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By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature1135°C. (2095°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm, at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By R. Floyd Farris

Al thorough knowledge of the behavior of cement slurries under elevated temperatures and pressures is necessary in order to solve properly the many problems presented in deep-well cementing operations. In the earlier days of the petroleum industry the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being ,given, for the present, to details of tech-nique and equipment for oil-field use. More specfically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries. Although it has long been recognized that cements thicken and set rapidly with increasing temperatures, practical methods for the quantitative determination of these effects are comparatively recent developments. In 1935 Silcox and Rule1 presented such a method, describing apparatus designed to measure the consistency-time relationship of cement slurries at relatively high temperatures. The practical importance of this apparatus in furnishing useful data for the evaluation of cement slurries for cementing operations has been emphasized in various technical publications by such writers as E. L. Davis,~ I. F. Bing-ham,3 and J. E. Weiler.4 A paper describing the numerous tests now used to evaluate cements for oil wells was presented in 1939 by W. W. Robinson.= Robinson describes the Consistometer and the Thickening-Time Tester, showing similarity of data from the two devices, and points out that the purpose of each apparatus is to determine the allowable time that a cement may be pumped at a given temperature. At the present time, however, it is believed that results from the Thickening-Time Tester and the Consistometer have not given a

Jan 1, 1941

By R. Floyd Farris

Al thorough knowledge of the behavior of cement slurries under elevated temperatures and pressures is necessary in order to solve properly the many problems presented in deep-well cementing operations. In the earlier days of the petroleum industry the depths of wells were shallow as compared to those of today, and the subsurface temperatures and pressures were not of sufficient magnitude to affect seriously the problem of proper control of cement-slurry properties. Today, however, the search for new reserves has extended drilling to such depths that bottom-hole temperatures of more than 200°F. and bottom-hole pressures of 3000 to 5000 lb. are not uncommon. Moreover, there is every indication that within the next few years wells will be drilled to even greater depths and bottom-hole temperatures and pressures will be correspondingly higher than those with which we are concerned today. It has been realized for some time that the behavior of cement slurries at high temperatures and pressures might be very different from that at atmospheric tempera-ture-pressure conditions, but while the temperature effects have been investigated with a reasonable degree of thoroughness, the pressure effects have received little public attention. While the trend toward deeper drilling may make changes in cementing technique and the choice of cements imperative, it was the purpose of this investigation to consider factors having a bearing on the latter, only secondary consideration being ,given, for the present, to details of tech-nique and equipment for oil-field use. More specfically, the purpose of this work was to consider the effect of temperature and pressure upon the behavior of cement slurries. Although it has long been recognized that cements thicken and set rapidly with increasing temperatures, practical methods for the quantitative determination of these effects are comparatively recent developments. In 1935 Silcox and Rule1 presented such a method, describing apparatus designed to measure the consistency-time relationship of cement slurries at relatively high temperatures. The practical importance of this apparatus in furnishing useful data for the evaluation of cement slurries for cementing operations has been emphasized in various technical publications by such writers as E. L. Davis,~ I. F. Bing-ham,3 and J. E. Weiler.4 A paper describing the numerous tests now used to evaluate cements for oil wells was presented in 1939 by W. W. Robinson.= Robinson describes the Consistometer and the Thickening-Time Tester, showing similarity of data from the two devices, and points out that the purpose of each apparatus is to determine the allowable time that a cement may be pumped at a given temperature. At the present time, however, it is believed that results from the Thickening-Time Tester and the Consistometer have not given a

Jan 1, 1941

By W. M. Yim

Experimental results are presented which indicate that transverse striations in horizontal zone-leveled Bi-Sb alloy crystals are due to irregular growth rate resulting from thermal fluctuations in the melt (Iring gowth. Thc thermal fluctutations arose from two different sources. The first type was brought about by periodic fluctuations in the furnace temperature. The second type can be attributed to turbulent therrrol conlcclion in the trzelt near the solid-liquid inteyace. Tile arrzplitlcde ond fvequency of the tetiperaticre fluctlrations vesultity from llle lhevnal con1,ecrrell. The striation spacings in Lhe crystals covvelale well with the periodicity 0.f the tempevature flueluatiors. Altliough the strialiors represenl corrlpositiozul inhoiHogeneity oh a rzicroscule, less than f.z cil. be1 S6 in Best's as deterrirzed by electron-pro be chalq'sis, the slriations roerre fbund to ILUL' no rrleusuanble effect on electical vesistirity rwr on weak field macgnetoresistance of. the Bi-Sb a1lu.y in the ternpevutue ),unge 4.Polo 300°K. DURING the course of an investigation on the horizontal growth of semimetals,' it was found that crystals of Bi-Sb alloys contained many closely spaced parallel arrays of striations. These striations occurred perpendicular to the growth direction and parallel to the solid-liquid interface. We shall refer to them as transverse striations, or just striations'', to distinguish them from lineage substructures or longitudinal striations which form parallel to the growth direction and have been known to be associated with cellular structures.' Similar transverse striations have been reported previously to occur in other materials prepared by horizontal growth: metals,4 semiconductors,5 as well as their alls. - Various methods of crystal preparation have apparently little effect on the occurrence of the transverse striations. They form whether the crystals were grown by the vertical Czochralski technique, withe1' or without'3- rotation, or by the horizontal zoning methd.- Thus, the transverse striations are not limited to any one class of materials, nor to any particular method of preparation. It is likely, therefore, that all of the observed transverse striations may have some common cause. Previously, workers agreed that periodic changes in the growth rate bring about the striations. However, no agreement exists as to the origin of the growth-rate fluctuations. Some attributed the discontinuous growth to a purely external cause, such as fluctuations in the furnace temperature, jerky motions in the crystal pulling mechanism, or a nonsymmetrical temperature distribution in the melt (in the case of crystals grown by the Czochralski technique with rtation). Others looked for the cause in some fundamental property of the growth process itself. For instance, a certain degree of supercooling is required to initiate growth from the melt. But, with further growth, the degree of supercooling decreases because of the liberation of the heat of solidification at the solid-liquid interface. Thus, crystal growth would be brought to a halt until sufficient supercooling is resotred and the cycle begins again.3'11 According to this model, periodic fluctuations in the melt temperature should exist at the solid-liquid interface. Since the periodic fluctuations in growth rate would result in changes in the segregation coefficient of solute atoms, crystals containing the transverse striations may, in some cases, show a periodic impurity fluctuation along the length, resulting in a degradation of electrical properties. The resistivity striations in doped germanium'9-10 or lnsbB are well-known examples of this microsegregation. The present work was undertaken to explain the exact origin of the transverse striations, and to assess the extent of their effect on chemical homogeneity as well as on electrical properties of Bi-Sb alloy crystals. Results from our previous study of the crystal growth of Bi-Sb alloys1 indicated that the transverse striations may arise from the temperature fluctuations in the melt during growth. This paper will show that the melt temperature fluctuations are indeed responsible for the occurrence of the transverse striations. I) EXPERIMENTAL Although the transverse striations have been observed in all slow-grown Bi-Sb alloys across the entire compositional range, we selected a composition, Big3Sbs, for the present study in view of the extensive data available on the crystal growth of this alloy from a previous study.' High-purity bismuth and antimony, both a 6-nine grade by the manufacturer's emission spectrographic analysis, were used throughout. Independent mass-spectrographic analysis showed, however, that the starting materials were more nearly a 5-nine grade. each containing metallic impurities of approximately 10 ppm atomic. In zone-leveled Big5Sb5 alloys, the total metallic-impurity content was slightly lower, about 7 ppm atomic, indicating that some degree of purification was achieved during the growth. None of the electrically active impurities, such as tin and lead (acceptors) and tellurium and selenium (donors), were present in significant quantity in undoped Bi95Sb5. Typical analysis of the undoped Bi95Sb5 alloy is shown in Table I. Nonmetallic impurities, such as carbon and oxygen, were detected, sometimes as much as 100 ppm, in both the starting materials and the zone-leveled alloys: but the data were only qualitative. Temperature fluctuations in the melt were monitored over 1 or more days by means of a 5-mil chromel-

