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By E. R. Smith

ANALYSIS of the requirements for gun perforation equipment suitable for penetrating casing and cement showed that these points would be involved: (1) Powder charges electrically detonated under high fluid lieads and at remote distances. (2) Selective firing of sliots in sequence. (3) Sufficient velocity for the bullet to penetrate at least two strings of seamless casing and all cement beyond the strings. (4) Heat-treatment of steels to withstand great pressures and penetration. (5) Esclusiorl of fluid under extremely high hydrostatic pressure. (6) Stranded steel wire line acting as weight - suspending and current - carrying medium. (7) Firing controls operated above the surface. (8) Determining gun depth and suspended weight by means of the wire line. (9) Portability for field use.

Jan 1, 1936

By J. B. Conway

RECENT studies of first-stage creep data have led to a special least-squares procedure for use in calculating the Andrade creep-equation constants. This procedure is easy to apply, uses only experimental data, and yields results which do not vary with the individual making the analysis. Taking logarithms of the Andrade equation I = lo(1 +ßl1/3)ekt leads to In l = In lo + In(1 + ßl1/3) + kt A residual can then be defined as the difference between the logarithm of an experimental length value and the logarithm of a calculated length value. Following the usual least-squares approach differentiation with respect to 10 and k of the expression for the sum of the squares of the residuals leads to two equations which cannot be solved directly for the three constants involved. However, values of ß can be assumed and corresponding values of lo and k can then be calculated. Then the sum of the squares of the residuals can be calculated. For a certain value of ß this sum will exhibit a minimum value to identify the least-squares values for ß, lo, and k. An illustration of the application of the above least-squares approach is obtained by employing the creep data for lead originally presented by Andrade' in the development of the one-third creep law. A plot of the sum of the squares of the residuals as a function of ß is shown in Fig. 1 along with the corresponding lo and k values. The minimum is seen to occur at ß = 0.0143 from which lo = 39.149 and k = 7.27 x 10-5. Based on these results the Andrade equation for these lead data is 1 = 39.149(1 + 0.0143 t1/3)e7.27 x 10-5t compared to the equation I = 39.13(1 + 0.01457/l/3)e6.95 X 10-5t developed by Andrade (calculation procedure not given but was probably a graphical solution). Calculating length values using the above equations and comparing with the experimental length values, residuals corresponding to the difference between experimental and calculated length values can be obtained. The sum of the squares of the residuals can then be calculated. For the case of the least-squares approach a value for this sum was found to be 2.37 x 10-3 compared to a value of 3.47 x 10" for the equation originally proposed by Andrade. In other words, while the constants proposed by Andrade provide an excellent fit for the lead data, a still better representation is afforded by applying the least-squares approach discussed above. A similar result was obtained for the lead data at 162oc.l The least-squares approach led to 1 = 9.866(1 + 0.0497 t1/3)el.011 x 10-2t compared to the equation I = 9.94(1 + 0.0433 l1/3)e1.06 X 10-2t given by Andrade. In this case, too, the sum of the squares of the residuals is slightly smaller for the equation based on the least-squares approach. It should be pointed out that a double trial and er-

Jan 1, 1965

By W. D. Forgeng, P. F. Wieser

MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.MnSi alloys containing from 2 to 24 at. pct Si have been investigated by metallographic and X-ray methods. Contrary to published data, the temperature of the ß-manganese to a-manganese transformation is lowered by the addition of silicon. The existence of two additional intermediate phases E and ( is demonstrated. E, ranging in composition from 12 to 15.5 at. pct Si, forms by a peritectoid reaction between ß manganese and the second new phase, (. The latter phase is homogeneous at silicon contents from 16.2 to 18 at. pct and forms peritectically from the 0 phase and liquid. The eutectic reaction occurs between the ( phase and MnsSi rather than the ß phase and Mn3Si. As a result of this investigation, a modification of the manganese-rich section of the MnSi equilihrium diagram is proposed. The binary diagram of Mn-Si, according to Hansen,' Fig. 1, exhibits in the low-silicon region (below 24 at. pct Si) a peritectic transformation at 900°C of 0 manganese + Mn3Si to a manganese as determined by R. Vogel and H. Bedarff2 as well as a thermal effect at 980°C between 16.2 and 22.6 at. pct Si reported by the same authors. The nature of the latter transformation was unknown. K. Amark, B. Boren, and A. westgren3 reported indications that possibly four more phases existed in the range of 10 to 27 at. pct Si. The present investigation deals with the phase relations in the range of 2.1 to 17.7 at. pct Si. A few spot checks were conducted up to 23.84 at. pct Si. EXPERIMENTAL PROCEDURE Small experimental heats were prepared by induction melting in a vacuum furnace using argon as a protective atmosphere. The crucible was of commercial-quality magnesia. The furnace charge consisted of silicon metal and dehydrogenated electrolytic manganese. The typical analysis for these materials is shown in Table I. The molten alloy was tapped into 2-in.-square, 7-in.-long ingots. After visual inspection, a small quantity of alloy in the middle portion of the ingot was separated for use in this investigation.

