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By W. S. Morris, R. R. Bradenthaler, G. Wade

Petroleum engineers generally are of the opinion that the flow conditions and, therefore, the formulas that apply to the flow of oil and gas in long pipe lines differ in many ways from flow conditions in oil wells. One of the reasons why the formulas in common use for pipe-line flow do not correctly apply to oil wells is that the flow lines are vertical and not horizontal. Another factor to be considered is that the fluid is a mixture of oil and gas and that the physical characteristics of these two components are affected differently by changing conditions of pressure and temperature during upward flour. Realizing the need for accurate data on flow in vertical pipes under conditions caused both by natural flow and the gas-lift, the U. S: Bureau of Mines has installed equipment at the Petroleum Experiment Station, Bartlesville, Okla., for the purpose of studying this problem. In additon a study will be made of the comparative effects of different natural-flow and gas-lift methods of producing oil on ultimate production from reservoir sands. Experimental Equipment The experimental equipment consists of a regular oil-field steel derrick, a large pressure tank installed in a concrete pit beneath the derrick floor, compressors and pumps, gas separators and absorbers, metering and control devices, and the necessary pipe connections. The crown-block level represents the derrick floor at an oil well, and the "producing sand" is the pressure tank below the derrick floor. The difference in elevation between the crown-block level and the tank is 90 ft. Figs. 1, 2 and 3 show the construction and exterior arrangement of the equipment. The success of the experiment will of course depend largely upon the accuracy of the oil and gas measurements and the temperature and pressure determinations. Because extreme accuracy is necessary, all oil and gas measurements will be checked at least twice, and in some

Jan 1, 1929

By Chester T. Sims

RECENTLY, a new type of superalloy material called TD Nickel* has been marketed.' It is a sim- ple, two-phased alloy, consisting of thoria particles dispersed in nickel of rather high purity (Ni-2 pct Thoz). Its mechanical properties appear relatively superior to previous experimental material attempting to use the oxide nonmetallic dispersion concept (except SAP), and superior to conventional nickel-base alloys at high homologous temperatures. This is derived from an interesting method of creating the dispersion, arising during chemical processing of the nickel and thorium salts in solution while reducing the nickel to metal. An evaluation of the thoria phase was conducted at this laboratory. Material and Procedure. TD Nickel was made available, consisting of several inches of 0.470-in. rod, extruded at a ratio of 64: 1, straightened, and centerless ground. Property determinations on this rod by the supplier at 1800°F showed an ultimate tensile strength of 11,400 psi, yield strength of 9600 psi, and 6 pct elongation. Specimens were removed from the rod for as-extruded metallography, and two 1/2-in. lengths supported on high-purity Al2O9 bricks were placed in a laboratory muffle furnace for exposure at 2000° F. The furnace door was left cracked to allow a slight amount of circulation. One specimen was removed at 200 hr for examination; the other was left for 2000 hr. Metallography. The micro structures obtained for the three conditions of exposure are shown in Fig. 1. Elongation of the grain structure in the extrusion direction is readily evident. The grains appear to be up to 0.001 in. (0.003 cm) long, with a length/width ratio of about 10: 1. Allowing for modest local in-homogeneities in structure, no significant change in thoria particle size or nickel alloy grain size occurred during the 2000°F exposure. However, etching depth varies slightly from one specimen to another, changing the number of particles visible. The thoria dispersion appears to be in the order of 0.01 (min) to 0.5 (max) p diam. The minimum diameter is difficult to estimate at X10,000, and may be less. Interparticle spacing appears to be about 0.1 p. Etching effects can be seen, depending upon grain orientation. A cubic etch-pit pattern appears in certain grains, apparently when etching is started by an anodic particle of thoria, Fig. l(c). The cubic pattern appears related to crystallographic orientation, and is prominent when the [ l00 ] direction is perpendicular to the plane of polish. The grains which present a ridged appearance in the photograph appear to be oriented with the [110} direction perpendicular to the plane of polish. Analysis. The thoria particle size was measured by a line intercept method perpendicular to the extrusion direction. Only particle sizes measuring 0.001 in. at X10,000 or larger could be extimated. Within limits of experimental error, particle size distribution appears to be unaffected by exposure, Fig. 2. To check structural stability further, a grain-growth evaluation was made. The number of grain-boundary intersections was counted at X500 on each of several traces normal to the extrusion direction for each condition. It can be seen from Table I that grain diameter appears unchanged by the 2000°F exposure. The slightly finer grain diameter after 200 hr may be attributed to variations in grain size from area to area in the original extrusion. From the present rather limited study of Ni-2 Th on, it appears that: 1) for time-temperature exposure up to 2000 hr at 2000°F (Larsen-Miller parameter = 57, homologous temperature = 0.8) thoria particles of the size studied are highly thermally stable; they do not significantly react, agglomerate, or diffuse; and