Jan 1, 1967

By S. Usui, I. Iwasaki

The effect of pH on the adsorption of dodecylamine at the mercury-aqueous solution interface was investigated by differential capacity and electrocapillary measurements. With dodecylammonium acetate, the differential capacity curves showed two desorption peaks in the cathodic branch with their relative intensities varying with the solution pH. With dodecyltrimethylammonium chloride, only one cathodic de-sorption peak was observed in the same pH range. Through thermodynamic analysis of the electrocapillary curves, the adsorption density of undissociated amine was evaluated separately from that of aminium ion. The adsorption densities of the un-dissociated amine and of the total amine increased with increasing pH. The ratio at the interface of undissociated amine to aminium ion was several orders of magnitude greater than the ratio in the solution and increased with increasing pH. The potential at the closest distance of approach of counter ions to the mercury surface was compared with values of zeta potential on quartz previously reported. The most important variable in the flotation separation of minerals is probably the pH of the pulp, and a number of theories have been proposed to explain its effect on the condition of the mineral surfaces, on the dissociation of collectors and of inorganic and organic species (accidentally present or intentionally added) in the pulp, and on the mineral-collector interaction. In the development of a theoretical background for oxide flotation systems, an experimental approach based on electrokinetic measurements has been of much value, although the effect of pH becomes confounded since it governs both the electrochemical conditions of the oxide surface and the dissociation of the collector. For investigation of the adsorption behavior of long-chain collectors on oxide minerals, however, electrokinetic potential measurements are the most widely used technique. Hydrogen and hydroxyl ions are found to be the potential determining species, thereby governing the interfacial electrical conditions. The electrostatic interaction between the charged mineral surfaces and ionized collectors is regarded as the driving force for the adsorption of the collectors. An association of alkylamine collectors adsorbed on quartz surfaces has been postulated from streaming potential measurements, and a term "hemi-micelles" has been proposed.' The possibilities of coad-sorption of undissociated amine along with aminium ion has been inferred from contact angle measurements? and from adsorption studies.~ Electrochemical titration as applied to silver sulfide provides a more quantitative approach to the analysis of the electrical double layer at an ionic solid-solution interfaceqG and the electrochemical evidence for the adsorption of amine at pH 4.7 indicates a specific affinity of dodecylammonium ion towards silver sulfide surfaces, whereas at pH 9.2 the adsorbed species might be free arnine." A combination of differential capacity and electrocapillary measurements on a dropping mercury electrode was reported to be a sensitive method of provid- ing reliable information on the adsorption behavior of dodecylammonium acetate (DAA) at a natural (near neutral) pH.? It was also shown that there were striking similarities in the properties of the double layer and in the adsorption behavior of the amine on mercury and on such ionic solids as quartz, silver sulfide, and silver iodide. The effect of pH on the differential capacity curves at a mercury-sodium fluoride solution interface has been investigated by Austin and Parsonss who reported that between pH 7 and pH 11 there was very little effect. In the present paper, the adsorption behavior of DAA was investigated as a function of pH through differential capacity and electrocapillary measurements and the information gathered was correlated with that available in literature on quartz and silver sulfide. Experimental The apparatus and the method used for determining the differential capacity and the electrocapillary curves were identical to those described previously.' The ionic strength of the supporting electrolyte was fixed at 0.1 M with potassium fluoride, and the pH of the solution with potassium hydroxide. Only the neutral to alkaline range was covered in order to avoid the dissolution of the glass vessel with hydrofluoric acid. Results In Fig. 1 the differential capacity has been plotted against the applied potential at a DAA concentration of 10-' M at three different pH values. The curves are characterized by one capacity peak in the anodic branch, by two capacity peaks in the cathodic branch, and by a marked depression in capacity between the peaks. The depression indicates an adsorption of the arnine in this potential range. One of the cathodic peaks appears at pH 7.3 near -1.4 v and decreases with increasing pH. The other appears at pH 8.9 near —1.2 v and increases with increasing pH. At pH 9.6 only the latter peak is observed. Beyond the cathodic peaks, all the curves tend to converge with the curve in the absence of DAA, implying that two different species are being desorbed in this potential region. The anodic peak near 0.0 v increases markedly with increasing pH. The well-defined anodic peaks at pH 8.9 and 9.6 were accompanied by an appreciable increase in the current flow (in excess of O.luA), and, therefore, is a "pseudo-capacity"'" due to a

