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By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By O. George Specht, Carl A. Zapffe

In recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge Iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experi- mentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. Group I: Reduction with Hydrogen Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1947

By O. George Specht, Carl A. Zapffe

IN recent print, some remarkably contradictory statements have appeared regarding the importance to be attached to sponge iron,1-6 a metallurgical commodity whose history goes back at least to the time of Diodorus Siculus in the fourth century B.C. This disagreement, however, expresses the lack of a satisfactory method for producing sponge iron rather than defection in the commodity. The blast furnace is admitted to have certain inherent disadvantages, such as a general unsuitability for magnetite and the heating and blowing of vast quantities of undesirable nitrogen, so that a workable sponge-iron process remains attractive. In this respect, low-temperature gaseous reduction shows especial promise; but confusion persists regarding the factors involved. The present paper, therefore, has three principal divisions: (I) an exhaustive examination of all previous work on low-temperature gaseous reduction, (2) experimentation on the reduction of a magnetite with hydrogen, and (3) development of certain thermodynamic relationships in reduction, with a summarized depiction of the factors in the general process. PREVIOUS INVESTIGATIONS Gaseous media used in the reduction processes under discussion can be classified in three types: (I) H2, (2) CO, and (3) other gases. In the second, the CO is often admixed with H2. The third principally comprises hydrogeniferous gases, such as natural gas and producer gas, and in addition includes chlorine. Because hydrogen therefore features in all three, a study of hydrogen reduction based on investigations using pure hydrogen alone may be incomplete. The present paper reviews the three groups of investigations in the listed order, paying particular attention to hydrogen reduction. For the benefit of future workers, an exhaustive bibliography has been prepared and similarly classified. GROUP I: REDUCTION WITH HYDROGEN Equilibria Although the present problem is specifically one of kinetics, a first consideration is the equilibrium of the system, since the reactions to be studied comprise that equilibrium, and their direction and end points are defined by it. The historic development of these researches is interesting and informative.

Jan 1, 1946

By J. A. Burkhardt

Field measurements and theoretical studies have been made of pressure surges—momentary variations in fluid pressure—produced by movement of pipe in mud-filled boreholes. Pressure measurements were recorded by five pressure gauges located at various positions in the borehole. An important positive pressure peak was found to occur as the casing moved with maximum velocity. Important negative peaks were found as the casing was lifted from the slips and as brakes were applied to stop pipe movement. A rigorously formulated theory has successfully predicted the sequence and magnitudes of these positive and negative surges and has established a basis for understanding how they occur. Both the measurements and theory indicate that the most important pressure surge is usually due to viscous drag of the flowing mud. The theory of viscous-drag pressure surges has been approximated by simplified graphs and calculation procedures to facilitate ready use in field operations. Comparison of measured results with those predicted by the simplified theory shows that the magnitude of this surge can be predicted accurately. INTRODUCTION It is widely recognized that raising or lowering pipe in a fluid-filled borehole produces momentary variations in fluid pressure, commonly called pressure surges. Both negative (or "swabbing") surges and positive (or "fracturing") surges may occur. In 1934, Cannon1 measured the negative surges and showed that they could be large enough to cause flow of formation fluids into the well-bore and, in extreme cases, lead to blowout conditions. Later, Coins2 measured the positive surges associated with lowering pipe. His results and subsequent field operations strikingly demonstrated that pressure surges could be an important factor in some cases of lost returns. In addition, although the evidence is less clear than in the case of blowouts and lost returns, other investigators 3, 4 feel that pressure surges probably play a part in many instances of minor gas cutting, salt-water flow and other hole trouble. The importance of pressure surges in drilling operations led naturally to attempts to explain the physical causes, nature and magnitude of the surges. Cardwell5 was the first to publish a theory which allowed the quantitative prediction of momentary pressure variations. He assumed that the drilling fluid was a 300-cp Newtonian fluid in turbulent flow. Most field muds have a considerably lower viscosity and are generally believed to be Bingham plastic in nature.6 However, card-well's results were useful because they were presented in a form convenient for field use and, in some cases, gave a reasonably accurate predicted value for the maximum pressure surge. Subsequently, Ormsby7 published a more comprehensive theory of pressure surges. He discussed both laminar and turbulent flow and considered the theory of mud-bypass devices for reducing pressure surges. As a consequence of his more rigorous approach, his results were more accurate but more complex and difficult to use. Further, both Ormsby and Cardwell considered only the pressure surge arising from viscous drag of the moving mud. Clark later published idealized graphs of surges and presented equations for predicting their magnitudes. In addition to pressure variations arising from viscous drag, he considered those caused by inertial effects. His theory was in this respect more complete than those of Cardwell and Ormsby, although he did not discuss pressures due to breaking of the gel. Furthermore, his equations, while not exceptionally complicated, were too complex for ready use at a drilling location. One difficulty common to all three theories is that none was tested rigorously by direct comparison with measured pressure surges. Their accuracy, therefore, could, not be demonstrated. Further, the two theories based on most realistic assumptions (Ormsby and Clark) required the solution of one or more rather complex algebraic equations. The research described in this paper was undertaken to supplement that described and to overcome some of the difficulties noted. It seemed obvious that a fully satisfactory study of pressure surges should encompass three main phases. 1. A valid theory useful in all field situations must be developed. This theory must be based upon realistic assumptions, must be formulated rigorously and should lead to clear concepts whereby the nature of pressure surges can be easily understood. 2. The theory, however complex and involved, ultimately must be presented in simplified form for convenient field use. This may involve extensive machine computations and the use of figures and empirical equations. 3. The accuracy of the simplified equations must be established by comparing measured pressure surges with those predicted by the theory. These must agree both in their characteristic nature and in magnitude. 'This means that careful measurements of surges occurring in actual field operations must be made.