Jan 1, 1963

By J. D. Hanawalt, C. E. Nelson, J. A. Peloubet

The subject of the salt-water corrosion resistance of magnesium alloys is somewhat like that of the pitting of stainless steels, in that it involves a relatively small. percentage of the applications but receives a much greater proportion of the publicity. Actually magnesium alloys are in use in many exterior applications as well as interior, with no trouble from corrosion. Magnesium and its alloys have a striking stability against atmospheric attack, being far superior to iron. Specimens exposed unprotected to atmospheric weathering for Io Years show only a superficial surface-film formation. The basic nature of magnesium and of its important alloys is that they are also resistant to the attack of salt water even in an unprotected state, giving substantially no loss in weight after one year of alternate immersion in 3 per cent NaCl solution (Fig. 1). This basic behavior is often masked because of the extreme sensitivity of these alloys to certain impurities and combinations of impurities. It is known, and the subject of increasing emphasis, that higher purity leads generally to greater stability for many materials, non-metallic as well as metallic. However, a review of the literature on the corrosion factors in magnesium alloys shows that almost all researchers worked with base metal in which metallic impurities varied in uncontrolled amounts. The major factor, that of metallic impurities, Probably greatly overshadowed the effects of minor ones such as flux inclusions, nonmetallic impurities, porosity, metallographic state, which these researchers presumed to study. In the present investigation the first observation of interest is that whereas magnesium of commercial purity (99.9 per cent pure) has a corrosion rate in alternate immersion in 3 per cent NaCl solution at room temperature of anywhere from 5 to Ioo mg. per sq. cm. per day, the corrosion rate of high.purity magnesium is 0.15 ± 0.05 mg, per sq. cm. per day. The principle followed in the experiments was to add to such base magnesium other elements, singly and in inin in controlled and known amounts and to observe the corrosion behavior of the resulting alloy. These experiments show the existence of what may be called tolerance limits" of magnesium and some of its alloys for certain impurities. The extremely small percentages of impurities involved and the sharpness of the corrosion discontinuities appear to be quite unpredictable, In order to carry on this work, it was necessary to develop an analysis technique suitable to the problem. In some cases it was necessary quantitatively to analyze impurities to less than 0,001 per cent. The experimental data to be presented are based on observation of about 5000 alloy specimens and on more than 50,000 quantitative analyses. while the primary purpose of this paper is to present the experimentally obtained data on corrosion rates as a function of composition, and particularly to demon-

Jan 1, 1942

By J. L. Fitch, B. G. Hurd

The presence of gypsum in samples subjected to standard core analysis introduces serious errors in the measurement of water saturation and porosity. The magnitude of these errors, depending upon the type of analysis procedure used, has been evaluated experimentally and theoretically. Water-saturated pore volumes determined by vacuum distillation or retort procedures may be too high by as much as 48 per cent of the volume of gypsum present. The maximum error in this value determined by Dean-Stark extraction with toluene is 36 per cent of the gypsum volume. If pore space is measured by a Boyle's law type porosimeter the maximum erorr due to gypsum is 38 per cent of the original gypsum volume present. The conscientious core analyst may eliminate the errors caused by gypsum by either of two methods. He may apply suitable corrections for the water of crystallization removed from gypsum, or take special precautions to prevent dehydration of gypsum during core cleaning and alzalysis procedures. These alternatives are discussed and methods for obtaining reliable core analysis data are proposed. Gypsum (CaSO4 . 2H2O) occurs as a common mineral in many of the world's sedimentary basins. In addition to its presence as primary bedded evaporitic deposits, it is often found as secondary replacement zones and pore-fillings in host rocks. That it may cause false indications in porosity, both on neutron logs and in standard core analysis, has been generally recognized. False porosity interpretations from neutron logs result because the chemically bound water in gypsum attenuates neutrons as effectively as free water. Errors in core analysis result when gypsum is dehydrated prior to or during the analysis. Vacuum retort procedures used by many laboratories to determine fluid saturation and porosity effect a complete removal of water of crystallization from gypsum. The crystal water, distilled and collected with free water from the sample, is counted as water-sat11rated pore space. Dehydration of gypsum results in a decrease in volume occupied by calcium sulfate and a corresponding increase in pore volume. Thus, if gypsum is dehydrated by sample cleaning and drying procedures, subsequent porosity measurements with gas expansion or compression instruments will be high. The qualitative effect of gypsum on porosity determinations by retort procedures was discussed in a recent article by Bynum and Koepl3. They concluded that since false porosity was interpreted as being water saturated, determinations of oil content were not affected. Others in the industry, however, have pointed out that porosity values are often used with values of water saturation determined independently, e.g., from electric resistivity logs in making reserve estimates. Values of water saturation calculated from the formation resistivity using the Archie equation, S4= are actually low if values of are high due to gypsum. In this case, false porosity values due to gypsum could cause serious errors in calculations of oil-in-place. This investigation was made to determine quantitatively the effect of gypsum on porosity values determined by different core analysis procedures. EXPERIMENTAL PROCEDURES Dehydration of Gypsum The extent and rate of removal of water of crystallization from gypsum under conditions encountered in core analysis procedures were studied. Taken for the experiments were three types of relatively pure, naturally occurring gypsum, viz. selenite, satin spar and massive gypsum. Although all samples probably contained trace chemical impurities, each type lost the theoretical amount of water upon complete dehydration. An automatic recording thermobalance, similar to one described by Mauer2, was used to obtain dehydration rate data for samples heated in dry air. Water

