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By Lawrence A. Roe

Talc, when it can be isolated as a pure mineral, has a composition of 63.36% SiO2, 31.89% MgO, and 4.75% H2O. However, as an industrial commodity, talc rarely approaches theoretical purity. Nevertheless, the impure talc products of commerce find a multitude of uses and few substitutes in many industrial applications. Minerals commonly associated with and sold together in talcose mixtures are tremolite, chlorite, dolomite, mica, and magnesite. Steatite was originally a mineralogical name applied to pure talc. In today's commerce steatite generally refers to the massive variety of talc suitable for electrical insulator manufacture. Block steatite ore can be machined into various shapes. Impure varieties of massive or block talc are still commonly referred to as soapstone. Soft massive talc, suitable for crayon manufacture, has been referred to as French chalk. It has been common practice to discuss talc, soapstone, and pyrophyllite under the same general heading. In the case of soapstone and talc, this is a natural thing since many different types of platy, soft minerals exhibiting a high degree of lubricity (commonly referred to as "slip") have been grouped together and called soapstone or talc. Further, there is a mineralogical relationship of pyrophyllite to montmorillonite and talc to hectorite. Thus, talc and pyrophyllite are sometimes referred to as clay minerals. When finely divided talc or pyrophyllite are combined with water in proportions to make a slurry, the end product does have the appearance of a clay-water mixture. Soapstone for utensils and ornaments was mined by prehistoric Indians on Santa Catalina Island, Calif. In the mid-1800s, soapstone from deposits along the western foothills of the Sierra Nevada mountains was used by white settlers for building and ornamental stone and in the linings and foundations of furnaces (Anon. 1956). Previous to 1916, the annual recorded production in California did not exceed 2000 tons. In the period 1912 to 1918, output rose sharply when the Talc City, Western, and Silver Lake mines were put into operation. From 1916 to 1935, the state's annual output of talc was in the range of 9,000 to 20,000 tons. In the mid-1930s, the use of talc in wall tile grew rapidly. In California, the production of talc grew to 63,000 tpy in 1943. The post-war building boom helped California production to grow to 120,000 tons in 1951. In 1968, production was 165,000 tons, 1969 was 145,000 tons, 1970 was 185,000 tons, and 1972 was 155,000 tons. Talc mining in New York state dates to about 1878 when a Colonel Palmer and associates opened the first commercial talc mine on the Nelson Freeman farm near Talcville, New York. In 1893, this operation was sold to the International Pulp Co. which changed its name to the International Talc Co. in 1944. Total production from seven New York mines, in 1948, was 130,000 tons. A new talc operation, the Gouverneur Talc Co. owned by the R.T. Vanderbilt Co., began operations near Balmat, N.Y., in 1948. The initial capacity of the processing plant was 200 tpd (Gillingham, 1950). Subsequent expansions have increased capacity to over 600 tpd. The Vermont talc industry began just after the start of the 20th century. Talc was discovered in the area of the present Johnson, Vt., talc mine in 1902. The American Min¬erals Co. initiated plant operations at Johnson in 1904. The Magnesia Talc Co. opened a plant at Waterbury, Vt., in 1913 (Burmeister, 1963; Trauffer, 1964) and acquired American Minerals Co. in 1923. The Waterbury mine has a long history as a producer of talc crayons. The Eastern Magnesia Talc Co. was formed in 1924 by a merger of the Eastern Talc Co.

Jan 1, 1975

By A. E. Jenkins, L. A. Baker, N. A. Warner

The electromagnetic levitation technique has been successfully applied to rate studies of the de-carburization of liquid Fe-C alloys from 5.5 to zero pct C at 1660°C using gas mixtures containing 1 to 100 pct CO2 with CO or helium as diluents. The rate was shown to be independent of carbon concen -tration in the melt and only slightly affected by total pressure. The results were shown to be consistent with control either wholly or predominantly by gaseous diffusion. As well as avoiding side reactions with the crucible, levitation allowed precise calculation of reaction rates since the geometry of the system was accurately known. It also enabled interpretation using the established mass-transfer correlations for a gas flowing past a single sphere, The existence of gaseous-diffusion control and the extremely high rates of reaction reported for gas flowing past small spheres are of great practical significance in relation to current investigations into the use of spray-refining techniques in continzcous steelmaking. PREVIOUS work on the kinetics of carbon removal from liquid iron has generally involved the use of oxygen as the gaseous oxidant. Investigations have been made on commercial steelmaking furnaces and in addition laboratory-scale experiments have been attempted with a slag phase present. The general lack of agreement and the obvious difficulty in interpreting the results is at least partly due to the complexity of the systems used. This work has been reviewed by carter1 and more recently by Bods-worth2 and ward.3 The gas-liquid metal reactions have also been studied with slag-free melts by the conventional technique of blowing oxygen onto the melt contained in a crucible. The reaction between the oxidant and carbon could be followed by sampling either the melt or the gas phase. Side reactions with the crucible material have precluded direct interpretation of the results. Fujii, 5-7 using O-A mixtures, attempted to correct for the crucible reaction and reported that the reaction between carban and oxygen occurred at the melt surface and was controlled by gaseous diffusion for carbon contents greater than a critical value and by carbon-diffusion control in the metal for carbon contents less than the critical. The critical value was given as approximately 0.15 pct C. However, whereas this was the case for oxygen contents in the gas stream up to 10 pct, between 10 and 20 pct the rate was found to be approximately independent of oxygen content, and Fujii attempted to explain this observation by postulating the presence of an oxide "film".7 Turkdogan et a1.' have studied iron fuming during decarburizing and suggested gaseous-diffusion control of the reaction above a critical carbon concentration, given as approximately 2 pct C. Filippov9-12 reports in a similar manner to Fujii but makes no mention of the crucible reaction with the carbon in the melt, even though this would be expected with the temperature, crucible material (MgO), and carbon contents used. Both CO2 and O2 were used as oxidant gases. In the present work the decarburization of liquid Fe-C alloys was studied using an adaptation of the electromagnetic levitation technique, and thus the complexities introduced by crucible side reactions were eliminated. In this technique a single sphere of the Fe-C alloy is freely suspended and heated by electromagnetic induction in a flowing stream containing the oxidant gas. The full range of carbon levels up to saturation was studied, the temperature of the melts in this instance being held constant at 1660°C. The oxidant was CO2 which was used either pure or in association with a diluent gas, the total gas pressure being maintained either at 1 atm or at a reduced pressure. Thus the reaction under study was:

