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By Edward Hart

The specimen of glazy iron used for analysis was highly characteristic in appearance. It was made at one of the furnaces of the Glendon Iron Works, working a light burden of ore with a highly silicious cinder. There are very few records of analyses of this variety of iron. I have been able to find but the two given by Bell, and I add these to my analysis for comparison. Bell. 1. 2. Iron,......89.47* 88.18 90.70 Carbon, combined,.... 0.00 0.79 0.71 Graphite,......2.88 2.59 2 68 Silicon,......5.47 5 13 5.13 Manganese,.....1.54 0.77 0.56 Sulphur,......0.04 0.17 0.23 Phosphorus,.....0.60 1.12 1.12 Titanium,.....- 0.26 0.18 Calcium,......0.00 0.22 0.20 Magnesium,.....0.00 0.06 0.03 100.00 9929 101.54

By K. E. Merklin, F. D. DeVaney

Students of the modern blast furnace seem unanimously agreed that they are observing a major revolution in practice. Rather than changing construction and operation of the furnaces, most of the great advances now under way deal with the raw materials feed. Prepared burdens have gained increasing significance during recent years. Sizing, concentration, and agglomeration have all become bywords to greater production and reduced operating costs. The remarkable results with test furnaces in which self-fluxing sinter makes up part or all of the ore charge foretell even greater improvements. Other investigators have reported many of these advances, and it is enough to predict here that more and more operators will turn to the use of self-fluxing sinter. This change in the operator's requirements comes at a time when one major section of the iron ore regions, the Mesabi, is finding it difficult to maintain, let alone improve, the tonnage and grade of its shipping product. To meet the new demands with respect to quality and structure, the iron ore producers of this area turned first to screening, crushing, and concentrating intermediate ores. More recently, declining higher-grade reserves have led to multimillion-dollar investments in plants to treat the low-grade magnetic taconites.1,2 To yield a suitable concentrate, the Minnesota magnetic taconites must be ground to about 80 pct through 325 mesh, too fine to be charged directly to the blast furnace or to make acceptable feed to the sinter strand. The pelletizing process was developed to meet the structure requirements laid down by the blast furnace operators. Taconite producers are succeeding in their efforts just when the attention of the blast furnace man is being drawn to the great advantages of self-fluxing sinter.3 The taconite operators are ready with an alternative. Why not produce sclf-flus ing pellets? At the Hibbing laboratory of Pickands Mather & Co., where much of the early work was done that led to Erie Mining's 7.5-million ton taconite plant at Hoyt Lakes, Minn., preliminary investigations have been made. Present Taconite Operations: Details of this work will be clarified by a brief review of agglomeration practice in commercial taconite plants. After the taconite has been ground to about 80 pct through 325 mesh to liberate the magnetite grains, the ore is concentrated on magnetic separators, thickened, and filtered to about 10 pct moisture. This structure and moisture fit in closely with the conditions required to produce good balls. It has been found with taconite concentrates that at least 60 pct of the feed to the balling drum must be —325 mesh to obtain good ball compaction within reasonable time. The filter cake moisture usually permits a slight water addition at the balling drum, and further balling control is obtained by adding about 12 Ib of bentonite and 1 1/2 lb of soda ash per dry short ton of concentrate. These additives, and occasionally small quantities of fine coal, are thoroughly mixed with the filter cake ahead of balling. The swelling property of bentonite improves the green and dry strength of the balls so they can be handled without breakage until they are fired. Soda ash is added for pH control to insure maximum performance of the bentonite, and coal is added for more heat in the firing process when required. The balls, normally 3/8 to l-in. diam, are brought to a temperature of 2350" to 2500°F in the indurating furnace. Heat for this process comes from three sources: 1) fuel burned in the combustion chamber, 2) oxidation of the magnetite concentrates to hematite, and 3) coal added to the balls. Pellet strength is developed by grain growth and bridging and, if enough slag-forming constituents are present, by slag bonding. Conversion to hematite is usually close to 100 pct in the fired pellets. Batch Test Procedures: Initial studies of self-fluxing pellets were made by producing balls on a batch basis under carefully controlled laboratory conditions. The l-in. balls, uniform in size, were fired in an oxidizing atmosphere in a standard laboratory muffle furnace. The firing procedure consisted of

Jan 1, 1961

By R. P. Olsen, A. K. Schellinger

Molten silicate salts, the important industrial byproducts termed "slags," are known to be electrolytic conductors at furnace temperatures. This property is due to their partial dissociation into ions with the ion kind and size being closely related to the slag composition. Ionic conductance, in liquids, is a function of the viscosity, which in turn is a function of the temperature. It could be anticipated, therefore, that a semi-log plot of conductivity vs. reciprocal absolute temperature might yield a straight line, in the case of molten silicates and salts. As liquids, the viscosity of these slags should follow the Shepard1 relationship: log viscosity = A/T + B Then, if the resistance of the molten slag is directly proportional to the viscosity: log Rs = A/T + B Resistance measurements of molten halide salts,2 and silicate salts34 by various investigators have, indeed, shown this straight line relationship between resistance and temperature. A further relationship between the conductivity versus the degree of ioni-zation, the size of the ions, and the slag composition is, also, to be expected. Large ions, and fewer ions, would move more slowly in a potential field and could not carry as much current as smaller, more numerous, and mobile, ions. Conductivity, therefore, would be smaller in the presence of such large ions and higher slag viscosities. The conductivity-composition relationship is of considerable interest in the case of the industrial slags produced in iron blast furnaces, and non-ferrous smelting furnaces. These slags usually approximate three component systems with several minor components as impurities. At least one of the major components is commonly purchased for the sole purpose of rendering the slag less viscous at a reasonable furnace temperature. Should the conductivity be related rather directly to the concentration of such a purchased slag component (that is, CaO) instrumental measurement and control at the furnace might be possible. Modern tele-metric control methods in aqueous chemical process industries are often based on the property of conductivity of solutions, and its variation with composition. Investigators3 of the phenomenon of electrical conductivity in molten blast furnace slags have established that these systems show lines of equal conductivity on their ternary diagrams at one temperature level. These isocon-ductivity lines form closed contours on the diagrams, and at times, minimum areas occur at which these contours are essentially closed down to a point. The conductivity reading at such a point, at one temperature , would, of course, locate one on the diagram, and give the slag composition. Research in this field is understandably scanty. The reactive nature of