By H. P. Stuwe

It is investigated whether a model of sphere packing permits the computation of the lattice parameters and their variation with concentration in various a phases; it does, except in phases containing silicon. Several observations indicate that a particular role is played by the "E-atoms" in the lattice. THE phase is formed by many alloys of the transition elements.'-' Its structure has been described by Bergman and Shoemaker,5,8 Dickins, Douglas, and Taylor,7 and Kasper, Decker, and elanger.' There are five kinds of crystallographically equivalent positions for the 30 atoms in the unit cell which have been designated by these authors I, 11, 111, IV, and V or, in the same sequence, A, B, C,D, and E, as shown in Fig, 1. For the purposes of the present paper two elements of the lattice will be discussed separately: The lattice planes perpendicular to the c-axis which are made up by the atoms A, B, C, and D and which determine the a-parameter; and the close-packed "vertical rows" of E-atoms which determine the c-parameter. asper,9 and Frank and kasper10 described the a phase and other complex structures as sphere packings. In these papers particular attention is paid to the coordination polyhedra. Lattice positions with an equal number of nearest neighbors are considered equivalent regardless of their crystallo-graphic description. This seems to work very well for the explanation of ordering phenomena in the a phase as far as information on this is available." If the description of the phase as a sphere packing is valid it should be possible to draw two further conclusions: 1) It should be possible to calculate the lattice parameters from the atomic radii of the components, and 2) It should be possible to predict the variation of the lattice parameters with concentration within one phase field. Both points are discussed in this paper. PROCEDURE Measurements of lattice constants were done with a symmetrical back-reflection X-ray camera. With Cr-radiation, about a dozen a1 lines could be observed with most samples. From the (550/710)- and 720-lines the a-value was computed. With this value the c-parameter was calculated from the (333)- and (413)-lines. Finally, the position of all the other lines was computed from the lattice parameters thus obtained. In this way the validity of the indexing could be checked and, at the same time, this proce- dure gave an estimate of the accuracy of the lattice parameters. A correction was made for film shrinkage. The atomic radii used in the computations are the Goldschmidt radii for coordination number 12. Actually, some of the atoms have a coordination number of 14 or 15, but the error thereby introduced is small. * For the computation of lattice constants from the atomic radii an "average atomic radius" of all components was used, i.e., complete disorder was assumed. Although this seems to be true for some systems like OS-Cr,4 it is not true in others.11,13,14 The ordering model, however, which has been suggested by Kasper on the basis of extensive research lets both kinds of atoms contribute to both the ''vertical rows" and the lattice planes perpendicular to them, so that even with ordering of this kind the assumption of complete disorder cannot introduce a very serious error in calculating lattice parameters. RESULTS Bergman and shoemaker6 gave a table of the interatomic distances in the Fe-Cr phase. If we disre-

Jan 1, 1960

By J. W. Pamplin

Some 40 miles east of Tampa is the center of the Florida pebble phosphate deposits. These are of Pliocene age and consist of several members of the Bone Valley formation.1 Physically the phosphate-bearing formation, locally called the "matrix," varies in thickness from nothing to about 25 ft., usually averages 10 ft., and consists mainly of clay, quartz and phosphate pebble, the latter particles varying in size from colloidal to one inch diameter. The pebbles range in color from dark gray, through white, to cream, and in hardness from that which must be broken with a hammer to that which can be scratched with the fingernail. They assay from 66 to 80 per cent bone phosphate of lime (called "B.P.L." in the trade) or tricalcium phosphate (Ca³P2O8) and are secondary apatites. They form from 15 to 50 per cent by weight of the matrix. Over the matrix lies a varying thickness (5 to 40 ft.) of overburden composed of quartz and clay. Briefly, mining consists of two operations2 in open pits about 200 ft. wide by 1/2 mile or more in length. In the first step overburden is removed by large electric draglines at the rate of about 700 cu. yd. per hour. This is followed closely by hydraulic mining of the matrix at the rate of about 300 cu. yd. per hour. This matrix yardage is moved from an improvised sump in the floor of the pit to an ore-dressing plant, sometimes a mile distant, by one, two or three "pit-cars" (pumping units) working on a 12-in. pipe line called the "rock line" to distinguish it from the high-pressure water line feeding the hydraulic giants, which is known as the "hydraulic line." This 700 yd. of overburden and 300 yd. of matrix—1000 yd. in all-amounts to about 1500 tons of material moved each hour. The overburden is dumped into the mined-out pit alongside the pit being mined. The matrix moves to the ore-dressing plant at the rate of about 7% long tons in 4000 gal. of water per minute—a ratio of approximately one to two by weight, or one to six by volume. This constitutes the "mill heads," but in the pebble district it is called the "matrix."