By John T. Thorndyke

MOST important of the naturalcalcium silicates is the meta¬silicate, CaSi03, known as wollastonite, after W. H. Wollaston. A large deposit of this mineral was dis¬covered some seven years ago near Code Siding, Rademacher mining dis¬trict, Kern County, Calif., the deposit being some 7500 ft. long and of an average width of 300 ft. It consists of a series of small domes striking north¬erly and southerly and with a dip of 81 ° to the south. This deposit was opened up by a series of small quarries showing a potential tonnage of 12,000,¬000 tons, allowing of cheap mining and transportation, the Southern Pa¬cific R.R. spur track being one mile north of the workings. Numerous sam¬ples taken from different points on the deposit, tested by Mr. Brinker, of the California Testing Laboratories, Los Angeles, showed an average as fol¬lows: Per Cent Silica (SiO2) 47.12 Lime (CaO) 41.72 Magnesia (MgO) 2.72 Alkalies (R,0) Trace Iron (Fe.,O,) 1.60 whereas the theoretical composition of of wollastonite, as given by William Shirley Bayley, is as follows: Silica 51.75 Lime 45.25 The tonnage and purity of this de¬posit led to investigations into its com¬mercial development. Early work es¬tablished the fact that wollastonite was ideal for the manufacture of a tough, almost unbreakable, glass similar to Pyrex. It also established the fact that wollastonite was particularly adapted for use in the manufacture of mineral wool, towards which further research was then directed. Briefly, the prin¬cipal advantages were the substantially unvarying chemical composition of the naturally occurring mineral and its characteristic of being relatively flexi¬ble and highly resilient when fused into a glass. A mineral wool produced therefrom is thus not only of highly uniform composition and color but is most desirable because of the high mechanical strength and length of the individual fibers constituting the wool. It is well known that mineral wool may be prepared by melting a suitable charge of raw material and then intro¬ducing a stream of a suitable fluid, such as air or steam, into a stream of the molten raw material. By this means the molten material is blown into threads or fibers, which are collected in a suitable chamber similar to a tun¬nel, from which they are removed from time to time or continuously. Com¬mercial manufacture of mineral wool has been carried on for only about 50 years, but volcanoes, specifically Kilauea in the Hawaiian Islands, have

