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By D. L. Luffel

This paper presents two main developments: (1) a short, constantly accelerated centrifuge method of measuring drainage capillary pressure properties of cores, and (2) a new analytic method of treatment of centrifuge measurements to obtain saturation-capillary pressure relations. Toward the first objective, a clever experimental method is presented which is certainly more rapid than previous centrifuge methods. Toward the second objective, a new analytic method is derived to eliminate the approximate method of Hassler and runner. The derivation of this new analytic method, however, appears to be in error. The new analytic solution is developed as Eq. 5 in Appendix A. At the beginning of this derivation, the average wetting phase saturation of a core is expressed as, where is the centrifuge angular velocity. Eq. D1.2 makes explicit the dependence of S and S upon The second equation shown in Appendix A expresses the relation between the three variables Since for a given porous medium the saturation is uniquely related to capillary pressure, the functional dependence of S upon P is trivial, i.e., Pc.ri does not actually appear. Thus, the function 5 (r, ) may be expressed as a new function, S*, of PC, , alone The author transforms the variable of integration in Eq. Dl through use of Eq. D2 and writes

Jan 1, 1965

By J D. McDonald

This paper outlines the function of the Safety and Compensation Division of the Mining Association of British Columbia. After a general discussion of safety and the safety program now being followed in B.C., the author goes on to describe the wide-ranging aspects of compensation payments and company assessment rates. Special attention is also given to the problem of silicosis in mining operations. In appendices to the paper, the experience rating plan of the mining industry is compared to that recently adopted for the construction industry. Introduction The Mining Association of British Columbia consists of fifty-five member companies, including virtually all the producing mines as well as the larger exploration, contracting and development companies. On completion of an extensive study of safety and compensation in the mining industry, the Mining Association of British Columbia instituted a Safety and Compensation Division in 1954. The director of the Safety and Compensation Division reports to the Executive Committee of the Association. There are two main functions of this Division. First is the prevenion of accidents by encouraging

Jan 1, 1965

By Frank E. Sullivan

The separation of liquids from granular materials has been widely studied by a number of: investigators over a period of years in an effort to more fully understand the physical phenomenon which occurs. Liquid may be removed from solids, or partially removed, by gravity separation, mechanical separation' or heat drying. Mechanical separation is advantageous when compared to heat drying principally from a cost saving standpoint and also on certain materials which are heat sensitive. It is realized however that mechanical separation of liquids has certain practical limitations. In order to evaluate the efficiency of mechanical separation and predict the extent of, liquid removal, it is first necessary to study the forces which hold the liquid to the solids. From a very practical observation using gravity drainage, it is soon obvious that a pile of coarse solids will drain faster and retain less liquid than a pile of finely divided solids of the same material. For commercial operations it is important to estimate the residual liquid which will remain after a mechanical separation. Batel (1) explored the various quantities of liquid present in the interstices of the bulk granular material. From his work and other authors which he has correlated in one of his recent papers, various formulas are now available which permit an empirical relationship to be developed showing residual moisture versus mechanical separating forces.

Jan 1, 1965

By I. L. Dillamore

A purely geomentrical analysis based on oriented-growth relationships is presented to derive annealing-texture orientations in bcc metals from their- known deformation textures. The analysis takes as its starting point a description of- the bcc deformation texture and follows previous work on fcc metals in considering pvobable nurleation sites for recrystallization and the textural limitations on grains growing into a deformed matrix. The analy-sis accounts for the prominent and the minor coinponents of the annealing textures formed from two the deformation textures and can account for the ob-sem:ed temperature dependence of the annealing texture of bcc metals. THERE have been a number of investigations of annealing textures in bcc metals but few attempts to relate these textures to the deformation textures. This has been largely due to the lack of definition of both annealing and deformation textures, neither of which shows sharply defined orientations. It is, however, necessary to get a better understanding of primary recrystallization textures in bcc metals in view of increasingly exacting demands upon the quality of steel sheet for drawing purposes and as a necessary step towards the control of textures through processing. An analysis is presented here which relates annealing textures to deformation texture, by a purely geometrical method. This takes as its basis the oriented-growth theory of recrystallization and makes some reasonable assumptions regarding the make-up of bcc deformation textures and the limitations on growth relationships in bcc metals. Detailed information on this latter point is not available at the present time, and the present analysis may need to be streamlined or extended when such information is at hand. It is felt, however, that despite these limitations the analysis provides useful results and a valuable aid towards understanding the effect of processing variables. 1) BCC ROLLING TEXTURES Different workers have used a variety of descriptions for the texture developed in bcc metals by rolling. For the present purpose it will be assumed that two different deformation textures can be obtained: 1) a texture containing a major (112)[li0] component and a minor (001)[1i0] component for which increasing deformation causes the (001)[li0] component to increase at the expense of the (112)[li0] component, as suggested by Dillamore and ~oberts' (this is the texture predicted to arise starting from randomly oriented material); 2) a t~xture containing the above components and (111)[110] and (ii1)[112] components. This texture could arise from a material with an initial (110)[001] or (iil)[112] texture. It is well-known that the (ll0)[001] orientation rotates to (ii1)[112]that on roll-

