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By Klaus Schwerdtfeger

Activities of lead in Pt-Pb and Pd-Pb melts in the temperature range of 800° to 1200°C have been detev-mined from electromotive-. force measurements 202th the cells Both systems display strong negative deviations from Raoult's law. The data obtained with cell [1] were combined with available data on the activity of PbO in silica-satuvaterl PbO-SbO2 melts to calculate the standard free cnergy of formation 01- liquid PbO. FREE energies of formation of oxides and activities of components in metal and oxide melts can be determined with galvanic cells consisting of a metal phase, an electrolyte containing the oxide of one of the components of the metal phase, and an oxygen electrode. This technique has been used previously to measure the standard free energy of formation of solid sio2, 1 and activities in Fe-si, CO-si,2 Ni-Si,2 and CaO-P2O5 3 melts. The present paper reports activities in Pt-Pb and Pd-Pb melts as measured with the same experimental technique. EXPERIMENTAL METHOD General Considerations. The following cells were used: Pbl (PbO-SiO2)liquid, SiO2 Pt-Pb 1 (PbO-SiOz)liquid, SiO2solidO2 [2] Pd-Pb (PbO-SiOz)liquid, SiO2solid O2 [3] Liquid alloy and' oxide melt were contained together in a silica glass crucible of essentially the same design as described previously.1'2 The PbO-SiO2 melts are ionic conductors.' During the experiment, the silica glass crystalizes in a layer adjacent to the electrolyte. The electrolyte equilibrates with solid silica and hence attains the composition of the Si02-liquidus curve in the system PbO-SiO2 at any particular temperature. Molybdenum wires were used to establish contact with the liquid metal. The oxygen electrode, which reaches the surface of the PbO-SiO, electrolyte from above, consists of a platinum wire inserted into a ceramic tube and provided with a 2-mm-diam platinum bead at its end. Gas of known oxygen partial pressure (pure oxygen of 1 atm: air, or N2 with 1.04 pct 0,) is blown through the ceramic tube onto the surface of the electrolyte. The cell reaction is Pb (metal) + 1/2O2 (gas) = PbO (electrolyte) [4] No oxidation of platinum or palladium ("displacement reaction") occurs. This is to be expected from the noble character of platinum and palladium, but was also shown experimentally, as described in the next section. The galvanic electromotive force of the cell is given by where AG is the change in free energy for Reaction [4], E(=2) is the number of electrical equivalents necessary to form 1 mole of PbO, and F is the Faraday constant. Formula [5] is valid only if no junction potential exists within the electrolyte. Junction potentials occur only when the compositions of the electrolyte are markedly different at the electrodes. Such differences are negligible in the PbO-SiO, electrolyte, as shown in the next section. Since molybdenum contact leads are used, appropriate corrections were made on the measured electromotive forces to account for the thermoelectric effect of the Mo-Pt couple. The thermoelec-tromotive forces were measured separately with a Mo-Pt couple, and were found to vary linearly from 19 mv at 740°C to 40 mv at 1310°C with molybdenum being positive and platinum negative (cold junction at 25°C). Extrapolation of these values to higher temperatures yields values which are in satisfactory agreement with those obtained previously in the temperature range 1440° to 1630°c.1,2 The change in free energy for Reaction [4] is expressed as where chemical potentials of the species. The value of constant for a given temperature because the slag composition is fixed. Inserting [6] into [5] and using appropriate expressions for upb and uO2 the relation

Jan 1, 1967

By C. Y. Ang, C. Wert

Quench aging of supersaturated solid solutions of nitrogen in columbium takes place in reasonable times in the temperature range 300&apos; to 500°C. Changes in internal friction, hardness, and electrical resistivity are found to accompany this change. THERE is practically no detailed information in the literature concerning interstitial solid solutions in either columbium or tantalum. The fact that both of these metals are used extensively commercially in both pure and alloyed states makes studies of their properties of value. While the plan is to study both these metals and their alloys extensively, so far only a small number of measurements have been made. This paper presents data obtained in the initial investigations of columbium. The principal interstitial impurities of columbium are likely to be hydrogen, carbon, oxygen, and nitrogen. The first of these, hydrogen, is outside the scope of internal friction measurements at present and nothing quantitative is known about the initial hydrogen content of the specimens. However, it is believed that it is completely absent after the preliminary heat treatments are carried out. The carbon content of the original samples is low and can be reduced still further during sample preparation. Oxygen is normally present to some extent in columbium and can also be added or removed easily. Nitrogen is also normally present in small amounts and can also be controlled within limits. Since it is not possible yet to remove all the nitrogen from columbium and since it is possible to remove essentially all the oxygen and carbon, initial measurements were made on the alloy system nitrogen in columbium. In this sense then, the alloys are true binary alloys. Little is known about the effects of nitrogen on the physical and metallurgical properties of columbium, so it was necessary to perform some rather elementary measurements on the specimens. These measurements are described briefly in the next section and are discussed in detail in later sections. Scope of the Work That internal friction is associated with diffusion of nitrogen in columbium has been known for some time. It is similar in nature to that for carbon and nitrogen in a-iron. In these latter cases, the information obtained from internal friction has been useful metallurgically.&apos; and it is not too much to expect useful information from similar studies on columbium containing nitrogen. The technique of internal friction measurements is adequately described by Ke2 At a frequency of 1 cps the internal friction peak for nitrogen in columbium occurs at 300°C and that for oxygen at 160°C." So that all the measurements will be meaningful metallurgically, the internal friction has been calibrated by making a measurement of the damping at the two peaks and a measurement of oxygen and nitrogen content by chemical analysis. A comparison of the two gives the following calibration factor: To go from damping capacity expressed in terms of 1/Q to weight percent of oxygen and nitrogen in solid solution in columbium, multiply the peak values of internal friction by about 4 and 3 respectively." Data from which these factors were calculated are presented in Table I. The increase of electrical resistance of columbium caused by the addition of oxygen and nitrogen as interstitial impurities has been quantitatively determined. At room temperature the percentage increase is small for small additions of impurities (<0.1 wt pct); as the temperature is lowered it becomes an increasingly larger factor of the total resistance. An empirical relation has been established to express the resistivity at — 195°C in terms of weight percent of oxygen and nitrogen in solid solution. It is easy to make supersaturated solid solutions of nitrogen in columbium and to observe aging phenomena. The optimum aging temperature, as in the case for carbon and nitrogen in a-iron, occurs at the temperature for which the time necessary for a single place-change in diffusion is about 1 to 10 millisec. This means for nitrogen in columbium that significant property changes should take place for this alloy at about 400" to 500°C in reasonable time intervals. Results of such aging experiments are