Jan 1, 1936

By Thomas Watson

INTRODUCTION THE users of barite in the United States derive their supply partly from the domestic production and partly from the imports from foreign countries. According to the Mineral Resource division of the U. S. Geological Survey, the domestic production of barite in 1913 was 45,298 short tons, valued at $156,275, or $3.45 a ton, and the imports of crude barite were 35,840 short tons, valued at $61,409, or $1.71 a ton. These figures clearly show a decided advantage in cost of the foreign over the domestic barite to users in the United States. The difference in cost is the only advantage to the consumer of foreign barite, for there are large reserves of the mineral in the United States of good grade. The production of many of the operating mines is capable of decided increase, and it is believed that the operating mines together with the large reserves of undeveloped deposits of barite are entirely adequate to meet the demands of the users in the United States. Deposits of barite are known in California, Idaho, Nevada, and Alaska, but most of them are undeveloped because there is, apparently, no market for the .material in that region. The domestic production is derived from Missouri and the Appalachian States, the greater part being obtained from Missouri. Following the outbreak of war in Europe many users of foreign barite in the United States have been forced to seek their supplies at home. It seems opportune at this time, therefore, that a general review be given of the barite industry in the Appalachian States, one of the two areas from which the domestic supply of the mineral is derived, and that attention be directed to the undeveloped deposits in the region. Briefly, then, this paper reviews the barite industry in the Appalachian States, and describes the occurrence, preparation, and uses of the mineral.

Jan 2, 1915

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By R. W. Heins, N. Street

Recently Hiller1 reported results on the impairment of the strength of quartz glass rods through wetting, indicating that there was general agreement with the prediction of the Griffith formula in that for the liquids used the rods were weakest in water i.e. the liquid which probably had the greatest free energy of immersion. The Griffith equation predicts that the tensile stress necessary to propagate a crack of length c is where ? is the interfacial free energy, E Young's modulus. Since for a solid immersed in a liquid of surface tension ?L and contact angle 8 at the solid-liquid-gas contact, ?s - ?SL = ?L cos ? where ?s is the surface free energy of the solid. Hence comparison between ?L cos 0 and strength impairment should be possible. In a study of the usefulness of the Kuznetsov pendulum2 as a means of studying rock drillability we have determined the effects of various liquids on the pendulum hardness of Bavarian limestone. The pendulum used had diamond points (Burgess Vibro-graver), a period of 1.14 sec and a total on sample weight of 1191 g. The decline of the pendulum oscillations was recorded by a light beam on light sensitive paper carried on a kymograph. Rehbinder's expression relating hardness to amplitude attenuation as a function of time can be written In A = - (1/H) t + In Ao where A, A, = amplitude at time t and initial amplitude respectively, H = hardness parameter, and t = time. The line of best fit to the experimental points was determined using the IBM 7090 electronic computer, the computer also gave A, by extrapolation to zero time. The results for the various liquids tested are given in Table I and Fig. 1. The limestone surfaces were highly polished before testing and each reported hardness value represents the average of at least ten separate determinations of the pendulum decline curve. On each newly prepared surface the water value was again determined (also

Jan 1, 1964

By Julian M. Avery

In its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary purpose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by combustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all ecorlomy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the efficiency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss call be successfully attacked by increasing the over-all pressure; i.e., the "top prcssure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity. In a broad sense, the suggestion of pressure operation of the pig-iron blast furnace is not new, for operation under moderately increased over-all pressure was suggested as early as 1871, by no less an authority than

Jan 1, 1938

By Julian M. Avery

In its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary purpose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by combustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all ecorlomy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the efficiency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss call be successfully attacked by increasing the over-all pressure; i.e., the "top prcssure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity. In a broad sense, the suggestion of pressure operation of the pig-iron blast furnace is not new, for operation under moderately increased over-all pressure was suggested as early as 1871, by no less an authority than