Jan 1, 1950

By D. N. Seidrnan

In the present note we present thermal-analysis data for the liquidus curve from 0 to 76 at. pct Se and for the selenium-rich monotectic reaction in the Pb-Se system. We have previously reported that no expey-imental eviderzce was found for a lead-rich monotectic reaction, at -860°C with a monotectic composition of -20.5 at. pct Se, as found by Nozato and Igaki.&apos; Our additional data substantiated this earlier finding and extended the composition range studied. The alloys were prepared from semiconductor -grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999+ wt pct pure as determined by the supplier. The impurities for lead were Fe (1 ppm) and Cu & ppm) while for selenium the impurities were Cu (< 1 ppm), As (< 1 ppm), Te (1 ppm), and C1 (<1 ppm). The general procedures used for thermal analysis were those specified by the National Bureau of Standards. A Pt/Pt-10 pct Rh thermocouple calibrated against the freezing points of zinc and copper purchased from the National Bureau of Standards and antimony (99.985 pct pure) purchased from A. D. Mackay, New York, was used for all the thermal analysis. The thermocouple electromotive force was measured with a Rubicon Type B potentiometer used in conjunction with a galvanometer with a sensitivity of 0.5 pV (mm) -&apos;. The absolute accuracy of this thermal-analysis system was *0.5"C. One-hundred-gram alloys of the desired composition were sealed in quartz crucibles, with a central thermocouple well, at a pressure of less than 10"1 Torr. The alloys were initially heated well above the liquidus curve and shaken vigorously to insure homogeneity. Cooling curves were then taken by the direct method at cooling rates ranging from -0.5" to 1.5"C (min)-&apos;. The phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis is shown in Fig. l.* An extrapolation of the selenium-rich portion of the liquidus curve to the monotectic reaction isotherm (678.3"C) gave a value of 76.1 at. pct Se for the monotectic composition. A tabulation of all the thermal-analysis data is given in Table I. As we previously reported no experimental evidence was found Fig. l—The partial Pb-Se phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis. For the sake of clarity the points for the 49.00 and 49.16 at. pct Se alloys were not drawn on this phase diagram, see Table I. for the lead-rich monotectic reaction found by Nozato and Igaki.&apos; This result was further substantiated by the fact that none of twelve lead-rich alloys, see Table I, examined for this monotectic reaction exhibited a thermal arrest in the temperature range (849" to 863°C) cited by Nozato and Igaki for the lead-rich monotectic reaction. Hence, our results tend to support the earlier qualitative work of ~elabon&apos; and Friedrich and ~eroux" in the 0 to 50 at. pct portion of the phase diagram, though the selenium-rich monotectic composition and reaction isotherm temperature were in agreement with the approximate values (75 at. pct Se and 672" to 680°C) given by Nozato and ~~aki. &apos;

Jan 1, 1967

By H. Brandhorst, C. G. Dunn

THE main purpose of the present note is to provide further information on the effect of orientation on strain-induced grain boundary migration in sheet material. A secondary purpose is to draw attention to the presence of a possible (hkl) dependent surface energy driving force, when the two grains of a bicrystal specimen have different (hk2) planes at the gas-metal interface, and to suggest means of eliminating this effect from the strain effect. If two grains A and B of a bicrystal have specific surface energies ? A and ? B respectively, there exists a driving force for grain boundary migration equal to 2(? B - ? A)/t, where t is the thickness of the specimen.&apos; When t is quite small and the residual strain energy densities €A and €B of grains A and B, respectively, adjacent to the boundary are nearly equal, it is possible that the surface effect may be larger than the strain effect. he difference € B - € A gives a driving force per unit area of grain boundary due to an applied strain.)2 However, with increasing t the surface effect decreases while the strain effect presumably remains constant. Therefore, at some sufficiently large value of t, it is possible to ignore surface energy driving forces.* On the other hand, the surface effect is eliminated for all value of t when both grains have the same (hkl) orientation or have identical values of surface energy. Although the previous study provided information on the effect of orientation on strain-induced erain boundary migration,&apos; no orientations with the (100) plane in the plane of the sheet were included. The present paper provides information of this kind. A seed crystal reorientation technique4 was used to prepare a large bicrystal of silicon iron (3 1/4 pct Si) consisting of two (100) grains in the (100) [001] and (100) [Oil] orientations. After a cold rolling strain (7 pct reduction to 3/4 mm final thickness), small specimens were prepared as before2 and then annealed in hydrogen. The boundary migration was such that the grain in the (100) [011] orientation always grew. After overnight anneals at 1100° or 1000°C, none of the initial (100) [001] grain remained. An anneal of 30 min at 950°c, however, provided information on the start of boundary migration. Fig. 1 shows both the initial position (lower line) and the final position (upper curved line) of part of the boundary, as revealed by thermal grooves. In a different area, part of the final boundary was not revealed by thermal grooves; the rate of boundary migration presumably was too high for the growth front to be defined by the time dependent thermal grooving process. In another area there was a vacated intermediate position connected to the initial position of the grain boundary. This indicates that only part of the boundary