Jan 1, 1965

By O E. Weightman

This paper describes the methods used for the ventilation of raises, sublevels and drawholes at Cominco's Sullivan mine. The problems involved in ventilation during blasting, drilling and scraping operations are first re-viewed, and then the air mover, a piece of equipment developed at the Sullivan mine, is described. The design of this device is discussed, along with the operating procedures used. Some figures are given to show the effectiveness of the method. THE Sullivan mine, located at Kimberley in the southeast corner of British Columbia, is owned and operated by The Consolidated Mining and Smelting Company of Canada Limited. Current daily production is approximately 10,000 tons. The mine is developed by sixteen levels over a vertical range of 2,000 feet. The total ventilation requirements, which amount to approximately 1,000,000 cubic feet per minute, are handled through a network of fresh air intake and foul air exhaust circuits. In addition to the many development and production headings, there are three crushing chambers and an extensive conveyor system which must be ventilated.

Jan 1, 1965

By S. Stopek, E. D. Hinkley, R. H. Rediker

Epitaxial heterojunctions have been prepared by melting the lower -melting-point semiconductor of the interface between two dijferent semiconductors. when the temperature is reduced, the melted material recrystallizes, having alloyed into the higher -melting-point semiconditctor. The electrical and elcctro-optical properties of such single-crystal heterojunctions between GaAs and Gash and between p-type InAs and n-type Gash are the subject of this paper. The forward current varies as exp (AV), where A is substantially independent of temperatuve. For Gds-Gash heterojunctions at temperatures above, 370°K, if the current-voltage relationship were to he expressed as exp (qV/nkT), then n would he less than unity. The injection luminescence associated with forward current is, for the most part, characteristic. of the lower bandgap semicondutctor. These results can he explained by carrier injection into the lower bandgap semiconductor by tunneling through a barrier at the interface. The photovoltaic effect measured for incident photons having energies in the range between the bandgaps of the two semiconductors is much smaller than that produced by higher-energy photon The smallness of this between -the-gap photovoltaic response can he explained by the low probability for penetration of the barrier by the carriers produced in the smaller -bandgap semiconductor. THE technique of interface alloying has been used to produce single-crystal junctions between dissimilar semiconductors.' Oriented wafers are placed on a carbon heater strip, Fig. 1. so that semiconductor S1, which has the lower melting point, is supported by semiconductor S2. Electrical current passed through the heater strip produces a temperature gradient such that S2 is at a higher temperature than S1. As the temperature is raised the lower face of S1 begins to melt. Before the entire wafer can melt, however, the heater-strip current is turned off and, as illustrated in Fig. l. the melted portion recrystallizes, having alloyed into S2. Junctions have been fabricated by the above procedure between GaAs and germanium, between GaAs and GaSb, and between InAs and GaSb. Mroczkowski, Lavine. and Gatos have described the metallurgical and chemical aspects of the GaAs-Ge junction.2 The transition from GaAs to germanium is not monotonic and a portion of the recrystallized region consists of the GaAs-Ge eutectic. Since gallium is an acceptor and arsenic is a donor in germanium, since germanium dopes GaAs, and since the electrical properties of the GaAs-Ge eutectic have not been investigated, any interpretation of the electrical characteristics in terms of simple heterojunction theory would be incorrect. That the rectification of GaAs-Ge heterojunctions is not a property of the impurity doping of the GaAs or the germanium, but is most probably due to the impurity distribution in the recrystallized region, is clear from the fact that forward conduction occurred for all the GaAs-Ge interface-alloy junctions (whether they be n-n,n-p. p-n. or p-p) when the germanium was biased positively. The electrical characteristics of these GaAs-Ge heterojunctions will not be discussed further in this paper. Electron-beam microprobe analysis of GaAs-GaSb heterojunctions showed that the transition from arsenic to antimony atoms was without structure. and that the transition occurred within a 2 to 3 region.' In this paper we will describe the electrical properties of the GaAs-GaSb heterojunctions as well as electrical and electro-optical properties of the InAs-GaSb heterojunctions. A band model for the junction will be proposed which can explain these properties. ELECTRICAL PROPERTIES OF GaAs-GaSb HETEROJUNCTIONS After interface alloying. in preparation for the electrical and electro-optical experiments, ohmic contacts were made by conventional means. For example. Kovar tabs clad with tin were alloyed to n-GaAs or similar tabs clad with Au-Zn were alloyed to p-GaAs. The units were mounted and then etched. All four combinations of conductivity types