Jan 1, 1954

By P. Somasundaran, D. W. Fuerstenau

The length of the collector is found to influence the flotation of the mineral even at incipient conditions, which are below the concentration at which interaction at the solid-liquid interface begins to take place to form hemi-micelles. To study this dependence, concentration for incipient flotation of quartz was determined as a function of pH with collectors of various chain lengths. The observed effect of chain length on flotation is ascribed to that of collector adsorbed on the bubble surface. In previous studies, it was shown that at low concentrations the alkyl collector ions adsorb at the solid-liquid interface as individuals.&apos;&apos;2 At higher concentrations, the collector ions adsorbed at the solid-liquid interface associate with each other to form two-dimensional aggregates called hemi-micelles. Above the hemi-micelle concentration, the length of the hydrocarbon chain is extremely important since the hydrocarbons are in effect removed from water during the association, making the energetic conditions more favorable for adsorption at the interface. Because of this enhanced adsorption, one observes a very rapid increase in flotation associated with the hemi-micelle formation at the solid-liquid interface. However, a dependence of flotation on the chain length at concentrations below that required for hemi-micelle association was also observed,&apos; and this cannot be explained by the above mechanism which postulated hydrocarbon chain interactions only at the solid-liquid interface. This prompted an investigation into other possible reactions of the hydrocarbon chains and an examination of the conditions at the bubble surface involved in the flotation system and how these observations might explain the reactions at the solid-gas interface which cause the particle-bubble attachment required for flotation. To obtain more information on chain length effects, flotation, under incipient conditions, was tested by vacuum flotation techniques. The collector-concen-tration-pH relationships for flotation of quartz with alkyl ammonium acetate collectors was delineated by observing the pH at which quartz particles begin to float to the liquid surface. By investigating flotation as a function of pH, it was also possible to study the effect of neutral molecules on incipient flotation conditions, since the aminium ions hydrolyze to amine molecules at higher pH values. EXPERIMENTAL WORK Brazilian quartz specimens were crushed and sized, and the 270 x 400 mesh fraction was used for flotation studies. The samples were leached with concentrated hydrochloric acid until no coloration of the acid occurred. The leached material was washed free of chloride ions and stored in distilled water. The vacuum flotation technique developed by Schuhmann and prakash3 was used to determine the critical pH-concentration curves. This method, which can be used to delineate conditions for incipient flotation, is fairly simple and rapid. About 0.5 gm of 270 x 400 mesh quartz was placed in a 100 ml graduated cylinder which was then filled to the 100 ml mark with the collector solution made from high-purity alkyl ammonium acetate salts. The water used for the test was conductivity water saturated with air that had been passed through a cleansing train consisting of Drierite, Ascarite, a water wash bottle, and a trap. After the pH was adjusted, the cylinder was then conditioned for thirty minutes. In the tests where an acid pH was desired, sufficient acid was added before the collector solution to avoid any effect due to slow desorption of collector from the quartz surface. After conditioning, vacuum was applied to the system and the flotation or nonflotation of the quartz was noted. The pH at which the quartz particles began to float to the liquid-gas interface was taken as the critical PH. Critical pH curves were thus determined for different concentrations of the various collectors. Hallimond tube flotation data were taken from the authors&apos; previous publication1 for correlation with that from the vacuum flotation. RESULTS AND DISCUSSION The results of vacuum flotation studies for determining critical pH-concentration curves, i.e., curves which delineate conditions for incipient flotation, are shown in Fig. I. In generaI, all the curves exhibit an upper and lower pH limit between which flotation will

Jan 1, 1969

By V. F. Hollister

The Queen Charlotte gold deposit (also known as the Specogna, Babe, or Cinola) was discovered in late 1970 by Efrem Specogna and Johnny Trico. They were prospecting along the trace of the Sandspit fault, and they sampled jarositic material that included veins from the fault zone. Their assays included some good gold values. They located the Babe Claims in 1971 and optioned them to Kennco Explorations Ltd. Kennco conducted stream sediment and soil geochem studies, geological mapping and drilling of 55.2 m (181 ft) in two drill holes. Kennco withdrew from the property, and by 1977, Cominco, Placer Development, Silver Standard, and Quintana Minerals had each successively worked on the deposit. Consolidated Cinola Mines bought the claims in 1977 and completed exploration of the deposit ultimately in a joint venture arrangement with Energy Reserves. Energy Reserves entered in late 1979, and by 1983, a total of 200 surface and 12 underground drill holes had been completed, totaling 28 600 m (93,832 ft). In addition, a 461.9 m (1515 ft) adit was driven in the ore body. Reserves published by Cinola aggregate 34 Mt (37 million st) of 1.7 g (0.060 oz) Au per tonne. All industry geologists working in the area agree that the Queen Charlotte gold is an epithermal gold deposit in porous volcaniclastic and clastic rocks that is genetically related to a Miocene-Pliocene rhyolite plug. The geologic description here follows the oral presentation made by G. G. Richards, J. S. Christie, and M. R. Wolfhard at a 1976 CIM meeting. Additional comments by the late C. S. Ney of Kennco Explorations are included with the Richards, Christie, and Wolfhard data to complete the geologic set- ting. The attached reprint by Champigny and Sinclair (1 980) provides additional data on the deposit. The Queen Charlotte (Babe, Specogna, or Cinola) gold deposit is located on Graham Island in the northern Charlotte Islands, at the fault boundary of the Skidegate plateau and the Charlotte lowlands. The Sandspit fault marks the physiographic boundary, and it is intruded by rhyolite porphyry at the deposit. Because displaced geochem anomalies, drain- age patterns, and topography suggest dextral and east side down movement for the fault, exposed east block rocks are younger than rocks west of the fault. The east block, which included the ore deposit, is a lowland largely masked by unconsolidated Pleistocene and Recent clastic rocks. Rocks west of the rhyolite plug, on the Skidegate plateau, are Cretaceous carbonaceous and calcareous shale unconformably overlain by a thin veneer of rhyolite tuff. The deposit is about 100 m (328 ft) above sea level. GEOLOGIC SETTING At the ore deposit, the Sandspit fault is a complex structure. However, lithologies on either side of the fault-controlled rhyolite porphyry plug are distinct. West of the rhyolite, the upper member of the Cretaceous Haida formation shale is the most common rock type. The member is composed of dark grey to black, poorly consolidated, and thinly bedded carbonaceous and calcareous shale. The sequence is silicified to an argillite or a hornfels near the rhyolite. West of the rhyolite porphyry plug, but not importantly involved in the mineralization, is a thin masking cover of rhyolite tuff. The tuff unconformably succeeds the cretaceous shale, but it is largely eroded in the mine area. East of the fault-controlled rhyolite porphyry plug is a thick section of conglomerate and sandstone of the Miocene- Pliocene Skonun formation. The ore body occurs within the coarse clastics, the rhyolite intrusive as the western boundary. Ore is entirely contained within the clastics. Original permeability of the clastic rocks was a major control for ore deposition and alteration, and for that reason, the Skonun formation is described in greater detail. The Skonun formation clastics unconformably overlie Haida shale. The Skonun is at least 300 m (984 ft) thick in the mine area, where it trends northerly and dips easterly 15º to 25º. The sequence is about 62 percent conglomerate, 3 1 percent coarse arkosic sandstone, and 7 percent interbedded siltstone and sandstone. Contacts between adjacent beds are generally sharp. Stratigraphic correlations between drill

