Search Documents

By P. E. Busby, C. Wells, M. E. Warga

Fundamental data on the rate of diffusion of boron in austenite and solubility of boron in the a and y phases of iron and steel have been obtained from deboronizing experiments and provide partial explanations for some of the phenomena observed in boron steels. The rate of diffusion of boron is about the same as carbon in austenite. The solubility of boron in austenite at normal heat-treating temperatures is less than 0.001 pct. A partial tentative Fe-B phase diagram in the important low boron concentration ranges and an equation representing the diffusion of boron in austenite are presented. A LTHOUGH a search of the literature revealed ALTHOUGHthat boron diffusion had not been studied quantitatively and systematically prior to 1948, a few qualitative observations which were made by following the diffusion of boron into iron packed in ferro-boron1-3 suggest that boron obeys normal diffusion laws and that the rate of diffusion increases with increasing temperature. The claim of Cornelius and Bollenrath1 that boron does not appear to influence the rate of carbon diffusion has recently been substantiated by Wells, Batz, and Mehl.4 Calculations based on data from the paper by Campbell and Fayv indicated that the diffusion coefficient (D) for boron in iron at 900°C is approximately 3x10 sq cm per sec; a value of 2x10-7 sq cm per sec at 1038°C has been reported by Digges et al in connection with decarburizing experiments on a commercial boron steel containing 0.43 pct C. During the period 1948 to 1950 several diffusivity constant (D) values for the diffusion of boron in the y phase of iron and steel and a number of solubility values for boron in both a and y phases were reported. It was concluded tentatively as a result of Metals Research Laboratory studies that D values for boron in y and a phases are about the same as for carbon in the comparable phasesa and that carbon up to 0.4 pct did not affect the rate of diffusion of boron in y iron above 1000°C within the limits of experimental error. Whether saturation of the y or a phases with carbon would significantly affect rates of diffusion of boron through them was then and still remains in doubt. The best estimate of Q (activation energy) was reported to be about 25,000 cal, somewhat lower than that for carbon in y iron. The solubility of boron in y iron at 1000°C was thought to be higher than 0.004 pct B but not as high as a more recent analysis of available data shows it to be. The solubility of boron in a iron at 700°C was reported to be 0.0004 pct B, but it would not have surprised the authors if the true solubility value is actually lower than this. Breaks in diffusion curves which were not understood when first obtained prior to 1950 have now been recognized as indicating solubility limits, and these are included in the present paper. Experimental Procedure Two methods were employed in an effort to determine diffusion coefficients (D) for boron in austenite. Early experiments involved the use of welded couples prepared in accordance with the procedure of Wells and Mehl,' but when the results of these experiments proved to be unsatisfactory for calculating D values, studies were continued by means of deboronizing experiments. In both cases, boron analyses following the diffusion anneal were carried out spectrographically and all D values were computed using the Grube solution of Fick's law. The precision of the spectrographic method used proved to be about equal to that reported by Corliss and Scribner" —average deviation from the mean about 5 pct of the amount present when the boron content is 0.003 pct. Concentration-penetration curves obtained from spectrographic analyses of welded couples generally indicated that practically no boron was transported across the weld interface during the diffusion anneal. Furthermore the concentration-penetration

Jan 1, 1954

By Jean-Jacques Prompsy, J. S. Rinehart

Some time ago a study was initiated at the Colorado School of Mines in an effort to arrive at a better understanding of the stress fields developed within drill bits under dynamic loading and the influence that these stress fields could have on the failure of the bits. Particular emphasis has been given to the influence that bit shape has on the establishment of highly localized, potentially destructive stress inhomogeneities within the bit. The study has been divided into three phases involving three velocity regimes: impacts at very low velocities, 0 to 20 ft/sec, a velocity range in which dynamic effects are just beginning to be found; impacts at velocities ranging from 20 to several hundred ft/sec, a range commonly encountered in practical drilling operations; and impulsive loading through the detonation of explosives, a region in which the dynamic effects are greatly exaggerated and made more identifiable. The ultimate objective is to provide basic data which will enable the mitigation through judicious design of the frequency and severity of these transient concentrations of intense stress, thereby prolonging and increasing drill efficiency. This paper presents results of the third phase of this study — the development of a better understanding of the dynamics and mechanics of failures caused by transient stress-wave interactions. The impulsive loading or transient waves in these experiments were generated by detonating small explosive charges placed on the ends of Plexiglas cylindrical rods terminating in truncated cones. Under such intense loading, dynamic effects are greatly exaggerated and, hence, made more identifiable. The explosion generates a high-intensity transient stress disturbance which moves through the rod, reflects from surfaces which lie in its path, and establishes momentarily narrow regions of high concentrations of stress where failure of fracture may occur. The peregrinations of these waves, their interactions and their effects have already been described in the literature (see, for example, Refs. 1 and 2). The locations and extent of the regions quite apparently are strongly dependent on specimen shape, making it possible through judicious shaping of specimens to relocate the highly stressed regions, minimize their extent, or eliminate them entirely. These experiments were designed, first, to identify more clearly the vulnerable regions in geometries relevant to drill-bit design and, then, to modify these regions in a predictable way by changing specimen shape. Through this latter process, it is anticipated that better bit design might evolve. The specimens used in the experiments were cylindrical rods, 1 1/2 and 1 1/8 in. in diameter, ended by a truncated cone, with the cone angles ranging from 45° to 130°. Upper cone face diameters were 1/2, 3/4, or 1 in. A small plastic-covered electric blasting cap detonated on the axis of the specimen produced the spherical shock wave. The detonators used were Olin Mathieson No. 6, which induced into the rod a transient saw-toothed stress disturbance of about 3-microseconds duration, corresponding to a wave length of 0.3 in. in the Plexiglas. Five distinct systems of fracture were observed: (1) along the axis of the rod, a lower system of fractures, the cracks focusing around one point for specimens having cone angles of 80° and 90° and, as the cone angle was increased, spreading downward; (2) just above these fractures, an upper system of fractures composed of horizontal cracks observable in some specimens but not of any appreciable extent; (3) a third system of axial cracks still above the latter, observable in the small cone-angle specimens; (4) in the upper part of the specimen, a system of radial fractures extending from the blasting point; and (5) circular spalling due to reflection of the wave on the boundary of the cylinder. Only the first three systems, the axial fractures, are examined here. LOWER TENSILE FRACTURE SYSTEM The first, lower system of tensile fractures, shown in the photograph of Fig. 1, was observed in almost all of the specimens. It was due to the reflected tensile wave coming in from the boundary of the cylinder as shown in Fig. 2. The reflected wave was cylindrically convergent and focused