Jan 1, 1964

By H. R. Hose

The total crude fluorspar reserves in Western Europe, including the USSR and the Soviet sphere, Thetotalare estimated to exceed 17 million metric tons. The total fluorspar production in 1951 in Western Europe, excluding the USSR and Soviet sphere, amounted to 371,109 metric tons. The chief fluorspar-producing countries in Europe, excluding Russia and the Soviet sphere, are France, Western Germany, Italy, Spain, and the United Kingdom. TOTAL crude fluorspar reserves in western Europe, containing more than 35 pct CaF2, are estimated at 12 million metric tons, while reserves in the USSR and Soviet sphere may exceed 5 million metric tons. The bulk of these reserves are concentrated in the USSR, Spain, United Kingdom, Western Germany, and Italy. Since published estimates of the tonnages of individual mines and explored deposits are not available for most countries in Europe, the estimates given in Table I for individual countries are necessarily approximate, as they have been compiled from various sources and modified and combined according to the author's judgment. The majority of fluorspar deposits in Europe belong to the late Paleozoic metallogenetic epochs and have been found within or along the borders of the Hercynian massifs. Deposits in the Central and Esterel massifs of France, those of Western and Eastern Germany, Sardinia, the Catalonian coastal range and the Sierra de los Santos in Spain, and those of Devonshire and Cornwall belong to the Hercynian metallogenetic epochs. The deposits in southern Norway and Sweden belong to the middle Paleozoic or later, those of northern England to the late Paleozoic or later, those of northern Spain and Greece to the late Mesozoic, and those of northern and probably central Italy and Switzerland to the early Tertiary. Fluorspar occurs typically in veins, lenses, and stringers, but also in bedded replacement deposits and pockets, and may be colorless to white, yellow, green, pink, brown, blue, or purple to almost black. Except for the colorless variety, the only kind which can be used for the optical industry, the color of the fluorspar does not affect its ultimate use. Crystalline cubic or octahedral fluorite of CaF2 composition, with 48.9 pct fluorine and 51.1 pct calcium, has a specific gravity of 3.18. The ore in place, however, usually averages 3.0 metric tons per cubic meter owing to the quantity of other minerals asso- ciated with the fluorspar in the veins and the physical state of the fluorspar, which may vary from sugary to massive crystalline or microscopic inter-growths with barite or quartz. Barite of 4.5 sp gr, quartz of 2.66 sp gr, and chert and calcite are commonly associated with fluorspar. Other minerals usually present in lesser amounts are celestite, wad, silver, lead, zinc, copper, iron, and uranium minerals. In some cavity fillings the rhythmic deposition of the fluorspar, barite, and quartz into successive crusts may make it possible to handpick the crude ore on belts or to separate the fluorspar from other minerals while the actual mining is carried on. Where metallurgical grade lump spar is required for foundries, separation of quartz and barite may be made also by jigs and heavy media, and in some mines the lead and zinc sulphides may be separated and recovered by vibrating tables. However, except in the case of unusually high grade deposits, acid grade fluorspar is obtained by flotation. By this process fluorspar deposits grading down to 35 pct CaF2 in the crude ore can be worked at a profit when fluorspar, lead, zinc, and silver prices are high, as the sulphides of these ores can be separated from the fluorspar by flotation and concentrated.

Jan 1, 1956

By D. E. Baldwin

A method has been devetoped for predicting the produced concentration profile for a miscible slug in a five-spot pattern. The technique consists of dividing the five-spot into radial etements and applying an approximate radial solution of the dispersion equation to each element. To test the method, laboratory experiments were conducted in five-spot models. The models were 2-ft X 2-ft X 2-in. Berea sandstone slabs simulating one quarter of a five-spot. An aqueous system was used with tritiated water as the tracer fluid. Effiuent concentration profiles were obtained for slug sizes ranging from 0.7 to 10.2 per cent of the pore volume. Agreement between predicted and experimental profiles was excellent. A prediction was also made for a field tracer test. For this case the predictive technique was modified to account for stratification by use of a layer cake model. INTRODUCTION Dispersion in porous media is of growing interest to the petroleum industry because of the increasing importance of secondary recovery operations. One of the controlling factors in the recovery of oil by miscible displacement or by the use of waterflood additives is the degree of mixing between the fluids of interest. Consequently, one of the prerequisites of any recovery prediction is an adequate method of predicting dispersion. Also, any quantitative interpretation of waterflood tracer tests is dependent upon the ability to determine the dispersion of the tracer as it flows through the reservoir. During the past few years there have been reported in the literature the results of a large number of investigations, both theoretical and experimental, concerning dispersion in porous media. (An excellent review of these results has been presented by Perkins and Johnston." Only a few of these investigations, however, deal with non-lin-ear flow systems. Raimondi et al.9 have presented an approximate solution of the dispersion equation for radial, diverging flow. Lau et al. 7 and Bentsen 1 have presented laboratory data for radial systems and have shown that the dispersion can be adequately predicted by Raimondi's solution. Bentsen has also presented a small amount of data for a radial, converging system. Brigham and Smith' have applied Raimondi's solution, with approximating assumptions, to a five-spot pattern to predict the behavior of a field tracer test. The afore-mentioned investigations have been concerned almost entirely with radial diverging flow and have neglected the effect of converging flow. For this reason the present investigation was undertaken to develop a method of predicting dispersion in a five-spot pattern including the effects of both diverging and converging flow. The method which was developed consisted of dividing the five-spot into diverging-converging radial elements and applying an approximate solution of the disperson equation to each element. DEVELOPMENT OF PREDICTION METHOD The development of the prediction method consisted of two phases: construction of a radial model of a five-spot pattern and derivation of equations to describe the dispersion in the radial model. FIVE-SPOT MODEL A radial model which simulated the flow characteristics of a five-spot pattern was constructed by dividing the five-spot into diverging-converging radial elements (Fig. 1). Because of symmetry the model represented only an octant of a complete five-spot. Each element had an included angle of l° (making a total of 45 elements) and a radius r, such that the sum of the individual element areas was equal to the area of the five-spot octant. The normal five-spot fractional flow behavior was determined by averaging the experimental five-spot data of Caudle and Witte,' Dyes, Caudle and Erickson 5 and Fay and Prats. 4 The resulting curve is shown as a solid line in Fig. 2. To match this curve with the radial model it was