Jan 1, 1965

By S. Atak, M. C. Fuerstenau

Clean quartz cannot be floated with a high molecular weight sulfonate as collector at any pH. Good flotation is achieved from pH 6 to 12 when Pb is added at low additions of sulfonate. The active species of lead responsible for flotation is shown to be Pb(OH), which in the presence of sulfonate forms precipitated lead-hydroxy-sulfonate, the apparent collector in these systems. The ratio of collector to metal ion addition is critical for flotation to be effected at a given value of pH. At low Pb++ additions, the constant, k, k = (hydroxyl activity)/(sulfonate addition)', must be equalled or exceeded for flotation to result. Similarly, at high additions of Pb ++, k1 = (hydroxyl activity)/(sulfonate addition) " must be exceeded. Previous work has shown that clean quartz cannot be floated at any pH with a high molecular weight sulfonate as collector.'" Flotation can be effected, however, when a polyvalent metal ion is added to the system in a pH region in which the metal ion is hydrolyzing to its first hydroxide complex. Although the basic phenomenon responsible for activation is apparently metal ion hydrolysis, the amount of collector added in relation to the amount of metal ion is critical. In fact, Schuhmann and Prakash,3 and Gaudin and Rizo-Patron4 have demonstrated that this ratio of collector addition to metal ion addition determines whether any flotation is possible at a particular value of pH. The object of this paper is to explain and quantify the relationship between collector and activator additions as a function of pH. For this work, Pb++ was selected as activator, and a high molecular weight sulfonate was chosen as collector. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate (mol wt 450) was used as collector. Reagent grade n-amyl alcohol was added as frother, and pH adjustments were made with KOH. Lead was added to the systems as the chloride salt. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Quartz was prepared by leaching the sized sample

Jan 1, 1965

By Edward E. Johnson

The Bureau of Mines publishes in its ?Minerals Yearbook? a series of indexes on the domestic minerals industry. Among these are the index of physical volume of mineral production, indexes of stocks, and indexes of average unit mine value and implicit unit value, This report describes the material coverage of these indexes and the methods used in their construction. Detailed descriptions are given for several other mineral-oriented indexes regularly published by other government agencies. These descriptions give the index user a better understanding of what each index purports to measure and aids him in selecting the most appropriate index for his purpose.

Jan 1, 1965

By T. Vasilos, J. T. Smith

THE mechanism of pressure sintering, or hot pressing, for ceramic materials, has been investigated by several researchers.1-8 Plastic flow has been suggested as the rate-determining mech-anism1,2 while grain boundary sliding3,4 and fragmentation processess have been found controlling in other studies. Vasilos and Spriggs5,6 have reported that pressure sintering occurs by a diffusion-controlled mechanism. For the pressure sintering of metals, investigations with lead7 and with tin6 have not identified the operative mechanism during consolidation of these powders. This note reports the results of a pressure sintering study initiated to determine the mechanism controlling the densification of spherical copper powder. Temperatures of 300°, 400°, 500°, and 600°C at 2500, 5000, 7500, and 10,000 psi pressures were investigated. The copper powder for this study was obtained from Metals Disintegrating Co., Elizabeth, N.J. The minimum purity was reported to be 99.9 pct. The powder size was -325 mesh and a lineal analysis showed the average size to be less than 1 p. An alumina die body and punches were employed. Graphite spacers were placed between the copper powder and the punches before pressing. It was expected that the graphite would form carbon monoxide with any entrapped air and form a reducing atmosphere within the die cavity. This condition was generally realized during pressing although a minor amount of oxidation occurred at 500" and 600°C. The oxide particles were located randomly in the pressed samples and were not considered to influence the densification process. Calibration tests showed the temperature of the copper pellet to be about 20°C less than the die wall temperature, probably resulting from heat losses through the punches. This difference was compensated during the experimental pressing operations. The hot pressing equipment employed for this work has been described by Spriggs et a1.9 and was calibrated with a Baldwin-Lima-Hamilton load cell. Travel of the punches was monitored with a dial indicator showing increments of travel to 0.0005 in. Relative density was calculated at selected time intervals for a known copper weight, punch travel, and die diameter. The accuracy of this calculation was *1 pct. Average grain size after hot pressing was obtained by lineal analysis. Typical densification curves are presented in Fig. 1 and Fig. 2 where relative density is plotted vs log time as a function of applied pressure for the 300" and 600°C pressure sintering temperatures, respectively. The curves for 400" and 500°C were similar to those at 300°C and consequently are not shown. The curves at 300°C as well as 400" and 500°C do not show an end-point or limiting density for a particular applied pressure. At 600°C, a density in excess of 95 pct of theoretical has been reached such that further densification is extremely slow for the 5000, 7500, and 10,000 psi pressures. It is suggested that further densification at these pressure levels may be retarded or prevented by discontinuous grain growth, by entrapped gases, and by other microstructural limitations as described by Cob1e.10 The curve for 2500 psi hot pressing pressure is a straight line over the time interval although a slight change in slope may be occurring at the last time intervals. The plastic flow models,1,2 derived for hot pressing, predict the existence of an end-point (or limiting) density dependent on the yield point of the material at the temperature of interest. The yield stress of copper at a 0.005 strain level has been