By C. P. Lawhon, J. P. Simpson, W. M. Evans

Data obtained under controlled test conditions using a microbit drilling machine showed that oil emulsified in water muds may either increase or decrease the drilling rate, depending upon drilling conditions. A low-viscosity oil such as diesel fuel can give drilling rates in limestone almost equal to that of water. Data obtained for water emulsified in oil muds showed little decrease in the drilling rate in water-saturated cores as the water percentage of the mud was increased above the 5- to 10-percent range. Changes in drilling rate were found to be dependent upon the oil or water concentration of the mud and upon the type of formation drilled. Changes in static filtration on paper (API filtrate) did not correlate with filtration while the mud was circulated across rock. INTRODUCTION Oil additions to water muds have been reported to increase drilling rates, provide hole stability and improve filtration control. Eckel' showed that water-base emulsion muds used in the West Texas area increased drilling rate with increasing oil concentration up to 15 percent oil by volume, but drilling rate decreased at a concentration of 20 percent by volume. Based on laboratory tests using water muds to drill shale, Cunningham and Goins' reported that drilling rates increased and tendency for the bit to ballup decreased with the addition of oil. Percentage increase in drilling rate varied with the particular formation. They showed oil additions to improve drilling rates ap proximately 75 percent in Vicksburg shale and as much as 150 percent in Miocene shale. Each investigation showed an optimum oil content for the particular formation. Most data that indicated improved filtration control due to oil additions were based on static API Eltrates through paper rather than dynamic filtration through permeable rocks. Some types of dynamic test give a better representation of filtration down-hole while drilling and might be more likely to show some correlation with drilling rate. Static filtration would be important, of course, in relation to hole stability and formation damage. This laboratory's drilling tests, conducted on water-raturated Berea sandstone, indicated that improvements in drilling rate were not evident with increasing oil concentration in water-base muds. Investigation also showed similarity between oil-emulsion (water-in-oil) muds and water-emulsion (oil-in-water) muds while drilling these formations. In Lueders limestone high concentration of water-in-oil muds and high concentration of oil-in-water muds provided the same relative drilling rates. In Berea sandstone there was a large reduction in relative drilling rate with both the oil and water muds that contained low percentages of emulsified fluid. Dynamic filtration rates of water muds on rock did not always decrease with increasing oil percentages even though the static API filtration rates on paper did decrease. Data observed in laboratory drilling of limestone and sandstone indicate that improvements in field drilling operations when water- or oil-emulsion muds are wed may not be the result of increased drilling rates but of improved hole conditions. In some cases, actual drilling rates might be slower but improved hole conditions will result in less total time on the hole. DEFINITIONS Mud pressure—Pressure of drilling fluid as measured after leaving the drilling chamber. This is considered as the approximate mud pressure just past the bit and at the face of the formation. Terrastatic pressure—Pressure representing weight of overburden. Formation pressure—Pressure of formation fluid as measured at outlet of drilling chamber. This is considered as approximate pressure of fluid in the pores of the formation. Differential pressure—Difference between the mud pressure and formation pressure. Relative drilling rate, percent—Drilling rate with experimental fluid divided by drilling rate with water times 100 equals percent. LABORATORY EQUiPMENT AND TESTING PROCEDURES The drilling equipment has been described in previous publications The microbit drill is a closed system (capacity, approximately 7 gal) that can be pressurized to 15.000 psi and heated to 500F. Main components are a drilling chamber, filter-heater, rotary-drive and variable-speed cir-

By B. J. Kochanowsky

TO improve blasting methods it is necessary to know how the explosive force acts and how rock resists this force. Because of the tremendous power developed within milliseconds and the great number of other factors directly affecting the technical and economic results, an analysis of the fundamentals of blasting theory is difficult. But since the rules used for layout design and for calculations of size of explosive charges are based on theoretical assumptions, complete knowledge of blasting theory has great practical importance in mining. Analysis of Blasting Theory: It is interesting to note the opinion of blasting experts with respect to contemporary blasting theories. F. Stussi; Professor of the University of Zurich, stated: "We do not have enough experience yet to change our army engineering regulations in blasting and base it on new fundamentals. It is our duty to collect more practical data and to do more research in blasting to close this gap." K. H. Fraenkel,2 editor of the Manual on Rock Blasting published in 1953 in Sweden and written by well-known Swedish, German, Swiss, and French blasting and explosive experts, said: "To the best of our knowledge no suitable formulas for civil blasting work are to be found in the American, French or German literature." Present blasting theory is based upon two assumptions. 1) The blasting force of explosive acts in concentrical and spherical form. 2) Rock resistance against the explosive force is directly proportional to the strength characteristics of the rock. The first classical formula based on theoretical fundamental in blasting theory for explosive charge calculation was introduced by Vauban, a military engineer who lived 300 years ago. It was Vauban who proposed the famous formula L = w3 q, where L is the explosive charge, w = line of least resistance, and q = specific explosive consumption proportional to the weight of rock. Later engineers used q as proportional to the strength of the rock. Since Vauban's time different suggestions concerning blasting theory have been proposed. However, the principles stated at that time so affected the thinking of later generations that his formula is still in use and practically unchanged. The first controversy concerned the form of crater. It was found that geological features of rock affected its form. The factor q was analyzed thoroughly by Lares3 and later by Ohnesorge," Weichelt,5 Bendel,6 and others, but the assumption remained that resistance against explosive force is directly proportional to the strength of the rock blasted. The greatest controversy, which has not yet been settled, concerned w. It was noted that w3 is more appropriate for long lines of resistance and w2 for lines of resistance less than 15 ft. Based on the assumption that the explosive force acts concentrically and spherically, spacings between charges were limited to distances not greater than the length of line of least resistance. Sometimes larger spacing is recommended, but this is due to the advantageous geological and physical properties of rock and not to the action of an explosive force as such. In addition to the classical formula, empirical formulas are used widely. These state that the explosive charge is directly proportional to the volume of blasted rock in cubic yards, and the amounts of explosive required are usually expressed in pounds of explosive per cubic yard of rock. Empirical and classical formulas are contradictory. In the empirical formula, but not in the classical formula, explosive charge is taken proportional to all three space axes: line of least resistance, spacing, and bench height. In spite of this contradiction, both formulas give good results. This is possible because as now practiced the explosive charge calculation for heavy burdens need not be highly accurate. Each, open pit or quarry, usually works with a certain relation between bench height and line of least resistance and between charge spacing and line of least resistance. When these relations are changed, however, the specific explosive consumption q changes greatly. This is one of the reasons why the principles on which the formulas are based appear to be incorrect. In addition to the formulas discussed, others exist and are based more or less on the same theoretical

Jan 1, 1956

By W. O. Philbrook, H. E. Burner, F. S. Manning

The equation of continuity for the hydrogen reduction of hematite in a fixed bed of closely-sized particles is solved assuming a flat velocity profile, negligible temperature gradients, md negligible axial diffusion. A kinetic expression from the literature is used which assumes the reduction process is controlled at the oxide-metal interface. The integral fractional conversion is computed, and the importance of particle diameter, flow mte, temperature, bulk axial diffusion, and inter- and intra-particle mass trarnsfer is predicted. Comparison with experimental data suggests one or more additional undefined variable(s) is significant. Equipment modifications are suggested for fidture experimentcll work. WITH the increasing desire to "design" the ore feed of a blast furnace, it has become necessary to define more quantitatively the process variables and to evaluate the extent of their control upon the reduction process. The bulk of the work reported in the literature has centered about the reduction of single particles; however, the blast furnace process more closely resembles reduction of a fixed bed than that of single particles. To simplify this analysis, the isothermal reduction by hydrogen of a natural hematite in a fixed bed of closely-sized particles is examined. With appropriate modifications in the kinetic and flow rate expressions, the approach employed should be extensible to mixtures of carbon monoxide, hydrogen, and inert nitrogen, and to adi-abatic conditions, thus approaching the blast furnace process more closely. The fixed bed variables which are investigated in this study are particle diameter, flow rate, temperature, and bulk axial diffusion, as well as inter-and intra-particle mass transfer. Of particular interest is the effect of particle size upon fractional conversion for a bed operating under constant pressure drop. The constant pressure drop concept bears a close resemblance to the blast furnace process, where regions of larger particles may provide a greater permeability to divert most of the reducing gas flow from the regions of smaller ore particles. Under such conditions one would expect qualitatively that, for sufficiently small particle sizes where the flow rate is small and the total surface area is large, the reduction rate would be limited by the gas flow rate. Initially the gas entering the bed reacts very rapidly and the composition approaches the equilibrium conversion value a short distance from the reactor inlet. This concentration "wave-front" then moves up the bed as the flow of reducing gas is continued, leaving in its wake an ever increasing layer of reduced particles. Providing that the reducing gas leaves the bed at equilibrium concentrations, conversion is expected to increase with an increase in flow rate, and hence with an increase in particle diemater. Conversely, for sufficiently large particles the flow rate will be high but the surface area available for reaction will limit the reduction rate. Since the total surface area decreases with an increase in particle size, conversion, in this case, is expected to decrease as the particle diameter is increased. It is clear then that between these two extremes an optimum particle diameter must exist. THEORETICAL DEVELOPMENT Above the temperature where wiistite is stable (about 560°C) the reduction of hematite proceeds through the series Fe2O3/Fe3O4/FeO/Fe. On the basis of microstructural studies and earlier work, Edström1 has postulated a mechanism for the reduction of an ideal hematite lattice: 1) Iron phase formation at the boundary between wiistite, iron, and gas (for sufficiently porous iron). 2) Diffusion of iron across a wustite layer. 3) Phase boundary reaction of Fe3O4 to FeO. 4) Diffusion across a dense magnetite layer. 5) Phase-boundary reaction of Fe2O3 to Fe3O4. According to the mechanism postulated, gaseous reaction product has to be removed only at the boundaries between wüstite and iron or gas, the only possible exception being enveloped Fe3O4 specks. On this basis McKewan2,3 has proposed that one may consider the hematite reduction process as a simple two-phase system of oxide/metal. If, for FeO and Fe3O4 layers of negligible thickness, the hypothesis is made that the rate of formation of a