Jan 1, 1938

By Carl Pierce

THE writer of this article has not attempted to write a technical paper; on the contrary, he has tried to express in "steel-plant English," for steel men, a viewpoint drawn from his practice and experience. It is not his thought that it shall be taken as the "last word" in the making of this class of steel, or that good rimming steel cannot be made by any other practice. The paper was written to serve as the basis of a discussion from which it is hoped much benefit may be derived. The paper deals only with rimming steel made by the open-hearth process, and with the lower carbon steels, such as sheet and tin bar, rivet stock, skelp, etc., although good rimming steel as high as 40 to 50 carbon can be made by having good open slags and giving proper attention to working and tapping temperatures.

Jan 2, 1926

By H. F. Hebley

In recent years, especially in the last decade, great interest has been shown and many advances have been made in the preparation and cleaning of coal. In the major coal-producing countries, the percentage of tonnage cleaned has been increasing ever since 1924. As separating media, both liquids and gases are used, these generally being water and air respectively. Some systems, instead of obtaining separation by the velocity of the medium in which the coal is cleaned, depend on the density of water mixed with sand, or coal dust and shale, or with chemicals such as calcium chloride. In studying the results of coal-cleaning equipment, it will be observed that the efficiency of the cleaning apparatus lowers as the size of the coal decreases. This inability to obtain any marked improvement in the fines has been partly responsible for the installation of dedusting equipment, to remove the fine sizes from the raw coal prior to cleaning. When considering the possibility of installing dedusting equipment, many factors must be taken into account. Very often, but not always, both the ash and sulfur content of the coal increase as the coal size decreases. When bituminous coal, containing soft powdery fusain, is subjected to a wet washing process, the porous fines of the fusain remain in the small coal or in the wash water and delay the dewatering of the washed coal and increase the difficulty of clarification in settling tanks or thickeners. When a dedusted coal is cleaned by a wet process, the sludge recovered from the settling tank often runs so high in ash that the sludge can be discarded without further treatment and still the loss is small. Where treatment of the sludge is desired, however, froth flotation may be used to advantage if the size of the feed is below 1/10 in. Dust from the deduster can be treated in a similar manner. Fusain, which is usually found in the fine sizes, has often a much larger ash content than other coal. Illustrative of this condition is a table of ash contents for the various petrographic constituents of Illinois coal (No. 5 bed) as given by Mitchell' (Table 1).

Jan 1, 1934

By Helmut Thielsch

MeTallographic specimens whose surfaces are to be investigated are too thick to allow either light or electrons to pass through them for microexamination by transmission. This difficulty is overcome with optical microscopes by illuminating the surface through the objective lens. For electron microscopes best results are obtained by preparing thin replicas of the surface of the specimen, placing them in the microscope and passing the electron beam through them. Since electron microscopes represent a rather recent invention, they have found little application as compared with optical microscopes. This is true because, aside from the cost of new equipment and development of new techniques, some of the older replica methods necessitated the destruction of the surface from which a thin transparent replica was obtained. In other processes in which the surface is preserved, either too tedious a procedure is required, unsuited to "mass-production" requirements of industrial laboratories, or replicas of insufficient contrast and sharpness are produced. In general, investigations with the electron microscope involve five steps: (I) polishing the surface of the metal specimen, (2) proper etching of the surface, (3) preparing the suitable replica from the surface, (4) examination and phorography in electron microscope and (5) interpretation. Preparation of Metal Surfaces Usual metallographic polishing is generclly satisfactory. It is important though that the final polish be applied very carefully, since otherwise evidence of a small amount of deformation might show up even on relatively deeply etched surfaces. A high-power microscope should be used to determine the suitability of the polish and etch. This, of course, is not different from optical examinations, but in these, if a deep etch is used, the problem is less serious. It is frequently difficult to detect with optical microscopes poor polishing aside fiom superficial scratches before etching. Figs. I and 2 show micrographs of "well" and "poorly" polished nickel etched by immersing the sample for 20 min. in a solution containing 8 grams cupric sulphate in 40 C.C. of concentrated HCl and 40 C.C. of Hz0 (Marble's reagent). The sample shown in Fig. I was polished in its final stages for 5 min. on a carborundum wheel followed by ro min. on a rouge wheel, whereas the sample shown in Fig. 2 was polished only I min. on the rouge wheel. Generally, this procedure does not guarantee that the surface of the specimen will be either undistorted or deformed. It was applied here merely to show the effects Of good and poor polishing. To the experienced investigator, plastic deformation is