Jan 1, 1964

By M. F. Burr, F. V. Lenel, G. S. Ansell

The mechanism of materials transport was studied in a model experiment in which a silver sphere was sintered to a silver plate under an applied external stress near 800° C. For this purpose the rate of growth of the neck between the sphere and the plate which is proportional to the strain rate of the creep process involved in a neck growth was determined by measuring the change in electrical resistance of the away. This rate of neck growth will depend upon the magnitude of the applied external stress. By measuring the rate just before and just after a change in the external load and therefore the applied stress, the relationship between strain rate and stress can be derived. For material transport by slip in a pure metal it is expected that the strain rate should be proportional to the 4.5th power of the stress, while for transport by diffusional flow the strain rate should be proportional to the first power of the stress. It was found that for stresses above 5 X 10' dynes per sq cm (70 psi) the exponent in the stvain rate-stress relationship was near 4.5 while for a stress of 0.7 x 108 dynes per sq cm (10 psi) an exponent of 1.8 was determined indicating that under the conditions of the experiment the transport mechanism for creep in silver shifts from diffusional flow to slip in the region of 0.7 x 106 dynes per sq cm (10 psi). The importance of these findings for an understanding of the mechanism of material transport in conventional sintering (without an external load) is pointed out. In a paper by Early et al.,' the mechanism of material transport during sintering was treated as a creep process. It was pointed out that two possible types of creep processes could operate during sintering. In one of these material transport takes place by vacancy diffusion due to a gradient in chemical potential. The vacancy sinks in this diffusion process may be either grain boundaries, as in Herring-Nabarro microcreep, or regions beneath a surface of small radius of curvature. The diffusive transport may be by volume, grain boundary, or surface diffusion. In the other mechanism, creep takes place by slip, i.e., dislocation motion with its rate generally controlled by dislocation climb. One method of distinguishing between these two modes of materials transport is to investigate the creep rate, i.e., the rate of material transport as a function of stress. For material transport by vacancy diffusion, the creep rate is proportional to the stress.' For creep by slip, controlled by dislocation climb, the creep rate is proportional to a power of the stress. For pure metals this power is 4.5;374 for dispersion-strengthened material a fourth power relationship can be derived.5 This difference in the stress dependence of the strain rate is illustrated schematically in Fig. 1, in which the logarithm of strain rate is plotted vs the logarithm of the stress for material transport in a pure metal by vacancy flux and by dislocation climb. The stress range in which the two types of material transport overlap would be expected to be relatively small. In the experiments described by Early and coworkers compacts pressed from spherical copper powder were sintered isothermally under an applied axial external load in a dilatometer. During sintering the magnitude of the applied external load was changed and the rate of axial shrinkage of the compact before and after the load change determined. In order to find the stress dependence of the strain rate the magnitude of the stress acting on the neck area between the spherical particles before and after the load change had to be calculated. This stress is the resultant of the stresses due both to the externally applied load and to surface tension. The stress due to surface tension is a function of the geometry of the powder compacts. It can be determined, at least for simple geometrical arrays,'76 but it is difficult to obtain exact values of the stresses for actual powder compacts when only average values of particle diameters and of neck diameters between particles are available. The calculation of stress and the strain rate-stress relationship is therefore only very approximate.