Jan 1, 1963

By Jun Hino, P. G. Shewmon, P. A. Beck

THE investigations of Crussard,' of Guinier and Tennevin,' and of Dunn and Daniels," indicate that the subgrains formed in a cold worked and annealed metal are capable of growing at each other's expense during annealing, if the temperature of annealing is sufficiently high and the time is long enough. The results of Dunn and Daniels are particularly convincing in showing that subgrain growth is essentially the result of the free surface energy associated with the subboundaries. In subgrain growth, as in ordinary grain growth, energy is gained as a result of the decrease in total subboundary surface area per unit volume. Recently, Wood and Scrutton4 found that the rate of subgrain growth upon annealing increased very considerably, if simultaneously a creep strain was applied to the specimen at a low strain rate. Working with 99.98 pct pure fine-grained aluminum, these investigators found that the continuous X-ray diffraction back-reflection rings of material strained at room temperature remained continuous after heating for ten days at 250 °C. However, when heated at the same temperature under a stress of 1000 psi even for only three days, the formerly continuous X-ray diffraction rings broke up into numerous dots, which were fairly clearly separated from each other. The continuous X-ray diffraction rings were interpreted as indications of a very small subgrain size, not resolved by the X-ray diffraction method used. The breaking up of the continuous X-ray diffraction ring during annealing under stress was taken as an indication of a great increase in subgrain size, so that the individual subgrains could then be resolved. The effect of simultaneous strain at a low strain rate in accelerating subgrain growth, discovered by Wood and Scrutton and designated by them as "cell growth," is of fundamental importance. The experiments described in this note were carried out in order to confirm Wood and Scrutton's results by direct metallographic observation. Also, information was sought as to the minimum creep strain necessary to produce this effect. A fine grained high purity aluminum strip was prepared by alternate 33 pct rolling and annealing treatments for 1 hr at 350°C. Specimens cut from this strip were subjected to a relatively fast creep strain of 7.2 pct in 3.5 min at 300°C under a constant load initially corresponding to 1185 psi. The subgrains set up were large enough (about 0.015 to 0.03 mm) to be clearly observed (Fig. 1) at X200 magnification with polarized light, after electrolytic polishing and anodic etching, producing a fine oxide film." The corresponding X-ray diffraction pattern is shown in Fig. la. After the fast creep strain treatment a portion of the specimen was subjected to a creep strain of 8.3 pct in 44 hr at 350°C under a constant load initially corresponding to 320 psi. Another portion, annealed under the same conditions, but not strained, served as control specimen. The subgrain size of a typical area of the specimen annealed under strain and of the one annealed without strain is shown in Figs. 2 and 3 (X-ray diffraction patterns, Figs. 2a and 3a). Annealing without strain produced clearly observable subgrain growth (subgrain size: about 0.03 to 0.05 mm). The effect of simultaneous strain was to increase greatly the rate of subgrain growth (resulting in a subgrain size of approximately 0.05 to 0.13 mm), in accordance with Wood and Scrutton. In another experiment, the effect of the amount of simultaneous strain was studied. The initial subgrain structure was set up by fast creep, as described previously. The specimen was then heated at 350 °C under a constant load initially corresponding to 320 psi, as above, for 2.2 hr (0.24 pct strain), and 8.8 hr (0.58 pct strain). Comparison with the corresponding unstrained control specimens by means of X-ray diffraction showed that 0.58 pct strain definitely had an effect, but the effect of 0.24 pct strain was doubtful.

Jan 1, 1953

By J. C. Sarace, S. M. Sze, C. R. Crowell

Thin films of tungsten 077 n-type germanium, silicon, and gallium arsenide were obtained by reacting tungsten hexafluoride with the semiconductor surface in an argom atmosplrere at temperatures between 325° and 400° C. Capacity-voltage, current-iloltage, and photoelectric measurements were used to investigate the characteristics of the tungsten -semiconductor diodes thus Produced. The junctions are shown to he very close to ideal Schottky barlp/ers with barrier heights measured with respect to the Fermi energy of 0.18, 0.65, and 0.78 1.1 jar W-Ge, W-Si, and W-GaAs, respectively. The electrical properties of the W-Si interface show no deterioration when heated to 1000°C in dry forming gas for 5 min. A theoretical value of the Richardson constant, A, appropriate to the semiconductor-hand structure has been used in evaluating the current-voltage characteristics. ThE W-Si surface-barrier diode was initially proposed for investigation because the eutectic temperature with silicon (1400°C) is much higher than that in the Si-Au system 1370°C).1 This would permit more flexibility in heat treatment and possibly provide greater reliability at elevated temperatures. The lower work function of tungsten (4.54 ev)2 compared with that of gold (4.78 ev)3 also suggested that a lower barrier height would be obtained with tungsten and hence a lower forward bias and lower minority carrier injection ratio for a given current density. The investigation was extended to include the characterization of W-Ge md W-GaAs surface-barrier diodes. The tungsten films have been produced by reacting WF6 with germanium, silicon, and GaAs surfaces in an argon atmosphere at temperatures from 300° to 500°C.4 This process is a very satisfactory alternative to the relatively difficult process of evaporating tungsten films in vacuo. To ensure an adequate electrical characterization of the tungsten-semiconductor interface, three types of barrier-height measurements have been performed. The mutually consistent results obtained lead to the conclusion that the tungsten-semiconductor junctions are indeed of the Schottky type. EXPERIMENTAL PROCEDURE The apparatus used for producing tungsten films is shown schematically in Fig. 1. It consists of an argon carrier gas line to which metered amounts of tungsten hexafluoride can be rapidly added. The mixture passes through a heated reaction tube containing the semiconductor slices and is exhausted to a hood. The argon is purified by passage through a 6-in. column of titanium turnings maintained at 800°C. The tungsten hexafluoride dispensing arrangement was designed by V. C. Garbarini and W. R. Bracht.4 A measured amount of liquid tungsten hexafluoride is injected into the argon stream and vaporizes. The mixture passes through a sodium fluoride absorption cell to remove traces of hydrogen fluoride, then into the nickel reaction tube. The tube is 12 in. long with an inside diameter of 1/2 in. The center section is heated by a furnace of the self-supporting wire-filament type. It was chosen for its rapid heatup and cooling. The wall thickness is 10 mils except for a 3-in. hot zone which is 30 mils thick to reduce thermal gradients along the length. The samples to be coated are placed on a sapphire plate and centered in this section. The tungsten is deposited with the following sequential steps: the loaded reaction tube is flushed with argon at a rate of 500 cu cm per min and heated to 370°C. Then 0.45 g of liquid tungsten hexafluoride is injected into the argon stream. The samples are held at this temperature for 2 min. The tube and samples are then cooled to room temperature and the samples removed. Tungsten films were grown on (111) faces of silicon and germanium polished with Linde A abrasive and lightly etched with HF-HNO3. The GaAs surfaces were (100) faces chemically polished with a H2SO4-H2O2 solution. The films have typical sheet resistances of 0.2, 8, and 15 52/0 when grown on germanium, silicon, and GaAs, respectively. After the tungsten deposition, ohmic contacts were alloyed on the back surfaces of the wafers. Ohmic contacts to the germanium and silicon were obtained by alloying Au-Sb at 370°C, ohmic con-