Jan 1, 1962

By George Comstock

IT seems a common opinion among metallographists that all light-gray inclusions seen with the microscope in polished sections of steel are manganese sulphide. Examples of this belief are continually appearing, as for instance in the paper by Dr. Henry Fay on manganese sulphide as a source of danger in steel rails,1 and in Lieutenant-Commander Cook&apos;s paper on Metallography of Steel for U S. Naval Ordnance.2 Slate FIG. 1-TRANSVERSE VIEW OF THE EDGE OF A SMALL HOT-ROLLED STEEL ROD. ETCHED WITH PICRIC ACID. X 200. colored inclusions are considered to be silicates, and dove-gray inclusions, manganese sulphide. To show the danger in the latter unqualified assumption, it should be sufficient to examine the edge of any piece of steel that is covered with a fairly thick scale, and that has been polished in such a way as to prevent the scale from breaking away entirely below the polished surface. This can be done by protecting the scaled edge of

Jan 12, 1916

By Walter R. Hibbard

THE increased strength of a polycrystal-line metallic aggregate compared with that of its individual crystals generally has been associated with complex stress distributions at the grain boundaries resulting from atomic irregularity between grains. This disregistry, together with the necessity for adjacent crystals to deform &apos;compatibly regardless of the single crystal crystallographic strain mechanism, complicates this mechanism so as to increase the metal&apos;s resistance to deformation. Although Taylor1 has shown from purely mechanical considerations the requirement for at least five active slip systems to absorb the complexities during the homogeneous deformation of polycrystalline face-centered cubic metals, experimental studies by Barrett and Levenson2 indicate that this is feasible only in a qualitative sense because of deviations from homogeneous deformation. Seitz and Read in their review3 state: "Unfortunately . . . present knowledge of the grain boundary influence is not sufficient to complement the work in single crystals and provide us with a good foundation for treating polycrystals." The purpose of this investigation was to attempt to clarify the gap between single crystals and crystalline aggregates by an analysis of the effects of deformational stresses. Some of the results were described by C. H. Mathewson in his 1943 Campbell Memorial Lecture.21 PREVIOUS INVESTIGATIONS Since the performance of single crystals deformed under pure stresses has been relatively thoroughly investigated, the most significant researches are concerned primarily with deviations from single crystal behavior of large grained specimens. Qualitative grain boundary effects involving the observed amount of slip were reported by Carpenter and Elam5 in 1921. Individual crystals in a two or three grained aluminum specimen deformed by tension acted in the normal manner described by Taylor and Elam4 except for marked modifications at the grain boundaries. There the power to withstand deformation was considerably increased, leaving a ridge on the specimen where decreased slip occurred, often noticeable 34 in: from the boundary. Adcock,6 Yamaguchi,7 Seumel,8 Hirst9 and others have also reported this phenomenon as a qualitative trend. Yet attempts by O&apos;Neill10 and Ljunggren11 to measure a difference in hardness at grain boundaries in undeformed specimens were unsuccessful. Miller12 measured quantitatively the reduction in slip near the boundary between the single crystal and polycrystalline areas of zinc specimens. These effects consisted of two parts: I. Next to the polycrystalline interface the distribution of stresses was so altered

Jan 1, 1948

By Robert Ammon

The purpose of this paper is to present a brief sketch of the development of this hindered-settling classifier, but primarily to show the actual results obtained in practice with the classifier working on the Butte copper ores at the Boston & Montana Concentrator at Great Falls and the Washoe Concentrator at Anaconda. The writer has endeavored to be as brief as possible, giving only the essential figures showing the efficiency of the classifier and leaving considerable interesting information to be derived by the reader from the statistics given. The paper deals with the practical work of the classifier under the following heads: 1. Desliming 4.0-mm. primary feed, overflow from 0.07 to 0.0 mm. 2. Desliming 1.25-mm. secondary feed, overflow from 0.07 to 0.0 mm. 3. Desliming Huntington Mill discharge, overflow from 0.07 to 0.0 mm. 4. Classifying 2.5-mm. deslimed secondary feed, overflow from 1.00 to 0.07 mm. 5. Classifying 2.5-mm. deslimed primary feed, overflow from 0.75 to 0.07 mm. 6. Classifying 4.0-mm. deslimed primary feed, overflow from 0.75 to 0.07 mm. 7. Classifying middling-tailing product from roughing tables, overflow coarse tailing. 8. Classifying 2.5mm. trommel undersize, not deslimed, overflow from 0.75 to 0.0 mm. 9. Remarks on the inner feed cone. In the following pages all overflows are given in quartz dimensions; i. e., by a 0.75-mm. overflow is meant an overflow whose maximum particle is a 0.75-mm. quartz grain. By the term "slime" is meant all material which will pass through a 200-mesh screen whose average opening is 0.07 mm. The development of the classifier was commenced in the fall of 1910,

Jan 1, 1914

By A. C. Heath, E. H. Dix

The importance of aluminum-silicon alloys in thc light alloy field is now generally recognized. Where silicon was once considered detrimental to the properties of aluminum, useful alloys now contain as much as 13 per cent. Furthermore, silicon is present as an impurity in aluminum of even the purest grades. Iron is another important impurity in aluminum and likc silicon is found in small quantities in the purest aluminum available today. The manner of occurrence of iron and silicon in commercially pure aluminum and many of its alloys exerts a very pronounced influence upon their properties. The effect of large quantities of iron in aluminum-silicon alloys is so detrimental that it has been found necessary to limit the allowable maximum percentage to as low a figure as is consistent with quantity production and satisfactory physical properties. The intimate relation existing between iron and silicon in aluminurn and alurninum alloys makes necessary a more complete knowledge of this ternary system. This paper is divided into two principal parts, dealing respectively with aluminum-silicon solubility equilibria and the constitution of aluminum-iron-silicon alloys. Part I.—Aluminum-silicon Alloys The early work on this system was largely confined to determining the general form of thc diagram and in this respect the results are in good agreement. Briefly, alulninunl and silicon form a simple eutectifcrous series without compounds. Until recently the solid solubility of silicon in aluminum had not been accurately determined. Ipraenkell (1908) stated that aluminum will retain 0.5 per cent. silicon in solid solu-t&apos;ion. Rosenhain, Archbutt and Hanson2 gave the maximum solubility as about 1.50 per cent. and added that "this solubility docs not appear