Jan 1, 1985

By S. J. M. van Leeuwen, R. Feenstra

The effect of jets on bit penetration has been investigated by means of a 50-ton drilling machine and 8½-in. commercial jet bits, drilling under representative bottom-hole conditions. The conclusions apply to the drilling of impermeable rock only. Penetration rate is in all cases primarily hampered by a differential pressure effect, known as dynamic hold-down. Jet action can reduce this slightly. Major gain in penetration rate, up to 25 or 50 per cent, is already ohtained at medium-high jet power. At high bit load, penetration by soft to medium-hard-formation bits is further hampered by bit-balling. Its alleviation requires intensive tooth scavenging, which is best performed by slanted nozzles with trailing, high-velocity, high-volume jets, hitting bottom in front of the teeth. Penetration may then improve by a 100 per cent. At high bit load, bottom-balling limits the penetration of insert-type bits. In this case bottom scavenging is required, which is most effectively performed with high velocity jets from nozzles extended close to bottom. As a result of this measure, penetration may improve 70 per cent in non-friable rock, and less in friable rock. This will make the insert-type bit more versatile. Toothed hard-formation hits suffer at high bit load from both bit- and bottom-balling. Slanted nozzles, possibly much extended, with high-velocity, high-volume jets then have best prospects. INTRODUCTION For years the use of jet bits in oil well drilling has been increasing, in conjunction with ever greater hydraulic horsepower. To the same extent, the need for efficient use of the horsepower has grown.&apos; This paper, it is hoped, will contribute to an understanding of how effective jet action may be obtained. It deals with the effect of jets on phenomena that are known&apos; " to hamper bit penetration. To study this effect, laboratory drilling tests were performed with 8½-in. commercial bits under bottom-hole pressures representative of deep wells. The investigation has been restricted to the drilling of practically impermeable rock. In the following sections, the increase in bit penetration rates due to jetting is discussed for conditions which made the troublesome phenomena stand out one at a time. A brief definition and interpretation of these phenomena is given in Appendix A. Appendix B gives the results of measurements of fluid velocities along the hole bottom, performed in stationary flow tests. Descriptions of equipment, bits, rocks and mud are collected in Appendix C. Unless otherwise mentioned, drilling conditions were kept standard as given in Table 1. CUTTING TRANSPORT TO THE ANNULUS Jet action was for some time believed to merely improve the transport of cuttings from bottom to annulus, resulting in a clean hole bottom. Flow tests performed in 1954 at the Battelle Memorial Institute6 showed, however, that jet velocities of the order of 40 ft/sec sufficed to clear even large (0.4-in.) chips from bottom in the time between two successive tooth actions. In the field, optimum jet velocities are appreciably higher, indicating that other effects must be involved. This much is confirmed by the results of our drilling experiments in soft rocks performed under atmospheric pressure, i.e., in absence of pressure-differential effects. Fig. 1 shows that variation in the nozzle velocity from 40 to 330 ft/sec had no effect on penetration rate, unless the bit penetrated more than 7 mm per revolution, which is about half the tooth height. At such high rates—150 ft/hr at 100 rpm—cuttings would be caught in the tooth cavities, leading to bit-balling, which was noticed on inspection of the bit. The jets thus assisted in keeping the tooth cavities clean. This is just perceptibly reflected in the penetration-rate curves of Fig. 1: Much the same results were obtained in hard rocks with hard-formation three-cone bits. The conclusion is that transport of loose cuttings towards the annulus does not require a powerful jet action. In the following sections we shall see that in deep-well drilling other phenomena are of greater importance. DYNAMIC HOLD-DOWN It is generally accepted that, in deep-well drilling, bit penetration is hampered primarily by the existence of a difference in pressure between the fluid in the hole and that in the rock at the depth of cutting.2-5 In the drilling

Jan 1, 1965

By J. S. Aronofsky

The first step in a quantitative analysis ot the mechanism of oil displacement by water in a fractured reservoir is usually conceded to be the solution of the differential equation describing the saturation distribution of two immiscible fluids flowing in a porous medium, where the capillary pressure is taken into account. In such a system the production mechanism may consist of displacement of oil both by the flow of water due to natural or artificially imposed pressure gradients and by imbibition, which implies a flow of water not due to external pressure gradients. Owing to the presence of the two oil displacement mechanisms, the mathematical model given by the differential equation intended to describe the system may not properly represent the behavior of the physical system. In fact, in the reservoir the rate of water advance may be very slow, and in the case of a fractured reservoir with a great number of large fractures, the pressure difference determining the flow of water through the matrix may be much less than 1 lb/&apos;psi over lengths of a few feet. In such a case, imbi-bition (the exchange between oil in the matrix and water in the fractures resulting from capillary forces) may become, with time. a significant element of the production mechanism. It occurred Lo the authors, however, that without going into a physical analysis of the process of production, it might be possible by means of simple abstract reasoning to throw some light on the variation of recovery with time under conditions occurring in a highly fractured oil reservoir with rising water table. The object of this paper is to present both the reasoning and its application to a reservoir of the highly fractured type. Specifically, the analysis given here was undertaken to try to explain the increase of recovery (as defined later) with time as observed in this reservoir, without having to assume unlikely variations in the reservoir parameters with depth. This attempt has been successful as will become clear upon comparison of the computed recoveries with the actual field data. ABSTRACT MODEL Let us consider a small volume. of porous matrix saturated with oil at time, t = 0. Let the process of oil displacement by water start at time, t = t,,. At some time, t, the process will have terminated. Then a volume of oil equal to or smaller than the original oil contained in the matrix will have been produced. The first basic assumption that describes the model and guides the forthcoming reasoning is that the oil production from the small volume. dv, is a continuous monotonic function of time and that it converges to a finite limit. Such an assumption is not inconsistent with the results of laboratory waterflood tests as well as with results of imbibition tests where this is, in fact, observed. The second basic assumption is that none of the properties which determine the rate of convergence change sufficiently during the process to affect this rate or the limit. Let it be assumed that the form of the function of time relative to production from the matrix volume. dv, is given by where V,(t) is the volume of oil produced up to that time t. R is the limit toward which the recovery converges, A is a constant giving the rate of convergence, and V,(t) is the volume of oil originally in place in the volume, dv. It should be noted that recovery at time I will be understood here to he It follows that r. tends to R as t tends to infinity. CONSTRUCTION OF RESERVOIR FROM ABSTRACT MODEL Let the reservoir consist of a series of identical blocks of porous matrix stacked vertically and separated by fractures. Let each of these blocks satisfy the conditions of our abstract model. These conditions are: (1) that recovery is a continuous mono-tonic function of time converging to finite limit, and (2) none of the properties that determine the rate of convergence change sufficiently to affect the rate or the limit. Let water be rising in fractures so that oil production from any part of the block starts when the water comes in conLact with it. TOTAL RECOVERY FROM THE RESERVOIR COMPARED TO RECOVERY FROM A SINGLE MODEL ELEMENT As stipulated in Eq. 1, in the case of the abstract model,

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown&apos;s paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).&apos; Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By D. S. Flett, A. W. Fletcher

Equilibrium studies on the extraction of nickel and cobalt with kerosine solutions of naphthenic acid have shown that an exchange extraction reaction occurs at pH 5.5. The nickel/cobalt separation factor is constant at 1.8 for constant total metal molarity and varying nickel/cobalt ratios. The separation factor decreases with increasing total metal molarity in the organic phase beyond 0.2 M and also decreases with increasing temperature. From the equilibrium data, it has been possible to derive a mathematical model for the separation of nickel from cobalt by exchange extraction in multistage systems. Experimental data from a continuously operated multistage mixer/settler apparatus has shown a reasonable correspondence with computer-calculated data. The effective separation of nickel and cobalt in sulfate solution remains a problem in hydrometallurgy and the hope that this would be solved by solvent extraction has not yet been fulfilled. With chloride solutions, advantage may be taken of the ability of cobalt to form anionic complexes with the chloride ion. It can then be readily separated from nickel, which does not form stable chloro complexes, by extraction with a suitable long chain amine. However, in hydro metallurgical operations, sulfate solutions are generally obtained in which no extractable anionic species are present. Thus, the possibility of using cationic extractants must be considered, and in this paper attention is directed to the use of carboxylic acids. The method of separation studied has been termed exchange extraction, which involves replacement of a metal in the organic phase with a more acidic metal in the aqueous phase. Thus, (BR2).+ (Az+)aqt=(AR,).+ (B2+)aq (I) where metal A is more acidic than metal B, R represents the acidic radical derived from the acid RH, and the subscripts e and aq refer to the organic and aqueous phases, respectively. Ashbrook and Ritcey&apos; have used this method for the separation of cobalt from nickel using the sodium salt of di-2 ethyl hexyl phosphoric acid, which preferentially extracts cobalt. Some nickel is coextracted, and this is removed by exchange with cobalt ions in the feed solution by suitable countercurrent operation in a pulsed column. Much work has been carried out by a number of workers in Russia on the general use of exchange extraction for the separation of metal ions using car-boxylic acids. Gindin et aL a have demonstrated that this technique could be applied to the separation of nickel from cobalt using a C--C. carboxylic acid and have applied the technique to the production of high purity cobalt solutions for electrolysis. Further worka was concerned with the development of a process for the separation of nickel from cobalt in a pulsed column. This system permitted the separation of iron and copper from nickel and cobalt in one system. The procedure involved center feeding with acid backwashing at the top and alkali addition lower down the column. Thus the system operated under a pH gradient and the metals were distributed in the column in the order of their basicities. A similar application was studied by Gel&apos;perin et al,4,5 for the removal of copper and iron impurities from a nickel anolyte by means of a C10-C,12 fatty acid fraction. Ginden et al,&apos; and Fletcher and Wilson&apos; have studied the effect of pH on the extraction of a number of metals with carboxylic acids. These studies showed that metals such as iron, copper, lead, zinc, nickel cobalt, and manganese are extracted at pH values close to the pH of hydroxide precipitation. Nickel is extracted at a slightly lower pH than cobalt and thus the nickel/cobalt separation factor has a value not much greater than 1. More basic work on complex identification has been reported by Fletcher and Flett: by Tanaka; and Jay-cock and Jones." These studies have suggested that at low loadings in the organic phase, the nickel and cobalt carboxylates appear to be dimeric and solvated by free carboxylic acid molecules. As the concentration of metal in the organic phase increases, the complex changes and larger polymeric species are formed. In order to permit assessment of the potential of carboxylic acids as extraction reagents for separation of

