions and normally is associated with shallow mining and thick soil relative to the thickness of rock.

Jan 1, 1985

By Suresh K. Bhatt, Gary L. Mowrey, Timothy R. Rehak, David K. Ingram

Coal and nonmetal mining used about 4.3 billion pounds of explosives and blasting agents during 2001 in the United States. A major part of this consumption was related to surface mining. Mine Safety and Health Administration accident data indicate that flyrock and lack of blast area security were the primary causes of blasting-related injuries in surface mining. Fatal injuries due to lack of blast area security were primarily caused by failure to clear blast area or inadequate access control to the blast area. At a coal mine, a neighbor walked into the blast area and was fatally injured. The blaster could not see the victim entering the blast area from the firing station. In another case, a passenger in a vehicle was fatally injured by flyrock because highway traffic was not monitored during the blast. In another example, a dozer operator entered a blast area due to lack of access control. Several fatalities resulted from using inadequate or no blasting shelter. A crane operator was fatally injured while standing in the open about 120 ft from the blast site. In another instance, a helper, standing about 150 ft away from the edge of a blast, was fatally injured by flyrock. In a limestone mine an equipment operator was fatally injured while guarding access roads in a pickup truck. This paper briefly describes six representative fatalities due to flyrock and lack of blast area security in coal and nonmetal mines. Several mines were visited to collect information relative to working practices aimed at mitigating blasting hazards. Salient information obtained through these visits is presented.

By Harry H. Power

The relative merits of air and natural gas as propulsive agents in pressure drive operations have been discussed for a number of years. When air or gas is introduced into the sand, various factors lead the operator to the selection of what he believes to be the proper propelling medium; but when the question of relative drive effect is raised, several physical and chemical premises must be taken into consideration in arriving at a conclusion as to the superiority of one medium over the other. Dow and Calkins1 and Beecher and Parkhurst2 have contributed fundamental experimental work on the effect of dissolved gas in lowering the viscosity and surface tension of crude oil. Herold; and Tickell' have indicated that whatever type of reservoir control obtains, gas plays other important parts in the movement of oil towards the well, namely: 1. The propulsive and expansive force of the gas. 2. The "Jamin effect," or resistance to the movement of oil in a porous media due to the formation of gas bubbles. When quantitative studies are made, parallel conditions must be selected whereby we may say definitely whether air is superior to gas as a driving medium, or vice versa. Examples of similar conditions are not easy to find in the field. However, in the laboratory we can make determinations which may lead to general conclusions when applied to the field. The experimental and research work described here was started at the laboratories of the University of California in January, 1927, and completed in private laboratories at Tulsa, Okla., in February, 1928. The apparatus used was designed especially for the work.

Jan 1, 1929

By Steven D. Scherer

The highest earthquake risk in the United States east of the Rockies is along the New Madrid Fault System, which extends for 193 km (120 miles) through the Central Mississippi Valley from northeastern Arkansas, through southwestern Missouri, western Tennessee and western Kentucky to southern Illinois. Historically, this fault has generated some of the most powerful earthquakes in U.S. history, notably three Magnitude 8 events in 1811. Apart from the West Coast, this region experiences more earthquakes than anywhere else in the United States, with more than 200 events recorded along the fault annually. These events are typically of much lower magnitude than those experienced in California. Most are too small to be felt. However, should a significant event occur, damage can be expected to be widespread because of the underlying geology. In recent years, earthquake preparedness and seismic upgrade of vulnerable structures has become a focus for a number of State Departments of Transportation, including those in Illinois and Missouri where there is a potential for future damage. This paper presents three case histories illustrating three different techniques used to retrofit interstate highway bridge foundations bearing on potentially liquefiable soils. Friction minipiles were installed at the approach span of the I-57 bridge crossing the Mississippi River near Cairo, Illinois to provide additional support to the pile caps in the event of liquefaction of the underlying sands during a seismic event. In St Louis, Missouri, rock-socketed minipiles were installed to increase the capacity of drilled shaft foundations supporting a section of Interstate 64. In Mounds, Illinois, compaction grouting was used to densify loose sand deposits beneath a pile-supported interstate bridge on I-57.