Jan 1, 1938

By John W. Cahn, David A. Karlyn, Morris Cohen

The massive B(bcc) — am (fcc) transformation in Cu-Zn alloys has been studied isothermally by pulse-heating the retained ß phase from room temperature to the reaction temperatures. The transformation is found to occur only in the single-phase a region of the equilibrium diagram. The massive growth rate is of the order of 1 cm per sec and is constant at each temperature, usually after a delay time of some milliseconds. The delay time depends on the reaction temperature in C-curve fashion, while the growth rate increases monotonically with temperature over the single-phase range. The absence of isothermal massive transformation in the two-phase region does not arise from slow growth rates at such temperatures, but because the reaction cannot get started there. It is proposed that the massive transjormation initiates at small preexisting a particles which have rejected zinc into the surrounding 0 matrix. Only within the single-phase region can these particles consume the excess zinc during diffusion-controlled growth and thereby accelerate to the steady-state massive growth rate. The onset of massive growth marks the end of the delay time, and the growth rate then becomes interface-controlled. These isothermal transformation characteristics explain why the usual composition range for massive-kinetic studies by quenching is so limited. The same principles can be extended to more complex alloy systems by recognizing that the single-phase region in which the massive transformation can occur may not be stable with respect to phases not participating in the reaction. MASSWE transformations are now recognized as a regular class of solid-state reactions involving no compositional change (like martensitic transformations) and no shear displacements (unlike martensitic transformations). The name was first coined by Greninger1 in 1939 to describe the coarse grains of fcc a solid solution generated via a fast reaction from the parent bcc 0 solid solution in Cu-A1 alloys. However, some 9 years earlier, phillips2 had already described a similar transformation in the Cu-Zn system. The fact that the massive a formed as a single phase during drastic quenching from the 0 region of the equilibrium diagram signified that compositional changes were precluded. and the reaction was presumed to take place as in a one-component polymorphic transition by nucleation and growth. Phillips also observed that the occurrence of the massive transformation in the Cu-Zn system was extremely sensitive to alloy composition. For example. in a Cu-37.3 at. pct Zn alloy. the ß — am (am = massive transformation product) reaction was found to predominate and was not suppressed by iced-brine quenching from the 0 region. whereas at compositions greater than 38.3 at. pct Zn the massive reaction did not appear at all. Knowledge concerning massive transformations has bee11 substantially enhanced over the years by Massalski and his coworkers; an excellent summary of his papers and the current understanding of this type of reaction has been published recently by Barrett and ~assalski." he massive transformation product grows in roughly nodular form. often with irregular boundaries but sometimes with almost planar interfaces. The latter may have simple crys-tallographic indices relative to the 0 matrix. or the indices may be complex just as in the case of mar-tensites.'1 Little is known about the existence of orientation relationships between the massive and parent phases. A striking feature of massive transformations is that the massive units start almost exclusively at grain boundaries of the parent phase and frequently propagate on a broad front across matrix grains and grain boundaries of various orientations. Because of the rapid growth rate, it is thought that the interface motion is controlled. not by long-range diffusion. but by thermally activated atom jumps across the transformation boundary.