Jan 1, 1967

By Richard H. Siller, Rex B. McLellan

A model for interstitial solid solutions has been considered in which a repulsive Potential exists between interstitial atoms in the solvent lattice. It has been shown that this model is consistent with the thermodynamic Properties of certain interstitial solid solutions. The model is then applied to the calculation of the variation of the diffusivity of carbon in au-tenite with composition. Although the energy levels at the saddle point, and thus the absolute values of dif-fusivity, cannot be calculated, it is shown that by taking the repulsive interactions between the diffusing atoms into account the functional form of the dependence of diffusivity on solute concentration can be derived. ThE composition dependence of the diffusivity, D, of carbon in austenite at a given temperature is well-known.'-3 smith3 tried to reconcile the observed composition dependence of D at 1000°C with the previously observed4 composition dependence of carbon activity using equations for D derived by arken5 and Fisher, Hollomon, and Turnbull,6 but was unsuccessful. In this paper we shall modify the approach of Fisher et al. by considering the "blocking" model7 for interstitial solid solutions, based on concept due to Speiser and Spretnak,' in which a repulsive potential exists between interstitial solute atoms in the solvent lattice, causing a certain number of interstitial sites to be "blocked" from occupancy by further solute atoms. We shall thus be able to describe the intimate relationship between the composition dependence of carbon diffusivity, a kinetic phenomenon, and the composition dependence of carbon activity in austenite. THEORY Consider for convenience one-dimensional interstitial diffusion in an fcc lattice in the [loo] direction. Fig. 1. Assume that solute atoms occupy octahedral sites only.7,9'10 These octahedral sites are located on {lOO} planes a/2Å apart. A solute atom, A, occupying an octahedral site on a {100 } plane denoted by 2, has twelve nearest-neighbor octahedral sites: four on plane 1, four on plane 2, and four on plane 3. Diffusion occurs when there is a net flux of solute atoms, through an imaginary plane shown with dashed lines, from plane 2 to plane 3. Fisher et al6. use the concept of activated complexes, as given in the theory of absolute reaction rates." They show that the number of solute atoms per cubic centimeter per second which pc — Fig. 1-Diagram showing the arrangement of octahedral sites (x) in the fcc lattice. pass in the direction of diffusion from activated to new interstitial position is: ?where C is the concentration of the solute in atoms per cubic centimeter, l/m + is the fraction of new interstitial positions corresponding to motion in the forward diffusion direction (transmission coefficient), ?F* is the free-energy difference between the activated complex and the reactants when each is in its standard state at the temperature of the reaction (independent of temperature and composition in the case of carbon in austenite), y is the activity coefficient of the solute species, and, finally, ym is the activity coefficient of the activated complex (assumed constant). The flux of atoms moving in the forward direction through an area of 1 sq cm perpendicular to the direction of diffusion is therefore: m+ Ym l ' atoms per second where is the distance between planes. The blocking model states that a nearest-neighbor octahedral site of a given solute atom has a probability, f, of being inaccessible to other solute atoms. The number of available sites for diffusion on a given plane will, therefore, depend on f, which is constant, and Nu, the number of solute atoms on that plane. The effect is to have more available sites in the diffusion direction, thereby increasing the net flux of solute atoms. This is reflected in the transmission coefficient, l/m. To calculate the transmission coefficient for solute

Jan 1, 1970

By E. S. Mardock, Robert E. Bush

The object of this paper is to report recent developments in the quantitative interpretation of radioactivity logs. The use of reference lines is described in the application of the new zero radioactivity reference line for the determination of neutron derived porosities is discussed. Illustrated examples are shown of logs from the reef limestone of the North Snyder Field and from the Lansing-Kansas City limestone of central Kansas. A method of using an interrelation factor calculated from the neutron and gamma ray curves, called the neutron Productivity number, for the estimation of productivity from sandstone formations is discussed. When used in a relative manner the neutron productivity number has aided in Predicting whether a given zone will produce gas or liquid or whether it is too shaly to produce. Examples of logs from wells in the Freites District, Venezuela, and in East Texas are shown to illustrate the application of the neutron productivitv number. INTRODUCTION The petroleum industry was introduced to some of the preliminary results of investigations into the quantitative interpretation of radioactivity logs in October, 1949." It was stated at that time that the methods presented were entirely relative because they involved the use of reference points obtained from the radioactivity log, i.e., shale reference lines, dense zone reference lines, or a combination of both shale and dense zone reference lines. These relative methods offered many advantages to the industry in interpreting radioactivity logs in terms of porosity with particular application to limestone and dolomite reservoirs. However, these relative methods did not offer the wide range of applicability desired because the esta1)lishment of reliable reference points from shale in some areas were difficult. It was recognized that a more reliable mean; of establishing reference lines was vitally needed. Such a method is now available through the introduction of an instrumeutal zero device. It is the purpose of this paper to discuss the application of this new zero reference to the quantitative interpretation of radioactivity logs. Previously all applications of quantitative interpretations of radioactivity logs have been made in limestone reservoirs with little or no emphasis placed on sandstone reservoirs. A brief resumé of investigations into the quantitative interpretation of radioactivity logs in sandstone reservoirs is presented here. This discussion deals primarily with the interrelation of the gamma ray and neutron curves and the response of the latter to the density of the fluids filling the pore space in relatively homogeneous sandstones of uniform porosity. The authors believe that the methods presented herein are only applicable locally to specific fields and reservoirs, and that they probably do not offer a wide range of applicability. However, tile authors believe that the wider use of the new instrumental zero references in sand areas will reveal more information about the specific response of the gamma ray and neutron curves to changes in lithology and saturation. Two applications of quantitative interpretation using the new instrumental zero references are presented. Examples are given which show the comparison of logs and porosity in the limestones and dolomites of West Texas and Kansas. Logs of wells in 'Venezuela and East Texas are compared with the drill stem test data, production data, etc.. to illurtrate the interrelation of the gamma ray and neutron curve: and the rise of methods involving these interrelations to determine certain saturation variables. THE QUANTITATIVE APPLICATION OF RADIOACTIVITY LOGS TO LIMESTONE AND DOLOMITE RESERVOIRS Tile theoretical basis for the gamma ray and neutron curves has been discussed elsewhere.9 he method of recording the logs and apparatus involved has also been thoroughly covered and will not be discussed here.'."".'" It has been shown that the neutron curve responds exponentially to liquid filled porosity over the 1 1/2 to 35 per cent

Jan 1, 1951

By Robert E. Bush, E. S. Mardock

The object of this paper is to report recent developments in the quantitative interpretation of radioactivity logs. The use of reference lines is described in the application of the new zero radioactivity reference line for the determination of neutron derived porosities is discussed. Illustrated examples are shown of logs from the reef limestone of the North Snyder Field and from the Lansing-Kansas City limestone of central Kansas. A method of using an interrelation factor calculated from the neutron and gamma ray curves, called the neutron Productivity number, for the estimation of productivity from sandstone formations is discussed. When used in a relative manner the neutron productivity number has aided in Predicting whether a given zone will produce gas or liquid or whether it is too shaly to produce. Examples of logs from wells in the Freites District, Venezuela, and in East Texas are shown to illustrate the application of the neutron productivitv number. INTRODUCTION The petroleum industry was introduced to some of the preliminary results of investigations into the quantitative interpretation of radioactivity logs in October, 1949." It was stated at that time that the methods presented were entirely relative because they involved the use of reference points obtained from the radioactivity log, i.e., shale reference lines, dense zone reference lines, or a combination of both shale and dense zone reference lines. These relative methods offered many advantages to the industry in interpreting radioactivity logs in terms of porosity with particular application to limestone and dolomite reservoirs. However, these relative methods did not offer the wide range of applicability desired because the esta1)lishment of reliable reference points from shale in some areas were difficult. It was recognized that a more reliable mean; of establishing reference lines was vitally needed. Such a method is now available through the introduction of an instrumeutal zero device. It is the purpose of this paper to discuss the application of this new zero reference to the quantitative interpretation of radioactivity logs. Previously all applications of quantitative interpretations of radioactivity logs have been made in limestone reservoirs with little or no emphasis placed on sandstone reservoirs. A brief resumé of investigations into the quantitative interpretation of radioactivity logs in sandstone reservoirs is presented here. This discussion deals primarily with the interrelation of the gamma ray and neutron curves and the response of the latter to the density of the fluids filling the pore space in relatively homogeneous sandstones of uniform porosity. The authors believe that the methods presented herein are only applicable locally to specific fields and reservoirs, and that they probably do not offer a wide range of applicability. However, tile authors believe that the wider use of the new instrumental zero references in sand areas will reveal more information about the specific response of the gamma ray and neutron curves to changes in lithology and saturation. Two applications of quantitative interpretation using the new instrumental zero references are presented. Examples are given which show the comparison of logs and porosity in the limestones and dolomites of West Texas and Kansas. Logs of wells in 'Venezuela and East Texas are compared with the drill stem test data, production data, etc.. to illurtrate the interrelation of the gamma ray and neutron curve: and the rise of methods involving these interrelations to determine certain saturation variables. THE QUANTITATIVE APPLICATION OF RADIOACTIVITY LOGS TO LIMESTONE AND DOLOMITE RESERVOIRS Tile theoretical basis for the gamma ray and neutron curves has been discussed elsewhere.9 he method of recording the logs and apparatus involved has also been thoroughly covered and will not be discussed here.'."".'" It has been shown that the neutron curve responds exponentially to liquid filled porosity over the 1 1/2 to 35 per cent