Jan 1, 1971

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of&apos; each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring&apos; and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman&apos; for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By R. D. Russell, R. M. Farquhar

SOTOPIC tracers have become an important aid in following the progress of chemical processes in the laboratory. It has recently been found possible to utilize a system of naturally existing iso-topic tracers to obtain information about the geological history of lead ores. Common lead, such as is found in lead deposits, is a mixture of four stable isotopes having atomic weights 204, 206, 207, and 208. Of these, the last three are identical with the lead isotopes produced as stable end products of the radioactive decays of uranium and thorium: the first, lead-204, is not known to be produced on the surface of the earth by any process. Since uranium and thorium Occur in the surface regions of the earth in amounts comparable with lead, and since the half-lives of uranium and thorium isotopes are of the same order as the age of the earth, they produce the radiogenic lead isotopes in amounts comparable to the amount of nonradiogenic lead present. Every significant exposure of a sample of lead to uranium and thorium will therefore lead to the permanent alteration of the lead isotope ratios in that sample. It is this unique property of lead that serves as a means of tracing the history of a lead sample in terms of its contacts with the radioactive elements. If lead from a lead mineral has been analyzed with a mass spectrometer, the measured isotope ratios are determined entirely by the isotope ratios of primeval lead, which are identical for all minerals, and by the particular history of the sample. It follows that for samples from any particular geological area, observed differences in the isotopic composition are enough to distinguish different geological histories. An illustration of the qualitative application of this statement is given in Table I by analyses of some galenas from the western Cordillera. Samples from deposits in Pre-Cambrian sediments have very different lead isotope ratios from those of the ores in the Paleozoic sediments. Although the two types are associated closely geographically, it is apparent that they have had quite different histories and have probably been emplaced at quite different times, as the ideas outlined in the following section suggest. Even when applied quantitatively, a lead isotope analysis can never indicate a unique history of any lead sample. However, it greatly restricts the choices available and combined with other geological and geochemical data can lead to a much better understanding of the genesis of lead ores. General Character of Lead Isotope Variations: Early isotopic analyses of common leads by Nierl showed that geologically younger leads were generally richer in isotopes of masses 206, 207, and 208, with respect to that of mass 204. This regularity of measured lead isotope ratios can be easily observed by plotting each of the ratios Pb207/Pbm and Pb205/ Pb204 against the ratio Pb206/Pb204. In both graphs the points lie scattered closely about a well defined mean curve. It was immediately supposed that this regularity resulted from the growth of all leads from a common primeval lead present at some time, To, early in the earth&apos;s history. Lead in the outer part of the earth would become continually enriched in the radiogenic isotopes as a result of the uranium and thorium intimately associated with it. The subsequent extraction of some of this lead and formation of a lead mineral free of the radioactive parents provide samples of lead existing in the earth at the time of mineralization, T. Younger leads in general will be richer in the radiogenic isotopes because they have been associated with uranium and thorium for a longer time. Then lead ratios would be given by the formulae: (Pb206/Pb204)YTPb^/Pb204) +f "(u201) kdt T (Pb207Pb204)r = (Pb208/Pb204)T0 + J (U295/Pb204) k&apos; dt T (Pb208/Pb204) t = (Pb208Pb204 + J (Th204) A." dt [1] where A, A&apos;, and A" are the decay constants of U238, U285 and Th232. Summaries of measurements of radioactivity of surface rocks, such as given by Faul,2 are of limited

Jan 1, 1958

By R. C. Buehl, M. B. Royer

High manganese slags of low phosphorus and iron content are produced by air oxidation of high phosphorus spiegeleisen in a basic-lined converter. Control of phosphorus and iron within specification limits for ferromanganese ore feed is obtained by a unique cyclic operating procedure. Various types of slags, or synthetic manganese ore, can be made. AN affiliated paper&apos; describes the production of high phosphorus spiegeleisen containing 14 to 23 pct Mn and up to 4 pct P in an experimental blast furnace from open-hearth slag or manganiferous iron ore. This phosphorus content is too high for use of the spiegel in normal steel-production operations. Consequently, a preferential separation must be effected whereby the manganese is concentrated in a product that is usable in industrial operations. The preferential separation methods being investigated for this phase of the work are confined to pyrometal-lurgical processes for ready incorporation into steel-plant operations. It is fortunate that manganese is more actively oxidizable than iron or phosphorus, and therein lies a preferential separation method for isolating manganese from these two elements. Silicon is more strongly oxidizable than manganese, and its oxidation precedes, or occurs simultaneously, with manganese. Therefore, manganese and silicon are separable into a high manganese oxide slag phase while the phosphorus and iron remain in the molten metallic state. Complete separation of these elements represents an ideal condition which is not generally attainable in actual operations. This pyro-metallurgical method for separating manganese from phosphorus and iron by preferential oxidation was investigated by blowing 500 lb of metal in a basic-lined vessel to obtain preliminary information on the effectiveness of the procedure. Certain conditions of attainment in the separation process are desirable in any method for removing manganese from high phosphorus spiegeleisen, such as: 1—High recovery of manganese in the oxidation product; 2—the product to be of equal or better quality than ferromanganese-grade ore—48 pct Mn minimum, less than 10 pct SiO2, and Mn-P ratio of 300:1; and 3—attainment of the enumerated objectives in a product amenable to industrial handling, such as a slag of high manganese content that will flow from the processing vessel and of sufficient fluidity for ready separation of metallic granules that may have become mixed with the manganese slag phase. Previous Work Recovery of manganese from low grade ores and industrial byproduct slags by smelting to spiegeleisen, with subsequent oxidation to synthetic ferro-manganese-feed ores, has been a subject for periodic investigation during the past four or five decades in the United States and Germany. Joseph&apos; and associates of the Bureau of Mines North Central Experiment Station, Minneapolis, Minn., smelted manganiferous iron ores of the Cuyuna range, Minn., to spiegeleisen and subsequently tried air and ore oxidation procedures for concentrating the manganese into synthetic ferrograde manganese ore. Joseph&apos;s results on the operation of a side-blown basic-lined converter for air oxidation of manganese from molten spiegeleisen were so discouraging that the procedure was abandoned after 11 blowing tests. Much slag was thrown from the converter vessel; phosphorus content was four to five times the maximum allowable for ferro ore; and a manganese-iron ratio of only 2 or 3:1 was obtained in the slag instead of the required 8:1. Oxidation of manganese from spiegeleisen with about 0.5 pct P, by adding iron ore to molten spiegel in an experimental open-hearth furnace, proved moderately successful in Joseph&apos;s experiments. The main drawback to the operation was the necessity for over-oreing for effective oxidation of the manganese with consequent too high iron oxide residual in the slag. Furthermore, the phosphorus content was proportional to the iron concentration and therefore much too high, so that several hours of reduction by a carbonaceous material were required to adjust the iron and phosphorus to the desired content of high grade ferro feed. A troublesome feature of the slag product of the spiegel oxidation process was its lack of fluidity if the silica content was less than 10 pct, the concentration considered desirable for the synthetic ore. Approximately twice the desired concentration of silica was required to impart enough fluidity for transfer from the vessel by pouring. The acute shortage of manganese in Germany