Jan 1, 1971

By C. L. Sollenbeger, R. B. Greenwalt

PERHAPS the most widely used dispersants or gangue depressants in nonmetallic flotation are sodium silicates, which vary in silica-to-soda ratio from 1 to 3.75. Typical manufactured silicates in order of decreasing solubility and increasing amounts of silica are Metso, silica-to-soda ratio of 1.00; D, 2.00; RU, 2.40; K, 2.90; N, 3.22; and S-35, 3.75.* References in flotation literature1,2 to the use of sodium silicates are often weak because they fail to mention the type of silicate used. Metso and silicate N have occasionally been mentioned, but when the type of silicate is not mentioned, it is usually assumed to be N, the cheapest of the soluble silicates and the one recommended by sodium silicate manufacturers as a flotation agent. In the All is-Chalmers Research Laboratories a systematic study was made of the effect of different alkali-silica ratios on the concentration by flotation of two scheelite ores. One of these was a high grade ore from the Sang Dong mine in Korea. The effect of such factors as pH; addition agents; and conditioning time, temperature, and pulp density on the flotation efficiency of this ore have been described previously. The other ore was a low grade ore from Getchell Mines Inc., Nevada. The mineralogy and techniques of concentrating this ore have been described by Kunze. Hereafter these ores will be referred to as the Korean and Nevada ores. Experiments were made with both to determine the effect of three factors—-type of silicate, concentration of silicate, and pH of the pulp—on recovery and grade of tungsten in a rougher concentrate. Average WO, content of the Korean ore was 1.50 pct and of the Nevada ore 0.27 pct. The predominant tungsten mineral in both ores was scheelite, which was accompanied by a small amount of powellite. The powellite and scheelite were finely disseminated through both ores and required a —200 mesh grind for liberation. Major gangue minerals in the Korean ore, in decreasing order of abundance, were amphi-boles, quartz, biotite, garnet, fluorite, and calcite. Bulk sulfides composed about 3 pct of the total weight. Gangue in the Nevada ore, in descending order of abundance, was garnet, alpha quartz, calcite, phlogopite, wollastonite, and amphiboles. Sulfide minerals were 3 to 4 pct of total weight. Batch flotation experiments were made with 500-g samples of ore, each sample wet-ground to 90 pct passing 200 mesh. The finely ground ore was floated in a Fagergren batch cell at 25 pct solids. The natural pH of the Nevada ore was 8.9 and of the Korean ore, 8.5. The D, RU, K, N, and S-35 sodium silicates were obtained in colloidal dispersions with varying amounts of water. The most alkaline, Metso, was in dry powdered form. For convenience in addition, 5 pct solutions by weight were prepared from each of the silicates, on the basis of dry sodium silicate dissolved in the correct amount of distilled water. Chemical analyses of the various silicates are given in Table I, together with the pH of the 5 pct solutions. A preliminary bulk sulfide float was made with secondary butyl xanthate as the collector and pine oil as the frother. The WO] analysis of the sulfide concentrate was nearly 1 pct for the Korean ore and about 0.1 pct for the Nevada ore. The tungsten contained in the sulfide concentrate constituted about 3 pct of the total tungsten in each ore. No effort was made to recover these tungsten values. The scheelite was floated with oleic acid. Adjustments in pH were made with sulfuric acid or sodium carbonate. A 1 pct solution of 85 pct Aerosol OT was sprayed on the froth and sides of the cell during the scheelite float to aid in dispersing the minerals and to decrease the entrapment of gangue particles. Six tests were planned for each of the six types of silicate in which concentrations of 1, 2, and 4 1b of silicate per ton of dry ore were investigated at both 6.5 and 10 pH. All tests were made at room temperature. The performance of each silicate was judged from the grade and recovery of WO, in the scheelite rougher concentrate. Tungsten recovery was calculated on the basis of the scheelite remaining in the ore after the preliminary sulfide float. Testing of each silicate at three levels of concentration and two levels of pH required 36 tests with each scheelite ore. Variance analyses were performed on the concentrate grades and recoveries to determine whether or not the type of sodium silicate, the concentration of sodium silicate, or the pH significantly affected recovery or grade. Results Concentrate Grade: A variance analysis of the concentrate grades for the Korean ore showed that concentration of the silicate and pH of the ore pulp were major factors in producing a high grade concentrate. Also, the silica- to-so da ratio was important as an interaction with pH. The concentrate grade vs silica-to-soda ratio is plotted in Fig. 1. The curves show that the concentrate grade improved with an increase in concentration of sodium silicate and also