Jan 1, 1965

By W. C. Hagel

In 1952, Hauffe and pfeiffer1,2 reported that parabolic rates of nickel oxidation are decreased by factors of two and four at 1100° and 1000°C, respectively, when Li2O vapor is present. Hauffe 's3 explanation was that monovalent lithium enters the crystal lattice of p-type NiO to decrease cation-vacancy concentration and, hence, diffusion of Ni2+ ions across the growing oxide. After first succeeding in adding lithium directly to molten nickel, the purpose of this investigation was to determine whether alloyed lithium is a more effective oxidation inhibitor than the external vapor. Seven 650-g heats were prepared by melting carbonyl nickel inductively under 1 atm of argon. Various amounts of lithium were added by dropping small chunks into the melt. Only about 10-pct recovery was achieved with the remainder lost by spattering and volatilization. Nominal and actual

Jan 1, 1965

By C. L. Meyers, A. V. Levy, G. Y. Onoda, R. J. Kotfila

This paper presents the hypothesis that solid-solution hardening of regions in the order of tens of angstroms thick along grain boundaries is the most important mechanism controlling the ductile -brittle transition behavior of poly crystalline bcc refractory metals. Further, a physical model is developed and a general equation is derived to describe the dependence of the solute concentration at grain boundaries on temperature, nominal impurity concentration, thermal treatments, vain size, and prior plastic deformation. Analytical curves of the solute concentration at grain boundaries us temperature, calculated by means of the derived equation, are found to have the same general form as curves of ductility us temperature plotted from experimental data. Senziquantitative relationships between the transition temperature and metallurgical variables can he determined by using the physical model. The room-temperature brittleness of the poly-crystalline refractory metals (tungsten, molybdenum, and chromium) is a result of their high ductile-brittle transition temperatures. Recently studies on single crystals have revealed that, when sufficiently pure, these crystals have much lower transition temperatures than polycrystalline specimens of similar purity.'-3 For example, the transition temperature (measured by reduction in area in tensile tests) for very high-purity tungsten crystals has been reported to be as low as -50°F whereas polycrystalline specimens of similar purity had a transition temperature near 400" ~.' These results suggest that the ductile-brittle transition behavior of these polycrystalline metals can be attributed principally to the influence of grain boundaries on plastic flow and fracture. This paper contains a discussion of the manner in which grain boundaries influence the ductility of the poly-.crystalline bcc refractory metals and proposes that the segregation of impurities to grain boundaries is the most important mechanism for controlling the ductile-brittle transition behavior of these metals. Further, this paper contains an analysis of the effect of the compositional and structural variables on the grain boundary-ductility relationship, and introduces a semiquantitative model that can provide a foundation for more theoretical treatment to describe the influence of these variables on ductile-brittle transition behavior. PHYSICAL MODEL FOR PREDICTING DUCTILE-BRITTLE TRANSITION BEHAVIOR Grain Boundary Segregation of Impurities. Based on their own observations and on theoretical grounds, numerous investigators have suggested that impurities segregate to the grain boundaries. Such segregation would be expected because regions exist where both large and small foreign atoms fit with less strain than within the undistorted crystal structure. Therefore, the concentration of impurities should be higher at boundaries than within the grain body. TO estimate the degree (i.e., the ratio of grain boundary to nominal bulk concentration) to which an interstitial solute tends to segregate at boundaries within a solvent metal, the solubility rather than the size misfit could be used as a guide because solubility expresses the joint effect of both elastic and electronic factors.5 The solubilities of interstitial elements such as carbon, hydrogen, nitrogen, and oxygen are low in the group V-A metals and very low in the group VI-A metals.6 These low solubilities suggest that segregation to grain boundaries should occur for each of these solutes in both refractory metal groups. The difference between the ductility of single-crystal and polycrystalline bcc refractory metals can be described in terms of two distinct effects.4 The first of these is the general observation that grain boundaries hinder slip within grains and slip transfer between grains, and the second is that deformation is more complex in each grain of a polycrystalline specimen than it is in a single crystal. Mc Lean has pointed out, furthermore, that strong slip-hindrance effects at grain boundaries should occur in metals having strong segregation of impurities to grain boundaries. Therefore, the effect of grain boundaries on the hindrance of slip is expected to be the dominating influence on the ductile-brittle transition behavior of these polycrystalline refractory metals. cahn5 has suggested that temperature and solute mobility should influence solute equilibrium segregation at grain boundaries, and Fig. 1 illustrates