Jan 1, 1970

By Arnt Solbu, Jomar Thonstad

The reaction between CO, and aluminum in cryolite-alumina melts in contact with aluminum has been studied by passing CO2 over the melt. In unstirred melts a homogeneous reaction between dissolved metal and dissolved CO2 was observed. In stirred melts in which convection was induced by bubbling argon through the melt, the dissolved metal apparently reacted mainly with gaseous CO2. The rate of formation of CO increased slightly with increasing depth of the melt, and it did not depend on whether CO2 was passed over or bubbled through the melt. The rate of formation of CO increased with increasing area of the metal/melt interface and with the application of anodic current to the metal. It is concluded that the dissolution of metal into the melt is the rate-determining reaction. THE current efficiency in aluminum electrolysis is determined by the rate of the recombination reaction between the anode gas and the metal: 2A1 + 3CO2—A12O3 + 3CO [1] as originally stated by Pearson and waddington.1 The occurrence of this reaction in cryolite-alumina melts in contact with aluminum was first verified experimentally by Schadinger.2 Thonstad3 has shown that the reaction may proceed further to give free carbon: 2A1 + 3CO— A12O3 + 3C [2] Normally only a few percent of the CO formed undergoes such reduction. The mechanism of these reactions has not yet been clarified. Aluminum, as well as CO,, is soluble in the melt. The solubility of aluminum in cryolite-alumina melts at around 1000°C corresponds to 75 x 10- 6 mole A1 per cu cm,4 while that of CO2 is only 3 x 10-6 mole CO, per cu cm.5 Taking into account the stoichiometry of Reaction [I], the ratio between dissolved aluminum and dissolved CO2 available for the reaction in a saturated melt is about 40. Therefore, as will be shown in the following, the reaction probably mainly occurs between gaseous COa and dissolved aluminum. The dissolved aluminum presumably consists of subvalent ions of aluminum and sodium.4'6 Since the interpretation of the present results is not dependent upon the nature of this solution, the dissolved metal will be designated solely as Al+ in the following. The reaction can then be divided into four steps: A) dissolution of metal, e.g., 2A1 + Al3 — 3A1+ [3] B) diffusion of dissolved metal through a boundary layer; C) transport of dissolved metal through the bulk of the melt; D) Reaction [1]. If dissolved CO, takes part in the reaction, three additional steps embodying the dissolution and transport of CO2 must be added. schadinger2 observed, when bubbling CO2 through the melt, that the rate of formation of CO (in the following designated rfco) did not depend on the distance from the metal surface. The results also indicate that the rate of bubbling did not affect the rfco. When passing CO, over the melt, Revazyan7 found that the loss of metal did not depend on the depth of the melt above the metal or on the flow rate of CO2, and concluded that Step A is rate-determining. In an unstirred melt, however, Gjerstad and welch8 found that the rfCo decreased with increasing depth of the melt, indicating that step C was rate-determining. It thus appears that the rate control of the process depends on the experimental conditions, particularly on the convection. In the present measurements the reaction has been studied in unstirred as well as in stirred melts. EXPERIMENTAL AND RESULTS The experiments were carried out at 1000°C in a Kanthal furnace with a 10-cm uniform temperature zone (±0.l°C). The melts were made up of "super purity" aluminum (99.998 pct), hand-picked natural cryolite, and reagent-grade alumina. In experiments where alumina crucibles were used, the alumina content in the melt was close to saturation (13.5 wt pct9); otherwise it was 4 wt pct. Pure Co2 (99.85 pct) was passed over the melt, and the exit gas was analyzed for CO2 and CO by the conventional absorption method.3 From the weighed amount of CO (as CO2) the rfco was calculated as the number of moles of CO formed per min per sq cm of the surface area of the melt. The amount of carbon formed by Reaction [2] was not determined. As already indicated the rfco is much higher than the rfC, by Reaction [2]. Since the rfC probably is proportional to the rfco, the measured rfco should then the proportional to, but slightly lower than, the total rate of Reactions [I] and 121. In general the scatter of results obtained in duplicate measurements was ±5 to 10 pct, while within a given run a precision of ±3 to 5 pct was obtained. The various crucible assemblies that were used will be described below. Measurements in Unstirred Melts. When carrying out aluminum electrolysis in small alumina crucibles. Tuset10 observed that after solidification the lower part of the electrolyte was gray and contained free metal, while the upper part near the anode was white and contained no metal. One may test for the presence of free metal by treating with dilute hydrochlorid acid.

Jan 1, 1969

By Henry M. Howe

This paper may be regarded as a report of progress of an investigation into the influence of prior exposure to different high temperatures, under different conditions, on the properties of steel after it has been cooled completely. The following are the chief divisions: II.—Experiments on toughening manganese-steel by sudden cooling. III.—A study of the critical points of common or carbon-steel, chiefly by examining the spontaneous retardations which occur in heating and cooling it, and by examining the ductility of pieces of steel which have been cooled suddenly from different temperatures by quenching them in water or brine. IV.—A brief note on Osmond's theory. V.—A study of the critical points by examining the ductility of pieces of steel which have been cooled slowly from different temperatures at, above, and below them. VI.—A description of the furnace used, with notes on thermoelectric pyrometry. It remains to throw further light on the questions studied by ascertaining the condition of the carbon and the hardness proper, and by studying the microstructure and the fracture of the many pieces treated. I hope to present later the results of experiments in some of these directions. With few exceptions, the experiments have been performed in my private laboratory. I tender sincere thanks to my assistant, Mr. William Haskins, S.B., on whom most of the labor has fallen, for his zealous and intelligent co-operation; to the Sterling Steel Co. for their extra hard steel, Series 17; and to Mr. Joseph Hartshorne and the Pottstown Iron Co. for their soft basic steel. Series 8, 9,10, and 18 were supplied by Messrs. Spaulding, Jennings & Co., of the West Bergen Steel Works; to them also my thanks are due. The temperature of the pieces treated has been very carefully