Jan 1, 2001

By J. W. Horne

The quantitative determination of salt in petroleum ins generally divided into two steps - (1) extraction of salt from the oil and (2) accurate measurement of the extracted salt. This paper presents a method used by the Bureau of Mines for quantitatively extracting the water-soluble chloride salts4/ from petroleum and discusses important details attendant on the success of the method. Among these details are homogeneity in the dispersion of salt crystals, emulsified brine and other impurities in the oil sample, complete solution of the salt, and total extraction and titration of all the aqueous phase. Recently, the chlorides of sodium, calcium, and. magnesium produced with and present in various oils have developed growing problems of salt deposition and corrosion in the petroleum industry. Therefore, a technical study of various emulsions and salts that accompany petroleum is being made by the Bureau of Mines in cooperation with the State of Oklahoma. One report (5)5 reviewing the literature pertinent to the study has been published.

Jan 1, 1940

By K. Koruyan

Although remote sensing technology has been available for many years, it has rarely been used for monitoring mining activity. Recent studies indicate that remote sensing is also a valuable tool for managing and planning certain aspects of the mining operation. In this paper, we examine areal expansion of marble quarries and the affected vegetation over a period of 10 years in the Mugla region in Turkey, using geographic information system (GIS) and remote sensing (RS) techniques. Images captured by ASTER Level 3A01 (3D Ortho Data Set), Landsat 5, and Landsat 7 satellites between 2001 and 2009 were used for the analysis. Changes in the natural vegetation as a function of the production level in the marble quarry were calculated using the normalized difference vegetation index. According to the study results, land cover and natural vegetation decreased by less than 3 per cent and 1 per cent respectively between 2001 and 2009, following an upsurge in mining activity in the region.

Jan 1, 2012

By G. W. Thomas

A mathematical tnodel of forward combustion in an oil reservoir is treated in this paper. The model describes a radial system having a vertical section of essentially infinite thickness, all of which is permeable to gas flow. Combustion, however, is presumed initiated over a limited thickness of the total vertical section. In the interval supporting cotnbustion, the mechanisms of radial conduction, convection and heat generation are taken into account. Above and below the burning interval, heat transport in the radial direction is by cottduction and convection. Vertical heat losses from the ignited interval are accounted for by conduction alone. A general solution is presented for the temperature distribution caused by radial movement of the combustion front. The results show that no feedback of heat occurs into the ignited interval when convection and conduction are acting in the bounding media. Peak temperatures are also 5 to 10 per cent higher than in the case where heat transport in the bounding media is by conduction alone. We arbitrarily define vertical coverage to be that fraction of the total ignited interval which is at 600F above atnbient, or greater, at any given time. The radial distance at which the vertical coverage becomes zero is the propagation range of the combustion front. It was found that an increase in vertical coverage results when the oxygen concentration, fuel concentration or gas-injection rate is increased. Moreover, the combustion front can be propagated 10 to 15 per cent further than in the case where only conduction is acting above and below the ignited interval. INTRODUCTION In the theoretical treatment of forward combustion in a radial system, one of the problems encountered is the determination of the transient temperature distributions caused by an expanding cylindrical heat source. Bailey and Larkin' and Ramey' simultaneously presented analytical solutions to the problem assuming heat transport by conduction alone. In a subsequent publication, Bailey and Larkin3 included the effects of both conduction and convection while treating linear and radial models. In this latter work, however, vertical heat losses were largely neglected. Selig and Couch' dealt with a radial model in which both conduction and convection were acting. Only a limiting case involving vertical heat losses was considered, however. Namely, temperatures on the boundary of the bed of interest were set equal to zero. Solutions thus obtained were representative of a system having a maximum vertical heat flux. Chu5 recently treated a more general case in which a permeable bed was considered bounded by impermeable media. Conduction and convection took place within the bed, and only conduction outside of the bed. The effects of vertical heat losses were included in his study. Solutions were obtained by numerical techniques. This paper is an extension of the theoretical work of other authors pertaining to forward combustion in a radial system. In particular, a mathematical model of the process is treated in which heat generation occurs over a small vertical interval of a larger permeable section. In the interval supporting heat generation, and above and below this interval, the mechanisms of radial conduction and convection are also presumed acting. Heat losses from the ignited interval are accounted for by vertical conduction. An analytical solution for the temperature distribution caused by radial movement of the burning front is presented. The effects of certain process variables are indicated and comparisons with Chu's results are made. THEORY To render the mechanism of forward combustion tractable to mathematical treatment, we idealize the problem to the extent of assuming continuous reservoir media possessing homogeneous and isotropic properties. The following additional assumptions are implicit in this analysis. 1. The thermal parameters, i.e., heat capacities, thermal conductivities and thermal diffusivities are invariant with temperature and pressure. Moreover, the bounding media possess the same thermal properties as the bed of interest. 2. The temperatures of the porous media and its contained fluids at any point and at any time are equal. 3. The reaction rate between the oxidant gas and the fuel is infinite. This assumption implies that the incoming oxygen concentration instantaneously goes to zero within an infinitesimal distance, i.e., the width of the combustion zone is negligible. 4. The rate of gas injection is constant and corresponds to the average rate throughout the lifetime of the project. 5. The fuel concentration is constant throughout the volume of rock swept out by the burning zone. 6. There is complete burnoff of fuel. This assumption demands that the rate of propagation of the burning front equals the rate of fuel burnoff. In a radial system, with a