Jan 1, 1965

By W. L. Worrell

R. C. Gifkins (CSIRO)—In this paper evidence is put forward to support the idea of grain boundary shearing in aluminum at 4.2°K and the phenomenon is explained in terms of a low-temperature "equicohesive temperature". It is stated that these findings show that grain boundary shear cannot be ruled out in any situation by temperature arguments alone. We believe, from our own recent study of "apparent grain boundary sliding'' at temperatures below 0.45 Tm, that it can be ruled out on temperature arguments alone.45 Our experiments were made principally with magnesium and a Ms-A1 alloy ("Magnox A12"). Careful examination of offsets of marker lines or steps at grain boundaries produced by deformation at room temperature (-0.3 Tm) showed many of these to result from curvature over narrow zones along the grain boundaries. A significant residuum did, however, appear as a sharp offset or step. It was found that the mean value of this step rose to a small value during the first 0.5 to 1 pct strain and then remained at this level with further strain. Moreover, exactly the same values were obtained (at the same stress) at 75°C instead of 21°C. That is, in this range of temperature the "apparent sliding" was not temperature-sensitive. At 125°C and above there was sliding which increased with strain and which was temperature-dependent. When this temperature-dependent sliding was used to calculate the sliding to be expected at room temperature, this underestimated the "apparent sliding" by a factor of 104. The conclusion drawn is that the "apparent sliding" consists of shear localized in a zone of a width measured perhaps in microns, whereas it seems that true sliding occurs on the boundary surface.46 A model for such localized shear has been developed in general terms, following a similar model of Urie and Wain.47 Other strong evidence for low-temper- ature sliding has been based on the offsets of marker lines consisting of a substructure seen using the electron microscope to resolve these.48 We have repeated this work and found that the effects can be accounted for in terms of cracks in an oxide film which is produced when the substructure is etched up; these cracks form over zones of shear rather than at actual interfaces. However, in aluminum at room temperature (-0.3 Tm) there is no "apparent sliding" which is optically detectable. We suggest that, when the temperature is much lower (and possibly the rate of strain higher, too), as in the experiments of Chin et al., then aluminum behaves like magnesium at room temperature, and a narrow zone of shear develops to accommodate differences in strain across the grain boundary. Such a zone could well give rise to triple-point cracks. It is hoped to investigate these suggestions further. B. Y. Chin, W. F. Hosford, Jr., and W. A. Backofen (authors' reply)—It is interesting to have Dr. Gif-kin's comments, although it is somewhat difficult to reply in detail without the reference containing the work that he describes. Apparently though, he does find a low-temperature temperature-independent sliding that would seem to be related to the observations reported here. Perhaps some of the difficulty has semantic origins, growing out of the distinction between ('true sliding" and "apparent sliding".

Jan 1, 1965

By Edmund C. Bitzer

The unit costs of dry crushing, within the efficient reduction ranges of equipment now available, are considerably less than those for the reduction of the same material in the same size range by wet mills using grinding media. This is a commonly recognized fact which cannot be disputed; still we find considerable imbalance in costs between the crushing and grinding sections of many operating mills. In other words, there are many instances where more reduction could be accomplished in the lower cost area of dry crushing. In addition, equipment is now available which enlarges this area and makes it possible to consider much finer crushing than has been heretofore economically feasible. There has been a tendency for the past two decades to utilize wet rod-¬milling in the reduction step. This actually amounts to a fourth stage of crushing in a size range formerly served by roll crushers which have fallen from favor on account of high operating costs, Some investigations have indicated that there is not sufficient difference in the operating costs of rolls and rod-mills to give a clear cut advantage to either method, There has for some time been a need and an opportunity for a dry crushing process to improve costs in the range now served by these two systems.