Jan 1, 1946

By G. P. Boomsliter

IN previous discussions on stresses in hoisting ropes, little has "been said concerning the effect of the elasticity of the rope itself on the stresses due to acceleration. Laschinger1 has calculated acceleration stresses. for several cases but he has ignored the elasticity of the rope as a factor, except as it compresses the drum and stretches itself as it winds thereon. He also deals with steam plants and he shows the effect of the "jerky" start of the engine. This effect would actually be reduced by the elasticity of the cable. With the advent of the motor-driven hoist, new conditions have arisen. The jerk mentioned by Laschinger has been eliminated and smoother starting made possible. But the elastic properties of the rope seem to introduce considerable periodic acceleration stresses in the rope. The following discussion of acceleration stresses is based on the assumption of a constant acceleration at the drum. To be exact, the mathematical work is based upon the assumption that the top is moving upward with a constant acceleration, and ignores the fact that the cable is shortening as it winds. However, the effect of the shortening would be inconsiderable during the first part of the acceleration period. Most hoisting engineers make the assumption of constant acceleration at the drum. Under the older method of calculating acceleration stresses, this would be true with a constant torque motor. But if stresses vary, as this paper attempts to show that they do, constant torque would not give constant acceleration, although the velocity-time curves obtained in the full size test herein described showed that they approach rather closely to this condition, at least as nearly as could be measured.

Jan 2, 1927

By Richard Paul Seelig

The following review covers published information on pressing of metal powders at room temperature. Only those operations are considered which occur between the time the powder is filled into the cavity and the compact is ejected from the die. Thus, this review does not concern hot pressing, coining or sizing feed or flow problems, commercial presses nor designs. It was also necessary to disregard to a large extent the effect of pressing on subsequent operations and on properties after sintering. 'The pressing operation is considered independently in its function to compact loose metal powder into useful shapes which can subsequently be handled. There are some comments by the writer in connection with a few of the findings quoted in the literature in order to stimulate thought and discussion. The selection of references quoted in the text is in some cases arbitrary although an attempt was made to favor papers containing novel ideas, techniques or results which mag stimulate future research. In order to enable the reader to check further into the subjects mentioned, the original, rather extensive, bibliography is appended even though not all the references are touched on in the printed version of this review. The equipment used by various workers, for example a die design created by Bridgman,22 is very interesting. 'The die insert has a conical external surface. The vertical pressure exerted on the punch transmits itself to the die which in turn is pushed harder into its tapered retainer. Thus, the higher the pressure exerted on the punch, the higher also the pressure exerted inwards on the die inserts. Inasmuch as this pressure counteracts the internal pressure from the compact the two stresses balance each other so that it is possible to obtain tremendous pressures without breaking the die. The die collar was made from an oil hardening tool steel, heat treated to a tensile strength of some 300,000 psi. The die was closed at the bottom by a plug made from special tool steels. Bridgman found that there is no steel which will withstand a com-pressive stress of 700,000 psi without continuous slow flow or immediate fracture. Therefore, the only material suitable for use in the pressing punch was sintered carbide. In view of the ingenious design it was possible to use special tool steel as die material. Jones22 raises the question whether this method of pressing has practical application in powder metallurgy. Although these tremendous pressures cannot readily be utilized without many special precautions, the tapered die and retainer idea is believed to be useful even for lower pressures. Bridgman, himself," alls attention to the fact that the properties