Jan 1, 1951

By G. R. Speich, S. A. Kulin

The isothermal formation of martensite at subzero temperatures has been studied in an austenitic stainless steel. The amount of martensite formed isothermally in a given time was found to follow a C-curve behavior with decreasing temperature. Since isothermal rnartensitic transformation occurs at temperatures above the true M. temperature of the olloy, the observed M. temperature is dependent on the cooling rate. It is believed that a general martensite theory must include the basic concepts of the strain embryo theory, and also the important role of thermal fluctuations. UNTIL recently the isothermal component of the martensitic transformation had been considered as a trivial effect in theoretical considerations of this type of transformation. One of the postulates used in defining a martensitic transformation was that the reaction was temperature dependent but not time dependent. Cohen and his associates1'2 were the first to report the isothermal formation of mar-tensite. They obsel-ved the time dependency of the martensite reaction at room temperature in plain carbon steels and certain tool steels. They found that a small amount of additional transformation occurred after the specimen reached the quenching temperature and that the rate of this isothermal transformation decreased rapidly with time. These authors considered this phenomenon to be a "tailing-off" of the main athermal reaction. Kurdjumov and MaksimovaL 5 studied the isothermal formation of martensite at subatmospheric temperatures in steels containing 0.6 pct C-6 pct Mn, 1.6 pct C, and in an iron-base alloy containing 23 pct Ni and 3.4 pct Mn. In each case it was found that both the initial rate and the total amount of isothermal transformation exhibited sharp maxima with decreasing temperature. They stated that it was possible to completely suppress the martensitic transformation in the 0.6 pct C-6 pct Mn steel by drastic quenching in liquid nitrogen. They interpreted their results in terms of a thermally activated process. The maximum in the rate of nucleation vs. temperature curve was assumed to be a result of the temperature dependence of the rate of growth of the martensite plates. It has been demonstrated," however, that martensite plates can form with great rapidity even at temperatures approaching absolute zero. In addition," attempts to confirm the reported suppression of the martensitic transformation by rapid cooling of a 0.6 pct C-6 pct Mn steel have proved unsuccessful. On this basis, and on other theoretical grounds, the validity of some of Kurd-jumov's results and conclusions is open to serious question. Cohen, Machlin, and Paranjpe' have proposed a theory of martensite formation based on the nucleation of strain embryos and a growth mechanism involving cooperative atomic displacements. According to this theory thermal fluctuations can make a strain embryo supercritical and thereby produce martensite isothermally. Das Gupta and Lement' have investigated the isothermal formation of martensite in a 17 pct Cr-0.7 pct C steel at temperatures below the ambient. They found that partial suppression of the martensitic reaction occurred on quenching into liquid nitrogen. That part of the reaction which can be suppressed is taken to correspond to the isothermal rather than the athermal part of the rnartensitic transformation. The initial rate of isothermal transformation for this steel was found to go through a maximum with decreasing temperature. This is in conformity with the findings of Kurdjumov and Maksimova for the steels used in their investigation. Das Gupta and Lement conclude that isothermal martensite formation occurs by the nucleation of new plates and is always preceded by some athermal transformation. An iron-base alloy containing 14 pct Cr-9 pct Ni was used in this investigation to study further the kinetics of the austenite to martensite transforma-

Jan 1, 1953

By F. R. Scauzillo

Equilibrium data which should be useful in the design and/or evaluation of glycol dehydration units were prepared from an analysis of various published data and the correlation of these data by the use of the thermo-dynamic equilibrium ratio. The equilibrium ratios of water are used to solve the glycol absorber problem; such solutions are necessary to define the number of trays and the glycol circulation rate needed to meet drying requirements. Activity coefficients were obtained which relate directly to the equilibrium ratios of water in the water-TEG-natural gas system. These activity coefficients have been used to calculate the equilibrium dew points for aqueous TEG concentrations of 60 to 99.9 weight per cent for the temperature range of 40° to 120° F. They also provide a means of calculating equilibrium ratios for water in the water-TEG-natural gas system; this applies to any desired TEG concentration and to the temperature range from 40° to 120°F. INTRODUCTION During the last several years, the drying of natural gas with aqueous triethylene-glycol (TEG) solutions has become very prominent. Most users of TEG as a drying agent have been satisfied with the performance of TEG solutions at the conditions used; however, there always has been some discussion of the drying ability of TEG solutions at conditions not commonly encountered such as temperatures below 50° or 60°F, but more particularly temperatures above 100°F, and pressures above 1,000 psia. Today, when higher wellhead temperatures such as 120°F are more commonly encountered many are skeptical of TEG's ability to dry sufficiently well to provide dew points around 32°F, which is generally the maximum tolerable when attempting to dry a gas to contract specifications of 7 Ib/MMscf. These views probably have evolved to some extent from the days when suppliers would not guarantee dew-point depressions in excess of 65° to 75 °OF. Also, the feelings about TEG drying may have arisen from the lack of information about the equilibrium relation of water in the drying operations. Porter and Reid' have reported equilibrium data for a 95 per cent TEG solution, while Townsend2 reported equilibrium data for 95, 98 and 100 per cent TEG solutions. Townsend also presented a calculational method which obtains activity coefficients in the liquid phase and, subsequently, the equilibrium water content of a saturated gas over glycol from published3 atmospheric dew points. Wise, Puck and Failey' presented activity data for the water-TEG system at atmospheric pressure. In the past, the equilibrium ratios published for water in a 95 per cent by weight aqueous TEG solution have been used indiscriminately by many for all concentrations of TEG encountered in gas drying operations. Since essentially all such gas operations require the use of more concentrated TEG solutions, a study was undertaken to correlate the existing equilibrium data for aqueous TEG and gas systems and to provide some means of calculating the equilibrium ratio of water in the natural gas-water-TEG system where TEG concentrations were other than 95 per cent. The data presented herein consider only the equilibrium drying ability of the TEG solutions and do not consider the effect of temperature and pressure on the tray eficiency of contactors. In other words, this paper is concerned primarily with the development of the equilibrium relationship between water in the dried natural gas and the water in the lean TEG entering the top tray of the absorber. BASIC EQUILIBRIUM RELATIONS A relationship which relates the K value of water in the natural gas-water-TEG system to the vapor pressure of water at the system temperature, the total pressure of the system and the activities of the liquid and gas phases has been evaluated. It is well known that, for any component of a mixture at equilibrium between a gas phase and a liquid phase,