Jan 1, 1965

By Harry R. Nicholls

Six different chemical explosives were detonated in a test series to com-pare their relative performance in granite. From 5 to 255 feet from the detonation point, strain, acceleration, and particle velocity were recorded and analyzed for amplitude and pulse shape. Strain energy was calculated from strain data, and displacement data were obtained from particle velocity data by integration. The results show that explosives which have a characteristic impedance more closely matching that of the rock generate larger peak amplitudes than explosives with a lower characteristic impedance. The results also show that as the ratio of characteristic impedance of exp1osive-to-rock approaches unity, more rock is crushed and a larger percentage of the avail-able explosive energy is transferred to the rock as seismic energy. The effect of characteristic impedance is shown to be greater than the effect predicted from acoustic theory and is believed to be indicative of shock wave effects at the explosive-rock boundary.

Jan 1, 1965

By Frederick Bradley Henderson

This study was initiated to investigate the occurrence of cinnabar in the oxidation zones of some mercury sulfide deposits. Seven mines or mine districts were visited and samples were taken from both the oxidation and primary zones of these deposits in order to compare their mineralogies and assess Vie chemical changes that took place during oxidation. As a result of the study of these specimens, several limiting factors are suggested for the chemical environments and processes active in both the deposition and oxidation of mercury sulfide deposits. The Mt. Jackson mine, near Guerneville, California (location map, fig. 1), was studied in some detail and forms the basis of this paper. The mine has not heretofore been described in detail in the literature. The Mt. Jackson mine is considered typical of mercury sulfide deposits occurring at the faulted boundaries of serpentinite bodies and enclosing sediments. Such mines are common in the California and Oregon Coast Ranges? Specimens collected by the author from the New Idria and New Almaden districts, the Mt. Diablo, the Culver Bear, and the Buena Vista mines in California, and the Opalite district (Cordero and Bretz, mines) on the Oregon-Nevada border were studied for comparison with the Mt. Jackson samples. The mine description, maps and sketches were composed from field maps kindly provided by Francis Fredericks, consulting geologist to the Sonoma Quick-silver Mine Inc. during the author's visit in 1962. Additional information was obtained from the company maps and minor corrections and interpretations were added by the author.