By Orville R. Lyons, A. C. Richardson

DURING the past few years there has been a growing demand by coal operators for detailed information about the performance characteristics of the various dryers now being manufactured, preferably in such a form that the information could be used to determine the type of dryer best suited to a particular drying problem. A few operators have been desirous of going even further, because they are of the opinion that present-day dryers are not properly designed and that fundamental studies of dryer design should be undertaken. This growing demand for a method of dryer evaluation and the indicated need for fundamental research resulted in the sponsorship by Bituminous Coal Research, Inc. of a project at Battelle Memorial Institute to investigate the thermal drying of coal. In investigating this problem, the most feasible method of attack appeared to be a survey of active operations to determine the present status of the thermal drying of coal. Data were obtained, usually by actual plant tests with the cooperation of the various preparation engineers and their staffs, for Q screen-type dryers, 8 rotary- type dryers, 3 continuous-pallet-type dryers, 2 flash-type dryers, I tray-type dryer, and I cascade-type dryer. The testing program provided: (I) data for 24 coal- drying operations, (2) information about dried, (3) information about the previous treatment that the coal had received, and (4) information about operating costs. The data obtained through the dryer survey and relationships determined from the data make it evident that all of the types of dryers included in the survey can be operated with the same degree of effectiveness if each type of dryer is used to dry the sizes of coal for which it is best suited. It should be noted that it is usually undesirable and often impossible to dry different sizes of coal in one type of dryer. By use of the data in the report, any prospective dryer user, having determined the surface moisture percentage and screen- size analysis of the coal to be dried, the tons of water to be removed per hour, and the final surface moisture percentage desired, should be able to determine with a fair degree of accuracy: (I) the difficulty of the drying problem, (2) the approximate cost of drying, (3) the required dryer inlet gas temperature and volume and exhaust gas temperature and volume, (4) the type of dryer to use, and (5) the size of dryer required. The method of testing the dryers and determining the difficulty of drying can be used by operators already having dryers to check the performance of their particular dryer and determine whether they are operating effectively. Considerably more information was obtained from the survey of thermal drying than was anticipated when the survey was first considered. However, a great deal of work still remains to be done in the field

Jan 1, 1948

By Francisco Cadena

THE construction of Norris Dam, built by the Tennessee Valley Authority on the Clinch River, a tributary of the Tennessee River, involved the production of coarse and fine aggregate for approximately 1,000,000 cu. yd. of concrete. A hammer-mill plant for the manufacture of sand from quarried rock was indicated as the most economical method of providing this material. The abrasive character of the feed as compared to the average hammer-mill feed made it necessary to control operations rather closely, and this resulted in the accumulation of many data bearing on production and maintenance. This paper will deal only with three specific sets of data, accompanied by such general information as may be necessary to explain the conditions under which they were obtained and followed by discussions on the relation of silica content to hammer wear, comparative costs of slugger and stirrup hammers, and comparative costs of tool-steel and manganese-steel grate bars. Coarse Aggregate Aggregate for the concrete poured at Norris Dam came from a dolomite quarry within 2000 ft. of the west abutment of the dam. Geologically this rock is known as a Knox dolomite. A typical chemical analysis is given in Table 1. TABLE 1 .-Typica.1 Chemica1 Analysis [PER CENT H20,1100F ............................................ 0.0&apos;2 Ignitionloss ............................................. 43.56 MgO .................................................. 19.19 CaO .................................................... 29.07 FezO .................................................... 0.39 A1203 .................................................... 1.94 FezO .................................................... 0.39 A1203 .................................................... 1.94 ..................................................... 5.75 SO2.. .................................................. Tr.] Rock was carried by 12-yd. dump trucks to a 42-in. gyratory crusher set at 6 1/2 in. The product of the primary crusher was taken by a belt conveyor to a double-deck vibrating screen followed by a 5 1/2-ft. cone

Jan 1, 1937

By P. W. Bakarian, C. H. Mathewson

THE greater part of the literature on the plastic behavior of magnesium dates back to that active period of research in crystal mechanics immediately following the widespread preparation of isolated metallic crystals large enough for the application of conventional methods of mechanical testing. These investigations, performed on single crystals, revealed an analogy between zinc and magnesium with respect to their fundamental mode of deformation, in the operation of glide and twinning, respectively, on crystallographically similar planes. Mathewson and Phillips (1928)1 by geometrical analysis identified the {102} ? plane in magnesium as the twinning plane, Schiebold and Siebel (1931)2 confirmed this twinning plane, established the basal plane as the plane of slip, and a digonal axis I as the slip direction. They also reported twin formation in a secondary role on the {101} plane. Schmid (1931)3 summarized and discussed the earlier evidence and presented the results of his own experiments on the effect of temperature and small amounts of soluble elements. From X-ray studies on extended wire single crystals, he concluded that slip along the basal plane in the direction of the digonal axis I closest to the stress direction was the sole slip system operating at atmospheric temperature. This conclusion was based on experiments with crystals of many different orientations relative to the stress axis. Special attention was directed to the basal plane and the digonal axis I, as the plane and direction of greatest atomic density. Determinations of resolved shear stress at the onset of plastic yielding-i.e., the critical resolved shear stress-were also made; the average of these calculations showing 82.9 grams per sq. mm. This value varied only slightly up to 300°C., at which temperature it was found to decrease to 70.5 grams per sq. mm. The extension of his crystals at temperatures above 225°C. further disclosed the presence of new slip systems. After the original specimens of circular section had been