Jan 1, 1959

By W. W. Vaughn, R. H. Barnett, E. E. Wilson

Soon after the search for uranium ores on the Colorado Plateau began in earnest, thousands of feet of drill core ranging from 1 1/8 to 2 1/8 in. diam became available for study. Although significant advances had been made in the technique of quantitative gamma-ray borehole logging, instrumentation was in the development stage, and complete reliance could not be placed on gamma-ray logs alone to interpret quantitatively the meaning of radioactivity in a drillhole. A method that would be faster than chemical analysis and still give reproducible and reliable results for various drill core sizes was desirable to provide additional information on the enormous footage of drill core being accumulated. A solid phosphor scintillation drill core scanner was designed and constructed. Basically the instrument was developed to measure radiation from a drill core which would not be clearly recorded by a gamma-ray logger using a Geiger tube as the sensitive element. Such data would be beneficial in constructing isorad maps to delineate ore-bearing zones. A calibration in the range 0.01 to 0.1 pct eU.,O, was provided; above 0.1 pct eU3O8 gamma-ray logs were available and were being used to calculate grade and tonnage of ore reserves. The core scanner, however, has been used to estimate equivalent uranium content of ore-grade materials containing as much as 2.2 pct eU3O8 with an accuracy of ± 10 pct, the sample being in the form of a BX drill core. Actually, an apparent calibration of eU3O8 vs counts per unit time is a straight line with a slope that is a function of the sensitive element and the geometry of the counting assembly. A true calibration that will show the expected departure from a straight line is due principally to the random nature of the pulse from a radiation source and the nonlinearity of the electron circuitry. Design and Construction: Three methods of detecting radioactivity were considered and applied in developing the core scanner now in use: 1) the Geiger tube, 2) liquid scintillation phosphors, and 3) solid scintillation phosphors. The desired sensitivity and long-term drift characteristics needed for this operation could be attained only by using solid scintillation phosphors. All three methods are discussed. Before scintillation counters were common, nine beta-gamma sensitive Geiger tubes 7/8 in. diam by 12 in. long were used, arranged to surround the drill core with tube axes parallel to the axis of the core. This arrangement of Geiger tubes was en- closed in a lead shield 1 in. thick, and provision was made to slide a 6-ft length of drill core manually into the counting chamber, one foot at a time. A count for each segment was taken with a scaler while the core remained stationary. The equivalent uranium content of the different sections of drill core could then be estimated with the aid of a calibration curve of counts per unit time vs percent equivalent uranium (eU). In rare cases the effects of the radioactivity concentrated in small areas within the core introduced errors in the readings made with the Geiger tube arrangement owing to the geometry of the measurement. The variability of counting rate due to a localized concentration of radioactivity in a spot in the wall of a drill core is illustrated in Fig. 1. This effect and the inherent low efficiency of the Geiger tube were considered major disadvantages of this counting arrangement. When liquid scintillation phosphors became available the core scanner in Fig. 2 was constructed to make a more accurate measurement of the equivalent uranium content of a sample. This instrument contains about 4 liters of liquid phosphor in a stainless steel coaxial cylinder 1 ft long, with inner and outer walls 0.060 in. and 0.125 in. thick, respectively. Four end-window type photomulti-plier tube with cathodes of 2 in. diam, immersed in the solution at right angles to the axis of the core, were used to observe light flashes in the phosphor. The liquid phosphor offered equal sensitivity to radiation originating at any point in the enclosure and represented geometrically the optimum in design. However, providing a semi-permanent leak-proof seal between the glass envelope of the phototube and the metal walls of the container proved to be a serious problem in constructing the equipment. The most effective seals were especially machined O-rings from sections of large tygon tubing. The tygon took a permanent set owing to cold flow characteristics and in most cases sealed completely. The light absorption characteristics of the liquid phosphor changed gradually with time, and after one month the counting rate had decreased to half the original value. The most sensitive liquid phosphor tested proved to be a solution containing 4 g of 2.5-diphenyloxazole and 0.01 g of 2-(1-naphthy1)-5-phenyloxazole per liter of toluene. With fresh solution in the chamber and with all photomultiplier tubes operating in parallel, the counting rate contributed by any one of the four photomultiplier tubes was about 85 pct of the counting rate from a single tube operated individually. From these observations it was concluded that owing to coincident loss and light attenuation within the liquid phosphor, the apparent sensitivity could not have been materially increased by additional phototubes. However, this approach to core

Jan 1, 1960

By James E. Lawver, James L. Wright

This paper describes the design of a cell used to measure the electrical conductivity, or the reciprocal resistivity, of granular materials. It also establishes a quantitative relationship between the electrical conductivity and the electrical separation of selected mineral samples. It is estimated' that the free world produces about 13 million tons of mineral concentrates a year by electrostatic or electrodynamic methods. At least 95% of these concentrates are produced by corona discharge type machines that separate minerals by exploiting the differences in their electrical conductivity. But, what is meant by the electrical conductivity of a mineral? How large a difference in the electrical conductivity of two mineral species is necessary to effect a separation? Just what is the role of conductivity in electrical separations with regard to capacity and selectivity? There is a considerable amount of information in the literature on both the mechanisms of conduction and the values of the electrical conductivity of pure single-crystal mineral specimens. In addition, some insight into the role of mineral conductivity can be obtained by referring to a Bureau of Mines publication' in which 95 minerals have been grouped as conductors or insulators as a function of temperature. The classification was made on the basis of the percent of weight that reported as "conductors" in an electrical separator. But, as is often the case in the mineral industry, practical application leads theory — and there is little useful information in the literature giving any kind of quantitative relationship between electrical conductivity and electrical separations. The problem is a bit complex because electrical conductivity per se — which can be rather easily measured on large, single grains — is not sufficiently informative to permit quantitative predictions of the separability of the mineral system. Practical "high-tension"* separations are made at such feed rates that the band of minerals on the rotor is multilayered in thickness. Thus, the effective conductivities of minerals as seen by a high-tension machine include particle-to-particle contact resistance, which is often a controlling factor in making a separation. This is particularly true when the mineral grains are coated with slime or with a dielectric surface film. From a high-tension separation viewpoint, one is actually concerned with the time required for corona-charged grains to lose enough charge so that the centrifugal force acting on the particles exceeds the image force holding the grains to the rotor. This calculation requires a knowledge of the effective mineral conductivity s. (The conductivity of the metal rotor is sufficiently greater than that of the minerals so that it need not be considered in charge decay calculations.) The charge density at time t can be approximated by the relaxation equation.3 where t 5 charge density at time t r, - charge density when t = 0 cr e total electrical conductivity £ = permittivity The time required for the charge density to fall to l/e of its initial value is called the relaxation time and is numerically equal to €/n. AS defined here, u is the conductivity of an element of homogeneous grains making contact with each other and with a grounded rotor. This paper deals with the design of a conductivity cell used to measure a, or its reciprocal p, the electrical resistivity. CELL DESIGN Initial test work was performed with a cell recommended by ASTM.4 Since the reproducibility with the ASTM cell was not satisfactory, it was decided to