Jan 1, 1953

By A. R. Troiano, A. B. Greninger

There is need for an adequate working hypothesis that would describe at least qualitatively the crystallographic mechanism for the transformation from austenite to martensite in steel. A general theory would not only be of great assistance in the correlation of existing data and in planning future experimentation, but would also form the basis for an eventual explanation of the property changes that accompany lattice transformations. The mechanism of martensite formation described in the following pages is the outcome of two new experimental determinations: (1) the accurate evaluation of the lattice relationship between austenite and individual crystals of martensite, and (2) the measurement and analysis of the change in position that a volume of austenite undergoes when it transforms into a crystal of martensite. For this latter study, the stereographic analysis of shear was employed; this method greatly simplifies the solution of lattice-shear problems, and some space is devoted to its description. Lattiice Relationships and Habits PREVIOUS WORK The lattice relationships between austenite and martensite in carbon steels have been studied by Kurdjurnow-and Sachs,&apos; and by Wassermann;2 and in iron-nickel alloys by Nishiyama.3 Wassermann,2 and Mehl and Derge.4 The studies by Kurdjumow and Sachs and by Wassermann were made on single (austenite) crystals of quenched 1.4 pct carbon steel, and the results of these two independent studies agree closely with the postulated lattice relationships: (III)r||(0ll)a [101]r [111]a [1] Both Nishiyama and Wassermann worked with an alloy of iron plus 30 pct nickel (all austenite at room temperature), and "martensitic alpha" was formed by cooling in liquid air. They agree that the lattice relationships for these conditions are: (lll)r||(011)a [112]r[011]a [2] Mehl and Derge worked with a range of iron-nickel alloy compositions centered about 30 pct nickel. They concluded that when the transformation takes place near room temperature or above, relationship [l] holds, but if the same specimen is made to transform at -195°C, relationship [2] obtains;intermediate temperatures evidently produced a combination of these two relationships. Sachs and co-worker~,1,7 as well as Nishiyama,3 have proposed transformation mechanisms for martensite formation.* Both of the mechanisms picture the transformation as initiated by shearing movements along the octahedral [Ill] plane of austenite, followed by suitable expansion and contraction to complete the transformation. These mechanisms have been described and commented upon by Mehl, Barrett, and Smith,8 Mehl and Derge,4 Wassermann,2 and others, and generally accepted by investigators in this field. Greninger and Troiano9 have recently published the results of a detailed study of the shapes and orientation habits of martensite crystals in plain-carbon and nickel steels. They found that, contrary to previous assumptions, martensite plates form not along the octahedral planes but along austenite planes of very high indices; these results were in line with those of previous studies of martensite reactions in nonferrous alloy systems by Greninger and coworkers.6,10 Greninger and Troiano concluded that the transformation theories of Kurdjumow and Sachsl and of Nishiyama3 are untenable. Phragmén11 reached a similar conclusion. EXPERlMENTAL METHODS The object of this particular study was the evaluation of (1) lattice relationship between austenite and martensite, and (2) relationship between the martensite lattice and the martensite plate. The technique used for solving these problems was similar to that used by Greninger6 on martensitic structures in 8 copper-aluminum alloys. Briefly, the method consists of grinding and polishing a specimen on a surface parallel to an individual martensite plate and thus exposing a single martensite crystal for an area of l to 3 mm. The orientation of this exposed martensite crystal is then determined by means of a back-reflection Laue X ray pattern.12 Another pattern is obtained from the matrix crystal, and a stereo-graphic plot of data from these two patterns then provides the solution to the problem. It is necessary to repeat this process on several crystals in order to determine whether or not the solution is unique.

Jan 1, 1950

By M. Cohen, D. Caplan

The scaling characteristics of three Fe-Cr alloys have been investigated by determining their weight gain vs. time curves at 1600° to 2000° F. The scales formed thereby have been examined using the techniques of X-ray diffraction and spectrographic and metal-lographic analyses in an attempt to explain the discontinuities in the curves and to elucidate the mechanism of scaling. DESPITE the considerable number of investigations that have been carried out on heat resistant alloys, the characteristics of the scales formed at high temperatures are not fully known. The research reported here was undertaken in an attempt to ascertain the mechanism of scaling of the stainless steels. Scaling experiments were carried out first, the weight increase of the specimens being followed continuously with time. It was observed that, as well as showing the expected decrease in oxidation rate with time, the oxidation curves showed breaks corresponding to intermediate periods of accelerated oxidation, after which protectiveness again increased. This phenomenon was observed with austenitic stainless steels (types 302, 309, and 330) and with Fe-Cr alloys (types 410, 430, and 446), but only the latter are treated in this report. An examination of the scales was made using the techniques of X-ray diffraction and spectrographic and metallographic analyses in an attempt to obtain a correlation between the nature of the scales and the oxidation curves. A search through the literature revealed only a very few previous reports of such periods of accelerated oxidation. Dunn&apos; found breaks in the oxidation-time curves of some Cu-Si alloys but saw no rational explanation of the phenomenon. Heindlhofer and Larsen2 attributed a discontinuity in the weight gain-time curve of iron at 1290°F to the formation of blisters, the subsequent cracking of which exposed an unprotected surface and permitted rapid oxidation until a new protective scale had been reestablished. They advanced no explanation, however, for what they termed the peculiar behavior of a 27 pct Fe-Cr alloy at 2000°F which gained weight very rapidly in between two periods of very slow weight gain. Portevin, Pretet, and Jolivet3 in describing breaks in the weight gain-time curves of Fe-A1 alloys suggested that they might be associated with the occurrence of localized and deeply oxidized areas on the specimens. Bandel4 in a general discussion of oxidation curves of heat resistant alloys considered that the discontinuities were due to a local disruption of the protective layer by the growth of iron-rich oxides. Day and Smith" in their report on the scaling of a large number of iron alloys noted but did not explain occasional relatively rapid changes in oxidation rate at higher temperatures. Chevenard and Wache6 found breaks, often two per specimen, in the oxidation curves of an 18-8 type alloy. They suggested that the cause might be a depletion in chromium of the surface layer of metal due to its selective oxidation, the resultant high concentration of iron and nickel in the scale leading to a poorly protective scale. McCullough, Fontana, and Beck&apos; explained the breaks in the oxidation curves of types 304, 430, and 410 alloys as due to mechanical ruptures. Experimental Work Table I lists the chemical compositions of the materials used. Cylindrical specimens 1/4 in. in diam and 11/2 in. long were machined from cold rolled % in. rod. After a fine finish cut with a sharp tool, the specimens were abraded while still mounted on the lathe with Nos. 2, 1, 0, and 00 metallographic grade emery papers. A 3/64 in. hole was drilled at a distance of 1/8 in. from one end to permit suspension in the furnace. Specimen Nos. 1, 2, and 3 were tested with this surface preparation. All others, after being similarly prepared, were electropolished in a perchloric-acetic electrolyte, electrical contact being made by pressing a tapered platinum hook into the drilled hole. The specimens were then washed in hot water, rinsed with distilled water, rinsed with methanol, dried at 120°F, and weighed. Thereafter,