Jan 1, 1943

By H. O. McLeod, J. M. Campbell

Data analysis of pentane and hexane adsorption from natural gas in a fixed bed of silica gel shows that constant length mass transfer zones form, the curvature of the adsorption isotherm controls the growth of the mass transfer zone and surface diffusion of molecules inside the silica gel particle controls the mass transfer rate. Curvature of the hexane isothem is more than the curvature of the pentane isotherm. Because of this curvature the hexane adsorption zones reached a constant length. In contrast, the pentane adsorption zones were always increasing in length during each run. A procedure was developed to obtain correct mass transfer coefficients using effluent curve slopes. These transfer roefficients increase with the amount of hydrocarbon adsorbed on the silica gel particle. The characteristic shape of the hexane effluent curves also show that molecular diffusion inside the silica gel particle controls the adsorption rate of pentane and hexane. INTRODUCTION The purpose of this study was to determine the mechanisms that control the dynamic adsorption of hydrocarbons from a natural gas onto silica gel. Before one can deal effectively with multicomponent adsorption, the transfer mechanisms by which a single hydrocarbon component is adsorbed from the gas stream must be defined. Two principal investigations of this system have been published &apos; and indicate that diffusion through the gas around the particle controls the adsorption rate. Some of the experimental observations in each study either do not support this transfer mechanism or are inconsistent with the mathematical model used in analysis. In this study surface diffusion of molecules inside the particle controls the mass transfer rate of pentane and hexane. This mechanism is indicated by the effluent curve shape for a constant length transfer zone and by the variation of the mass transfer coefficient with concentration of the adsorbed hydrocarbon. THEORY AND DEFINITIONS — MATHEMATICAL MODELS Mathematical solutions for the isothermal adsorption of a trace component from a carrier gas are derived from three relationships: the mass balance or continuity equation, the equilibrium relationship between the gas and solid phases, and a mass transfer rate equation. The transfer rate is proportional to the adsorbate concentration gradient within either the gas or solid phase. Mathematical solutions of these equations usually give the adsorbate concentration as a function of time and distance from the bed inlet. That part of the bed in which the adsorbate concentration changes from a maximum to a minimum value is called the transfer zone. This transfer zone is directly related to a plot of the effluent concentration vs time which has a characteristic S-shape. This general shape is determined by the continuity equation and occurs in many processes of diffusional transfer.

Jan 1, 1967

By K. F. Veit, R. L. Marovelli, T. S. Chen

There is an error at the bottom of the right-hand column of p. 11, and the top left-hand column of p. 12. The first paragraph of the section EXPERIMENTAL RESULTS should read: "Thermal shock tests were conducted on circular discs of basalt, quartzite, and taconite. Average grain sizes ranged between 0.10 and 0.25 mm. Individual discs were tested only once, either in a cooling or heating shock. Several discs of the same rock type were shocked at a temperature, and the temperature level then was increased for another test by 10° to 20°F until complete fracture occurred when a specimen was quenched. The minimum temperature difference required to initiate cracking, TmiN was observed and used, together with other property values, to compute the dimensionless stress o*max . The observed ?Tmin for cooling shock in different media is tabulated in Table I. The property values E, St, a, and K are shown in Figs. 6, 8, 10, and 11, respectively. Discs of various rocks shocked in different isothermal baths gave o*max values for a wide range of Biot numbers. These o*max values were then compared with the theoretically predicted values."