Jan 1, 1947

By Robert D. Pike

IN November 1939, on behalf of the Harbison-Walker Refractories Co., the author undertook the study of the problem of utilizing the dolomite of northwestern Ohio for the manufacture of calcined magnesia suitable for use in refractories. Grateful acknowledgment is made of the unfailing assistance and encouragement throughout this work from the executive and technical staff of Harbison-Walker Refractories Company. The dolomite of the Niagara formation that is exposed or near the surface of a wide area in northwestern Ohio1 constitutes a vast supply of almost pure dolomite. It offers a virtually unlimited supply of cheap raw material of uniform dependable analysis for the manufacture of magnesia. A typical analysis of dolomite from the vicinity of Luckey, Ohio, follows: [ ] Brines containing magnesium chloride or sea water can be reacted with calcined dolomite to produce magnesia.2,3 In such reactions the MgCl2 of the brine supplies some of the magnesia and the amount of dolomite required is thereby reduced by an equivalent amount, but brines of commercial importance containing magnesium chloride are some distance away from the purest grades of the dolomite of northwestern Ohio. It was decided therefore to concentrate upon the development of a suitable process for separating the lime and magnesia of dolomite, depend¬ing upon the dolomite itself as the sole source of magnesia. This would make it possible to place a plant at the dolomite quarry, thus eliminating the cost of transporting the stone and also rendering the calcined magnesia available at a most convenient production point, considering the cost of delivery throughout the steel industry. The selection of a process depending solely upon the dolomite as a source of magnesia also necessarily entails production of the lime content of the dolomite as a by-product. It was recognized that if such a lime by-product could be produced in a suitable form, a plant location in northwestern Ohio would also be advantageous for marketing the lime. The problem, therefore, was the discovery and development of a low-cost process for separating the magnesia and lime of the dolomite of northwestern Ohio and producing each in a form relatively free from the other, and meeting the respective requirements of established markets. A satisfactory solution of this problem has been found, and it is the

Jan 1, 1947

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960

By J. R. Jargon, H. K. van Poollen

Non-Newtonian fluids may be injected into a reservoir during secondary recovery operations. The non-Newtonian fluid used in this work is a power-law type of fluid that is, the viscosity of the fluid decreases as the flow rate or rate of shear increases. This paper presents equations for steady-state linear and radial flow of such fluids, transient behavior results from a finite difference model of a radial system, and transient behavior results from a field test. The equations that describe the flow of a non-Newtonian fluid are non-linear and are solved numerically. Finite difference solutions are presented as curves of dimensionless pressure drop at the wellbore us dimensionless time for a constant injection rate. Solutions were obtained for 5-percent, 10-percent and 100-percent PV of a non-Newtonian fluid for injection rates of 1, 10, 100 and 1000 cc/sec and for a 5 percent PV of non-Newtonian fluid located at T = Tw' 3, 10, 20, 50 and 100 ft for a flow rate of 1 cc/sec. The buildup curves do not exhibit a stmight-line portion as is the case for Newtonian flow through porous media. Correlations also are shown for the productivity index vs rate for the computer model study and the field tests. INTRODUCTION During various secondary recovery operations non-Newtonian fluids are injected. Such fluids, in general, include thickened water and gelled fluids. The term "non-Newtonian" implies that the viscosity is not only dependent upon temperature and pressure, but also on the rate of shear that is applied to the fluid. For example, water, which is a Newtonian fluid, will have essentially the same viscosity no matter what rate of shear is applied. A pseudo-plastic fluid exhibits a decreasing viscosity when higher rates of shear are applied; a dilated fluid has an increasing viscosity with increasing rates of shear. The objective of studies performed and described in this report is to obtain relationships and mathematical and empirical descriptions of the flow of non-Newtonian fluids through porous media. Simple mathematical relationships, computer studies that include the unsteady-state behavior of such fluids, and field tests are used. PREVIOUS LABORATORY STUDIES Laboratory studies have been performed by several investigators. The fluids used in one investigationl were surfactant-stabilized dispersions of water in hydrocarbons. Its Fig. 6 is reproduced as our Fig. 1. This effective-viscosity vs frontal-velocity diagram shows that this fluid is of the power-law type over a fairly large range of frontal velocities. Gogartyl developed an equation for the effective viscosity as a function of shear rate that reduces to Eq. 2 for frontal velocities greater than about 2 ft/D. The fluid characteristics used in the present study are similar to those reported by Gogarty. Christopher and Middleman2 performed experiments with power-law fluids flowing through pipes packed with glass beads. They used a modified Blake-Koteny

Jan 1, 1970

By Edwin R. Phelps

In the year 1900 about 212 million tons of bituminous coal were produced in the United States. Almost none of this was produced by surface mines (Fig. 1), because there was no large equipment suitable for stripping overburden at that time. By 1915 the surface mines had built up their capability largely through use of the steam shovel to the point that they produced 2.8 million tons of the nation's total production of 443 million tons. Over the intervening years between 1915 and 1970 surface mining provided a continually increasing percentage of the nation's bituminous coal, stimulated by the growing availability of giant surface mining machines, some of which are presently capable of removing 220 cu yd of earth with one bite of their mighty buckets. In 1970 the nation's surface mines produced 244 million tons of bituminous coal, over 40% of the total national production. On the other hand, the nation's underground mines hit a peak of 560 million tons in 1920, dropped to a low of 273 million tons in 1961, and are presently on a very slow rise. Environmental pressures generally oppose surface mining, and have forced coal companies to consider more underground mining in future planning. Also, since strippable reserves are decreasing in the eastern states, an increase in underground mining is expected over the coming years. However, in the western states there are enormous reserves to be extracted by surface methods. Why has surface mining increased, while underground mining has decreased? It's largely a matter of economics. The cost per ton is greatly reduced by surface mining because of the relative ease of obtaining the coal. Also, there is a much greater percentage of coal recovery-nearly 85% in surface mines within the minable area, as compared to an average of about 50% in underground mines. Much surface mining recovers coal that could not be extracted by underground methods because of coal bed thinness, or multiple beds close together, split seams, the nature of the roof, and other geologic conditions. What are some of the limitations of surface mining? First of all, with presently available machinery it is difficult to surface mine at depths