By Charles E. Mann, Douglas J. Lootens, Rufino B. Bomasang

INTRODUCTION The economy of the Philippines, like that of many other developing nations, has been severely strained by the rapid escalation of imported crude oil prices over the past decade. In an effort to reduce its dependence on imported crude, significantly increased emphasis, both in the public and private sectors, is being placed on the rapid development of Philippine coal resources. This paper is designed to present an overview of the Philippine coal industry, its historical development, present status, and future potential. COAL RESOURCES AND RESERVES In 1977, a British consulting firm collated all available data on Philippine coal resources and estimated the total coals potential at about 0.9 to 1.4 billion metric tons (mt). In 1981, using more recent data the Philippine Bureau of Energy Development (BED) estimated the potential at 1.7 billion mt. The BED estimated the proven coal reserves at 257 million mt. These coal resources are scattered throughout the major islands comprising the Philippine archipelago. However, about 52 percent of the currently proven reserves are located in the tiny island of Semirara between the islands of Mindoro and Panay. About 25 percent is located in the Cagayan Valley in northeastern Luzon while 13 percent is located in Mindanao. The remaining 10 percent is scattered in the islands of Cebu, Samar, Mindoro, Negros, Polillo, Batan, and Catanduanes. The bulk of Philippine coal is sub-bituminous in rank. Some bituminous coal with coking properties has been reported in Malangas, Zamboanga del Sur in western Mindanao, and in Catanduanes, but the exact tonnages have not been accurately established. It is believed, however, to be at most 5 million tons. A little semi-anthracite coal exists in Malangas with the remaining unmined reserves estimated at a little more than one million tons. Table 1 shows the quality ranges of Philippine coal deposits.. Figure 1 shows the distribution of known Philippine coal resources PHILIPPINE COAL PRODUCTION In 1981, total coal production was 330,720 mt. Though modest by world standards, this was the highest production figure in Philippine coal mining history. This came from 25 mines, mainly small scale underground mines of capacities varying from 10 to 100 tons per day (tpd). The actual production capability was about 800,000 mt in 1981, but the producers had to scale down production to the level of local demand. Even then, some 50,000 tons of coal remained unused by year-end. The 1981 production came from the following areas: Cebu 224,751 mt (68%) Zamboanga del Sur 57,095 mt (17%) Semirara 13,222 mt (4%) Polillo 17,132 mt (5%) Cebu has always been the main source of Philippine coal production. Coal mining has been carried out in Cebu for the last 50 years, although it has been characterized by a very crude mining technology. Due to the limited size of coal deposits and complicated geology, however, Cebu's share of the total national production is expected to go down to only 10 percent by 1985. Except for Semirara's open-pit production, the balance of Philippine coal production comes from underground mines. These underground mines generally use room-and-pillar methods, except for those at Zamboanga del Sur and Polillo which use modified longwall methods patterned after those used in Taiwan. Due to the much higher mining recovery, most underground mines are now planning on switching to longwall. At Semirara, an open pit mine is now being developed for a one million ton per year capacity by 1984, and will then be the largest Philippine coal mine. While present earthmoving work is done with bulldozers, loaders, and trucks, the main coal extraction equipment will be bucket wheel excavators imported from Austria. PRESENT COAL UTILIZATION Existing coal production is sold mainly to coal- fired cement plants and power plants. The balance is sold to a sugar central, a coconut oil mill, a food processing plant, and two plants producing carbide and ferro-silicon alloys.

Jan 1, 1982

By R. I. Lahring, C. G. Inks

A surfactant waterflood, using a block copolymer of ethylene and propylene oxide (PLURONIC L64*), wa., started in 1956 in Kansas to determine the commercial feasibility of such a process. The production formation was the Bartlesville sand at a depth of 1,400 ft. Leares in the test area had attained both primary and secondary production peaks, and were on a normal decline when the tests were initiated. The injection wells were taking water at a reasonable pressure and none of the operating conditions were particularly unusual. The leases were selected primarily because of normal operating conditions, and not because of any serious problems demanding remedie>,. Oil production and water injection data were recorded during the 10-year test period, and their compilation indicates that the surfactant resulted in an increase of about 9 percent in secondary oil production. Other benefits derived from the surfactant injection were lower injection pressure that resulted in reduced power consumption and reduced erosion of the pumps; and lower calcium scale buildup. These fringe benefits more than offset the cost of the surfactant used. Introduction During the past several decades, considerable research has been carried out on secondary recovery of crude oil that remains in the producing formation despite the most efficient, current primary production practices. Methods are constantly sought of increasing recovery of oil, while at the same time improving the economic efficiency of operations. One method that has received intensive study over the years is the use of a surfactant as a waterflood additive. Laboratory tests show conclusively that dilute solutions of surfactants remove considerably more oil from uncon-solidated sand cores than does water alone.'- The loss of surfactant by adsorption at solid-liquid interfaces has caused serious doubt that surfactants can be used economically as waterflooding additives. This is especially true with anionic and cationic surfactants, and to a lesser extent with nonionic surfactants. This work was undertaken to determine the effectiveness in increasing oil production by injecting water containing small quantities of a nonionic surfactant. The surfactant selected was PLURONIC L64*, a block copolymer based on ethylene and propylene oxide, having the following structure The selection of the test site, a typical shoe-string sandstone type of field located at Batesville pool, Toronto District of Woodson County, Kans., was made because of its normal primary and secondary recovery operating conditions, and not because of any serious operating problems. When the tests were begun, the field was experiencing the customary post-peak production decline of a waterflood. Using for the tests a field that was on a normal production decline, while maintaining constant all variables other than the addition of the surfactant. was of varamount importance if success or failure was to be attributed to a particular cause. It was reasoned that if a surfactant was added to the injection waters and nothing else was done to influence the oil production or injection of water, the effects of the surfactant on the flood could be determined precisely. Production History The first well in the tested field was drilled in 1935. Gas repressurization began immediately, but it was not until Aug., 1938, that the major portion of the field was developed. During the period of repressurization, 1,700 MMcf of gas was injected. As can be seen from the curves of Fig. 1, the production peak from gas injection was attained in 1937 and a normal production decline followed. Early in 1942, water injection wells were drilled and injection of water Was initiated. The amount of water injected increased as more injection wells were drilled until a peak injection rate of 2,700 BID was reached in