Jan 1, 1968

By W. A. Backofen, R. L. Fleischer

Single crystal, bicrystal, and polycrystal tensile tests of aluminum at 4.2°K, 77°K, and 300°K have been used to examine the role of grain boundaries in the deformation process. Results indicate that a grain boundary may affect the extent and slope of easy glide. The stage II hardening rate, on the other hand, is independent of the presence or absence of grain boundaries. This conclusion allows the size of the region of multiple slip caused by an incompatible grain boundary to be determined. For the size of bicyystal sample used in this study, multiple slip occurs in about half of the cross section. PREVIOUS studies of the stress-strain characteristics of bicrystals of face-centered-cubic metals have been limited to aluminuml-5 at room temperature. Recent results, however, indicate that the stress-strain curves of single crystals of such metals may be separated into at least three stages6 in which different deformation processes are occurring7 provided testing is done at sufficiently low temperatures.' Since for aluminum a well-defined stage II develops only below room temperature, previous studies have not been able to relate effects of grain boundaries to all of the three stages of deformation. It is therefore to be expected that low-temperature deformation of aluminum single crystals and bicrystals should clarify the effects of grain boundaries on the different processes of deformation. EXPERIMENTAL PROCEDURE Single crystals and bicrystals were grown from the melt by the standard techniqueg with aluminum reported by Alcoa to be 99.993 pct pure. Ridges in the boat were used to guide the grain boundary during growth, assuring that the boundary would bisect the sample.10 The rate of furnace motion during growth was 1.0 cm per hr. During growth zone purification resulted, as evidenced by the ability of the first material to freeze to recrystallize at room temperature following severe deformation. Samples were approximately 4.4 X 6.6 mm in cross section and 103.5 mm in length between grips. Samples were annealed at 635" i 5°C for 40 hr and furnace cooled over a 7-hr period. They were then electropolished in a solution of 5 parts methanol to 1 part perchloric acid at a current density of 15 amp per sq dm for about 30 min at temperatures below 0°C. Tensile testing was performed at 295" (room temperature), 77" (sample in liquid nitrogen), and 4.2"K (sample in liquid helium) on the hard-type machine indicated schematically in Fig. 1. The machine con- sists basically of a tube surrounding a rod; one end of the sample is attached to each member, and the rod is pulled up the tube to extend the sample. The rod is rigidly mounted and is moved vertically by a system described by asinski." The pulling force is measured continuously by an electrical strain gage load cell, and the relative displacement of the tube and rod is also recorded continuously by a soft cantilever beam with electrical strain gages. Maximum stress and strain sensitivities were ±2g per sq mm and * 3-10-5. In all tests the strain rate was approximately 5.10-5 per sec. The thin wires in the tensile apparatus introduce softness, which may be corrected for, however, by measuring load vs displacement with the sample replaced by an elastic member. For loads greater than 15 kg the spring constant is 1.875.106 g per cm. The flexible wires also served to reduce substantially the large shearing forces which may arise in the case of grips having horizontal rigidity.'' As in any gripping system, however, bending moments will arise in the course of deformation by single slip. Engineering stress, s = (load)/(original cross-sectional area), and strain, E = (increase in length)/ (original length), are used for stress-strain curves unless otherwise indicated. Tables list resolved shear stress, T=mo and shear strain ? = dm, where m is the usual Schmid resolved shear stress factor for the primary slip system at the start of deformation. The first group of samples to be described forms an isoaxial set, all of the crystals making up the single crystals or bicrystals having the same tensile axis, the orientation of which is indicated by the cross in Fig. 2. For this orientation the primary slip plane and slip direction make angles of 45 deg with the tensile axis and the Schmid factor m has its maximum possible value of 0.5. Rotations about the tensile axis are indexed by means of an angle 0 between the small-area surface of the samples and the projection of the primary slip direction onto the cross section, as defined in Fig. 3. In single crystals, values of 0 were 0 and 90 deg, while in bicrystals 0 values were (0 deg, 180 deg), (90 deg, 270 deg), and (0 deg, 90 deg) as indicated in Fig. 4.

Jan 1, 1961

By Parke A. Hodges

CHROMIUM, one of the most vital of the strategic metals, has constantly increasing importance as research expands potential uses in alloy steel metallurgy. All signs point to a steadily growing use for chrome ore, and the general subject has received a great deal of attention recently.1 A relatively little known country, Southern Rhodesia produced a total of 5.949 million tons, or 18.6 pct of the total world chrome output, between 1906 and 1950, according to figures from the U. S. Dept. of Commerce. According to U. S. Bureau of Mines figures, Southern Rhodesia produced 291,525 tons in 1950 and 300,267 tons in 1951, or approximately 13 and 11 pct, respectively, of world production for the two years. In 1953 the Rhodesian Vanadium Corp. produced about 85,000 tons of which probably 7,000 tons were concentrate. Production by other companies was high. Large in themselves, the figures assume even greater significance because most of this output is of metallurgical grade.

Jan 8, 1954

By J. L. Huiatt, D. G. Foot

The Bureau of Mines devised a direct flotation method for treating low-grade carnallite (KCl*MgC12*6H20) and sylvinite (a mixture of KC1 and NaCl) ores characterized by a high content of water-insoluble impurities. The procedure consists of flocculation-depression of the insoluble slimes; decomposition leach (carnallite only); potash rougher, cleaner, and recleaner flotation; and final product leaching. The technique eliminates the necessity of removing the water-insoluble slimes by mechanical or flotation desliming. Laboratory results demonstrated that the direct flotation procedure, when compared with conventional techniques, yielded equivalent or improved flotation results with equal or less reagent consumptions. The direct flotation method recovered 81.6% of the solid phase KC1 from camallite ore and 79.7% of the KCl from sylvinite ore in final products containing 60.5 and 60.9% K2O, respectively. A flowsheet incorporating the described flotation procedure is presented.