Jan 1, 1965

By Albert S. Trube

The purpose of this paper is to clarify the definition of compressibility and to present a uniform basis upon which instantaneous compressibilities of liquids and gases can be compared. The equations gaverning the instantaneous compressibilities of imperfect gases are derived and the concept of pseudo-reduced compressibility is introduced. Part of the data presented by Brown, Katz et a1 on compressibility factors for natural gases has been rearranged. A graph of pseudo-reduced compressibility vs pseudo-reduced pressure for various pseudo-reduced temperatures is presented. The need for additional work in relating the compressibilities of liquids and gases is discussed. This information should be of value to reservoir engineers in making non-steady state performance calculations in gas reservoirs. It should be of further use irz pointing the direction for additional research in the nature of liquid and gas compressibilities. INTRODUCTION With the increasing use of steady and non-steady state well and reservoir data, there is a corresponding increase in the importance of the various factors entering into such calculations. Increasing emphasis is being placed on the necessity for obtaining reasonably accurate estimates of the physical properties of the reservoir fluids well in advance of the more accurate laboratory data. One such factor is the isothermal coefficient of expansion of the media which are transmitting and attenuating the non-steady state pressure waves. The average isothermal coefficient of expansion, or "compressibility" is a complex function controlled by the physical properties of the formation and the fluids contained therein. The isothermal expansion coefficients for reservoir gases are usually quite variable, in many cases being highly-pressure sensitive. The coefficients for reservoir liquids tend to be pressure sensitive, but not nearly so much as reservoir gases. The coefficients for solids, usually expressed in terms of a "modulus of elasticity" are relatively insensitive to pressure variations within their elastic limits. For this reason, and also because many previous applications have been limited to rel- atively small pressure ranges, there has been a tendency to ignore the variable nature of isothermal expansion coefficients and treat them as constants. Also, the term "compressibility" by which these coefficients are generally designated is commonly confused with a similar term, z, used to define the deviation of an imperfect natural gas from the perfect gas laws. A clear distinction should be made at the outset between the term "compressibility", which is an isothermal coefficient of expansion of a substance, and the term "compressibility factor", z, which refers to the deviation of a gas from the perfect gas laws. Although the scope of this paper is limited to the compressibility of single phase natural gases, it is definitely related to the problem of accurately estimating the compressibilities of single phase hydrocarbon reservoir liquids, which will form the basis of a future presentation. BASIC PRINCIPLES The coefficient of isothermal compressibility of a substance, c, is usually determined from pressure-volume or pressure-length -measurements depending upon whether the substance is single phase gas, liquid, or solid. A convenient method for making such estimates for a finite change in pressure and volume at constant temperature is to use the well known equation V1-V2/V1 (p2 - p1) .....(1) Eq. 1 is negative because the volume of a confined substance decreases as the pressure is increased. In this case V1 > V2 and p2 > p1. This equation is useful in approximating the compressibilities of single phase gases and liquids undergoing small pressure changes. It is evident, however, that this equation is almost identical with the determination of Young's modulus of elasticity for solids. If the assumption is made that change in length is directly proportional to change in volume, as would very nearly be the case for a steel rod in tension within its elastic limit, then E5=-L1 (p2 - p1)/L1 - L2 .......(2) in which E. is the isothermal expansion coefficient, or Young's modulus of elasticity, for a solid. And further, for this special case L1 (p2 - p1)/L1 - L2 .......(3)

Jan 1, 1958

By John E. Young

U.S. Steel Corp.'s Winifrede mine is operated by Lynch District in the mountainous region of eastern Kentucky. This region is characterized by narrow finger ridges and precipitous slopes, which present both an opportunity and challenge in the design and selection of coal-handling facilities for the movement of coal from the section belts to the railrod cars. Lynch District selected diesel-powered locomo¬tives and 100-ton articulated cars capable of negotiating sharp curves. The drop¬bottom mine cars are equipped with longitudinally hinged doors that are auto¬matically opened and closed. Lynch District selected a large-diameter steel-lined borehole for lowering the coal approximately 1000 ft from the seam level to the valley floor railroad load-out point. Taking advantage of gravity, the presized coal is "lowered" vertically approximately 720 ft to existing entries of a previously abandoned mine. The coal is then conveyed horizontally into storage. The coal¬handling facility from the mine-car dump to the railroad load-out point is fully automatic through use of tone control. TV cameras are installed along the facility to continuously monitor the strategic points. The diesel locomotives are either directly operated or remotely radio-controlled, depending on the functions Per¬formed. U.S. Steel Corp.'s Winifrede mine is operated by Lynch District in the mountainous region of eastern Kentucky. This region is characterized by narrow mountain ridges and precipitous slopes which present both an opportunity and challenge in the design and selection of coal-handling facilities for the movement of coal from the section belts to the railroad cars. The narrow finger ridges precluded use of under¬ground haulage and, thereby, presented the opportunity to use high-capacity equipment on the outside bench. The precipitous mountain slopes, steepest at the Wini¬frede seam horizon, presented a challenge to select a solution for lowering the coal approximately 1000 ft from the seam level to the valley floor railroad load-out point. It was evident from the start of planning that these two factors predominated; namely, rail haulage and coal lowering, and solutions to these would determine the final design of the Winifrede mine coal-handling facilities. The Winifrede mine derives its name from the Wini¬frede Seam which comprises the total reserve recov¬erable from this facility. The seam is 5 ft high with a good siltstone bottom and competent shale or sandstone roof. The seam is at an elevation of 2700 ft where the mountain ridges are long and narrow. This configuration of the reserve was ideal for conveyor belt installation to transport the coal from the working face to the outside bench. The preclusion of underground rail haul¬age permitted an opportunity to review the type of locomotive power and to select high-capacity equipment without the limitations associated with underground systems. Since the basic electrical design of the mine was al¬ternating current, with rectification to direct current for shuttle cars required only in the face areas, there was no point in bearing the burden of additional cost of dc trolley installation. And, since the haulage would re¬quire only a few tunnels to negotiate sharp points and to reach the back side of the reserves, diesel power was selected for the haulage locomotives. To provide stability on the almost continuously curv¬ing track and to provide the maximum width of haul¬age equipment, both locomotives and mine cars, stan¬dard railroad gage was chosen to offer the largest choice of equipment. The decision was made to select a standard 45-ton railroad diesel locomotive but to lower the cab height to reduce tunnel excavation requirements. The mine car was the next challenge. Past experience in Lynch operations indicated that drop-bottom cars would be a successful application with the free-flowing coal. The search was for a drop-bottom car within the dimensions of the locomotive to discharge the coal in the shortest time. Numerous types were considered and visits made to various sites to observe cars in operation.

Jan 1, 1972

By J. H. Jackson, J. G. Kura, M. C. Udy, L. W. Eastwood

The melting and casting of any commercial metal depends upon the success with which the problems attendant to the handling of the specific metal are overcome. Common difficulties encountered in the handling of commercial metals are tendencies to burn or oxidize excessively, low fluidity, entrapment of dross, hot cracking, cold embrittlement, cold shuts, and un-soundness caused by gas evolution. Beryllium is not only subject to these same difficulties but is generally more sensitive to them than are the more common metals, thus necessitating more exact founding precautions. Characteristics of Beryllium Certain characteristics of beryllium which make it particularly difficult to handle in the plant or laboratory are as follows: 1. The melting point of beryllium is about 2400°F and pouring temperatures vary from 2600 to 2900°F, depending upon the degree of fluidity required. The extreme chemical activity, combined with the high temperatures, makes necessary the use of inert atmospheres, slags, or vacuum for protection during melting and pouring. Furthermore, beryllium tends to react with the melting crucibles, tools, and molds, thus requiring the selection of suitable materials and proper maintenance of these items. 2. The very marked absorption of gas by molten beryllium and the subsequent evolution of gas during solidification causes a great deal of difficulty with unsoundness. Beryllium castings may also be subject to unsoundness as a result of gas formation by chemical reaction with the mold surface during solidification. 3. The very marked chemical affinity between molten beryllium and the normal atmosphere causes the formation of dross. On relatively quiescent melts, this dross forms a very tenacious film which, if carried over to the mold, can cause defects such as the formation of skins or dross in the interior or on the surface of the casting; folds or defects similar to cold shuts may also be found. 4. During the pour and attendant turbulence, the dross may be mixed into the metal and then carried to the casting. There it may be entrapped during freezing and cause internal defects, or it may float to the surface and cause severe dross defects on the cope side of the castings. 5. Solid beryllium is very weak at a temperature near the solidus line; brittleness is also a problem at lower temperatures. Thus, hot and cold cracking must be guarded against. Scope of the Experimental Work All of these problems have been given consideration in the work at Battelle. Before the work was started at Battelle, it was customary to melt beryllium in a vacuum furnace or under flux in graphite-lined induction furnaces. Because of the difficulty of preventing gas unsoundness in beryllium castings, an investigation was undertaken primarily to study this particular problem and, secondarily, to devise methods of overcoming the other difficulties encountered in the founding of beryllium. The objectives of the laboratory work were multifold: 1. To devise a practical method of melting, other than vacuum melting, by means of which consistently sound beryllium castings could be produced. 2. To obtain fundamental data which would promote a better understanding of the causes of gas unsoundness in beryllium. 3. To develop a casting technique which would permit low melt temperatures, minimize dross defects and hot cracking, and eliminate reaction with the mold surface. Up to the present time, a considerable amount of progress has been made on the first and third objectives, with the result that it can now be safely stated that consistently sound castings can be made by the open-pot melting method, using argon as a protective atmosphere and a proper casting technique. There has been some progress on the second objective of the project, but it cannot yet be safely stated that the problem is completely understood. Most of the experimental work has been conducted in an enclosed melting and pouring apparatus in which very-close control of melting variables has been effected. Findings based on the results of the work conducted in this small experimental apparatus have been applied to large-scale melts which have been made by techniques suitable for duplication on a commercial scale.