Jan 1, 1969

By E. P. Sadowski, L. P. Trudeau, C. R. Cupp

The apparent high radiation resistance of two varieties of maraging steel is described and an indication is given of some phenomena that require further study. Two aspects were included in this work: a) effects of neutron irradiation on the room-ternperature tensile properties of 18 Ni (250) maraging steel; b) effects of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5pct Cr-3 pct Mo maraging steel. Subsize tensile and impact test specimens were used. The 18 pct Ni steel was irradiated to a neutron fluence of 3.3 x 10 n per sq cm (>1 mev). The 12-5-3 variety was irradiated to two neutron fluence levels: 1) 1.5 x 10 per sq CTTL (>I mev) 2) 3.1 x 10'9nper sq cm (>1 mev) In all respects both varieties showed unusually high resistance to change in strength and ductility after neutron irradiation. There was no noteuorthy over-aging in fully aged specimens. The aged 18 pct Ni variety showed a 4 pct drop in yield strength upon irradiation with little or no decrease in ductility. The aged 12-5-3 variety showed a 5 pct increase in yield strength on irradiation with a very slight decrease in ductility. The impact transition of the 12-5-3 variety only increased 35 to 45 Co upon irradiation, and the shear energy fracture value for the subsized specimens decreased only half as much as expected frorn experience with conventional steels. THE development of new reactor concepts and nuclear technology now depends to a large extent on the availability of new alloys capable of operating in stringent reactor environments. One of the most important new types of metallurgical material that has been developed in recent years is the maraging steels. This type of alloy is notable for its remarkable retention of toughness at high strength levels. In the course of a research program which incorporated ambient temperature radiation effects studies to determine the mechanisms of strengthening of 18 pct nickel maraging steel,' it became evident that the resistance of the alloy to neutron-induced changes in mechanical properties should be studied. This paper is to present evidence for the apparent high radiation resistance of maraging steel. The experimental program was in two parts: a) Effect of neutron irradiation on the room-temperature tensile properties of 18 Ni (250) maraging steel. b) Effect of neutron irradiation on the room-temperature tensile properties and on the impact resistance of 12 pct Ni-5 pct Cr-3 pct Mo maraging steel, a cobalt-free alloy. EXPERIMENTAL PROCEDURE 18 Ni (250) Maraging Steel. Tensile test specimens were machined to the dimensions shown in Fig. 1 from $-in.-diam hot-rolled bar of the composition shown in Table I. All specimens were austenitized for 1 hr at 1500°F (815°C) in argon and water-quenched. Half of the specimens were then mar aged for 3 hr at 900° F (482°C) in argon. The specimens were irradiated in a fast neutron transformer rod at approximately 120°F (50°C) to a neutron fluence of 3.3 x 10 10 n per sq cm (>1 mev). The irradiation was performed in the NRX reactor of Atomic Energy of Canada, Ltd., at Chalk River, Ontario, Canada. In all cases, the thermal neutron flux was three times as high as the reported (> 1 mev) fluxes. The room-temperature tensile tests were performed with an Instron tensile testing machine operating at a crosshead speed of 0.05 in. per min. The loading frame of the machine, mounted in a hot cell, was remotely controlled. The specimens were tested either

Jan 1, 1968

By F. W. Jessen, N. Mungan

The plastic flow characteristics of clay water suspensions were first recognized by Binghaml in 1916 and further studied by Ambrose and Loomis' in 1931-1932. Many physical and chemical properties of clay suspensions are deeply influenced by particle size distribution as well as by the exchange cation. Separation of a number of fractions is particularly helpful in making a detailed study of a suspension. A limited amount of work has been conducted on the effects of particle size on specific properties of mud drilling fluids. A knowledge of particle size distribution is essential for a better understanding of fundamental properties of clay suspensions, particularly viscosity and gel strength. The purpose of this investigation was to study the effect of particle size on the viscosity and gel properties of clay suspensions and to determine any changes in mineral composition accompanying variation in size. EXPERIMENTAL PROCEDURE Numerous methods may be used to fractionate a poly-dispersed clay suspension into nearly mono-dispersed systems. Particles larger than 44 micron (325-mesh) may be obtained by wet screening. For sizes from 44 to 1 micron, the fractionation may be accomplished by sedimentation, elutriation plus microscopy,' or turbidimetry.6 When dealing with systems which contain a major portion of particles below l-mi-cron size, slit ultramicroscopy,7 centrifuge methods of Svedberg,5 eams,9 and McBain,l0 and X-ray methods" may be employed. The Sharples super centrifuge has been proved suitable for the economical separation of suspended particles of submicron range.12,13,14 Three-hundred and forty-five gal of 1 per cent by weight Aquagel suspension was mixed in a high-speed 5-gallon mud mixer and the suspension was allowed to stand in 5-gal glass bottles for 30 days to assure full hydration. All particles larger than 44 microns were removed by wet screening. Five fractions in the range of 44 to 1 micron were obtained by sedimentation. The Sharples super centrifuge method described by Hauser and Reed.13 Norton and Speil,14 Ha user and Lynn,15 and Hauser and Schachman,10 as employed to yield five fractions of submicron size. A super centrifuge operation chart prepared by Fancher, Oliphant, and Houssierre12 was used to determine operating conditions for the desired particle ranges. The clay suspension, after removal of all material above 1-micron size, was centrifuged. During rotation of the bowl, the particles were deposited on a thin plastic liner which fit closely inside the bowl. After passing 5 gal of suspension through the centrifuge, the liner was removed and the particles on the liner were scraped off, remixed and recentrifuged. This was repeated five times. Thus, Fractions H, I, K, and L were obtained. The finest fraction, M, remained in an approximately 0.4 per cent suspension. Water was evaporated under reduced pressure from this suspension to yield the finest particles. Results of the fractionation are included in Table 1. In order to achieve proper orientation and humidity conditions for X-ray diffraction analysis, the following procedure was employed. The dilute suspensions were placed on glass slides and allowed to dry at room temperature. This was repeated several times. Previous to measurement each sample first was placed in a water desiccator for half an hour and then allowed to stand for 15 minutes at room temperature. thus yielding an equilibrium condition of about 52 per cent relative humidity. The relative humidity of the room in which the X-ray diffraction was carried out was maintained at approximately 50 per cent so that there was no change in the spacings during the X-ray examination. Samples

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations

By C. Gatlin, C. E. Nemir

A common cure of lost circulation is the introduction of granular bridging agents into the mud system. Many materials, such as ground nut shells, are used for this purpose. If the trouble causing void (fracture, fissure, vug, etc.) is not too large, the granular agent forms a "bridge" across or within the opening. Successively smaller particles in the mud stream then accumulate on and/or within this bridge until normal filtration is finally established. The efficiency of many bridging agents has been studied in the laboratory using various slot testers.',' Many investigators have remarked that a granular bridging material should have the proper particle size distribution. With the exception of the broad range specified in the patent of Goins and Nash,3 here is apparently no definition as to what this distribution should be. A bridge may be initiated when several particles of lost circulation material lodge against each other in a fracture or other void. Smaller particles then may bridge the openings between the larger, previously bridged particles. This process continues until the voids become quite small and the problem becomes one of filtration. It would seem logical that an optimum particle size distribution exists, i.e., one containing the proper quantity of properly sized material to fill the successively smaller voids of the bridge. The filtration characteristics of drilling fluids may be subject to a similar analysis. It has been clearly demonstrated by many workers that the filtration behavior of various muds can be altered by particle size control.'.' Slusser, et al, divided filtration into three periods and showed that particle sizes affecting a given period did not necessarily affect other portions of the filtration curve. An analagous problem is the proper sizing of gravel, liner slots and screen sizes in various sand-exclusion problems. Here the situation is reversed in that a proper "void" size, rather than the size of the bridging agent, is sought. The classic work of Coberly 9 forms the quantitative basis for most sand-exclusion processes. It is interesting to note that, in general, Coberly's work has been overlooked by most drilling-mud researchers. Other investigators have made various studies of the effect of particle size distribution .on drilling-mud properties. As a part of their studies, Fancher and Oliphant reported 30-minute filtration loss of a variety of mixtures of particle sizes.'' Gates and Bowie noted an effect of particle size distribution on filtration, as well as on other physical properties.' MAXIMUM DENSITY THEORY A maximum density mixture has been mentioned as the possible solution for both lost circulation and mud filtration problems. Furnas 12 derived mathematically a method for obtaining maximum density of beds of packed solids, having either a given number of component sizes or a continuous gradation of sizes. This work was verified experimentally by Anderegg.13 or mixtures having a continuous grading of sizes, the interval between sizes is taken as successive screen sizes of interval 2 The ratio of the quantity of each size and the next smaller size is given by the equation Fig. I, number of size intervals of ratio 2 taken from Furnas' paper, gives the value of n + 1 for any given values of + and K, where K is the ratio of the diameter of the smallest particles to the diameter of the largest particles. Measurement by weight assumes, of course, constant density for all particle sizes. Choosing the quantity of the smallest particle size as a unit weight, the required weights of the successively larger interials are then r1 r2 r3 . ®1,2,3. Thus, the grading curve of a maximum density mixture represents a geometric pro gression of ratio r.