Jan 1, 1968

By A. Ghosh, T. B. King

The kinetics of the discharge reaction: 20&apos;- (in silicate melt) = O,(g) + 4e- at a platinum anode in lithium silicate melts have been studied al 1350°C by galvanostatic methods. Plots of the sleady-state overpotential, q, as a function of the logarithm of the current density, i, showed injlections and were linear only at high current densities. The value of the overpotential was influenced by bubbling gas through the electrolyte. The ocer potential was also studied as a function of time. The rise and decay of overpotential were very slow processes. At low current densities transport is the likely rate-controlling process but at high current densities passivation of the electrode, Presumably by an oxide film on the surface, seems to be a contributory functor. IT is well-established that molten silicates behave as electrolytes&apos;5 and, except in a few cases,6 conduction is entirely ionic. Moreover, it is supposed that a possible, and perhaps predominant, mechanism for phase boundary reactions between metals and slags is similar to that in corrosion whereby anodic and cathodic processes occur at unrelated sites, the metal serving to conduct electrons.1&apos;8 Thus electrochemical studies of some slag-metal reactions would seem to be a useful way to diagnose the rate-controlling steps in the overall reaction. The electrochemical method is, in principle, a better diagnostic tool than the direct chemical method for the following reasons: 1) The partial electrochemical reactions, which are simpler than the overall reaction, may be studied individually. 2) The rate of reaction can be controlled at will and independently of the concentrations of reactants. 3) Fast reactions can be studied by relaxation methods.&apos; Esin and his coworkers5&apos;10"12 have pioneered such studies in silicates and have deviloped some ingenious techniques. Not all of their findings, however. can be accepted without a good deal of further work. In this investigation, the kinetics of the oxygen discharge reaction: 202- (in silicate melt) = Oz(g) + 4e- [I] at a platinum electrode were studied by both steady-state and transient galvanostatic techniques. Interest in this reaction was first developed as a result of the findings of Fulton and chipman13 that the reduction of silica, in a silicate slag, by carbon, dissolved in liquid iron, is a very slow reaction. Subsequent work, for example, by Rawling and ~lliott,&apos;~ has demonstrated that the reaction under these conditions must be slow, because the rate is limited by diffusion of oxygen in the iron to the metal-crucible phase boundary at which a CO bubble may be nucleated. Further work by Tarassof,&apos;~ in which the reduction of silica by aluminum dissolved in copper was studied, has shown that under these conditions, where carbon monoxide evolution is not involved, control of the reaction rate resides in diffusion of silica in the slag phase. However, there is no practical way of inducing sufficient convection in the system to make it clear that the phase boundary reaction is indeed fast. The overall reaction of silica reduction involves the discharge of silicon ions at cathodic sites and oxygen ions at anodic sites. In the examples cited, the discharged ions are dissolved in a liquid metal. In the present study of oxygen ion discharge, gaseous oxygen may be evolved at high current densities or oxygen may simply dissolve, possibly as oxygen molecules, in the silicate at very low current densities. The discharge of an oxygen ion at an anode must, in silicates less basic than the orthosilicate composition, be preceded by a reaction in the vicinity of the electrode, such as: which makes oxygen ions available. Platinum was chosen as the working electrode since it is comparatively inert to oxygen and is, therefore, expected to come rapidly into equilibrium with the electrolyte and with gaseous oxygen. Minenko, Petrov, and Ivanova16 have measured the electromotive force at a platinum electrode in molten silicates as a function of the partial pressure of oxygen in the atmosphere, the concentration of oxide ions in the melt, and the temperature. They found platinum to behave as a reversible oxygen electrode. At two different oxygen pressures, Po2 (I) and Pq (11). the electromotive force is given by: where F is the Faraday constant, equal to 23,060 cal per v equivalent, indicating that the electrode reaction is as written in Eq. [I.]. Platinum has been similarly used in molten silicates by other inve~ti~ators. "&apos;~~ In this investigation platinum was used only as an anode, since a current deposits other elements on its surface and changes its characteristics.

Jan 1, 1970

By W. W. Krech, T. E. Perkins

As fractures are propagated through rocks, energy is absorbed near the extending crack tip. Apparent surface energies for several rocks have been measured by cleavage under dynamic con-ditions. At nominal crack velocities from 0.5 to 500 in (min, measurements showed that fractures propagated in discrete jumps. Calculated surface energies and moduli were relatively insensitive to nominal rate of cleavage. in another set of experiments, rocks were cleaved under high confining stresses. The rocks were submerged in low leak-off fluids which formed a filter cake on the freshly cleaved surfaces (similar to the hydraulic lracturing process). Apparent surface energies were increased substantially as the surrounding fluid pressure was increased. Moduli in bending increased significantly upon application of the first 1,000 psi but were insensitive to stress level at greater pressures. INTRODUCTION For almost 20 years, hydraulic fracturing processes have been utilized effectively to stimulate oil and gas wells. During this period, some process improvements have resulted from studies of fracture orientation, mechanics of fracturing, areas generated, conductivities of cracks, etc. Yet many questions remain concerning the conditions and pressures needed during fracture propagation. In this paper we will report additional studies of the mechanics of fracture extension. It was shown previously3 that large rock samples could be cleaved under controlled conditions so as to measure the apparent surface energy (that amount of energy absorbed per unit area of new surface created). In this paper we consider the effects of two additional factors on surface energies, viz.: (1) effect of cleavage rate and (2) effect of confining stress level. THEORY Cleavage experiments were conducted on rock samples similar to that illustrated in Fig. 1. Blocks of rock several inches wide, 2- to 3-in. thick, and up to 3 ft in length were grooved longitudinally with shallow guide slots. A crack was initiated and allowed to extend along the web as the top of the rock specimen was pulled (or pushed) apart. Auxiliary equipment permits the measurement of (1) force applied at the top, (2) separation at the top and (3) crack length. (Further experimental details will be given in the next section.) The rock beams created by the crack are considered ton be cantilever beams. The deflection (or separation of the rock beams) at any point is calculated 4,5 by the beam Eq. 1.