Jan 1, 1965

By N. S. Stoloff, R. G. Davies

A study has been made of the efject oj different dislocation-precipitate interactions upon the temperature dependence of the flow stress of aged Ni-14 at. pct A1 alloy. It is observed that when the dislocations bow between widely spaced (-20004 coherent Ni3Al particles the flow stress decreases with increasing temperature in the normal way. However, when the dislocations cut closely spaced (-5004 particles the flow stress is independent of temperature from -100 to 600°C, due to a balance between softening of the matrix and an increase in strength of the particles with increasing temperature. The retention of strength at high tempera-tures of commercial nickel-base alloys, which are strengthened by the precipitation of a phase based upon Ni3Al, is thought to be due to the unusual strength properties of Ni3Al. The flow stress of Ni3Al increases continuous1y from -196"C to a maximum at -600"C. It is concluded from a series of thermal-mechanical tests that the sevenfold increase in flow stress over this temperature interval is due to a lattice effect and is not diffusion-controlled. The flow stress of precipitation- or dispersion-hardened materials depends on the resistance to dislocation motion within the matrix and the extra energy required for dislocations to bow between or to cut particles. If the dislocations bow between the particles or if the strength of the cut particles is constant with temperature, then the flow stress of the precipitation-hardened alloy must decrease with increasing temperature due at least to the decrease in elastic modulus of the material. There will be softening also from thermally activated cross-slip or climb, offering an additional degree of freedom for dislocations to avoid particles. For example, in the case of nickel containing a dispersion of thoria,' which most probably deforms by dislocations bowing between particles, the flow stress decreases by about 50 pct between 25" and 650°C. In A1-Cu alloys2 aged to produce the 8" precipitate, dislocations cut the particles, and the flow stress decreases by about 20 pct between -269" and 25°C. However, many commercial high-temperature nickel-base alloys, for example Inconel-X and Udimet-700, exhibit little or no decrease in flow stress with increasing temperature up to about 700°C. A characteristic feature of these alloys is that they are strengthened by the precipitation of a phase based upon Ni3A1. Guard and westbrook4 and flinn' have shown that Ni3Al (and alloys in which a third element such as molybdenum or iron is substituted for part of the aluminum) is unusual in that the hardness and flow stress increase with temperature to a maximum at about 600°C. For the flow stress of a precipitation-hardened alloy to be independent of temperature we propose that the particles must be cut by dislocations moving through the matrix and that the strength of the particle must increase with increasing temperature. Theories of precipitation hardening do not take into account the flow stress of the dispersed particles that are cut during deformation; the only dissipative process usually considered7 is the creation of interface within the particle and between the precipitate and matrix. The purpose of the present investigation has been to study in detail the temperature dependence of the flow stress of a nickel-base alloy strengthened by the precipitation of Ni3Al in two structural conditions such that when deformation occurs it does so by dislocations a) bowing between the particles and b) cutting the particles, respectively. A simple binary Ni-14 at. pct A1 alloy was chosen because considerable information is already available for this system concerning phase equilibria and precipitation reactions and rates.' Dislocation-precipitate interactions in the binary alloy should be similar to those in the more complex commercial alloys. In addition, the mechanical and physical properties of NisAl were studied in detail in the hope of elucidating the mechanism by which the strength increases with increasing temperature up to 600°C. EXPERIMENTAL PROCEDURE For the study of the effect of precipitation of Ni3A1 upon the temperature dependence of the flow stress, an alloy containing 14 at. pct A1 was utilized; a Ni-8 at. pct A1 solid-solution alloy was employed as a comparison material. Vacuum-cast ingots were hot-rolled at 1000°C and cylindrical compression samples, 0.20 in. diam by 0.40 in. high, were prepared from the 1/4-in.-diam rod. Specimens were recrystallized and solution-treated at 1000°C for 1/2 hr and then water-quenched. A preliminary study revealed that, when the Ni-14 at. pct A1 alloy was aged for 1 hr at 700°C, significant precipitation hardening was obtained, and that the structure was free from grain boundary discontinuous precipitation; an overaged condition was produced by annealing the aged specimens at 850°C for 1 hr. To circumvent the difficulties involved in the hot rolling and swaging of Ni3A1, compression samples,

Jan 1, 1965

By W. W. Weller

Heat capacity measurements of anhydrous cobalt sulfate (CoSO4), copper sulfate (CuSO4), nickel sulfate (NiSO4), and zinc sulfate (ZnSO4) were conducted over the temperature range 51° to 298° K. The results were used to evaluate the following entropies at 298.15° K (cal/deg mole): CoSO4, 28.1; CuSO4, 26.8; NiSO4, 24.8; and ZnSO4, 26.4. Entropies were combined with heats of formation to give free energies of formation.

Jan 1, 1965

By R. D. H. Wigmore

"The title of this paper probably sounds quite simple and self-explanatory. The problem, however, was not a simple one, and proved somewhat baffling and expensive over a period of years. After outlining the problem, and the methods which were used to overcome it, we will present our solution, or perhaps it would be more accurate to say the partial solution which we reached.We have in the cyanide circuit at Upper Canada two Dorr Single Tray Thickeners with 30 ft. diameter wood stave tanks 12 ft 4 1/ 2 in. deep. In the years prior to 1948, when the tonnage was 250 to 280 tons per day, two stage thickening was practised. As the tonnage was increased to 450, 500, and finally 560-600 the thickeners were used in parallel.Some settling problems were encountered, and in those days the means to combat these problems were very few. The only remedy was to dump in pounds and pounds of lime. Then along came a few reagents, and the writer remembers one in particular, - 11 Carboxel11 (carboxymethlycellulose). When water or solution was added to this reagent, the result was a gooey mass somewhat resembling tapioca. One drawback was that it stayed in this state, and didn't go anywhere. A method was finally developed of containing the mass (or mess) on a fine screen, and dissolving some of it was a fine spray of solution. The only thing the writer recalls was that it was not a very effective settling agent.Shortly after this time, along came the new flocculents, first a few, and then many, and our settling problems were over.But when the settling problem was solved at Upper Canada, some other problems were creeping up on us."