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By C. B. Alcock, L. I. Cheng

By the use of radiochemical methods for the study of the gas-liquid equilibria at low temperature, and for the determination of the sulfur contents of metal beads which had been equilibrated with H2S/H2 mixtures of known sulfur potential, it has been possible to obtain the liquid solubility and the free energy of solution of sulfur in liquid tin and lead at temperatures between 500°and 680°C. THE gas-liquid equilibrium method has proved in the past to be most successful in the determination of the thermodynamic behavior of dilute solutions of sulfur in liquid metals.1,2 One of the basic requirements for success with this method is that the volatility of both the metal and its lowest sulfide should be small, otherwise sulfide will be deposited at the cool end of the furnace, where it may react with the outgoing gases to form either sulfur-rich lowest sulfide or higher sulfides. The resultant value of the apparent equilibrium constant will then be lower than the correct one. This argument applies even at sulfur potentials below that in equilibrium with a separate condensed phase of the lowest sulfide at the reaction temperature, T. The mass of sulfide which is deposited at the cold end of the furnace, and hence the extent to which further reaction occurs with the outgoing gases, depends on the time taken for equilibrium to be reached between metal and gas. Since this will depend principally on the bulk of the metal phase which is used, one should clearly attempt to uie as small metal samples as possible. These considerations are important in the study of dilute solutions of sulfur dissolved in liquid tin and lead which both have moderately high vapor pressures as metals and form volatile sulfides. The limit on the size of the metal samples which may be used is set chiefly by the difficulties of analysis for very small amounts of sulfur. The oxygen or carbon dioxide combustion method, followed by iodimetric determination of the sulfur dioxide which is formed,has been found to be successful for the determination of small amounts of sulfur in copper, iron, cobalt and nickel.4 This method was unsatisfactory for sulfur dissolved in tin and lead, mainly because the sulfur dioxide was to some extent absorbed by the copious tin or lead oxide deposits which were formed on the walls of the combustion tube. Furthermore some of the sulfur was found to segregate on the surface of the beads as flaky sulfide crystals which would easily be lost in the transfer of a bead from a boat in the gas equilibration apparatus to one in the combustion apparatus. Oxidation in aqueous media to sulfate ion followed by precipitation as barium sulfate was, therefore, adopted as the analytical procedure. The gas-metal equilibrium experiments were all carried out with radioactive sulfur and thus the analysis involved the counting of barium radiosulfate. Furthermore the use of the radioisotope meant that the approach to the gas-metal equilibrium could be followed continuously by gas counting.' The metal beads were held separately in glass crucibles during equilibration and were transferred from the furnace to the beaker for dissolution in nitric acid still in the crucibles, and thus the possibility of sulfur loss by detachment of the sulfide segregates was eliminated. The temperature range of this investigation was 500° to 680°C. EXPERIMENTAL APPARATUS AND METHOD The apparatus consisted of two furnaces placed in series in a gas recirculation system, Fig. 1. One furnace F1, which was vertical was used to heat the alumina crucible, A, holding six metal beads in separate glass crucibles. The beads weighed between 300 and 700 mg each. The crucible assembly was introduced and removed from the furnace mechanically under a stream of oxygen-free argon. The other furnace, F2, was horizontal and was used to heat a cobalt Co9S8 mixture, held in an alumina boat, and made with radiosulfur containing about 1/2 millicurie per g of sulphur. This mixture, which was finely powdered, was used as a source of known H2S/H2 mixtures6 for a given furnace temperature. The recirculation system also contained a gas re-circulation pump (P), an end window Geiger-Miiller counter (N)—placed downstream of F1 so as to monitor the H2S pressure in the gas leaving this furnace— a sample volume for chemical analysis of the gas phase (G), gas drying tubes (D), filling taps and other standard ancillary equipment. The gas sampling volume was principally used in the cali-