Jan 1, 1953

By W. S. Row

This mine is operated at 4000 to 4500 tons daily through a single shaft, with one rock hoist and one senice hoist. Latest shaft construction is concrete with wooden dividers. Economics of drifters and air-leg drills are compared, as well as costs of shrinkage and sub-level stoping. Economy of large haulage equipment and underground crushing is shown. THE property of Kerr-Addison Gold Mines is located in the Larder Lake district of Ontario about 3 miles from the Quebec boundary on the highway between Kirkland Lake and Noranda. It is roughly 320 miles due north of Toronto and 365 miles north of Buffalo, N. Y. The property was staked in 1906 and after several development efforts finally came into continuous production at 500 tons per day in 1937. In 1939 the daily tonnage -was increased to 1200 and in 1941 to 2100 tons. At the end of the war, because of the shortage of labor, tonnage was down to 1100 tons per day, rising to 2200 in February 1947. A further plant expansion inaugurated in 1946 was completed by December 1948, bringing the capacity of the mine and mill to a production rate of 4000 tons per day. Current production, with 880 men employed, is 4400 tons per day. Changes in mining methods and equipment, required by the recently completed expansion program, have yielded interesting comparative results, some of which are described in this paper. Hoisting of ore and waste from the mine, as well as all service facilities for handling men and supplies underground, are provided for in a single vertical five-compartment shaft. Ore and waste are hoisted in 12½-ton skips in balance by a 14-ft diam hoist with drums 115 in. wide, grooved for 2?-in. wire ropes. This hoist, with a total rope pull of 85,000 lb, was designed to operate at a speed of 2600 ft per min to a depth of 4000 ft, hoisting 15 tons of ore in each skip. It is amplidyne-controlled and powered with dual drive dc motors of 2250-hp each, through flexible couplings to two pinion shafts, one on each side of the main gear. Each motor has a peak load rating of 4500-hp at point of greatest duty. Direct current power to the hoist motors is supplied from a motor generator set consisting of a 5000-hp synchronous motor driving two 1750-kw dc generators. The loading pockets used so far are at depths of 1500 and 2725 ft respectively. Consequently the present hoisting speed is 2000 ft per min and the skips capacity only 12½ tons. Now that the shaft has been deepened the new pockets at 3934 ft will be increasingly used so that the speed and the skip size will be increased up to original specifications as required. Some difficulty in meeting the required hoisting cycle is expected because of the shape of the skips. As now in use the cross-sectional dimensions of the inside of the skip are 4 ft 6 in. x 3 ft 8 in. To hold 121/2 tons, therefore, they are 14 ft 10 in. deep. Since the skips are the conventional overturning or Kim-berley type, considerable hoisting time is lost in retardation in entering the headframe dump and in acceleration when leaving. It is expected that to obtain the specified tonnage from this hoist when the skip size is increased to 15 tons it may be necessary to resort to bottom dump skips. This type of skip could reduce considerably the present excessive acceleration and retardation times. Analyses of the skip-hoisting operation are made monthly, and every effort is made to reduce controllable delays. For a nine-month period in 1951 such an analysis shows that the hoist was in operation 92.5 pct of the available time, which was allotted as shown in Table I. Overall hoisting costs, cage and skip, for the year 1951, averaged $0.168 per ton of ore milled. The mine is serviced entirely by means of a single cage, capacity 35 men or 15,700 lb, operating in con-

Jan 1, 1954

By N. K. Chen, R. B. Pond

IN the study of slip band* formation, there have been many examples to show that they do not always appear as lines traversing the entire crystal, but as segments whose ends seem to vanish in their path through the crystal. This characteristic appearance of slip bands has been witnessed under the optical microscope at various magnifications&apos;-&apos; and also under the electron microscope.&apos; A typical example of this behavior seen with the optical microscope is shown in Fig. 1. However, the slip band studies were generally conducted on polished surfaces of single or poly-crystalline metals which had been previously deformed; i.e., the load was generally released so that the observation could be made. Any picture of slip bands so obtained can represent the surface phenomenon only in a static state of the strained material. The conditions prior to their formation cannot be definitely and clearly assigned. Thus, while a segmented slip band may suggest that slip is a growth process as supposed by the theory of the nucleation of slip,V he usual appearance of suddenly and fully developed slip bands around the crystal has generally been considered as a consequence of uniform shear of the entire slip plane akin to a cataclysmic process. Little clear-cut information is available with regard to the speed at which a slip band forms, its direction of motion, the geometry of its position with regard to its neighbors, and its dependence on orientation. A description is given in this paper of experimental apparatus by which the progressive formation of slip bands can be recorded while the specimen is undergoing deformation. Qualitative and quantitative data on the dynamic formation of slip bands will be presented with special interest concerning the propagation of slip bands, the spacing of slip bands, and their relations to strain hardening. Views on the formation of slip bands are discussed and a mechanism of the unit process involved in the formation of a slip band is proposed. Preparation of Specimens Single-crystal specimens of high purity aluminum (99.997 pct), 1/8 in. square in cross-section and 1% in. long in gage length, were made by the method of gradual solidification from the liquid state. Since no machining work could be introduced in preparation of crystals of such small size, a special mold was designed for casting them to final shape. The mold consisted of two, separate, high purity graphite blocks. Generally, 20 molds were packed together in one container so that 20 specimens could be obtained by one casting operation. This was desirable since it was possible by this method to obtain groups of crystals with similar orientations. The as-cast crystals were carefully clipped from the gate, etched, and homogenized for 24 hr at 600°C. They were then very gently polished using a 4/0 paper, re-etched, and finally electrolytically polished after the method previously described by Chen and Mathewson.6 The crystallographic orientations were determined using a back-reflection, Laue method. Tensile Testing and Photographic Method The tensile testing equipment for these tests was composed of a specially designed microtensile machine, microload cell and microclip gage with necessary appurtenances. The members of the microtensile machine consisted of three parts, as shown in Fig. 2. The chassis is equipped with an oil cylinder, A, and piston, the piston being part of the movable cross-head, B. Pressure in the oil cylinder is controlled and regulated by an external pneumatic-hydraulic cell, C, which is connected to the cylinder by a Vs in. high pressure copper tube. This cell is half filled with hydraulic oil and has a needle valve, D, on the oil exit side as well as a needle valve, E, on the gas inlet side. A quick-acting valve, F, as well as a pressure gage is provided for the gas side. The oil exits into the load piston on the microtensile machine. By connecting a tank of inert gas to the gas inlet, regulated pressures were provided over the oil so that the oil would leave the cell at a rate determined by the setting of the exit needle valve, the gas pressure, and the pressure of the oil in the load piston of the microtensile machine. With this pneumatic-hydraulic appurtenance it was possible to

Jan 1, 1953

By F. D. Rosi

The plastic properties of extended silver and copper crystals of varying purity were studied as a function of crystal orientation in the early stages of flow. Variations in the gross shape of the shear stress-shear diagram and in the properties of critical Variationsshear stress and shear-hardening coefficient were correlated with changes in slip-band developments. The phenomenon of work hardening is discussed in terms of the existing dislocation theory. IT appears certain from the early studies on the deformation characteristics in metal crystals1-3 that plastic flow takes place in a preferred crystallo-graphic slip system which is determined by the geometry of the crystal (law of maximum shear stress), and that the value of shear stress for this system is independent of crystal orientation (law of critical shear stress). Experimentally, it has been demonstrated further that the law of critical shear stress can be extended to include extensive plastic flow.&apos; Thus, the shear-hardening coefficient, which is defined as the slope of the shear stress-shear curve, also is considered to be independent of orientation. It is noteworthy that deviations from this empirical shear-hardening law have been reported in cubic crystals whose initial orientation favors slip on more than two systems.&apos; Moreover, this law appears to have been derived from stress-strain data relating to relatively high values of shear strain (0.5 to 4), where widespread slip and complex distortions can be expected, regardless of crystal orientation. Since existing data indicate that the strain inhomogeneity in a crystal is manifested particularly in the early stages of flow, it would appear that a more exacting test as to the fundamental nature of the shear-hardening law would be to investigate systematically the shape of the stress-strain curve as a function of crystal orientation in the earlier stages of deformation. With regard to the general form of the shear stress-shear curve for cubic crystals, early studies show a parabolic hardening law, where the shear 1 stress is proportional to the square root of the shear-strain. Since this law was predicted theoretically by Taylor" in his original dislocation model for hard- ening, it has been accepted widely as a fundamental flow characteristic of cubic metals. However, it was recently pointed out by Masing6 hat the parabolic law is not the elementary form of hardening in cubic crystals, but instead is a consequence of complexities in the flow process (e. g., deformation bands and unpredicted secondary slip). Thus, in the very early stages of deformation (< 2 pct extension) where the occurrence of such complexities is unlikely, a different strain-hardening behavior might be anticipated. This view is supported by the recent work of Rosi and Mathewson7 on high purity aluminum where a linear law was obtained for extensions up to 2 pct. A linear hardening over a wider range of deformation also was reported by Rohm and Kochendorfer8 ho deformed aluminum crystals under conditions approximating pure shear. Even more pertinent is the recent evidence of Masing and Raffelsieper9 on high purity aluminum crystals. It was found that for crystals having initial orientations near a <l00> or <1ll> axis, a high hardening was obtained, whereas crystals with a <110> orientation exhibited a low and linear hardening curve followed by a region of more rapid hardening. Since much still remains obscure concerning the details of strain hardening as well as slip-band formation in face-centered-cubic crystals in the early stages of deformation, the present study was undertaken to evaluate the effect of crystal orientation on these two important manifestations of glide. It is important to note here that at the time of this study, Lucke and Lange11 presented information on the orientation-dependence of the shape of the strain-hardening curve in aluminum of various purities. Their work, which essentially represents an extension of that of Masing and Raffelsieper, in many respects is parallel to that of the present study. Experimental Procedure Production of Single Crystals: Single crystals of silver and copper of varying purity were used in