Jan 1, 1965

By R. S. Rickard, H. D. Peterson, J. D. Miller, M. C. Fuerstenan

Pure chrysocolla is floated with chelating agents that form insoluble complexes with copper at ambient temperature. Complete flotation is obtained with potassium octyl hydroxamate as collector at pH 6. Flotation response is enhanced with increased temperature when low additions of hydroxamate are involved. A natural ore was floated with 0.4 1b per ton octyl hydroxamate at pH 6.5 and 58°C, and a flotation recovery of 76% was obtained with a concentrate grade of 31.6% copper. The flotation characteristics of the oxide copper minerals, malachite, azurite, and cuprite, have not presented the difficulty for concentration as have those of the copper silicate, chrysocolla. The copper carbonates and oxides respond reasonably well to flotation with conventional collectors, whereas chrysocolla will not respond to flotation with fatty acids or xanthates under normal flotation conditions. In this view then, other reagents will have to be devised to function as collectors for chrysocolla. The most obvious general class of reagents for this purpose would seem to be the organic copper chelating compounds. The utility of chelating agents as collectors in flotation systems has already been demonstrated. For example Vivian1 has floated cassiterite using ammonium nitrosophenylhydroxylamine. Holman2 studied the flotation of nickel oxide ores with dimethylglyoxime and also suggested the use of taurine on oxidized lead ores. A rather detailed study on the application of certain chelating agents to some flotation systems was presented by Gutzeit.3 This work indicated that the formation of surface insoluble chelates is probably responsible for flotation in many cases. The role that soluble chelating agents assume was also presented, that is with effective removal of polyvalent cations by complex formation, effective depression of quartz can be obtained. DeWitt and Batchelder4,5 have shown that oximes function well as collectors for chalcocite, malachite, azurite, and cuprite. Ludt and DeWitt6 have presented the possibility of using dyes, such as octyl malachite green, as a collector for chrysocolla. These works presented by DeWitt et al suggest that organic copper chelating compounds offer considerable promise for concentrating chrysocolla, but that the most suitable chelating reagent from the standpoint of cost and flotation response has yet to be determined. The present investigation was undertaken to study the flotation response of chrysocolla to selected copper chelating compounds, that is ethylenediamine, hexamethylenetetramine, potassium octyl hydroxamate, dimethylglyoxime, and benzoin a-oxime. EXPERIMENTAL MATERIALS Chrysocolla: The chrysocolla used in the microflo-tation studies was from New Mexico and analyzed 20.8% copper. X-ray diffraction showed this material to be amorphous in character, but some faint lines of quartz were noted. A natural oxide copper ore from Utah was also used in the investigation. This ore contains malachite principally but also contains chrysocolla and tenorite together with some sulfide copper. The sulfide copper comprises from 15 to 20% of the total copper content of the ore. Water: Conductivity water was used in the microflo-tation experiments, while Golden tap water was used in the experiments with the natural ore. Reagents: Reagent grade n-amyl alcohol was used as frother in the experiments with pure mineral, while MIBC was used in the work with the ore. Ethylenediamine, hexamethylenetetramine, dimethylglyoxime and benzoin a-oxime were reagent grade in quality. Pure potassium octyl hydroxamate was prepared as follows: 1) 1.0 mole of KOH in 140 cc of methanol was combined with 0.6 mole of hydroxyl-amine hydrochloride in 240 cc of methanol at 40°C (KC1 precipitates under these conditions and to effect complete removal of KCl, the system was cooled to 10°C and filtered), 2) a light methanol wash was then given the KC1 cake, 3) the filtrate was agitated at room temperature and 0.33 mole of the methyl ester of the organic acid (i.e. methyl octanoate) was

Jan 1, 1965

By Adrian J. Mathias

For many years excavations were made in rock exclusively by conventional blasting methods, and without concern for damage to the rock surfaces which remained after the excavation was completed. Recently, however, there is an increasing awareness for the importance of making rock excavations with as little damage as possible to the remaining rock surfaces; consequently, several revolutionary new precision blasting techniques have been developed during the past few years. These techniques, variously known as cushion, smooth- wall, perimeter, pre-shear, and pre-split blasting, basically involve the creation of a fracture plane in the rock between a series of blasted holes. The variations in each of these techniques are largely due to the differences in hole diameters, hole spacings, methods of charging, and sequence of blasting used to achieve certain specific results. The development of these precision blasting techniques was initiated by Canadian Industries Limited in 1953 at the time the Sir Adam Beck No. 2 Hydro-electric Project was under construction by the Hydro-Electric Power Commission of Ontario. Since then, these techniques have been somewhat advanced, and they have been applied with varying degrees of success to a number of projects. These projects include railroad and high- way cuts, dam spillway channel excavations, canal excavations, tunnel driving, shaft sinking, and other underground applications.

Jan 1, 1965