Jan 1, 1973

By M. E. Nicholson

IT has been suggested by a number of investigators, I including Hume-Rothery and Raynor,' that certain intermediate phases in metal systems take on interstitial crystal structures because of an appropriate ratio of radii of the two atoms. If the size factor is an important parameter in determining whether or not an intermediate phase will have an interstitial structure, then it would appear reasonable that the relative sizes of interstitial atoms should have a direct relation to their solubilities in interstitial compounds. It was on such a basis that Petch,' in his discussion of the cementite structure, concluded that nitrogen is the only possible element which could replace carbon. Recent X-ray studies by Jacka indicate that the solid solubility of nitrogen in cementite is negligible. If this is the case, then on the basis of size factor it would not be expected that any element can replace carbon in FeaC, since according to Schwarzkopf and Kieffer4 the covalent atomic radii of nitrogen, carbon, and boron are 0.71, 0.76, and 0.87A, respectively. Nevertheless, Vogel and Tammann in 1922 indicated that a quasi-binary relation exists between the interstitial compounds FeaC and Fe2B and that the solid solubility of boron in FeaC at approximately 1150°C is 1.4 pct B by weight. Because of the apparent disagreement between theory and experiment, the solid solubility of boron in FeaC has been reinvestigated. In addition, the influence of boron on the saturation magnetic moment (per gram) and Curie temperature of cementite was determined. Experimental Procedure A series of Fe-B-C alloys which varied in boron content from 0 to 5.4 wt pct B were prepared by arc melting a 50-g ingot using carbonyl iron, Ache-son AUC graphite, and Cooper grade A boron for starting materials. The composition of these alloys is listed in Table I and shown graphically in Fig. 1. The samples represented by the solid circles were used for X-ray analysis and Curie temperature measurements; by the squares, samples used for quantitative metallography; and by the triangles, samples used for saturation magnetic moment measurements and Curie temperature measurements. After arc melting and subsequent quenching from 1000°C, so that all phases in the resulting microstructure were brittle, one half of the 50-g ingots were pulverized until a powder was obtained which was less than 100 mesh. These powders were then homogenized in evacuated Vycor capsules at 1000°C for 24 hr and water quenched. Although the homogenized powder had sintered somewhat, it was suitable for saturation magnetic moment and Curie temperature determinations, for which the 60 to 100-mesh fraction of the powder was used. For X-ray analysis the homogenized powder was crushed again until a 300-mesh powder was obtained. After crushing, the powder was mixed with Alundum of approximately the same grit size to prevent sinter-

Jan 1, 1958

By T. M. Broderick

InveStIgations into the possibilities of economically mining and concentrating low-grade iron ores of the Lake Superior region are attracting increasing attention. Among the organizations that are carrying on the work are the United States Bureau of Mines, the State of Minnesota (which spends about $80,000 annually on problems of the iron and ferroalloy ores of Minnesota), and the State of Michigan (which spends about $10,000 annually of its iron-ore research). Several of the mining companies are also financing research. Of the states in the Lake Superior district, Minnesota has done most in iron-ore concentration. In 1930, thirty-seven concentrating plants were in operation on the Mesabi Range, beneficiating about one-third of the total ore shipped. About one-half of these plants reduced silica; the others reduced moisture or improved the structure of the ore.' Research into the possibilities of magnetic concentration of the Eastern Mesabi magnetite ores indicates that vast tonnages of that ore may be utilized at a profit in the not distant future. Magnetic concentration has also been tried at Sellwood, Ontario, on the Moose Mountain deposit, and at the Berkshire mine in Wisconsin on the magnetic ores of the Western Gogebic Range. There have been few attempts to concentrate Michigan iron ores. In order to determine the possibilities of such concentration, iron-ore research has been carried on at the Michigan College of Mining and Technology for the past few years. After a general survey of the iron ores of the state, a program of more detailed experimentation was outlined, starting with work on the Ironwood formation of the Gogebic Range. The results of this research led to the belief that gravity methods will produce fairly satisfactory concentrates from the parts of the iron formation that are made up of comparatively thick alternating beds of rather high-grade ore and lean chert. About 85 per cent of the iron and steel produced in the United States comes from ores of the Lake Superior district. The reserves of direct