Jan 1, 1950

By Joseph E. Worthington

The present-day Northumberland gold mine is one of the deposits generally characterized as a Carlin-type occurrence. It lies at the crest of the Toquima Range in Nye County near the center of Nevada. Gold mineralization occurs in two modes, in argillaceous and in silicified limestones, and is generally very fine-grained or micron gold. The Northumberland district has had a history that is typical of many western gold districts: minor production prior to World War II and intermittent exploration thereafter until a combination of geological insight, improved economics, and the advent of heap leach technology created the Northumberland gold mine. Nye County, Nevada, was sparsely populated and little explored in the early years of the settlement of the west; the Northumberland district was not established until 1866. Initial interest was in silver and the district operated as a very small producer for the next seventy years. The disseminated gold occurrences in silicified limestones were recognized and Northumberland Mining Co. was organized to develop the property in the late 1930s. Northumberland Mining Co. actually conducted drilling operations (over 200 drill holes) and mined from small open pits in the silicified limestones. They ultimately produced almost 936 kg (33,000 oz) gold before being shut down by War Production Board Order L-208 in 1942. After World War II gold mining activities were essentially nil for over a decade due to the poor economics of gold production. The property was, however, a known gold producer and attracted recurrent exploration attention. About 45 holes were drilled under the direction of Peter Joralemon for private interests between 1959 and 1963. Next Kerr McGee drilled about 25 holes during 1963 and 1964. Some- what later, in 1968, Homestake drilled 20 holes. The property was then acquired by Idaho Mining Co. which drilled about 30 more holes between 1972 and 1974. By this time the Northumberland mine was becoming somewhat shopworn with over 300 holes drilled. Interest in gold prospects was increasing substantially in Nevada, how- ever, due to rising gold prices in late 1974, and several companies were interested in continuing exploration at Northumberland. In 1975 Cyprus Mines Corp. was successful in obtaining a joint venture arrangement with Idaho Mining Co. for further exploration and development of the property. The overall Cyprus exploration program was under the direction of James G. Hansen, Vice President Exploration. The geologist recommending acquisition of Northumberland was Peter E. Chapman who reported to Joseph E. Worthington, Manager of U.S. Exploration for Cyprus. The basis for selection of the Northumberland mine as an exploration target for Cyprus by Chapman was essentially prior knowledge of regional and 16cal geology and of the mine. Exploration for the next few years was directed by Chapman under the supervision of Worthington. During 1975 and 1976 rotary and check core drilling were conducted that indicated that a substantial Carlin-type or disseminated, low-grade gold deposit occurred in two separate bodies. Drilling was based on geologic mapping and rock chip geochemical sampling. Both ore zones were reflected at the surface as gold and arsenic anomalies in rock chips. Heap leach tests attempted in 1977 were aborted by a flash flood, but were completed in 1978. Engineering studies occupied the next couple of years until the property achieved production in the fall of 1981. It is now producing by open-pit mining with gold recovery by heap leaching and cyanide extraction at a rated capacity of approximately 2722 t/d (3000 stpd) ore. Metal recovery has been projected (probably conservatively) at 5 10 kg/a (18,000 oz per year) gold and 1.6 Mg/a (59,000 oz per year) silver. Reserves are reported to be adequate for ten to fifteen years of production. REFERENCES Anon., 1981, "Gold in Nevada," Span Magazine, Vol. 21, No. 3, Standard Oil Co., pp. 6-9. Koschman, A.H. and Bergendahl, M.H., 1968, "Principal Gold- producing Districts of the United States, Professional Paper 610, US Geological Survey, p. 193. Kral, V.E., 195 1, "Minerals Resources of Nye County, Nevada, Bulletin, Vol. 45, No. 3, Geology and Mining Series 50, Nevada University.

Jan 1, 1985

By E. N. Smith, J. C. Redmond

The increasing need for materials capable of withstanding higher operating temperatures for various applications such as gas turbine blading and other parts, rocket nozzles, and many industrial applications, has brought consideration of cemented carbide compositions. The well known usefulness of cemented carbides as tool materials is attributable to their ability to retain their strength and hardness at much higher temperatures than even complex alloys. However, it has been found that the temperatures encountered in cutting operations do not approach by several hundred degrees1 those involved in the applications mentioned above where the interest is in materials possessing strength and resistance to oxidation at temperatures of 1800°F and above. At these latter temperatures, the tool type compositions which are made up essentially of tungsten carbide are found to oxidize very rapidly and to produce oxidation products of a character which offer no protection to the remaining body. As a further consideration, the density of the tungsten carbide type compositions is high, from about 8.0 to 15.0. The refractory metal carbides as a class are the highest melting materials known as shown by Table 1 which summarizes the available data from the literature for the carbides of the elements which are sufficiently available for consideration for these uses. The density is also included in the table, since as mentioned above it is an important consideration in many of the applications for which the materials would be considered. It has been established that in the tool compositions the mechanism of sintering with cobalt is such as to result in a continuous carbide skeleton and that the properties of the sintered composition are thus essen- tially those of the carbide.2 On the hypothesis that this mechanism holds to a greater or less degree in cementing most of the refractory metal carbides with an auxiliary metal, it appears from Table 1 that titanium carbide compositions would offer possibilities for a high temperature material. Titanium carbide has extensive use for supplementing the properties of tungsten carbide in tool compositions. Although the literature contains several references to compositions containing only titanium carbide with an auxiliary metal,3,4,5,6 it may be inferred from the meager data that such compositions were deficient in strength and were considered to have poor oxidation resistance.7 Kieffer, for instance, reports the transverse rupture strength of a hot pressed TiC composition at 100,000 psi as compared to up to 350,000 psi for WC compositions. The work described herein was undertaken to determine the properties of compositions consisting of titanium carbide and an auxiliary metal and to improve the oxidation resistance of such compositions. It appeared possible that the inclusion of one or more other carbides with titanium carbide might improve the oxidation resistance and also that this might be more desirable than other means from the point of view of maintaining the highest possible softening point. Consideration of the available carbides in Table 1 suggests tantalum and columbium carbides because of their high melting points and general refractoriness. The work on improving oxidation resistance was concentrated on the addition of tantalum carbide or mixtures of tantalum and columbium carbide. The auxiliary metals used included cobalt, nickel and iron. It was also desired to learn the general physical properties of these compositions. Experimental Procedure The compositions used in this study were made by the usual powder metallurgy procedure applicable to cemented tungsten carbide compositions. The powdered carbide or carbides and auxiliary metal were milled together out of contact with air. In some cases cemented tungsten carbide balls and in other instances steel balls were used to eliminate any effect of tungsten carbide contamination. A temporary binder, paraffin, was then included in the mix and slugs or ingots were pressed with care to obtain as uniform pressing as possible. The ingots were presintered and the various shapes of test specimens were formed by machining, making the proper allowance for shrinkage during sintering. Thereafter the shapes were sintered in vacuum at temperatures of from 2800 to 3500°F. Final grinding to size was carried out by diamond wheels under coolant. The titanium carbide used contained a minimum of 19.50 pet total carbon and a total of 0.50 pet metallic impurities as indicated by chemical and spectrographic analysis. It was found by X ray diffraction examination with