Jan 1, 1970

By R. D. Satterley

The Sherwood mine is an iron-ore mine owned and operated by the Inland Steel CO. in the Iron River district of the Menominee Range in Michigan. The property consists of an 80-acre tract in the village of Mineral Hills, about a mile north of the city of Iron River. The Ore mined is a reddish brown, nonbessemer hematite and limonite. The ore bodies lie in a large syncline having an east-west strike and are associated with a rock structure that is folded in a complex manner. The two 40-acre tracts run north and south and the shaft is at about the center of the north forty. The shaft is 1286 ft. deep, with the principal operating level at a depth of 1000 ft. from surface. A new level at a depth of 1200 ft. is in process of development. The ore body at the 1000 ft. level is east and west at approximately the line between the north and south forties and at this elevation is from 50 to 250 ft. wide and extends above the level at varying heights of from 50 to 250 feet. The 1000-ft. haulage drift extends south from the shaft, through the east-west ore body to the slates on the south side of the body. The ore body was intercepted in the drifting at about goo ft. from the shaft and was about 200 ft. wide at that point. A crosscut was extended to the east and west property lines along the south boundary of the ore body. This east-west ore body is laid out in areas go ft. wide for stoping with pillars 40 ft. wide. With this plan a stope is approximately 80 by 200 ft. and has a pillar on both sides that is approximately 40 by 200 ft. The ore has a height of from 50 to 250 ft. above the elevation of the level, therefore the height of the stopes varies in accordance with the height of the ore body at each location. From the crosscut, two main raises, each 6 by 7 ft., are put up into each 80 ft. stope area (Fig. 1). One of the main raises serves as a manway and the other as an ore raise, through which the ore is transferred from the stope to the tramming equipment. The original layout as for scraping of the ore from under the stopes into the ore raises. The ore raise is put halfway (east and west) along the 80-ft. stope area and usually is in iron formation. The manway and ore raise are on approximately 15-ft. centers. These main raises are Put up to a height of from 22 to 30 ft. above the level floor, then from the toll of the ore raise a scraper drift (8 X 8 ft.) is driven across the width of the ore body, which is in the neighborhood of 200 ft. From the scraper drift, mill raises are put up at 12½-ft. centers, staggered on opposite sides of the drift, and these are extended 23 ft. above the elevation of the scraper-drift floor. The sublevel connecting the top of these mill raises is called a mill "sub." Other sublevels are developed parallel to the scraper and mill subs at 25-ft. vertical intervals above the mill sub. The mill sub and the other subs above the mill sub are known as sublevels or dog drifts, and are 4 ft. wide and 6 ft. high. These dog drifts

Jan 1, 1946

By R. D. Satterley

THE Sherwood mine is an iron-ore mine owned and operated by the Inland Steel Co. in the Iron River district of the Menominee Range in Michigan. The property consists of an 80-acre tract in the village of Mineral Hills, about a mile north of the city of Iron River. The ore mined is a reddish brown, nonbessemer hematite and limonite. The ore bodies lie in a large syncline having an east-west strike and are associated with a rock structure that is folded in a complex manner. The two 40-acre tracts run north and south and the shaft is at about the center of the north forty. The shaft is 1286 ft. deep, with the principal operating level at a depth of 1000 ft. from surface. A new level at a depth of 1200 ft. is in process of development. The ore body at the 1000 ft. level is east and west at approximately the line between the north and south forties and at this elevation is from 50 to 250 ft. wide and extends above the level at varying heights of from 50 to 250 feet. The 1000-ft. haulage drift extends south from the shaft, through the east-west ore body to the slates on the south side of the body. The ore body was intercepted in the drifting at about 800 ft. from the shaft and was about 200 ft. wide at that point. A crosscut was extended to the east and west property lines along the south boundary of the ore body. This east-west ore body is laid out in areas 80 ft. wide for stoping with pillars 40 ft. wide. With this plan a stope is approximately 80 by 200 ft. and has a pillar on both sides that is approximately 40 by 200 ft. The ore has a height of from 50 to 250 ft. above the elevation of the level, therefore the height of the stopes varies in accordance with the height of the ore body at each location. From the crosscut, two main raises, each 6 by 7 ft., are put up into each 80 ft. stope area (Fig. I). One of the main raises serves as a manway and the other as an ore raise, through which the ore is transferred from the stope to the tramming equipment. The original layout was for scraping of the ore from under the stopes into the ore raises. The ore raise is put halfway (east and west) along the 80-ft. stope area and usually is in iron formation. The manway and ore raise are on approximately 15-ft- centers. These main raises are put up to a height of from 22 to 30 ft. above the level floor, then from the top of the ore raise a scraper drift (8 X 8 ft.) is driven across the width of the ore body, which is in the neighborhood of 200 ft. From the scraper drift, mill raises are put up at 12 ½ -ft. centers, staggered on opposite sides of the drift, and these are extended 23 ft. above the elevation of the scraper-drift floor. The sublevel connecting the top of these mill raises is called a mill "sub." Other sublevels are developed parallel to the scraper and mill subs at 25-ft. vertical intervals above the mill sub. The mill sub and the other subs above the mill sub are known as sublevels or dog drifts, and are 4 ft. wide and 6 ft. high. These dog drifts