Jan 1, 1983

By Benjamin C. Koskiniemi

Introduction When evaluating any ore body, one of the first questions concerns the ore reserves. In the case of an open pit mine, this is not possible to answer reliably until the ultimate (final) pit limits have been established. Techniques used in designing an ultimate pit are classed as (1) manual, (2) computer, and (3) combined manual-computer. This chapter will describe how manual techniques can be utilized in designing an ulti¬mate pit Certain economic and design criteria must be established before the actual design begins In order to begin designing an ultimate pit, it will be assumed that the engineer already has the following data available (1) vertical sections, (2) horizontal sections for each level, (3) stripping curve, (4) bench height, (5) bank slope angle between levels, (6) level berm width, (7) roadway width, (8) pit slope angles at ultimate pit limits (estimated average including roads and ramps and between roads and ramps), and (9) minimum width of pit bottom

Jan 1, 1979

By K. N. Clark, N. B. Carter, C. G. Thomas, V 7. 0 / 300 dpi

A statistically designed, experimental study showed how gangue minerals, flux additions, fineness of grind, firing temperature, and time affect the properties of acid pellets made from a Western Australian hematite ore. Alumina has less effect than silica and lime, but interactions between the six variables occur, which influence abrasion index, reducibility, and cold compression strength. Finer grinding has little influence on reducibility but improves the other two properties. The major variable is firing temperature, which interacts with all other variables to affect pellet properties. Calculations based on the data show the implications for straight-grate pellet plants and optimum hood temperature ranges.

Jan 1, 1982

By F. C. Bond, J. T. Wang

H. J. Kamack (E. I. du Pont de Nemours & Co., Inc., Wilmington, Del.)—Rittinger's law usually is stated to the following effect: "The work (or energy) consumed in particle size reduction is proportional to the new surface area produced." The law has been stated substantially in this way by Taggart20 Berry21 Dalla Valle22 Coghill and DeVaney,23 Richards and Locke," Gross,25 and many others, and, according to Gaudin,26 was originally expressed by Rittinger in the same form. Consequently there can be little doubt that this is the understanding of the law among most workers in the field of particle size reduction. Bond and Wang, however, express the law in the form "the useful work accomplished . . . ." (italics theirs). The distinction is critical, for in the form used by Bond and Wang the law becomes, as they themselves remark "merely a more or less arbitrary definition of useful work," while in its usual sense the law expresses a physical hypothesis which has been verified experimentally within certain limitations. Considering the way the law has been used, it might be stated more explicitly as follows: "In a given machine operating under a given set of constant operating conditions, the work consumed in the particle size reduction of a given material is proportional to the new surface area produced." Or, as Coghill and deVaney have said,27 "the (Rittinger) law holds only when the tests being compared are made under analogous conditions." There are occasions when the law transcends these limitations; for example, the surface area produced per unit energy consumption for a given material in a ball mill does not vary much over a fairly wide range of operating conditions. But by and large, the surface area production per unit energy consumption will vary with the operating conditions, the type of machine, and the material. The essence of Rittinger's law is that the surface area production per unit energy consumption is independent of the particle size, and this has been verified experimentally by numerous workers for numerous materials, within certain limits. An important limitation is that when one grinds to very small particle sizes, agglomerative forces may tend to interfere with size reduction so that the surface area increases less rapidly than Rittinger's law would predict. Within such limitations, Rittinger's law can be regarded as empirically established. The law has, however, certain theoretical implications, and it seems to be chiefly against these that Bond and Wang direct their criticism. Solids are believed to possess surface energy which is proportional to surface area. Thus, Rittinger's law implies a proportionality between surface energy produced and mechanical energy expended (for a particular material in a particular machine). It does not imply that all or most of the mechanical energy is transformed into surface energy; in fact it is known that most of the mechanical energy is transformed into heat. Bond and Wang assert that most of this heat arises from the damping of elastic vibrations of stressed particles. This may possibly be true for crushing (with which they are chiefly concerned), although in grinding it is probable that much of the heat arises from friction between particles. However, the fact that the surface energy is small compared to the heat energy does not invalidate Rittinger's law, which implies merely that they are proportional. The authors also criticize Rittinger's law on the grounds that "this theory cannot be justified mathematically, since work is the product of force times distance, and the distance factor is ignored," and "energy input must be the product of force times distance, and the Rittinger theory completely ignores large variations in the distance (strain dimension or deformation) throughout which a force must act to produce breakage of different materials." However, the quantities force and distance as such are irrelevant to Rittinger's law, which considers energy input as an integral quantity. The fact that different materials require different forces and strains (hence, different amounts of energy) to break them is incontrovertible but again is irrelevant to Rittinger's law, which, as mentioned before, applies -only to a single material. Even in theory, it would not be expected that the surface area produced per unit energy consumption would be the same for different materials, because the surface energy per unit area is presumably specific to each material. Bond and Wang advance another argument of a