Jan 1, 1950

By J. T. Norton, J. G. McMullin

The ternary system of gold-silver-copper is characterized by a solid solubility gap and a two phase region in which copper-poor and silver-poor phases coexist. At about 30 pct gold, the two phases become mutually soluble at temperatures below the melting temperature. As the gold content is increased, the solubility temperature of the alloys decreases until at about 80 pct gold, the two phases are soluble down to the lowest temperature at which the alloys will recrystallize. Although the general form of the two phase region is known, its boundaries do not seem to have been investigated extensively. In an X ray diffraction study, Masing and Kloiberl have outlined the boundaries of this two phase field at 400 and 750°C. Using only microscopic techniques, Pickus and Pickus2 determined a vertical section of the ternary diagram showing the 14 kt alloys (58.3 pct gold). These two reports are riot in complete agreement. It has been shown3 that some of the ternary alloys are susceptible to age hardening and that the hardening is caused by the separation of a homogeneous alloy into two phases at the aging temperature. While the gold-copper binary system is an outstanding example of super lattice formation, Hultgren4 has shown that a few per cent of silver added to gold-copper destroys the tendency for ordering. Because of the age hardening possibilities of these alloys, it seemed advisable to investigate the boundaries of the two phase field more in detail using an X ray diffraction method, so as to permit a better understanding of the aging phenomena and enable predictions as to the behavior of other alloys to be made. This is especially true for the 18 kt alloys (75.0 pct Au) at the lower temperatures since they are known to exhibit age hardening. Twelve ternary alloys were prepared having the compositions shown in Table 1 and graphically in Fig 1. The gold used was fine gold bars supplied by Handy and Harmon. The silver was a bar of high purity silver from the U. S. Bureau of Standards. The copper was a bar of vacuum-treated, high conductivity copper from the National Research Corporation. The pure metals in the form of powder were weighed out in proper proportions and melted in graphite in a high frequency induction vacuum furnace. They were heated to 1100°C and slowly cooled. The ingots were then removed from the crucible, inverted, returned to the crucible and remelted. This remelting procedure was intended to reduce segregation in the ingots. After remelting, the ingots were checked for weight loss. The weight loss in each ten gram ingot was held to less than 25 mg. The remelted ingots were cold rolled and then given a homogenizing heat treatment of 16 hr at 760°C to remove any remaining segregation. Powder specimens were prepared by cutting the ingots with a fine file, one half the required amount of powder being taken from each end of the ingots. When the X ray diffraction pattern showed any difference in lattice constant between the ends of the ingot, the ingot was remelted and given an additional homogenization treatment. All powder samples were sealed in evacuated pyrex tubes for heat treatment. Ordinary pyrex proved satisfactory for temperatures up to 650°C but above that temperature it was necessary to use a special high temperature pyrex glass. Annealing at temperatures below 500°C was done in a salt bath whereas for temperatures of 500°C and above an electric muffle furnace was used. In both furnaces the temperature control was ± 5°C. In all annealing treatments samples of cold worked powder were placed in a furnace which was already at temperature. In this manner the specimens recrystallized directly to the equilibrium structure for that temperature. Time at temperature was selected so as to allow complete recrystallization, but very little grain growth. Specimens were quenched from the annealing temperatures by breaking the pyrex tubes in cold water. X ray diffraction photograms were made of all the heat treated powders using copper radiation and a Phragmen

Jan 1, 1950

By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967

By T. O. King, Y. P. Gupta

The self-diffusion of sodium in two sodium silicate liquids was measured in the temperature range 850" to 1500°C by the capillary-reservoir technique. Radioactive Na 22 was used as the tracer. The total count and autoradiographic methods were used for determination of the total Na 22 depletion and diffusion profiles of the dqy-used specimens. The diffusion coefficients obtained by the autoradiographic technique are slightly smaller than those obtained by a total count method. Error analysis of the two methods suggests that more confidence be placed in the results of the total count method. The experimental results were analyzed in terms of the existing activated rate process theory. The activation energy for diffusion was shown to decrease markedly as the temperature increased. This was attributed to a variation in the heat of activation with temperature, probably related to a change in the distribution of anions associated wilh the cation. In terms of a model, suggested for diffusion in liquid silicates, differences in the aclivation energies for diffusion and electrical conduction may arise from the effect of the electric field applied in conduction measurements. It is generally accepted that liquid silicates consist of cations and an equilibrium distribution of complex anions determined by temperature and composition. Transport properties in molten silicates are of interest, not merely because of their relevance to the kinetics of pyrometallurgical reactions and glassmak-ing processes, but also because they are useful to development of the theory of such ionic liquids. Self-diffusion is one such transport process that may, if studied for liquid silicates of widely varying compositions, indicate structural changes through changes in the activation energy for diffusion. The self-diffusion of calcium, silicon,' sulfur: aluminum, 4 and oxygenS in lime-alumina-silica melts and of iron6 in molten iron silicates have been measured. Unfortunately, the errors in some of the reported activation energies for diffusion are too large to allow firm conclusions concerning structure and the mechanism of the diffusion process to be drawn. The research reported here was a study of the self-diffusion of sodium in liquid sodium silicates. The soda-silica system was chosen since: i) a reasonable composition range can be covered in the binary system at moderate temperatures; ii) suitable isotopes of sodium (radioactive Na 22 and NaZ4) can be obtained; iii) data on the electrical conductivity and viscosity of sodium silicate liquids are available. However, the range of composition actually used in diffusion experiments was limited, to 20 to 35 wt pct soda, by the relatively high viscosity of silica-rich compositions and by evaporation of soda from basic melts. EXPERIMENTAL PROCEDURE The capillary-reservoir technique was used, wherein a radioactive tracer, Na 22, incorporated in the capillary melt, was allowed to diffuse out of the platinum capillary tube into a large reservoir of silicate liquid containing a chemically identical melt, but without radioactive tracer. After a specific diffusion time, both the total depletion in the tracer concentration and concentration-distance profiles of the diffused samples were measured by procedures to be described later. The diffusion cell assembly was similar to that used by Koros and King.' The temperature of the diffusion cell was measured with a calibrated Pt, Pt-10 pct Rh thermocouple located at the center of the liquid reservoir. The same thermocouple was used to obtain the temperature profile in the reservoir. The temperature at the top of the reservoir was slightly higher (2°C) than that at the bottom, to minimize convection in the capillary tubes, which were placed, open end up, in the reservoir. Convection was not expected to be a problem since the length-to-diameter ratio of the tubes was about 12:1 and the maximum capillary diameter was 1 mm. The diffusion cell was heated in a molybdenum-wire resistance furnace, previously used by Koros and King, but somewhat modified. A Pt, Pt-10 pct Rh thermocouple enclosed in an alumina tube and located near the furnace winding was used in conjunction with a preamplifier and Micromax proportional controller for temperature control, within 4°C, at temperatures near 1500°C. Before starting a diffusion run, the furnace was heated to the desired temperature and an alumina guide assembly for the capillaries was slowly lowered to within 2 cm of the liquid reservoir. The capillaries were thus heated to about the temperature of the bath. The run was started by lowering the assembly till the open ends of the capillaries were about 1 cm below the surface of the liquid. The run was ended by raising the assembly to about 15 cm above the liquid bath. Later, the sample assembly was slowly withdrawn from the furnace. Six diffusion samples were usually run at the same time. Three runs made with the open ends of the capillaries down were discarded because in the majority of these samples air bubbles trapped at the open end were observed. Some glass adhered to the outside of the capillary on withdrawal. This was carefully removed and used to check that the Na 22 activity in the sink remained at a low level. Materials. Nonradioactive sodium silicates were prepared by melting, in a platinum crucible, weighed quantities of sodium carbonate and powdered silica. To prepare radioactive sodium silicates, Na2 obtained in HC1 solution, was first checked for radioactive impurities by obtaining a y-ray energy spectrum, then the chloride ions were removed by anion-ex-