Jan 1, 1967

By C. E. Tsoutrelis

A new method for determining rock drillability in diamond drilling is discussed; the method takes into consideration both penetration rate and bit wear. The method is based on drilling a rock specimen under controlled laboratory conditions using a model bit. The technique used for determining the experimental variables is extremely simple, quick, and reliable. Drillability is then determined by the mathematics of drilling. In considering the different factors that affect diamond drilling performance, the nature of the rock to be drilled is of outmost importance since it affects significantly the drilling costs and such other variables as bit type and design, drilling thrust, and bit rotary speed. Many attempts have been made to study this effect by correlating actual drilling performances either to certain physical properties of the rock being drilled1-? or to test drilling data obtained under laboratory conditions.7-13 These attempts were aimed at providing a reliable method of predicting by simple means the expected rock behavior in actual drilling, thus giving the engineer a tool to use in estimating drilling performances and costs in different types of rock. The purpose of this paper is to describe such a method by which rock drillability (a term used in the technical literature to describe rock behavior in drilling) could be determined in diamond drilling. It is believed that the proposed simple and reliable method will cover the need of the mining industry for a workable method of measuring the drillability of rocks. It should be emphasized, however, that since drill-ability depends on the physical properties of rock and each drilling process (diamond, percussive, rotary) is affected by different or partly different rock properties,14-l6 the proposed method of determining rock drillability cannot be extended to the other drilling processes. The results presented in this paper form part of an extensive three-year research program carried out by the author in the laboratories of the Greek Institute of Geology and Subsurface Research. During this period the effects of the physical properties of rocks and of such operational variables as drilling thrust and bit rotary speed in diamond drilling were investigated in detail. DRILLABILITY CONCEPT The literature is not devoid of drillability studies. While there are a number of investigators1,3,5-7,9-0,12-13,17 who have attempted to establish by direct methods (i.e., drilling tests under laboratory conditions) or indirect (i.e., through a physical property of rock) an index from which the drilling performance in a given rock may be estimated, very few6-7,9,12, of the proposed methods seem to be of much practical value to the diamond drilling engineer and none to date has been universally accepted. Commenting on the proposed methods for assessing rock drillability, Fish14 remarks that "for a measure of drillability to be accepted it is essential that penetration rate at a given thrust and bit life are elucidated as otherwise the method is of little value." This statement should be examined in more detail by making use of the penetration rate-drilling time diagram obtained in drilling a rock under constant operational conditions. Furthermore, the merits of using this diagram to describe rock drillability will be pointed out. At the same time reference will be made to this diagram when discussing some previously proposed methods. Fig. 1 illustrates such a diagram for three rocks,A, B, and C, which have been diamond drilled under identical conditions. It is assumed here that rocks A and B have the same initial penetration rate, i.e., VOA = Vog, but since rock B is more abrasive than A, rapid bit wear occurs and as a result the fall of its penetration rate with respect to time is more vigorous than in rock A. This is shown graphically by a steeper V = f(t) (0 curve in this rock than in rock A. Rock C has a lower initial penetration rate, due to higher strength properties16 but since it is not very abrasive, only a slight fall of its penetration rate occurs during drilling (in this category are some limestone and marbles with compressive strength above 1000 kg per sq cm). It follows from the foregoing considerations that the characteristic for each rock curve (I) is a function of (i), the penetration rate of the rock Vo recorded at the instant of commencing drilling, which determines the starting point of the curve (1) on the y-axis and (ii), the abrasive rock properties which determine the rate of fall of Vo with respect to time. Thus, curve (I) provides an actual picture of the rock behavior in drilling for given operational conditions, and it can be used with complete satisfaction to assess rock drillability. It can be seen clearly from Fig. I that proposed methods for assessing rock drillability by measuring the

Jan 1, 1970

By R. J. Fruehan, F. D. Richardson

Electrochemical measurements have been made of the activity of oxygen in copper and its alloys with silver and tin at 1100" and 1200°C. The galvanic cell used was Pt, Ni + NiO/solid ellectrolyte/[O] in metal, cermet, Pt The results do not support any of the equations so far designed for predicting the activities of dilute solutes in ternary solutions from activities in the corresponding binaries. If, however, a quasichemical equation is used with the coordination number set to unity, agreement between observed and calculated activities shows that this empirical relationship can be useful over a fair range of conditions. SEVERAL solution models have been proposed for predicting the activity coefficients of dilute solutes in ternary alloys from a knowledge of the three binary systems involved. Alcock and Richardson1 have shown that a regular model, and a quasichemical model,&apos; in which the dissolved oxygen is coordinated with eight or so metal atoms, can reasonably predict the behavior of both metal and nonmetal solutes when the heats of solution of the solute in the separate solvent metals are similar. But when this is not so, neither model gives useful predictions unless coordination numbers of one or two are assumed. Wada and Saito3 subsequently adopted a similar model to derive the interaction energies for two dilute solutes in a solvent metal. Belton and Tankins4 Rave proposed both regular and quasichemical type models in which the oxygen is bound into molecular species, such as NiO and CuO in mixtures of Cu + Ni + 0. However, their models have only been tested on systems in which the excess free energies of solution of the solute in the two separate metals differ by a few kilocalories. Ope of the reasons why more advanced models have not been proposed is because few complete sets of data exist for ternary systems in which the solute behaves very differently in the two separate metals. For this reason measurements have been made of the activities of oxygen dissolved in Cu + Ag and Cu + Sn. Measurements on both systems were made by means of the electrochemical cell, Pt, Ni + NiO/solid electrolyte/O(in alloy), cermet,Pt [1] The activity of oxygen was calculated from the electromotive force and the standard free energy of formation of NiO, which is accurately known.5 Before investigating the alloys, studies were made of oxygen in copper to test the reliability of the cell and to check the thermodynamics of the system. Of the previous studies those by Sano and Sakao,6 Tom-linson and Young,7 and Tankins et al.8,7 have been made with gas-metal equilibrium techniques; those by Diaz and Richardson,9 Osterwald,10 wilder," Plusch-kell and Engell,12 Rickert and wagner,13 and Fischer and Ackermann14 have been made by electrochemical methods. EXPERIMENTAL The apparatus employed was the same as described previously,9 apart from slight modification. The molten sample of approximately 40 g was held in a high grade alumina crucible 1.2 in. OD and 1.6 in. long. The solid electrolytes were ZrO2 + 7½ wt pct CaO and ZrO2 + 15 wt pct CaO; the tubes 4 in. OD and 6 in. long were supplied by the Zirconia Corp. of America. They were closed (flat) at one end. In one experiment with Cu + O, both electrolytes were used in the cell at the same time. The reference electrodes inside the electrolyte tubes consisted of a mixture of Ni + NiO. They were made by mixing the powdered materials and pressing them manually into the ends of the tubes, with a platinum lead embedded in them. The tubes were then sintered overnight in the electromotive force apparatus at 1100°C. By sintering the powders inside the tubes (instead of using a presintered pellet9) better contacts were obtained between the electrolyte, the powder, and the platinum lead. Troubles arising from polarization9 were thus much reduced. The electromotive force was measured by a Vibron Electrometer with an input impedence of 1017 ohm; the temperature was measured with a Pt:13 pct Rh + Pt thermocouple protected by an alumina sheath. The couple was calibrated against the melting point of copper. The cermet conducting lead of Cr + 28 pct Al2O3, previously found to be satisfactory9 for use with Cu + 0 was also found satisfactory with Cu + Ag + 0 and Cu + Sn + 0. Superficial oxidation was observed, but it did not interfere with the working of the cell. The reaction tube containing the cell was closed at each end with cooled brass heads and suspended in a platinum resistance furnace. The tube was electrically shielded by a Kanthal A-1 ribbon which was wound round it, and the ribbon was protected by a N2 atmosphere between the furnace and the reaction tube. The cell was protected by a stream of high purity argon which was dried and passed through copper gauze at 450°C and titanium chips at 900°C. All the metals used were of spectrographic standard. Procedure. In studies of the system Cu + 0, be-