Jan 1, 1952

By C. D. Keen

In the latter part of the summer of 1913 the Conservation Commission of the State of Louisiana, under presidency of M: L. Alexander, decided to stop the waste of natural gas going on at the "burning gas-well," Located about 2 mile southeast of Oil City, La. On several occasions, both in newspapers and in reports, comment had been made on the condition of this well, its harmful effect on the Caddo gas field, and the considerable loss, estimated at several thousand dollars each month, caused by the escape of the valuable fuel., But nothing had been done to bring the well under control and prevent further waste of gas until the State Conservation Commission took the matter in hand. The gas fields of Louisiana are among the greatest in the country. So far most of the gas has been found in the Caddo field proper, although considerable development has been done in and around the city of Shreveport and near the town of Mansfield in DeSoto parish. To extend the life of the gas fields and to prevent the quick exhaustion of the supply of the natural fuel are matters of vital importance for this section of the country. Four gas companies have entered the Caddo field and supply the surrounding towns and cities With gas. The Arkansas Natural Gas Co. has pipe lines to Little Rock, Ark., and supplies gas to the following cities and towns in that State: Texarkana, Hope, Garland, Emmet, Prescott, Boughton, Beirne, Gurdon, Arkadelphia, Gum Springs, Mal-vern, Dsnaldson, Gifford, Perla, Beaton, Beauxite, Mabelvale, Bryant, Sheridan, Pine Bluff, Little Rock, Argenta, Pulaski Heights, and Hot Springs. The Southwestern Gas & Electric Co. transports gas to Mooringsport, Blanchard, Caddo, Rodessa, Oil City, Vivian, Bloomburg, Hosston, Ida, Dixie, Belcher, and Shreveport. The Marshall Gas Co. supplies gas to the town of Marshall, Texas. The Louisiana Co. has a line to Shreveport. In, the oil field the gas is used for drilling purposes, and the operators either have their own gas system or buy from the gas companies. At the present time the surrounding territory depends for its fuel supply on the Caddo field, and the importance of the conservation of the natural-gas

Jan 1, 1915

By J. N. Ong

The oxidation of tantalum is assumed to occur by four simultaneous first-order chain reactions; solution of oxygen in the metal, nucleation and growth of a suboxide phase at the metal surface and two phase boundary processes which give rise to two different modifications of Ta2O5. A rate equation is then formulated which accounts for all principal details of oxidation behavior, unifies and correlatss the results of the principal investigations, and expresses the rate as a function of pressure, temperature, and time. For purposes of practical application, the expressions: may be used below and above 700T respectively to determine the regression rate of tantalum in cm per hr, where T is to be expressed in "K and P in atmospheres pressure of oxygm. The equations will reproduce within a factor of two all reported experimental rates in the temperature range 475" to 1400°C and pressure range 0.000026 to 40.8 atm 0. 1 HE oxidation kinetics of tantalum have been investigated thoroughly in the temperature range 50" to 1400 and pressure range 1.32 x l0-' to 40.8 atm pressure of 0,and as a result, the principal features of the oxidation of tantalum are known and have been described in considerable detail. The exposition of the characteristics of the behavior of tantalum in oxygen has been largely descriptive, with considerable attention being devoted to elucidating the structure, composition, and morphology of the resulting oxide products. The weight change vs time results have usually been reported graphically. With the exception of the linear rate below 700 C and the process of diffusion of interstitial oxygen into the metal,6'9 no effort has been made to characterize the reaction rates in functional form. It is the purpose of this paper to demonstrate that when the fundamental principles of chemical kinetics are rigorously followed, the results of the principal investigations will be correlated and unified and the oxidation rale may be expressed as an analytic function of pressure, temperature, and time. In addition to accounting for the temperature and pressure dependency of the oxidation rate, the following minor features will be accounted for as a result of the basic analysis: the initial period of nonline-arity in rate at low temperatures, which decreases with increasing temperature;3'5'7 the rate vs temperature cusps obtained at constant pressure"5 the concentration gradient of oxygen interstitially dissolved in the metal.5'7 The analysis will also be consistent with the overall chemistry of reaction and with all visual, microscopic, and X-ray observations. DEVELOPMENT OF RATE EQUATION As a fundamental basis for the treatment of metal-oxygen reaction kinetics, it will be regarded that the rate of reaction is determined by the concentration and not the activity or chemical potential. It is further assumed that all metal-oxygen reactions are first order complex chain reactions" whose rate is dependent on the concentration of an intermediate species which is a complex function of the oxygen concentration, or oxygen pressure, only. The basic rate equation is therefore: is the weight of oxygen consumed by the reaction, A is that portion of the area of the metal over which the reaction is occurring (cm2), t the time (sec), kf the rate constant for forward reaction, C the intermediate species concentration and f '([Oz]) and f (Po,) are complex functions of oxygen concentration and Oxygen pressure respectively. Reverse reactions may usually be neglected in metal-oxygen systems since a large negative free energy generally accompanies these reactions. Eq. [I] takes different forms when the rate of reaction is controlled by diffusion into or through a phase or at a phase boundary. For diffusion into the metal phase, the rate is given by1' Di is the diffusion coefficient of species diffusing into the metal phase (cm2/sec), and Q is the corre-