Jan 1, 1968

By R. F. Krueger

Results are presented from tests of dynamic fluid-loss rates to cores from clay-gel water-base drilling fluids containing different commercial fluid-loss control agents (CMC, polyacrylate or smt,ch), organic viscosity reducers (quebracho and complex metal lignosulfonate) and oil at several different levels of concentration. In the dynamic system the most effective individual additives to the clay-gel drilling fluid, based on cost-equalized concentrutiom, were found to be starch and the viscosity reducers. These results do not conform with the rankings determined by API fluid-loss rests, which indicate CMC, polyacrylate and starch to be the most effective and comparable. Generally, minimum dynamic fluid-losr rates were attained at cost-equalized concentrations of additive (including thinner) of about $1.00/ bbl, or less. For chernically treated clay-gel drilling fluids, both the standard and the high-pressure API filter-loss tests were found to he inaccurate indicators of trends in dynamic fluid-loss rates under the test conditions used, particulurly for drilling muds containing viscosity reducers. From a practical field viewpoint, restrictions on the applicability of the API fluid-loss test are such that it is open to question whether or not results of this test can be used routinely with confidence as an indicator of control of down-hole fluid loss under field treating conditions. INTRODUCTION The petroleum industry spends large sums of money during drilling operations to control the fluid-loss properties of drilling fluids based on the standard API filter-loss test,' which is a static filtration system. Laboratory studies' ' of dynamic filtration have shown that in a given time period filtrate loss from a circulating mud stream is greater than from a static system and that it is a function of linear mud velocity, pressure and the properties of the drilling fluid. Ferguson and Klotz' and Horner, et al," observed that (I) the dynamic fluid-loss rates for the drilling fluids used were not related to the extrapolated API filter loss and (2) the drilling fluids with the lowest API filter losses did not have the lowest dynamic fluid-loss rates. However, there has been no published information on the relative effects on dynamic fluid-loss rate as a given drilling fluid is treated with increasing amounts of chemical additive to reduce the API filter loss. Such information is economically important because drilling-fluid costs rise rapidly as chemical requirements increase. This paper presents the results of a study of dynamic filtratioi rates to cores from a clay-gel water-base drilling fluid treated with various commercial viscosity reducers and chemical fluid-loss control agents. The dynamic fluid-. loss rates to cores are compared with the standard API filter-loss values at several different levels of additive concentration. Dynamic filtration rates were obtained in each experiment under two different simulated wellbore conditions: (1) filtration just above the bit through a new mud cake laid down dynamically on a freshly drilled formation and (2) filtration up-hole through a mud cake formed by deposition of a static filter cake on top of the initial dynamically formed cake. The latter case corresponds to the bottom-hole conditions existing above the bit when mud circulation is restarted after a stand of pipe has been added or a round trip has been made to change the bit. Except for the short-duration, high-rate filtration beneath the bit where no mud cake can form, these two conditions probably represent the two extremes of dynamic filtration. Because thickness of a dynamic mud cake formed on freshly exposed formation is limited by the shearing action of the mud stream, the filtration rate for this condition is high. On the other hand, once circulation is stopped and a static mud cake forms on top of the dynamic cake, re-starting circulation has only a small effect on the cake properties and filtration rate is much lower thereafter. A discussion of the mechanics of mud-cake deposition and dynamic filtration is outside the scope of this paper but may be found in more detail in publications by prior investigators. APPARATUS AND EXPERIMENTAL CONDITIONS The test equipment used to simulate the dynamic flow conditions existing during drilling was a modification of that described previously by Krueger and Vogel: A schematic flow diagram is shown in Fig. 1. In general, a power-driven, high-pressure mud pump capable of delivering up to 60 gallmin was used to circulate drilling fluid parallel to the faces of 1-in. diameter sandstone cores mounted in a 2 3/4-in. ID high-pressure test cell. Pump rates were controlled by means of a magnetic clutch to maintain an average axial fluid velocity of 110 ft/min in the annular space between the cell wall and a 1 1/2-in. rod positioned on the center line of the cell. The core specimens were Berea sandstone plugs sealed with plastic inside 1 1/8-in. OD tubes and were fluid-saturated prior to use. Burettes were used to accumulate fluid discharged from the cores. The mud sump shown was used for treatment and storage of the drilling-fluid samples during a particular test. The valve arrangement permitted either (1) circulating drilling fluid through the by-pass line while treating with

By G. A. Vissac

The drying of fine coal involves special techniques, which are discussed and analyzed. Types of dryers employing these techniques are described. Calculations are presented for new methods of dealing with the entrained dust that is always present in fine coal drying operations. NEW conditions, new requirements, and new methods have increased the demand for more efficient and more economical methods of drying fine coal. Dewatering of larger sizes may reduce the surface moisture to 8 or 9 pct. It is more difficult, however, to dewater sizes below 1/4 in., and some filter cakes still contain as much as 20 or 25 pct moisture. Increased freight rates and stricter consumer specifications have resulted in a demand for further reductions in moisture content. This can be obtained only by heat drying. Most modern methods of heat drying disperse or spread the mass of coal to be dried, in an atmosphere of dry hot gases. The more intimate the contact between coal particles and hot gases, the quicker and more efficient the drying operation will be. Two different techniques are generally employed, using either a fluidized condition or an entrained condition of the coal to be dried. Fluidized Condition Fluidization of a body of sand was defined and explained by Fraser and Yancey in a paper published in 1926.' This condition was artificially obtained and maintained by proper regulation of the rate of air flowing through the sand body. "The sand bath 'boils' uniformly on the surface," they write, "and feels like a fluid." The fluidization technique was also described and analyzed by Steinmetzer2 in connection with the operation of an air cleaning table. His main conclusions are as follows: "Fluidity is, for the particles involved, the possibility of motion with minimum friction. . . . Then fluidity requires the introduction of various forms of energy capable of neutralising frictions. Two solutions can be used— air and/or mechanical motions (such as the shaking motion of the carrying deck of the air table). The combination of mechanical and air energy will give the widest margins of size ratios and of bed thickness, translated in capacity per unit area of the carrying table." Richardson and Langston3 have indicated results obtained with a dryer working with a fluidized bed. They used a vertical tube type of dryer, however, without the assistance of any mechanical energy, and without any lateral motion of the fluidized bed. The capacity of such a dryer is too limited for practical applications, since the speed of the acceptable air currents is held to the speed of fall of the particles involved. Capacities as low as 182 Ib of coal per hr per sq ft of dryer area are indicated. As stated by Richardson: "A basic limitation to a fluidised bed dryer is that the velocities of the gas must be held within a definite range; with velocities of 10 ft per second, all coal minus 6 mesh in size will be entrained, and the operation is then similar to that of a Flash dryer." A fluidized bed must be virtually static. The coal particles simply kept in suspension offer a minimum resistance to the flow of gases, insuring the most favorable conditions for rapid evaporation of surface moisture. However, very wet fine coal, i.e., over 12 pct of surface moisture, will be delivered in the forms of mud balls, or as a soggy, sticky mass, almost impossible to disperse, sticking and acting as a wet blanket on the deck. Strong currents of gases and wide deck perforations will be required to punch holes in the wet mass and gradually loosen and fluidize it. The mechanics of fluidizing a bed of coal in a gas medium for the purpose of obtaining the most efficient drying condition are entirely similar when the fluid used is water and the purpose is to break up and distend a bed of coal to be cleaned so that perfect stratification according to densities will be insured. Purely mechanical energy is used in the basket-type jig, water pulsations in the piston and in the Baum-type jigs. A combination of mechanical motion and of air pulsation offers the most efficient and favorable conditions. Entrained Condition The most critical factor to be considered in the design of a dryer employing the entrained condition technique is the speed of the hot gases to be circulated in the drying column. With insufficient gas velocity, excessive amounts of the largest sizes will drop to the bottom of the dryer column without being thoroughly dried. On the other hand, high gas velocity will cause degradation, dust losses, and high power consumption. Figs. 1 and 2, reproduced from Hanot,4 show the relative importance of speed and temperature for various sizes of particles. It can be seen, for instance, that to maintain in unstable equilibrium particles of 1/4-in. size in a gas current at 500°C, a speed of 30 meters per sec, or 6000 fpm, will be required. For % -in. particles an almost prohibitive speed of 45 meters per sec, or 9000 fpm, will be necessary. In practice, maximum gas velocities of 3000 fpm are recommended; since power increases as the cube of the velocity, it can be seen that beyond certain limits such dryers would not be economical. If the particles were moving at the same speed as the hot gases they would remain in the same