Jan 1, 1955

By Strathmore R. B. Cooke

On the basis of experiments conducted on quartz using a bubble pick-up method, it was shown in an earlier paper1 that this mineral will preferentially adsorb hydrogen, calcium, or sodium ions, depending on the relative concentrations of those ions in the solution in which the quartz is immersed. For quartz particles ranging in size from 0.2 to 1 mm, it was demonstrated that the concentration of calcium in solution (assumed present as ions) necessary to completely activate quartz for flotation is given by the expression: Ca++ = [H+] X 106 + [Na+] X 10-3 In this expression, ionic concentrations are in mols per liter. It was further shown that the pick-up method is apparently more sensitive to changes in reagent concentration than the standard captive-bubble method, and that induction times are apparently much reduced. Since completing these earlier tests, a new type of cell has been constructed; this is shown in Fig 1 and 2. In Fig 1, A is a ground joint, B is a central tube reaching to within a few millimeters of the bottom of the cell, and C is a stopper which may be removed for reagent addition, and serves the further purpose of excluding carbon dioxide from the air during the test. The entire cell is constructed of Pyrex glass, and does not give the trouble experienced with the earlier cell, in which activating ions were released from the glass at high pH values. The only critical factor in the construction of the cell is the clearance between the central tube and the bottom of the cell. This clearance should be sufficiently small that the bubble can be pressed directly on the mineral grains lying on the bottom of the cell. In the pick-up tests to be described in this paper, the reagents used were all of C. P. grade, except the sodium oleate, which was Merck&apos;s "neutral powder." The quartz employed was water-clear vein quartz, sized on screens, cleaned with both hydrochloric acid and sodium hydroxide, and given a thorough final washing with distilled water. Experimental procedures were the same as described in the earlier paper. EFFECT OF SIZE OF QUARTZ ON PICK-UP To ascertain the effect of particle size on the adsorption of calcium ions, the quartz was sized from minus 14 plus 20 mesh through the intervening screen sizes to minus 270 mesh plus 400 mesh. Each size was thoroughly cleaned, and then tested in the cell at different calcium chloride and sodium hydroxide concentrations, and at a constant sodium oleate concentration of 20 mg per liter. All particles, within the size range given, exhibited complete pick-up within the curve expressed by the equation above. This presumably means, when the conditions imposed by the equation are satisfied, that this maximum is independent of particle size. However, it was found that the range through which partial particle pick-up occurred progressively broadened as particle size decreased. This is shown in Fig 3, in which curves B, C, and D show the limits at which pick-up just commences (as the pH is increased) for particles of minus 14 plus 28 mesh, minus 65 plus 100 mesh, and minus 270 plus 400 mesh size, respectively. These results indicate that for satisfactory activation, at any given pH, a lower calcium ion concentration is required for fine particles than for coarse particles. EFFECT OF HIGH ALKALINITY ON PICK-UP At calcium concentrations of between 1 and 10 mg per liter, and at high alka-linities, it was noticed that pick-up ceased as soon as calcium hydroxide commenced to precipitate. This effect was investigated at other calcium concentrations, with the same results. Solutions of calcium chloride, containing 105, 104, l03, and l02 mg of calcium per liter were made alkaline with sodium hydroxide until calcium hydroxide just started to precipitate, according to the following equation: CaCl² + NaOH -+ Ca(OH)2 + 2NaCl The beginning of precipitation was taken as that point at which either a faint opalescence appeared in the solution, or a Tyndall cone became ap-

Jan 1, 1950

By Tibor Stefansky, John E. Dorn

MOTT and Nabarro1-5 were first to illustrate the importance of the flexibility of dislocations in accounting for the strengthening that metals undergo due to the presence of internal-strain centers. Such strain-centers might arise from a number of causes such as radiation damage, the presence of semicoherent and coherent precipitates and clusters, as well as individually dispersed interstitial and misfit substitutional solute atoms. Each strain-center induces positive and negative shear stress fields on the slip planes of the surrounding alloy matrix. In order to effect plastic deformation, therefore, the alloy must be subjected to sufficiently high applied shear stresses to push dislocations past all such internal stress fields. If dislocations were inflexible and moved as rigid lines, they would be equally pushed and pulled by internal stress fields. At this extreme the strengthening would be vanishingly small. Dislocations, however, are not rigid; they are flexible and extensible. They wiggle between positive and negative strain-centers, thus increasing their line energy at the expense of their interaction energy with strain-centers. cottrel16 and Friedel7,8 have independently presented lucid reviews of the significance of the Mott-Nabarro dislocation-flexibility concept to the strain-center strengthening of alloys. Their analyses however were only semi-quantitative. There is evidence in the recent literature of renewed interest in a more rigorous analysis of flexibility. Thus, Gleiter9 and Gerald" have shown that the calculated strain-energy interaction between a dislocation and the stress fields of coherent precipitates can be seriously in error if the flexibility of the dislocation is not taken into account. This report will be concerned with a more detailed analysis of the problem based on the following approximations: 1) Although many types of strain-centers exist, the following analysis will be limited to the case of solute-atom strain-centers in fcc substitutional alloys. 2) To facilitate the analysis by avoiding statistical considerations, the strain-Centers are assumed to be in regular arrays on the slip plane. Although the quantitative results are somewhat dependent on the type of array that is assumed, the qualitative trends are similar for various arrays that were studied. 3) An adjustment of the results from those for square arrays to those for the more realistic case of a random distribution of strain-centers is accomplished by adopting the interesting statistical theory first introduced by Kochs,11,12 elaborated on by Dorn, Guyot, and stefansky,13 and analyzed by Foreman and Makin14 in their computerized experiments. 4) For simplicity the dislocation lines are taken to wiggle about their edge orientation and no correction is applied to their line energy for deviations from edge configurations or for the elastic interaction between segments of the now curved dislocation. It will be shown that for extremely low concentrations of atomic strain-centers the strengthening increases with the square root of their concentration. For slightly higher concentrations the strengthening rate becomes less rapid. At a critical concentration a maximum strength is obtained and a decrease in the strengthening takes place as the concentration of solute atoms is further increased. These trends are a direct consequence of dislocation flexibility. They arise from changes in the amplitude of the waviness of the dislocation line at the yield stress with solute atom concentration. Despite the simplifying assumptions that were made, the results agree qualitatively with appropriate experimental data. I) STRESS FIELDS ON SLIP PLANES Internal stresses are introduced in a lattice whenever a host atom of radius ro is replaced by another that has a different atomic radius. According to the classical theory of linear elasticity,15 the stress field about a solute atom at the origin of a spherical coordinate system is given by arr=-4G€(?_0)3 ffflfl ="W =2G€{t) f°rr^ro(l+e) UJ where G is the shear modulus of elasticity and Y, = ro(l + E) is the radius in situ, of the substituted atom. As shown by ~shelb~,&apos;~ this approximation assumes that the bulk modulus of elasticity of the substituted atom is identical with that of the host species. ~abarro&apos;~ suggested that the strain E can be deduced