By J. F. Held

In a study of the influence of cold rolling on mechani cal properties of steel, it was found that the specific rolling procedure influenced crystallographic orientation. Properties developed by several rolling modes were determined and related to crystallographic orientation. Sanzples were cold-rolled various amounts on a laboratory mill. When palm oil was used as a lubricant, the crystallographic orientation was homogeneous throughout the thickness of the samples. Other samples were rolled without lubrication. Variations in intensity of the recrystallization texture components persisted throughout more than 50 pct of the volume of these samples. When the average plastic strain ratio, which is dependent upon crystallogvaphic orientation, was plotted as a function of percent reduction, a maximum was found at 40 pct in the samples which contained the observed texture variation. No maximum was found for the samples with the homogeneous texture distribution. Other mechanical properties, such as tensile strength and yield strength, were not influenced by the variation in crystallopaphic orientation. MECHANICAL properties of steel sheets depend, in general, upon the structural properties of the steel. For example, the Petch equation describes the relationship between yield strength and grain size. Other properties, such as hardness, vary with chemical composition. The plastic strain ratio, or R value, has been found to be dependent upon crystallographic orientation . In the course of investigating the effect of cold rolling on mechanical properties, it was found that a previously reported relationship between percent cold reduction and R value was not always observed. Published data had shown that the optimum cold reduction for best R values is 70 pct for aluminum killed steel.' However, by altering the rolling conditions, the optimum reduction can be shifted to much lower values, or it can be moved to very high values. This paper describes the rolling conditions that lead to shifting of the optimum cold reduction. The effect of rolling conditions on the various structure parameters and the resulting mechanical properties are evaluated. EXPERIMENTAL PROCEDURE Samples of three low-carbon aluminum killed steels were cold-rolled various amounts on a 9-in.-diam 2-high laboratory mill. Hot-mill thermal practice and steel chemistries are listed in Table I. Steel A was rolled with palm oil lubrication and heavy reductions on each pass; i.e., a total reduction of 75 pct was ac- complished with a maximum of five passes. Steel B was rolled without lubrication, and light reductions were given on each pass. After approximately 75 pct reduction, it was necessary to use a small amount of light oil to achieve any additional reduction in thickness. Following cold reduction, the samples were box-annealed at 1300°F for 10 hr. The heating rate between 800" and 1300°F was 50°F per hr, and the cooling rate following the soak period was 50°F per hr. Tensile specimens were machined from the annealed material and these were used to measure yield strength, tensile strength, and the plastic strain ratio (R value). Recrystallization textures were determined by an inverse pole figure technique.*'3 Integrated intensities of the (110), (002), (112), and (222) reflections were recorded for those planes lying parallel to the sheet surface. Examinations were made on both surfaces of each sample, and also at various levels beneath each surface to approximately 0.010 in. depth by etching techniques. RESULTS R Values. The R values obtained in steels A and B are shown as a function of percent cold reduction in Fig. 1. No optimum cold reduction was observed in steel A, rolled with palm oil lubrication. It is likely, however, that an optimum reduction would have occurred had higher reductions than 88 pct been employed. The optimum reduction in steel B occurred at 40 pct. The behavior in both of these steels is quite

Jan 1, 1968

By H. J. McQueen, G. C. Kuczynski

ThE useful properties of k6-Alfenol and the thermenol alloys (summarized by J. E. Nachman and W. J. Buehler') have encouraged research into those alloys which, having compositions near 25 at. pct Al, 75 at. pct Fe, undergo an ordering transformation between 500° and 550°C. The equilibrium diagram of the iron-rich iron-aluminum alloys was first determined by Bradley and Jay.2,3 They distinguished three structures: the disordered, which is bcc; FeAl, which is simple cubic with one Fe atom and one Al atom per lattice site; and Fe3Al, which is fcc with three Fe atoms and one Al atom per lattice site. This last structure may be conceived as eight body-centered cubes with Al atoms at the centers of alternate ones, so that Al atoms have only Fe as first and second nearest neighbors. Later, Osawa and Murata4 determined the boundaries of the different superlattice regions in the iron-rich Fe-Al solid solution by dilatometric and X-ray methods. Two of the six phases, which they found between 0 and 50 at. pct Al, were never identified by other workers. A. Taylor and R. M. ones,' concurrently with and independently of this research, redetermined this diagram by measuring lattice parameters at temperature. Further reference will be made to their results. EQUILIBRIUM DIAGRAM A) Experimental Procedure—The alloys were prepared from NRC gas-free iron (99.9 pct Fe) and 99.99 pct Al. They were melted in alumina' crucubles under vacuum in an induction furnace. If the ingots were unsound or showed more than a 3 pct weight loss, they were rejected. The ingots were homogenized at 1100°C for 24 hr before hot-rolling at 700" to 900°C from 1 in. to 0.25 in. thick. It is interesting to note that alloys containing more than 28 at. pct Al were able to take an 80 pct reduction of area in the ordered FeAl region. The dilatometer specimens and specimens for chemical analysis were cut from these plates. A Leitz dilatometer was used to measure the coefficient of linear expansion as a function of temperature. The specimens were slowly cooled from 900" to 300°C where they were annealed for 10 hr before slowly cooling to room temperature. The expansion was recorded photographically as the alloys were heated and cooled at 1.5oC per min between 100" and 1000°C. The magnetic measurements determining the Curie points were performed on the dilatometer specimens in the dilatometer, by using direct current in the furnace windings both to heat the specimen at 1.5°C per min and to serve as the primary coil. The regular specimen holder was replaced by a thin alundum tube on which was wound, as a secondary, a closely spaced coil of fine copper wire. A reversal of current in the furnace windings produced, in the secondary, an emf which was proportional to the induction in the specimen, and which could be detected on a galvanometer. In this way, it was possible to determine the Curie points of alloys to within * 5°C. B) Results and Discussion—The coefficients of linear expansion, as obtained from the dilatometer curves, are plotted as a function of temperature and composition in Fig. 1. Since in many cases the heating and cooling curves were superimposed, it was decided to measure slopes of heating curves only. Definite high peaks, due to the transformations, were observed on each curve between 400" and 520°C, and, for alloys containing more than 23 at. pct Al, a second set of smaller peaks at temperatures above 660°C. The sharpness of the peaks indicates that ordering to Fe3Al is a first-order reaction. The compositions and the temperatures of these peaks are listed in Table I. When these temperatures are plotted as a function of the composition, the result is the constitution diagram presented in