Jan 1, 1945

By Dean Goodermote, Carla S. Stone

I Introduction Coal fuels China. Roughly 70 percent of all commercial energy demand is supplied by domestic coal production and with the recent Chinese opening to the West, the Chinese Coal Industry may figure prominently in the export market as well. Because of the importance of China's coal industry to the future of China and the Pacific Rim energy balance, this paper reviews the industry and offers some cautious projections for its outlook. II Energy's Position in the Current Political and Economic Climate Traditionally, Chinese society has been dominated by the policies of its most important government leaders. Deng Xiaoping, Vice Chairman of the Communist Party is the current leader of China. Deng and his proteges are pragmatists. Although China's government structure is based on Marxist/Leninist tradition, Deng and his followers are promoting experiments with market economics and expanded relationships with Western Countries, which have encouraged foreign investment in China. Energy companies represent just one type of industry that is interested in helping the Chinese to develop their abundant natural resources. Although China's leadership is committed to a program of economic modernization, that program currently is experiencing what the Chinese government terms "readjustment". Readjustment cuts back in imports due to deficient foreign exchange and deemphasizes heavy industry, while it encourages agricultural and consumer goods output and, most imporant, energy production. Increased Chinese coal and oil production is essential both to fuel industry and, equally important, to provide foreign exchange. If sufficient energy production is not forthcoming, then economic growth will be severely retarded. China's 1979 per capita GNP of $260 is only slightly better than the weighted average achieved by low income countries of $230. (1) Delays in growth could lead to social unrest, threatening the position of the current leadership. Since there is no institutionalized mechanism for leadership succession and policy continuation, it is reasonable to assume that leadership changes could result in energy policy changes. III Energy Consumption Energy production is important to China's future economic health as highlighted by the World Bank. If China's economy grows rapidly, 5 percent to 6 percent during this decade, the Bank noted, a significant energy shortfall could occur as early as 1985. This state of affairs contrasts sharply with China's current position as a net hydrocarbon exporter. (2) To assure a healthy economic future, China's leadership is attempting to reduce its rate of increase in energy demand through conservation as well as to boost energy output. A massive conservation promotion program has been underway since 1979 and there is much room for improvement. China's industrial sector is only about half as energy efficient as is U.S. industry. (3) During the last two decades, each percent of increase in GNP has been accompanied by a 1.8 percent of increase in energy consumption. (4) This compares rather poorly with the United States where a less than one-to-one relationship exists. IV Energy Supply The short term prospects for oil production are uncertain. Production increases were rapid in the 1960's and early 1970's, averaging 20 percent annually, but most of this increase came from one field, Daquing. Now that Daquing's production has peaked and the offshore potential has yet to be developed, petroleum production has maintained a plateau of 2.1 million b/d, at least temporarily, of which approximately 15 percent is exported. (5) Output

Jan 1, 1982

By H. R. Brannon, F. M. Perkins, Weldon O. Winsauer

Both the abnormal resistivity exhibited by shaly reservoir materials and their potential are due to adsorption of ions. Interrelationships between the two have been derived and verified by laboratory results. These relations which have resulted from this work may be used in a qualitative manner to estimate whether or not a particular shaly reservoir contains hydrocarbons, and also to estimate the porosity of shaly sands. INTRODUCTION In spite of the progress which has been made in the last decade toward a better understanding and utilization of the electric log, there remain a number of problems in the interpretation of the log. One of these which is often troublesome is that of divining the nature of the fluids in sandstones or carbonate rocks which contain appreciable amounts of shale. It was shown by Patnode and Wylliel in 1949 that shaly rocks exhibit an abnormally low resistivity when saturated with solutions of low ionic concentrations. This phenomenon has been demonstrated to be due to the adsorptive properties of shale or clay in the rock.' In estimating the fluid content of shaly sands or carbonates from the electric log, it is desirable and sometimes necessary to correct for the abnormally low resistivity. A similar correction is likewise often necessary if attempts are made to estimate the porosity of a stratum from resistivity measurements. The correction may be made from data obtained on core samples and from information on salinity of interstitial water. Cores, however, are not always available. Moreover, even if cores are at hand, their examination is time-consuming. It would be most desirable, therefore, to make corrections of this nature from the log itself. Since both the abnormal resistivity and the potential' are consequences of the adsorption of ions on shale, it should be possible to utilize the potential curve to give better interpretation of resistivity data obtained in logging shaly materials. The work described in following sections was directed toward this end. THEORY Relation of Resistivity of Shaly Reservoir Rock to Adsorpttve Properties In discussing the effect which the presence of shale or clay exerts on the resistivity of a reservoir rock, it is convenient to make use of the resistivity factor.4,5 This quantity has been defined as the ratio of the resistivity of the rock when it is completely saturated with an electrolyte to the resistivity of the electrolyte itself. When the rock, such as a clean sand or carbonate, is free of shale the resistivity factor is virtually independent of the ionic concentration of the electrolyte used to saturate the sample, so that F = R0/Rw = constant for a clean rock . . (1) where F is the resistivity factor, R0 is the resistivity of the rock saturated with electrolyte, and Rw is the resistivity of the electrolyte. When the rock contains argillaceous material, the resistivity factor as defined above is no longer independent of the concentration of the electrolyte used to saturate the rock, but decreases as the ionic concentration of the electrolyte decreases. In explanation of this behavior, it is instructive to consider a sample of shaly porous rock placed in contact with a large volume of a dilute electrolyte. The sample is considered to become saturated with the electrolyte, and to attain equilibrium with it. As a result of adsorption by the shale surfaces within the rock, there is a greater concentration of ions in the solution adjacent to the shale particles in the interstices of the sample than there is in the external solution with which the

Jan 1, 1955

By G. R. Speich

A cellular precipitation reaction in which cells consisting of an Ni3Ti (DO24) phase and austenite are formed has been studied in an austenitic Fe-30 Ni-6 Ti alloy. The variation of the growth rate and interlamellar spacing of the Ni3Ti cells with temperature has been determined m the range 400" to 975°C; the interlamellar spacing is proportional to the degree of undercooling; the growth rate can be expressed by an equation of the form G = K?T)2 exp(-Q/RT). The habit of the Ni3Ti lamellae is (001)Ni3Ti (111)y;[010]Ni3T2 [010]y. An almost perfectly coherent interface is formed between Ni3Ti lamellae with this orientation rela -tionship and the intervening austenite. This first Ni3Ti cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. CELLULAR precipitation reactions have been studied in copper-base,1,2 Au-Ni,3 pb-sn,4 and iron-base ferritic5,6 solid solutions, and this mode of precipitation has been treated theoretically by smith," Turnbull,8,9 cahn,10 and more recently by bohm.11 In the case of substitutional austenitic iron-base alloys little or no data are available, Cellular precipitation reactions are well known in austenitic nickel-base alloys12,13 but usually these reactions do not proceed to completion because of general precipitation occurring in the matrix, and they have not been studied in detail. Precipitation from an austenitic Fe-30 Ni-6 Ti alloy was studied as part of a larger investigation of the mechanisms of precipitation from substitutional iron-base alloys. This alloy, austenitic at high temperatures, decomposes at lower temperatures by a double cellular precipitation reaction. The first decomposition product consists of alternate lamellae of an Ni3Ti(DO24) phase and austenite. The reaction proceeds to completion, consuming all of the original austenite. This first cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. The first cellular reaction was studied in detail by light and electron microscopy, hardness measurements, and by X-ray and electron diffraction. Interlamellar spacings and growth rates were measured during isothermal aging in the range 400" to 975°C. The orientation relationship between the Ni3Ti and austenite lamellae was determined and indicates that an almost perfectly coherent interface exists between the two phases. This first Ni3Ti cellular reaction is of particular interest because it occurs over such a wide temperature interval. This allows cellular growth rates and interlamellar spacing data to be obtained for much larger degrees of undercooling than reported hitherto. MATERIALS AND EXPERIMENTAL PROCEDURE The Fe-30 Ni-6 Ti alloy was prepared from electrolytic iron, Mond nickel shot, and sponge-purity titanium* by vacuum melting in a zirconia crucible