Jan 1, 1894

By B. C. Craft

The principal events in the oil and gas operations for Louisiana during 1933 have been the rapid development of the Converse field in Sabine Parish, the discovery of three new salt domes, one in North Louisiana and two in South Louisiana, increased development in the Iowa field on the Calcasieu-Jefferson Davis Parish line, and extensive geophysical operations over a wide territory. Other miscellaneous events worthy of mention are the continued leasing of prospective oil lands over a wide area, extension of production at the East Hackberry field, Cameron Parish, discovery of deep sands at Caillou Island, Terrebonne Parish, and the completion of several important wildcats. Despite proration, oil production showed a substantial increase during 1933. The total output for this area was 25,599,802 bbl. as compared with 22,507,387 bbl. during 1932. North Louisiana There were 111 oil wells and 47 gas wells completed in North Louisiana during 1933 as compared with 109 oil wells and 33 gas wells during 1932. North Louisiana oil production decreased approximately 692,625 bbl. in 1933 from its 1932 figure. The normal decline in the old fields was partly offset by increased production at the Zwolle and Converse fields in Sabine Parish. Acid treatment of wells in the Zwolle, Converse and Monroe fields was highly successful. The method of application has been described by H. K. Shearer, Geologist, Pelican Natural Gas Co., as fo1lows:l With tubing in the hole and standing valve removed, the casing is filled with oil to the surface. The limestone solvent is pumped in through the tubing, at the same time bleeding off enough oil from the casinghead to equal the volume contained in the tubing plus the volume of open hole to be treated. The amount of solvent used in most of the wells treated was 1000 gal., which is enough to dissolve about 11 cu. ft. of chalk or limestone. After the computed amount of oil is bled off, the casinghead is closed and the remainder of the solvent is pumped in at whatever pressure is necessary to force it into the oil-producing horizon. The solvent is followed up with enough oil to

Jan 1, 1934

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By C. C. Hawes

SILICA is the main impurity in iron ore. It is intimately associated with the iron oxide, sometimes free but more often in the combined state, as a mineral silicate. Its separation and purification sometimes present difficult problems to the analyst. In the absence of any definite knowledge to the contrary, orthosilicic acid. H4SiO4, is supposed to be the only silicic acid made, all other forms, such as metasilicic acid, H2SiO3, representing different degrees of its dehydration. These acids are exceedingly weak but form the most stable compounds found in nature. They are known as the silicate minerals and are formed by the combination of the different metallic oxides

Jan 1, 1936

By Robert B. Coleman

The recent surge in demand for uranium in the US, accompanied by a significant increase in price, has stimulated the search for and development of lower grade ore bodies. At the mill, this translates into much larger throughputs and-compounded by many recently enacted environmental considerations-has made the cost of milling a critical factor in today's uranium production economics. The three conventional milling methods employed in the extraction of uranium ores are reviewed in the following sections.

Jan 10, 1978

By E. M. MacKevett

The only source of uranium ore in Alaska that has been mined commercially is the Ross-Adams de- posit, a gently inclined, fusiform orebody in alkali granite in which uranothorite and uranoan thorianlte are the chief ore minerals. In mode of occurrence, apparent genetic association with the granite, and to a lesser extent in mineralogy, this type of deposit is uncommon. The mine is in the southern part of Prince of Wales Island (Fig. 1) at an altitude of about 950 ft on the southeast flank of Bokan Mountain. A steep unpaved road 1 ¾ miles long leads to the dock on the West Arm of Kendrick Bay, which can be reached by boat or seaplane from Ketchikan, some 35 miles to the northeast.

Jan 9, 1959

By Frederick Laist

I. INTRODUCTION The new slime-concentrating plant at the Washoe Reduction Works, Anaconda, was put into operation during March, 1914. This plant, which has a capacity of 26,000,000 gal. of slime pulp carrying 2,500 tons. of solid matter per day, consists of Dorr thickeners and Anaconda multiple-deck slime concentrators.' This plant is the culmination of a great deal of experimental work extending over a considerable period of time, which work will be described briefly in the following pages.

Jan 8, 1914