Jan 1, 1962

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By Charles C. Peterson, Ronald E. Enstrom

Significant improvements have been made in the ursine systern for epitaxial vapor gvowtlz of Gds. The electron concentration has been reduced to below 1015 cm-3 with electron-mobility values as high as 7200 sq on per v-sec at 30PK and 60,000 sq cw7 per v-sec at 77°K. These high-purity layers have been successfully gvown on n&apos; layers with thicknesses as snzall as 1 p and as large as 125 p. Furthermore, high-purity layers have been incorporated into an structure without degradation of electrical properties. Different impurity gradients at the n&apos; to n interface were achieved. Using these structures, Gunn oscillators have been operated at frequencies as low as 0.4 GHz and as high as 40 GHz, which equals the highest valzle yet reported. The frequencies nleasured are in reasonable apeenlent with those calculated fron7 the n-layer widths and the transit times. CW operatiolz has been achieved from 3 to 20 GHz. In Gunn devices for >40 GHz operation (i.e., witk an n-layer tkickness below 2.5p), the n layer has been generally too pure to permit oscillations to occuv. ThE mechanism of the Gunn oscillator&apos; is now generally understood.2-5 Electron transfer from the (000) minimum to the ( 100) minima leads to a voltage-controlled negative resistance, which results in the formation of domains of high and low electric fields which travel through the crystal with a characteristic velocity of about 107 cm per sec. When a constant voltage is applied to the sample, this domain motion generaliy leads to oscillations at the transit time frequency, fT = 107/L, where L is the thickness of the active n layer.&apos; In this case, a single high-field domain is nucleated at the cathode and grows until it reaches the anode, where it is absorbed; a new domain then forms at the cathode.5 There are related modes of oscillation of the same device in which a tuned circuit causes a periodic variation of the voltage across the device. The frequency then may be either above or below fT. It has been shown that oscillations will occur when n • L 2 1012 cm"2, where n is the carrier concentration in the active region. At lower doping densities, 10" 5 n . L 5 lo&apos;&apos;, the doping is said to be subcritical for oscillation and the description of the device operation changes since the domains become comparable in thickness to the device thickness, L. Nevertheless, such devices have been found to be "active" and, in fact, are useful as amplifiers.778 For CW operation, one wishes to minimize the power dissipation, which is related to the electric field, E, and the low-field resistivity, p. Below threshold, the power dissipation density is approximately Typically, at threshold where E -- 3 x 103 v per cm, the dissipation density is 107/p watts per cu cm, p in ohm-cm. Furthermore, it is desirable to provide good conduction of the heat generated in the active region. The temperature rise, AT, across the active layer of a sandwich structure, with a heat sink on one side, is given by AT = (E&apos;/P)(L~/~~) where it is assumed that the thermal conductivity, u, and resistivity, p, of GaAs do not vary appreciably over the range of temperature and electric fields existing in the layer. This expression shows that, subject to maintaining an appropriate (n . L) product, CW operation is favored by a higher resistivity, a lower threshold field, and a thinner device. The above device requirements place some severe restrictions on the materials to be used, especially for high-frequency (>10 GHz) operation. Here, it is necessary to prepare very thin (<10 µ) layers of GaAs, in a state of high purity (-1 ohm-cm), complete with very low-resistance ohmic contacts. Problems of handling such thin and fragile samples become inereasingly severe as the frequency is raised. Furthermore, while good low-resistance ohmic contacts are easily applied to low-resistivity GaAs, contacting difficulties are encountered for these higher-resistivity materials.

Jan 1, 1968

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10-5 cm. in size.