Jan 1, 1963

By J. Suiter, H. F. Ryan

H. F. Ryan and J. Suiter (CSIRO)—In this paper the authors have presented "a physical model which has as its central hypothesis the solution strengthening of regions along grain boundaries in the order of tens of angstroms thick", and their calculations have used 40Å as the zhalf-width of this boundary region. Selection of this value by the authors suggests that they were unaware of a number of recent field-ion microscope observations of grain boundary structures (e.g., Refs. 29 and 30). The accompanying figure, Fig. 9, shows a portion of an ion micrograph of a tungsten specimen containing a grain boundary, and the regular arrangement of atoms in various crystal planes in each grain can be seen, except in the boundary zone which is not more than two atom diameters in width. Since it is expected that solute atoms will segregate only to the region where the lattice is disturbed, it would seem that a value of 4Å for the half-width of the boundary region would be more appropriate than the value of 40Å assumed by the authors. If the former value is used in Eq. [8] of their paper to obtain curves showing solute concentration in the grain boundary as a function of temperature, the resulting curves differ significantly from those obtained by the authors. Although there are only relatively slight changes in the regions corresponding to higher temperatures (i.e., grain boundary concentrations of approximately 1 at. pet), at lower temperatures the curves are no longer realistic. For example, the curve corresponding to u = 7000 cal per mole gives a solute grain boundary concentration in excess of 100 pet at a temperature of approximately 360°K, and "flattens out" at a grain boundary concentration of about 300 pet! Similar results are obtained with each of the other curves. Ion microscopy of dilute solid-solution alloys has shown that solute atoms give rise to image points which in most cases are of higher intensity than those of the solvent atoms.31 If the same behavior occurs when the solute atoms are present in much lower concentrations then ion microscopy should provide a sensitive tool for studying the segregation of impurities to the grain boundary regions. Although many grain boundaries in tungsten have been examined after different thermal and mechanical treatments, there has not been, as yet, any systematic study of such segregation. In general the micrographs show no clear indications of marked grain boundary segregation, but occasionally areas are found where the grain boundary contains an appreciable number of image points of high intensity in a very narrow zone, see Fig. 9. If it is assumed that these correspond to impurity atoms then it is possible to estimate the impurity concentration both in the grain boundary and within the body of the grains. Application of this method (to a larger area

Jan 1, 1965

By Charles E. Nelson

THIS paper will outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as jar as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper and will be discussed briefly.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, this paper will deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. The outline of this discussion will closely follow that of an earlier paper,2 with such changes and additions as seem necessary to bring it up to date. TYPES OF MELTING PRACTICE All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux, which provides protection during melting and a molten pool of flux into which the solid magnesium melts. The flux is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies;, on quiet standing, it separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is desirable. The open-pot method is used generally in the following processes: (I) alloying and remelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drys out or thickens after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to

Jan 1, 1946

By G. E. Archie

The usefulness of the electrical resistivity log in determining reservoir characteristics is governed largely by: (I) the accuracy with which the true resistivity of the formation can be determined; (2) the scope of detailed data concerning the relation of resistivity measurements to formation characteristics; (3) the available information concerning the conductivity of connate or formation waters; (4) the extent of geologic knowledge regarding probable changes in facies within given horizons, both vertically and laterally, particularly in relation to the resultant effect on the electrical properties of the reservoir. Simple examples are given in the following pages to illustrate the use of resistivity logs in the solution of some problems dealing with oil and gas reservoirs. From the available information, it is apparent that much care must be exercised in applying to more complicated cases the methods suggested. It should be remembered that the equations given are not precise and represent only approximate relationships. It is believed, however, that under favorable conditions their application falls within useful limits of accuracy. Introduction The electrical log has been used extensively in a qualitative way to correlate formations penetrated by the drill in the exploitation of oil and gas reservoirs and to provide some indication of reservoir content. However, its use in a quantitative way has been limited because of various factors that tend to obscure the significance of the electrical readings obtained. Some of these factors are the borehole size, . the resistivity of the mud in the borehole, the effect of invasion of the mud filtrate into the formation, the relation of the recorded thickness of beds to electrode spacing, the heterogeneity of geologic formations, the salinity or conductivity of connate water, and, perhaps of greatest importance, the lack of data indicating the relationship of the resistivity of a formation in situ to its character and fluid content. On the Gulf Coast it is found that the effects of the size of the borehole and the mud resistivity are generally of little importance, except when dealing with high formational resistivities or extremely low mud resistivities. Fortunately, little practical significance need be attached to the exact values of the higher resistivities recorded. Low mud resistivities are not common, but when this condition is encountered it may be corrected by replacing the mud column. With the present advanced knowledge of mud control, invasion of mud filtrate into sands can be minimized, thereby increasing the dependability of the electrical log. The effect of electrode spacing on the recorded thickness of a bed is often subject to compensation or can be sufficiently accounted for to provide an acceptable approximation of the true resistivity of the formation. As development of a field or area progressively enhances the knowledge of the lithologic section, the resistivity values of the electrical log take on greater significance, ultimately affording acceptable interpretations. The salinity, and