Jan 1, 1970

By Strathmore R. B. Cooke, Paul B. Queneau

The kinetics of the dissolution of scheelite in basic solutions of carbonate and fluoride were investigated. Work was also done with solutions of alkali metal chloride, hydroxide, phosphate, and mixtures of phosphate and fluoride. The study was conducted at 90 psig and at temperatures ranging from 100" to 155"C, and both natural and synthetic scheelite single crystals were used. The interaction of scheelite with carbonate solutions generally followed a parabolic rate law, and resulted in the formation of calcite crystals on the attached surface. The transport of the CO3 through the calcite to the scheelite surface was probably rate -controlling between 115" and 135°C. Positive deviations from Parabolic behavior were observed at 100" and 155?C, presumably due to the calcite grain growth, and to the formation of a noncoherent calcite layer, respectively. The leaching of scheelite with alkaline fluoride solution produced a calcium fluoride reaction-product which covered the surface as a sheet-like layer. Below 110°C the dissolution rate was parabolic; at 115" and 135°C it was linear. In the linear region, the periphery of the calcium fluoride layer lifted from the sample. Only the lower layers, braced by the scheelite substratum, remained unbroken. This bound layer, approximately constant in thickness, limited the rate at which the fluoride could attack the scheelite. The phosphate and phosphate-fluoride leaches dissolved scheelite at a linear rate; solid reaction products were respectively hydroxyapatite and fluorapatite. Sodium hydroxide and chloride were not effective leachants, and did not produce observable solid reaction products. THE feasibility of pressure leaching of scheelite pulps with basic solutions containing either carbonate or fluoride ions, as indicated by the following equations, has been established by previous investigators:1-3 200°C CaWO4s + CO37q - CaCO3s+WO4aq [1] 200°C CaWO4s + 2Faq ^ CaF2s+WO4aq [2] It is to be noted that a commercial process employing reaction [I] is in use at Union Carbide&apos;s operation near Bishop, Calif. In the earlier work referred to, it was apparent that the precipitation of the solid reaction-product on the scheelite particles sharply reduced contact of the leachant with the scheelite. We have extended this work by studying the kinetics of dissolution employing single crystals of scheelite of known exposed surface area. In addition, the effectiveness of solutions of phosphate, of phosphate with fluoride, and of chloride and hydroxide as leachants for scheelite have been investigated. EXPERIMENTAL Apparatus. The low-pressure autoclave used in this wo (100 psig maximum) is essentially that of J. Halpern4 as modified by F. A. Forward.5 Constructed entirely of 316 stainless steel, its maximum capacity is 4000 ml. The temperature in the autoclave was regulated to *0.5?C by a Wheelco thermocouple controller. A 4-in. diam, three-bladed impeller, circulated solution upward against the sample, and a strobo-scope permitted holding the stirring rate to *15 rpm. A check valve and a "pop" type safety valve were installed, a sample holder was fixed to an externally adjustable rod, and a water-cooled condenser was placed in series with the sampling valve. The stainless steel sample holder, Fig. 1, held the epoxy-mounted sample (f) five mm above the impeller. Tightening the tapered sleeve (d) positioned the epoxy-resin specimen-mount by forcing it back against the spacer (c). The mount (e) was 1 in. diam. Sample Description and Preparation. Both synthetic and natural scheelite crystals were leached. The former were single crystals of 99.95 pct purity which were leached approximately perpendicular to the "c" axis; they were supplied by the Gallard-Schlesinger Chemical Manufacturing Corp. The natural crystals, supplied by Minerals Unlimited, were transparent, analyzed 99.8 pct CaWO4, and in ultraviolet illumination exhibited the characteristic blue glow of substantially molybdenum-free scheelite. To permit exposure of an essentially constant surface area of scheelite to the leachant, the samples were mounted in Scotchcast Brand Resin No. 250 (Minnesota Mining and Manufacturing Co.). The mount-

Jan 1, 1970

By T. A. Pollard, C. R. Sandberg, E. B. Elfrink

This paper presents an evaluation of compressibility factor data and a discussion of their application to the estimation of gas reserves. A correlation is presented which provides compressibility factors for use in both two-phase and single-phase hydrocarbon systems. Accuracies comparable to those obtained previously for single-phase systems only can be expected. A simple means of predicting the presence or absence of a liquid phase in a condensate system of known composition is illustrated. The correlation is based on 1,030 compressibility determinations from 21 hydrocarbon samples taken from eight oil fields. Of the data used, 75 per cent were from California, 15 per cent were from the Mid-Continent area, and 10 per cent were from South America. The average numerical deviation of the experimental data from this compressibility chart is 1.22 per cent. Charts and tables are included and discussed which illustrate the errors involved through the misuse or nonuse of compressibility factors in estimates of gas-in-place. INTRODUCTION The compressibility factor is a coefficient which expresses the deviation of a gas of given composition from the Perfect Gas Laws. A factor such as this is necessary in any calculation involving volumes of gaseous mixtures, and finds extensive application in the estimation of natural gas and condensate reserves. It is used in the decline curve, the volumetric, and the material balance methods of gas reserves estimation. The behavior of gases at high pressures has been investigated extensively in recent years and considerable data have been assembled on the compressibility characteristics of a number of gases. Notable among the investigators of high pressure gas relationships are Kvalnes and Caddya, Kay" Sage and Laceys, and Brown, Standing" and Katz4. Other contributors are Smith and Watson, Roland and Kaveler&apos;, and Stevens and Vance". The data on compressibility factors assembled by these investigators have been presented and correlated in numerous ways; particularly noteworthy is the method first presented by Kay5 which relates compressibility factor "Z" to pseudo-reduced temperature and Pseudo-reduced pressure. Other investigators have used this empirical relationship successfully and numerous charts covering a large number of gases have been constructed on this basis. It is the purpose of this paper to evaluate compressibility factor data and to illustrate the importance of their proper use in the estimation of gas-in-place for both gas and condensate reservoirs. EVALUATION OF COMPRESSIBILITY FACTOR DATA The compressibility chart presented by Standing, Katz, Brown and Holcomb in 1941 is probably the most recent and reliable chart for natural gases. The reliability of the Katz chart has been investigated by the writers for a fairly large number of gases (single-phase) in the pressure range from 500 to 10,000 psia and temperature range from 80 to 400°F. A summary of this comparison is presented in Table I. The numerical average deviation of the chart compressibility factors from the experimental compressibility factors is 1.05 per cent, and the algebraic deviation is -0.28 per cent. The Katz correlation appears to be quite accurate for single-phase hydrocarbon systems. It was based on single-phase systems and does not necessarily provide a means of accurately predicting the behavior of two-phase systems which might be encountered in condensate work. Data published recently by Sage and Oldsl&apos; have enlarged the knowledge of phase behavior in condensate systems by covering extensively the Compressibilities of systems in the two-phase as well as single-phase regions for a wide range of temperatures, pressures and gas-oil ratios. An evaluation of these data indicates that conditions can arise, especially in condensate systems having fairly low gas-oil ratios, in which two phases occur and the usual gaseous compressibility factors do not accurately apply. The measured PVT data of Sage and Olds covering two-phase systems have been correlated with additional such data from the Mid-Continent area and South America; these are presented in Fig. 1. This chart is the result of 1,030 compressibility* determinations from 21 hydrocarbon samples taken from eight oil and condensate fields. Of the data used, 74.75 per cent were from California, 15.45 per cent were from the Mid-Continent area, and 9.80 per cent were from South America. The chart construction is based on the original

Jan 1, 1949