Jan 1, 1962

By H. Y. Jennings

An extensive field and laboratory experimental program was carried out to compare the waterflood behavior of carefully preserved soft and unconsolidated cores with measurements on the same cores after extraction. Results obtained from using idealized consolidated and unconsolidated porous media in which wettability could be carefully controlled were contrasted with the preserved core data. The controlled tests on idealized porous media investigated the effect of wettability, flood rate, core length, core permeability and consolidation on the displacement of high viscosity oils. It was concluded from these studies that waterfloods are more favorable when carried out with crude oil in preserved soft and unconsolidated cores than with the same cores after they have been extracted and re-saturated. Waterfloods are usually more favorable when carried out with crude oil in extracted .soft and unconsolidated cores than with refined oil of the .same viscosity in the same cores. The less favorable behavior of extracted soft and unconsolidated cores compared to preserved cores is due to alteration of the core by extraction. Preserved cores saturated with native water and oil should be used for laboratory displacement experiments because they more accurately reflect true reservoir behavior INTRODUCTION The demand for low gravity crude oil created by refinery modernization has focused attention on increasing the production of this viscous crude oil. Billions of barrels are in place in fields that are depleted, or nearly depleted, by primary production mechanisms. Since low gravity reservoirs are relatively recent, geologically, the solid matrix material is usually soft and unconsolidated sand. Such formations are also characterized by a high clay content. Evaluation of sophisticated oil recovery processes with the associated high capital investments has increased the demand for special core analysis tests on material from these soft and unconsolidated sand reservoirs. Data in this paper have resulted from an extensive field and laboratory experimental program. The initial objective vras to provide soft and unconsolidated sand cores for laboratory measurements with as little alteration as possible from their reservoir condition. A secondary objective was to compare the waterflood behavior of these carefully preserved cores with measurements on the same cores after they had been extracted and resaturated. When the comparison showed markedly different behavior the final objective was to attempt to explain the difference by making measurements on idealized porous media free of clay in which initial wettability could be carefully controlled. EXPERIMENTS MATERIALS Core Material The preserved cores used in this study were obtained with as little alteration as possible from their reservoir conditions. Special techniques were developed to satisfy this objective. The cores were cut with native crude whenever the crude had the necessary properties to satisfy the minimum drilling fluid requirements. A pure hydrocarbon chromatographic tracer was added to the crude to provide a simple, safe and inexpensive method to distinguish between oil filtrate and formation oil. Details of the tracer technique used in this study and the procedures used to handle and process the soft, unconsolidated cores have been published.' The core samples were then preserved and packaged at the well site with a dip-applied strippable plastic, or by using a rubber sleeve from a rubber-sleeve core barrel. The final step was to insure that the carefully taken and preserved samples were not altered by processing in the laboratory. Some soft and poorly consolidated sands were carefully shaped in the lab and encased in a protective mounting without disturbing their three-dimensional integrity. Many samples were so poorly consolidated that they literally flowed from the package when the seal was broken. A technique was developed to obtain cylindrical plugs from these samples by using liquid nitrogen as the drilling fluid in a conventional core-drill, drill-press assembly. The idealized porous media consisted of sintered rods of Alundum RA 139, outcrop sandstone identified as Al-hambra sandstone and packs of No. 130 Nevada sand. This sand is 95 per cent 140-200 mesh. (Physical properties of these porous media with those representative of preserved cores are in Table 1.) The natural cores and most of the idealized porous media were 1 1/2-in. in diameter and 3-in. long. The samples used to study the effect of core length were 1 1/2-in. in diameter and 12-in. long. Liquids Water and oil produced from the formations being studied were protected from the atmosphere and collected in carefully cleaned glass or plastic-lined containers. The production was free of chemical additives such as emulsion breakers and corrosion inhibitors. The crude oil was