Jan 1, 1942

By G. E. Archie

The usefulness of the electrical resistivity log in determining reservoir characteristics is governed largely by: (I) the accuracy with which the true resistivity of the formation can be determined; (2) the scope of detailed data concerning the relation of resistivity measurements to formation characteristics; (3) the available information concerning the conductivity of connate or formation waters; (4) the extent of geologic knowledge regarding probable changes in facies within given horizons, both vertically and laterally, particularly in relation to the resultant effect on the electrical properties of the reservoir. Simple examples are given in the following pages to illustrate the use of resistivity logs in the solution of some problems dealing with oil and gas reservoirs. From the available information, it is apparent that much care must be exercised in applying to more complicated cases the methods suggested. It should be remembered that the equations given are not precise and represent only approximate relationships. It is believed, however, that under favorable conditions their application falls within useful limits of accuracy. Introduction The electrical log has been used extensively in a qualitative way to correlate formations penetrated by the drill in the exploitation of oil and gas reservoirs and to provide some indication of reservoir content. However, its use in a quantitative way has been limited because of various factors that tend to obscure the significance of the electrical readings obtained. Some of these factors are the borehole size, . the resistivity of the mud in the borehole, the effect of invasion of the mud filtrate into the formation, the relation of the recorded thickness of beds to electrode spacing, the heterogeneity of geologic formations, the salinity or conductivity of connate water, and, perhaps of greatest importance, the lack of data indicating the relationship of the resistivity of a formation in situ to its character and fluid content. On the Gulf Coast it is found that the effects of the size of the borehole and the mud resistivity are generally of little importance, except when dealing with high formational resistivities or extremely low mud resistivities. Fortunately, little practical significance need be attached to the exact values of the higher resistivities recorded. Low mud resistivities are not common, but when this condition is encountered it may be corrected by replacing the mud column. With the present advanced knowledge of mud control, invasion of mud filtrate into sands can be minimized, thereby increasing the dependability of the electrical log. The effect of electrode spacing on the recorded thickness of a bed is often subject to compensation or can be sufficiently accounted for to provide an acceptable approximation of the true resistivity of the formation. As development of a field or area progressively enhances the knowledge of the lithologic section, the resistivity values of the electrical log take on greater significance, ultimately affording acceptable interpretations. The salinity, and

Jan 1, 1942

By E. A. Gulbransen, W. S. Wysong

The behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a a Or as an important component in alloys in high temperature Oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a micro-balance study of the following problems: (1) the oxidation behavior in the ternperature range of 25 to 550°C (') the reduction with pure hydrogen Of thin Oxide films formed On tungsten, and (3) the volatility Of thin Oxide films On tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the Oxide to to ratio is greater than one, the oxide is not considered protective, ('1 the meta1 readily Oxidizes at temperatures from 30" to 55o°C (3) the oxides WO² and WO³ are reduced at temperatures as low as 500°C. by hydrogen, and (4) the Oxide WO3 is volatile at temperatures from 800 to 1100°C. Literature The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°c. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides, Schei14 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bed-worth's5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.? They have reported that WO3 is the stable oxide in contact with the metallic substrate up to approximately 600°C while wo³ forms first at 7oo°c. Hagg and Magneli8 have recently reported a study of the lattice structures . observed in the tungsten oxidcs using the X-ray diffraction method. In addition to an a-phase WO3 and a '-phase WO2, they reported the existence of two new phases. A 8' phase, homogeneous between

Jan 1, 1949

By W. T. Isbell

IN the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 14000 to 1500°F and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace was expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. EQUIPMENT AND ITS USES Dezincing Machine.-The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig I). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.-The treating cham¬ber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1947

By W. T. Isbell

In the Parkes process of lead refining, after desilverization has been completed by means of the addition of zinc, there remains in the lead from 0.5 to 0.6 pct zinc. At this stage in the refining operations virtually all impurities are reduced to refined lead specifications except zinc and antimony. All excess copper, nickel and cobalt have been removed by the zinc additions. The silver remaining should not exceed 0.1 oz per ton. It then remains only to remove the zinc and antimony in order to produce refined lead. At the Herculaneum plant of the St. Joseph Lead Co., practice formerly was to complete the refining by means of oxidation in a reverberatory furnace. This process consisted of heating the lead to 1400O to 1500OF and allowing it to come in contact with excess air passing over the surface of the lead and periodically agitating the bath of lead with air. This procedure not only resulted in the loss of zinc but of a considerable quantity of lead converted to the oxide in the form of dross and fume. The fume, collected in the baghouse, together with the dross was returned to the blast furnace, thus adding appreciably to the circulating load on the blast furnace and refinery. In addition, operation and maintenance of the reverberatory furnace were expensive and required the performance of disagreeably hot and somewhat hazardous work. The process of dezincing with high vacuum was developed at this plant as a substitute for the oxidation process and finally led to lower operating costs, the practical elimination of dross and fume and the direct production of metallic zinc, which is very suitable for re-use in the desilverization process. Essentially this process consists of subjecting the lead to high vacuum, in a kettle provided with means for heating, a bell-shaped member open at the lower end so constructed that it can be immersed in the molten lead, and means for evacuating the interior of the bell and for sealing an agitator. Metallic zinc is thus produced and collects on the upper cooled part of the bell member. This metallic zinc is periodically removed and re-used in the desilverization process. The process is quite simple. It is conducted at a low temperature, thus permitting the use of iron equipment, and shows a material saving in refining costs over the old method. Equipment and Its Uses Degincing Machine.—The equipment employed in this process consists of a dezincing machine, a steel kettle of 120 tons capacity, a vacuum system and equipment for handling the dezincing machine (Fig 1). The dezincing machine consists of a compact assembly, suitable for handling with an overhead crane, consisting of a treating chamber and the agitating mechanism. Treating Chamber.—The treating chamber is a bell-shaped shell (4), similar in shape to a hemispherical kettle with a lid

Jan 1, 1949