Jan 1, 1935

By George S. Rice

The subject of violent bumps in coal mines has been again brought to attention by a recent succession of such occurrences in the coal mines of the Cumberland field of eastern Kentucky and southern Virginia, which have caused fatalities and injuries to underground employees, a report on which is being issued by the United States Bureau of Mines1. The A.I.M.E. has had two valuable papers on bumps in the No. 2 Mine, Springhill, Nova Scotia, each followed by general discussion on bumps and their causes2. This paper gives a brief review of suggested causes and remedial measures given in English, Canadian and United States reports on blimps in coal mines, and then presents suggestions arising from the writer's recent investigation of the bumps in the Cumberland mines, made at the request of the mine operators, to determine the causes and remedies. These bumps, which occur under the simplest natural conditions, provide better opportunity for analysis of causes and effects than afforded under more complex conditions. The simple conditions in this field consist of relatively thin and level coal beds and uniform roof strata free from folding and faulting. Definition of Bumps Bumps in coal mines, as defined in this paper, are sudden violent bursts of coal that usually occur without warning in the extraction of pillars and may or may not be accompanied incidentally by falls of draw slate, upheaval of bottom and smashing of timbers. They are not known to occur where the advancing longwall method of mining, accompanied by

Jan 1, 1936

By J. J. Rutledge

On Sept. 4, 1914, Mine No. 1 of the Union Coal Co., Adamson, Oklahoma, suddenly caved, entombing thirteen miners whose bodies were never recovered. The seam of coal mined, the Lower Hartshorne, averaged 5 ft. in thickness and dipped at an angle varying from 22" to 30n. The strata overlying the coal seam were sandstones and shales. The mine was worked by the pillar-and-room method, the rooms being driven directly up the dip of the seam. All coal was blasted off the solid. Rooms were turned on short centers and room pillars were thin and irregular, as shown in Fig. 1. Fig. 2 is a cross-section of the form; showing the mine workings. Some cracks had been observed on the surface, it is said, at least a month before the squeeze occurred, but the collapse of the mine workings came very suddenly. As is usual when squeezes occur on such steep dips and the pillars fail, the crush progressed rapidly down the dip until it reached solid coal; there was a line of break, or draw, over in the solid coal. Several well-defined cracks appeared on the surface, after the mine had squeezed, but there was no appreciable subsidence of the surface, the weight seemed to be thrown entirely to the dip. About one year after the squeeze, and after the workings of the adjoining mine, NO. 4, had been retimbered and made safe, the writer inspected the tenth north (right) entry, or lift, off of No. 4 slope, which was below and fairly near the lowest caved portion of mine No. 1. The roof shale was composed of thin layers, which had been bent in somewhat the same manner as the leaves of a book having flexible covers are bent when the book is folded or rolled up in the hands. Though the mine workings are immediately beneath the streets and buildings of the mining town of Adamson, business was not disturbed by the squeeze, so far as any subsidence of the surface was concerned. No surface monuments were available and no elevations were taken, but the mine workings had been accurately surveyed and traversed, and the streets of the town overlying the mine workings had been carefully platted on the mine map, so that it was possible to locate accurately the cracks on the surface.

Jan 1, 1923

By E. Houdremont, H. Schrader, H. Bennek

The different influences exerted by the various alloying elements in iron and iron-carbon alloys give rise to a great number of complexities, which are difficult to grasp. It is important therefore to study any systematic relations that may exist between the effects exerted by the various alloying elements, in order to obtain a general classification and thus a clearer conception of the nature of alloy steels. A systematic survey of the alloys of iron, based on an investigation of the binary equilibrium diagrams, was recently published by Wever. Although his work deals little with properties of importance in works practice, its purpose being rather to point out the theoretical agreement among the types of binary equilibrium diagrams and the position of the alloying elements in the periodic system (atomic radii, etc.), the classification proposed nevertheless also suggests relationships among the properties of the alloys in question, even though the alloys may contain carbon in addition to iron and the alloying element. Wever divided the alloys of iron into one group exhibiting an open or enlarged gamma field and another exhibiting a closed or restricted gamma field, with both groups capable of further subdivision depending upon whether a continuous series of solid solutions is formed, or, owing to the separation of compounds, etc., only a limited series. Thus all alloying elements which with iron form a closed gamma field, a "gamma loop," produce alloys that beyond the composition corresponding to the greatest extent of the gamma loop are composed of ferrite alone at all temperatures. Alloys of this composition accordingly are not susceptible to ordinary heat treatment because of the lack of transformations. Steels of this class may thus be divided into steels that contain less than the critical amount of alloying element, and are subject to heat treatment, and those that contain more than the critical amount of alloying element and are not subject to heat treatment. Thus chro-

Jan 1, 1935