Jan 1, 1940

By N. P. Goss

ASTERISM appearing in X-ray Laue dia-grams is an extremely sensitive index of changes in the internal structures of indi-vidual grains of polycrystalline metals. It indicates the existence of various forms of subboundary structure or subdivision within the grain. The present viewpoint is that the grain is made up of lattice blocks having substantially the same size and shape.1-4 When these blocks all assume exactly the same orientation, the crystal is perfect and asterism is absent. Cleaves and Thompson5 observed that the hardness of iron is virtually constant over a range of grain sizes. It is quite possible that the subboundary structure caused this, and that the latter is just as important as grain size itself. While the experiments reported here are not con-clusive, they do support this viewpoint. Metals can, under certain conditions, be prepared entirely free from asterism, but this preparation does not necessarily require long heating or slow cooling, as will be shown here. In this paper a distinction is made be-tween mosaic and distorted grain struc-tures but the difference is only a matter of degree. In a previous paper9 it was shown that the grains can become distorted even during heat-treatment. The block structure exists inherently, even in a perfect crystal; the size and shape of these crystallites, or lattice blocks, varies, depending upon a number of factors. Goetz, for example,7 has shown that a metal before crystallizing from the molten state must go through a paracrystalline phase with oriented groups of atoms about 10-14 to 10-15 c.c., or 10 5 cm. in size.

Jan 1, 1940

By W. R. Toeplitz

Probably a more descriptive title would be "Much Ado About Nothing." By "nothing," of course, I refer to the porosity which is the main feature of this type of bearing. Porosity has a decided effect on the manufacturing techniques, the structure and physical properties, the oil content, and on the installation and service of oil-retaining porous bronze bearings. A simple curve can be drawn by plotting specific gravity along the abscissa and percentage of porosity by volume on the ordinate. A bronze composition, analyzing 89 Per cent copper, 9.75 Per cent tin, and 1.25 per cent graphite, has an absolute solid specific gravity of 8.5. At this specific gravity, of course, occurs the point of zero porosity. Conversely, at loo per cent porosity, the specific gravity is zero. A similar curve can be drawn for bearings impregnated with oil; the only change being that the specific gravity at loo per cent oil will be 0.89 if we assume that that is the specific gravity of the lubricant. The curve is useful in determining the oil content by volume for any specific gravity. The normal range of oil content for porous bronze bearings of this composition is from 35 to 16 per cent, which is in the specific gravity range of from 5.8 to 7.3. In addition to the amount of porosity, the type of porosity is important. The first consideration here is that the porosity must be intercommunicating. This can be determined by a number of simple tests. The first method, which is very accurate, is to extract the oil in the bearing by cycling

Jan 1, 1945

By R. J. Lytle

Geophysical exploration for engineering purposes is conducted to decrease the risk in encountering site uncertainties. Such studies are needed in construction of underground facilities. Current responsibilities, opportunities and challenges for those with geophysical expertise are defined. These include: replacing the squiggly line format, developing verification sites for method evaluations, applying knowledge engineering and assuming responsibility for crucial national problems involving rock mechanics expertise.