Jan 1, 1954

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today's most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By G. W. Brownell, H. T. F. Lundberg, R. W. Pringle, K. I. Roulston

The rapid improvement of the airborne scintillometer and the perfection of its efficiency for counting low energy gamma radiation has made it possible to work out a technique to map in great detail the radiation pattern at the earth's surface. On such maps low radiation over certain areas appears to indicate the existence of oil accumulations, forming a pattern similar to that obtained by the geo-chemists. RADIOACTIVE analyses of samples from the surface of oil fields were carried out more than 10 years ago in Alberta by the alpha particle ioniza-tion chamber technique,' but large enough tracts could not be covered in these investigations to make possible any evaluation of the method as a means of oil exploration. Considerable interest has recently been revived, however, as a result of certain striking advances which have been made in the instrumentation available -for the measurement of radioactivity. It is the object of this paper to indicate the nature of these improvements in radiation technology and then to describe the attempts that have been made to interpret the radioactive patterns obtained in the course of airborne recordings with the new instruments. Since the survey can be carried out from the air and records can be accumulated over vast areas in a short time, the result may easily lend itself to statistical treatment. Areas have been surveyed in Alberta, British Columbia, Saskatchewan, Quebec, Texas, New Mexico, Nebraska, Colorado, Utah, and Montana. Producing fields in Alberta and West Texas have been flown over several times in different directions, Fig. 1. The operations were then extended into unknown territory and drill holes were put down on the anomalies which looked promising. The results from these drillings were encouraging and have given hopes for the development of an entirely new method of oil exploration. Any large scale method for the survey of radioactive anomalies must be based on the measurement of gamma rays, as beta and alpha rays have much too short a range to be of any significance. Thus the essential improvement which has made the present stage of this work attainable is the development of new highly sensitive detectors for gamma radiation. In the past the only detectors of any consequence that were available were the ionization chamber and the geiger counter, but both of these suffer from the defect that only a small proportion of the gamma rays passing through the counter are detected, possibly 0.1 to 0.2 pct. The recent development of the scintillation counter2,3 has completely transformed the situation and has had a considerable impact on many branches of nuclear technology. The detection of alpha particles in zinc sulphide screens by visual observation of the individual scintillations which these particles produce dates back to the early spinthariscope of Rutherford and Crookes, but the combined use of an appropriate scintillating phosphor and photomultiplier tube had to await the technical development of the latter many years later. With this development came the modern era of the scintillation counter and a knowledge of phosphors which have a large light output under the bombarding action of gamma radiation. Some of these phosphors are relatively dense and are capable of stopping a large proportion of the incident gamma radiation. As the sensitive region is the whole volume of the crystal, a very high detection efficiency, 50 pct or more, can be obtained for medium energy gamma rays. Scintillation counters for geological purposes were first developed in 19494-6 in an attempt to utilize this remarkable improvement in efficiency, which has the attractive consequence that only a small portion of the normal background of the counter is due to cosmic radiation. In 1949 tests were made in northern Saskatchewan by Lundberg Explorations Ltd. with portable scintillation counters which gave excellent results in the search for uranium and served to indicate unknown uranium deposits in areas previously closely surveyed with geiger counters. Portable scintillometers (registered in Canada) are now commercially available and in regular use,' and the adaptation of the instrument to radioactivity oil well logging has also been very successful.8 Initial attempts to measure radioactivity from aircraft with scintillation counters were made during this period in the same area and yielded most encouraging results. It would be appropriate to consider some specific requirements for airborne investigations. The essential problem to be met in the detection of any radioactive source is the necessity of obtaining a signal greater than the statistical fluctuations of the background counting rate for the instrument. It is possible to show that Nt>2k2 is the condition for detectability of a signal where N = average background counting rate for the detection. t = time constant of the counting rate meter, used to determine the average number of counts arriving in a certain predetermined time interval. N' = average source counting rate at the detector. k = N/N', and N>>N'. Sample values are given in Table I. Assume that the aircraft carrying the equipment is travelling at 120 mph, in which case it will cover 176 ft in 1 sec. Assume also, as a first approximation, that a point source target is in range when the air-

Jan 1, 1954

By P. R. Sperry, A. P. Beck

It has been shown1 that in poly-crystalline strips of high purity aluminum with a fairly random orientation distribution, grain growth progresses gradually until the average grain diameter reaches a value approximately equal to the strip thickness. Recent work at this laboratory led to the realization that grain growth might be impeded to a considerable extent in the presence of a sharply defined texture, where orientation differences between neighboring grains are small. In order to investigate this effect the following experiment was carried out with the same lot of high purity aluminum previously used for grain growth studies in randomly oriented material.' Very large grain size was developed by grain growth at 650°C in specimens of 0.200 in. thickness. These specimens were then rolled to a thickness of 0.050 in. or 1.25 mm—a reduction of 75 pct. In the rolled strip each large grain corresponded to an elongated area easily identified by etching. After annealing for 1 to 25 min at 600°C and re-etching, these elongated areas were again recognizable. Within each area, corresponding to a single large grain before annealing, there formed by recrystallization a multitude of new grains with a fairly well developed preferred orientation. The orientation and the size of the new grains formed in areas corresponding to different large grains, varied widely depending on the orientation of the parent grains with respect to the rolling direction and the plane of rolling. Many areas were found where the average grain size was considerably smaller than the specimen thickness. Such an area occurred in a specimen cut in half before annealing. One half, containing a portion of the area in question, was annealed 1 min at 600°C, the other half, with the remaining portion of this area, for 25 min at the same tempera-Aluminum killed low carbon steel, § which is now used extensively for severe deep drawing or other difficult forming operations, is unusual in that its grain structure, after cold reduction and box annealing in accordance with conventional continuous sheet or strip mill practice, often is elongated, although at times it is equiaxed. Since this unusual structure has been found superior for many, but not all, severe forming operations, recrystallization of the steel, both at constant temperature and on continuous heating, was investigated and compared with that of rimmed steel in the hope that something might be learned about the mechanism of, and the factors controlling, the formation of such elongated grains. In this structure, the grains are elongated both in the lengthwise direction of the strip and transverse to this direction, even though nearly all of the extension in both hot and cold rolling is in the lengthwise direction. The grains are thus roughly pancake-shaped, being longer and wider than they are thick, as observed also by Burns and McCabe,1 and as illustrated by the typical structures shown in Fig 1. Fig la, representing a conventional longitudinal section, shows the length and thickness of the grains, whereas Fig Ib shows their length and width as seen by examining a section parallel to the sheet surface. Both illustrate the very irregular grain boundaries usually associated with the elongated grain shape. A finer equiaxed grain structure in this same grade is shown in Fig Ic. Either the elongated or the equiaxed structure may be present in the annealed product, and in rare instances the two types may coexist in a single specimen, as shown in Fig 1 d. Isothermal Recrystalliza-tion of Rimmed and Alamimum Killed Steel An aluminum killed steel known to have an elongated grain structure after conventional processing (Steel B, Table l), was selected for the initial recrystallization studies; for comparison, a rimmed steel, A in Table 1, was used. Samples of each in the form of hot rolled strip 0.075 and 0.095 in. thick, respectively, were cold rolled on a small laboratory mill in steps of about 0.010 in. per pass to obtain total reductions of 40 and 60 pct. Small pieces of the cold reduced strip were heated in lead at selected constant temperatures for one of several periods of time, then cooled in air. Rate of heating in the lead was, of course, very fast. Hardness of the cooled specimen was measured and a longitudinal section examined metallographically. Isothermal recrystallization curves for these two steels at 1050°F, based on hardness of the air cooled specimens, are shown in Fig 2 in which the amount of recrystallization corresponding to each plotted point is indicated. The marked difference in the behavior of these two types of steel is evident. After a corresponding amount of cold reduction, the rimmed steel recrys-tallizes in a much shorter time than the killed steel and the shape of its recrystallization curve, (plotted on a logarithmic time scale), is very different. The curve for rimmed steel indicates that recrystallization is analogous to isothermal transformation of aus-i.enite in that it proceeds at a progressively faster rate up to some 50 pct recrystallization, then at an increasingly slower rate. For the aluminum killed steel, however, the start of

Jan 1, 1950