Jan 1, 1967

By A. H. Larson, R. J. McClincy

ALTHOUGH arsenic has a very high vapor pressure and vacuum distillation appears to be a likely method for its removal from lead, the published literature contains virtually no information concerning the vacuum removal of arsenic from lead. Caldwell, Spendlove, and St. Claire1 mention arsenic in their investigation of the removal of volatile metals from lead by vacuum distillation. They do not, however, give any data for arsenic removal or refer to any actual experimental work involving arsenic dissolved in lead. Moriyama, Kozuka, and Miura2 have determined the activity of arsenic in dilute As-Pb alloys in the temperature range from 450" to 600°C using a closed galvanic cell. They found that the activities of both arsenic and lead showed a positive deviation from ideality at 600°C. In view of the lack of experimental data regarding the vaporization of arsenic from As-Pb alloys, a limited vapor pressure study was made on liquid alloys containing from 0.5 to 3.3 wt pct As in lead at 703°C. The pressure of As4(v) above the alloys studied was determined from weight-loss data collected by means of the inert-gas saturation method. The experimental apparatus and procedure used were similar to that discussed by Alcock and Hooper9 with modifications as described by the authors., The technique involved was one of passing a known volume of inert gas over the alloy to be studied in a known amount of time and determining the loss in weight of the sample. Because of the low vapor pressure of lead at 703"C, the observed weight loss could be attributed solely to the vaporization of arsenic as the tetratomic molecule AS43 Measurements of the apparent vapor pressure were repeated at different inert-gas flow rates until from three to five values were obtained which were independent of inert-gas flow rate. This value of the apparent vapor pressure was taken to be the equilibrium vapor pressure of the alloy under consideration. The vapor pressures measured in this investigation have been converted to the activities of arsenic in As-Pb alloys, Table I, by use of the data compiled by Elliott and Gleiser5 for the vapor pressure of pure arsenic. The standard state for arsenic was chosen as the pure, hypothetical, supercooled liquid. The activity of arsenic was calculated from the fourth root of the ratio PAs,/PAS,. The low magnitude of the vapor pressures given in Table I explains the difficulty en- countered by earlier workers in successfully vacuum distilling arsenic from very dilute As-Pb alloys. The data shown in Fig. 1 indicate that the As-Pb system behaves ideally. The apparent outlier represented by the alloy containing 1.43 mol pct As is a result of the fact that the pressure of As, above the alloy was barely detectable by the experimental procedure used in this investigation. Because of this, the apparent vapor pressure determined for this alloy could be in considerable error. Moriyama, Kozuka, and ~iura' have reported that arsenic shows a positive deviation from ideality in dilute solution in lead. However, details of their results have not been made available. This research was made possible by a grant from the National Science Foundation (GK-196) for which the authors are very appreciative.

Jan 1, 1970