Jan 1, 1960

By Gordon H. Geiger, John M. Svoboda

One mechanism of metal penetration into mold aggregates by cast steels is vapor state mass transport. In order to further understand and quantify this mechanism, the steady-state diffusion of metallic vapors was studied at 1250" to 1600°C in controlled oxygen pressure atmospheres by measuring the weight loss from a metal bath whose vapors were allowed to diffuse through a porous aggregate compact held at constant temperature. Mass transport rates substantially greater than those predicted from the assumption that the vaporizing species was the elemental metal vapor were observed. Vaporization rates were found to increase with an increase in the oxygen partial pressure in the gas atmosphere with maximum vaporization occurring at oxygen partial pressures just below those in equilibrium with a liquid oxide layer at the given temperature. When the liquid oxide layer was present, no vaporization was observed. Metal carbonyls were ruled out as the vapor species involved because of their thermodynamic properties. The species with the enhanced volatility were deduced to be gaseous metal-oxygen molecules, probably the polynuclear oxides (FeO)2 and (Mn0)2. Diffusion followed the ordinary diffusion mode, and Knudsen diffusion is not important in normal foundry molds. The interdiffusivities of the metallic vapors and the mold atmosphere, through the porous aggregates, were measured. The effective interdif-fusivity of the vapor species and mold atmosphere through the aggregate may be expressed as follows: Deff,12 - — where E is the void fraction of the aggregate and 7 is the "tortuosity factor". Aggregate material had no effect on diffusion rates, and the only relevant parameter was the void fraction. Values for 7 ranged from 3 to 6 for normal foundry aggregates with 4 being considered a good representative value. An area of interest in high-temperature metallurgical processes which has received little attention in the past is the diffusion of metal vapor species in porous aggregates. Research into the metal penetration phenomenon' in foundry molds has shown that a major penetration mechanism is the vapor transport of metallic species into the porous foundry sand molds, followed by condensation of metallic films on the sand grains. Considerable study of the vaporization of metallic species has been reported in the literature, and the vapor transport properties of many metallic species have been determined.2'3 Many instances have been observed where the vaporization behavior could only be explained by the existence of a metallic species with a vapor pressure greater than the elemental metallic species. These species were identified or, in some cases, presumed to be carbonyls,4,5 hydroxides,6-9 or vaporous oxides.10-16 The diffusion of gases through porous aggregates has received considerable attention in the literature pertaining to catalysis, although primarily at low temperature, and more recently in the literature concerned with ore reduction.17-22 The following experiments were devised and carried out in order to determine the nature of the metallic species involved in the metal penetration phenomenon, and the effective diffusivities involved. EXPERIMENTAL APPROACH Steady-state diffusion was selected for experimental convenience. The experimental systems used, shown in Figs. 1 and 2, consisted of a porous aggregate specimen contained in an impermeable alumina tube held above, and just separate from a metal bath. The entire system was held at constant temperature and pressure in a furnace with a controlled oxygen partial pressure atmosphere. After a brief period of nonsteady state behavior, a steady flux of metal vapor through the porous aggregate will develop due to the concentration gradient of metallic vapor in the gas phase. The flux of metallic vapor from pressure may be neglected because there is no pressure gradient. There is no flux from convection because there is no net flow of gas within the metal-aggregate system, and thermal diffusion is negligible compared to the flux from ordinary diffusion. If the material being studied is allowed to vaporize until steady-state behavior is attained, the experimental results may be analyzed using Fick's First Law.

Jan 1, 1970

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen' and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported'-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.',',',' Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.',2

Jan 1, 1963

By Nigel B. Pearson

INTRODUCTION Chingola Division of Nchanga Consolidated Copper Mines Limited is situated in the Copper- belt of Zambia, approximately 30 kilometres south of the border with Zaire. It is the country's leading producer of copper and its principal foreign exchange earner, and has been, in its time, the largest single copper producer in the British Commonwealth and the second largest in the world. There are two 'primary' copper sources at the Division, namely Underground producing approximately 100 000 tonnes of contained copper annually, and the Open Pits, producing approximately 200 000 tonnes annually. Following the commissioning of the Tailings Leach Plant in 1974, treating final tailings, metallurgical recovery increased from approximately 70% to in excess of 80%. Extensive deposits of cobalt are present and following the rise in the market price in 1979 and 1980, plans were made to extract this separately. Cobalt production commenced in 1980 from Underground and will increase substantially when the Open Pit cobalt reserves become available in approximately 2 years time. This paper covers the development of the production method of the principal Underground Orebody, known as the Lower Orebody, and the control systems applied to it. HISTORY The Lower Orebody, formerly known as the Nchanga West Orebody, was discovered by extensive Diamond Drilling operations in the late 1920's. Development of the Shaft complex and the orebody commenced and continued until 1931 when flooding from development on the 480 foot horizon necessitated closure. The mine remained closed until 1937 and production commenced from the Lower Orebody in 1939. Various expansion schemes of the Metallurgical Plants and the Underground workings were completed over the years with the result that Underground production increased steadily to in excess of 150 000 tonnes copper annually in the 1960's. In recent years production has levelled out at slightly less than 100 000 tonnes annually. This decrease is as a result of producing from a lower grade reserve, available within a more limited production front, and the application of production constraints in the light of experience gained. GEOLOGY Within the Nchanga Mining Licence Area of Chingola Division, there are a total of 14 known copper orebodies in the basal part of a thick succession of sediments of Pre-Cambrian age. The sediments rest on a Basement Complex of granites, gneisses and schists. Three superimposed stratiform orebodies, known locally as the Lower, Intermediate and Upper Orebodies, occur over a vertical interval of approximately 150m. Current annual copper production is approximately 300 000 tonnes. The ore originates from four different mining operations, one Underground mine and three Open Pits. Approximately 9 million tonnes of ore grading between 3 and 3.5% copper are milled annually. The two largest sources of ore, the Under- ground mine and the Nchanga Open Pit are on the gently dipping south limb of the Nchanga Syncline (Figure 1). In the Nchanga Open Pit the major source of ore is the Upper Orebody with lesser tonnages from the Intermediate and Lower Orebodies. In the Underground mine the Lower Orebody is the only orebody being mined, underground mining of the Upper Orebody being suspended for economic reasons in 1978. The typical stratigraphic column is illust- rated in the legend on Figure 1. The footwall rocks comprise either Nchanga Red Granite or the Arkose formation, both of which are hard competent rocks, offering generally good mining conditions for footwall development. Copper mineralisation of the Lower Orebody extends from the upper part of the Arkose to the top of the Lower Banded Shales. Overlying the Arkose is the Transition zone (0-18111 in thickness). The Transition zone comprise a lower member, Transitional Arkose, consisting of incoherent kaolinised sandstone, and an upper member, Transitional Lower Banded Shales consisting of normally soft bleached and silicified shale. The soft nature of the Transitional rocks is

Jan 1, 1981