Jan 1, 1982

By David D. Rabb

Leaching or solution mining, a relatively simple and economical process for beneficiating metallic ores, is likely to find increasing application in the treatment of low-grade ores that are impractical to mine by any other means. This process may be carried out in two different ways: 1) dump leaching, where the ore is moved from its original location to be leached at another site; and 2) In-situ leaching, where the ore is leached in place by introducing the leach solution at the top, letting it flow down through the ore under gravity, and then recovering it plus the dissolved metals it contains. Whichever leaching method is used, it is almost always necessary to break up the ore before leaching. In this paper a study is reported which indicates that rock broken by an explosion-in particular, an underground nuclear explosion-is significantly more amenable to leaching then is rock broken by other methods. These results suggest that the leaching speed and efficiency could be increased by nuclear fracturing of the ore. Not only would the leach time be shortened, but the resulting increase in strength or richness of the solutions would decrease plant installation expense as well as reduce pumping and processing costs. A considerable fund of experience has been accumulated in the course of several hundred experimental underground nuclear explosions, so that the gross results of any given nuclear explosion can now be predicted with a fair degree of confidence.&apos; From this knowledge it seems clear that, under the proper conditions, large ore bodies can be fractured much more economically-macroscopically speaking-by nuclear explosions than by other methods. The present study concentrates on smaller scale effects that is, the cracks in the chunks of rock broken by the explosion-and shows that here too, in the microscopic domain, there are important advantages to nuclear fracturing. The intense shock produced by the very fast acting, high-brisance nuclear explosive fractures the rock in a way that should significantly improve its leachability. Experimental Procedure This study compared rocks broken by nuclear explosives with rocks produced by conventional mining, quarrying, or core drilling. The test samples, granite chunks 6 to 8 in. on a side, plus core sections, came from the area of the Hardhat*2 nuclear explosion and were taken both before and after the explosion. For comparison, several samples of quarried granite were obtained from a local gravestone monument company. The general procedure was to soak the test samples in leaching solution and then determine the extent of penetration. A standard commercial copper leaching solution was used (10 gpl Cu, 10 gpl H2SO4, 5 gpl ferric Fe, 15 gpl total Fe, pH about 1.5), to which a water-soluble penetrant dye, Zyglo 1-c, had been added. Details of the procedure were as follows: 1) Sample leached in solution containing Zyglo penetrant dye. 2) Washed with water. 3) Air-dried. 4) Cut with granite wire saw. 5) One face polished with granite monument polish. 6) Sent directly to be photographed, or heated at 110°C for 2 hr and then sent to be photographed. 7) Photographed under ultraviolet light to show crack patterns. Results After 10 days of leaching at 70-75°F, the samples were removed from the solution, washed, dried, and cut in half with a granite wire saw to study the penetration of the leach solution. Since the Zyglo dye in the leach is visible under ultraviolet light, the degree of penetration of the leach (and hence the cracks in the samples) can be studied on photographs of the crosscut samples made under ultraviolet light. The photos in [Fig. 1] show how the leach solution penetrated various representative samples. Of the 71 rock samples examined, fractures were most frequent and prominent in samples from the rubble produced by the nuclear explosion [(Fig. 1D)]. Fracturing was less apparent in shaft-mined rock [(Fig. 1B)], still less evident in drift-mined rock [(Fig. 1C)], and practically nonexistent in cored or quarried specimens [(Fig. 1A)]. The samples in [Fig. lA-C] were from the same general area as the nuclear explosion, but they were obtained before the explosion. Results of the crack studies are summarized in [Table 1]. The Zyglo-treated leach solution penetrated the test samples at the rate of about 1/2 mm during the first hour, 1 mm by the end of 4 hr, 2 to 3 mm in 12 hr, and 4 to 6 mm in 10 days, showing a progressively slower rate with time.

Jan 1, 1972

Agnico-Eagle Mines Ltd. comprises a Gold Division at Joutel, Quebec, and a Silver Division at Cobalt, Ontario. In 1979 the Silver Division milled 41,700 mt (46,000 st) of ore at a recovered grade of 139 g per mt (4.06 oz per st) for a production of 5,816 kg (187,000 oz) of silver. The 100 -year -old mining, camp of Cobalt has long been noted for its high-grade silver ores, and now seems to be on the threshold of being revived with several companies operating in the area. In 1979, the Gold Division milled at the rate of 27,200 mt per month (30,000 st) and processed 333,000 mt (367,000 st) at a grade of 6.58 g per mt (0.192 oz per st) with a mill recovery of 91.670 to produce 2,013 kg (64,700 oz) of gold. The average total cost per ton milled was $22.10 per mt ($20.05 per st) which was $3.66 per g ($1 13.90 per 0s). These figures make Agnico-Eagle one of the lowest cost producers in North America. Gold occurrence in the Joutel ore is fine-grained and contained within sulfide facies composed mainly of pyrite with minor pyrrhotite. Two underground mining methods are employed with long hole stoping accounting for about 75% of the ore mined and shrinkage stoping the remainder. Ore from underground is hoisted into a 545 mt (600 st) coarse ore bin from where it is conveyed to a 45 mt (50 st) surge bin ahead of the 10-51 Hydrocone crusher. Crushed ore is then screened to make a 13 mm (112 in.) product with the oversize being recrushed in a 7-60 Hydrocone. Mill feed is conveyed to two 900 mt (1,000 st) fine ore bins. The Hydrocones were installed as part of a new crushing plant in March of 1980 and have contributed substantially to an increase in mill capacity. Space has been left to install a third crusher in the future. The fine ore bins discharge to a 2.75 m by 3.66 m (9 ft by 12 ft) rod mill, followed by a 3. 7 m by 5.5 m (12 ft by 18 ft) ball mill in closed circuit with a Krebs 380 mm (15 in.) cyclone to produce a 7070 minus 37 micron (400 mesh) .flotation feed. This pulp is first treated in a 34 cu m (1, 200 cu ft) Maxwell flotation cell and then in an additional twelve 2.8 cu m (100 cu ft) cells. Combined flotation concentrates are reground to 9070 minus 37 microns (400 mesh) in a 1.8 m by 4.9 m (6 ft by 16 ft) ball mill in closed circuit with a single Krebs 254 mrn (10 in.) cyclone. Flotation tailings are sent to the tailings dam. Reground concentrates are then aerated with lime to a single Pachuca and thickened in a 16.75 m (55 ft) diameter thickener with the addition of diesel fuel to render any activated graphite inert to adsorption of

Jan 1, 1981