Jan 1, 1970

By AIME AIME

ON May 5, the Washington, D. C., Section, A.I.M.E., devoted its meeting to the many-sided and perplexing question of mineral stock-piling for peace. Opening the symposium, Harry J. Wolf, of the War Production Board, outlined the problem under six heads: (1) Technical. Mechanical, chemical, or metallurgical importance of specified materials, emergencies that might arise, relative scarcity, and critical value of stock piles during emergencies. (2) Economic. Cost to Government, influence of Government stocks on commercial relationships and markets, effect of availability of items as a con¬structive influence on industry, Administration policies now and during postwar period. (3) Legislative. Need for immediate legislative action, need for legislation on postwar conditions as well as on current requirements, a constructive basic policy to prevent political manipulation. (4) Military. Consideration of re¬quirements and supplies bearing on national safety and needed for manufacture of equipment, and adequate reserves of scarce materials for research or experimentation by military agencies. (5) International. Interests of the United Nations in contradistinction to those of the United States; effects of nonisolation policy on nature, location, and administration of stock piles. (6) Negative stock-piling. Question of United Nations&apos; legislation to prevent stock-piling by Axis nations after the war and who shall purchase stock-pile materials and during what periods.

Jan 1, 1943

By Howard Martens, Pol Duwez

IN two papers published in 1949, alloys of chromium with the refractory metals tungsten, molybdenum, tantalum, and columbium were investigated in view of their possible use as high temperature resisting materials. For the Cr-Ta system, a partial phase diagram was presented and the only intermediate phase was identified at Ta2Cr3. A phase of the same composition was also observed in the Cb-Cr system. The X-ray diffraction data presented in these papers, however, were insufficient for crystal structure determination. It is shown in the present study that the only intermediate phase in both the Ta-Cr and the Cb-Cr systems corresponds to the ideal stoichiometric ratio TaCr2, or CbCr2. Both structures are cubic, MgCu, type. At high temperature, however, TaCr2 has a hexagonal MgZn, type structure, which can be retained at room temperature by fast cooling. The alloys were prepared by melting in a helium arc furnace on a water-cooled plate. The design of the furnace was essentially the same as that described in ref. 3. Some alloys were also obtained by sintering compacts made of the mixed powders pressed at 80,000 psi. The sintering was carried on for 4 hr at 1375°C. The tantalum and columbium powders were supplied by Fansteel Metallurgical Corp., North Chicago, 111. The tantalum powder was the reagent grade, with a particle size smaller than 400 mesh and a total impurity content less than 0.1 pct. The columbium powder was smaller than 325 mesh and contained approximately 0.1 pct C and traces of Fe, Ti, and Zr. The electrolytic chromium powder from Charles Hardy, Inc., New York, was smaller than 300 mesh and contained about 0.1 pct Na, 0.05 pct Ca, and traces of Cu, Al, Mg, Si, and Co. Powder diffraction patterns were obtained with a 14.32 cm camera, using copper Ka radiation filtered through nickel foil. The powder pattern of the TaCr2 alloy obtained by sintering at 1375&apos;C was different from that obtained on the same alloy rapidly cooled from the melt. Contrary to this result, the powder pattern of CbCr2 was the same, whether the alloy was made by sintering at 1375°C or by melting, and was similar to that of the TaCr, sintered. It was also found that the structure of the TaCr2 specimen obtained by melting was retained after heating for 4 hr at 1590°C, but transformed into the structure found in the sintered specimen after heating for 4 hr at 1375°C. Hence, the structural change of TaCr2, appears to be a reversible polymorphic transformation. CbCr2 and ToCr2 Structure, Low Temperature Form By using large scale Hull-Davey charts, the powder pattern of CbCr, and of the low temperature form of TaCr2 were readily interpreted on the basis of a face-centered cubic lattice with a parameter of approximately 6.95 kX. The indices of the reflections together with the values of sin&apos; 0 are given in Tables I and 11. From this list of observed reflections, it appears that the (200), (600), (024), (046), and (028) reflections are missing. The lack of (h00) reflections for h 4n indicates a four-fold screw axis. The missing (Okl) spectra for k + 1 An indicate the existence of a diamond glide d. The combination of these symmetry elements can be found in the O— Fd3m space group, which is therefore the most probable one. After having determined the approximate density of TaCr, by the immersion method, the number of molecules per unit cell was calculated and found to be nearly eight. This information, added to the fact that the most probable space group is O leads to the consideration of a structure of the MgCu2 type, in which the atoms have the following positions: 8 magnesium in a and 16 copper in d. On the basis of this structure, intensities were computed by means of the usual formula: 1 cos&apos;20 I a sin2 cos where F is the structure factor; 8, the Bragg angle: and p, the multiplicity factor. As shown in Tables I

Jan 1, 1953