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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

By Nicholas J. Grant

It is the purpose of this paper to examine a number of the recent developments in powder metallurgy, being most concerned with those which are yet to prove themselves rather than those which have achieved commercial maturity. Such developments include the production of very much coarser and very much finer powders, down to the near-micron size range. Also considered are activated sintering, direct powder rolling and extrusion (both hot and cold), brazing and welding, hydrides of reactive metals, oxide dispersion strengthened alloys and theoretical evaluations. Introduction T HERE surely can't be very much argument with the fact that powder metallurgy has made large advances on many fronts during the past ten or more years (1). These advances have taken place in raw materials, in processing, in product development and in a better understanding of many of the phenomena which occur in the various steps involved in powder metallurgy. It should be clear, in view of such growth, that it will not be possible to highlight all of the new developments in the present paper. Many of these developments,

Jan 1, 1965

By I. Iwasaki

The interaction of starch and calcium ions in soap flotation of activated silica from iron ores was investigated using the response surface method. The results were correlated with adsorption studies and into pilot plant tests. It was reported previously1,2 that in soap flotation of activated silica from iron ores there existed an optimum combination of the amounts of starch and calcium chloride addition, and that corn starch as a depressant for iron oxides became effective when a critical amount of starch was added, beyond which excess starch appeared in measurable quantities in the aqueous phase. Further, adsorption studies2,3 with various starch products on hematite or quartz showed that the adsorption of starch at a given pH was markedly enhanced by the presence of calcium ion in solution. From these observations it becomes of interest to investigate the interaction of starch and calcium added to the ore pulp, and their influence on the selectivity of flotation separations. This paper describes an empirical relation between such dependent variables as the grade and recovery of iron in the concentrate and the residual concentrations of starch and calcium ion in solution as a function of two independent variables, namely the amounts of starch and calcium chloride addition, as determined by using the general technique of response surface methodology. The results thus obtained are correlated with the adsorption studies on hematite and quartz, and with a typical pilot plant operation. MATERIALS AND METHODS The ore sample used in the batch flotation studies was the fine fraction of a Mesabi gravity concentrate produced by pilot plant grinding and classification. The sample analyzed 55.21% iron and 14.70% insol, and consisted of 85.81% minus 325 mesh (corresponding to Ore C). 2

Jan 1, 1965

By R. C. Gifkins

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 D. J. Pye

Certain high molecular weight synthetic polymers in very dilute solutions decrease water mobility in porous media 5 to 20 times more than would be expected from the solution viscosity. This indicates that increasing water viscosity to reduce adverse mobility ratios in water floods is economically feasible in many situations. Laboratory results are consistent with accepted theory with respect to improved areal sweep, permeability distribution and displacement efficiencies as would be predicted from the solution mobility measured in the core. The laboratory results have been confirmed by field pilot floods which recovered 80 per cent and 100 per cent more oil than comparative water-flood pilots in fields containing 16 cp and 130 cp oil respectively. Economic analyses based on pilot data indicate the method to be profitable. INTRODUCTION The desirability of improving the water-oil mobility ratio in waterflood-ing operations has long been appreciated, especially for high viscosity crudes. Methods of reducing the oil viscosity by application of heat, gas resaturation and miscible drives have met with some success. Conversely, it has been generally conceded that increasing the water viscosity would also be effective, but the amount of thickening agent required to effect an appreciable increase in viscosity is discouragingly high. The use of such materials as glycerin, sugar, or glycols is completely out of the question economically, so that considerable attention has been given to the use of the much more efficient synthetic water-soluble polymers as viscosity improvers; but even these materials are not economically attractive. If increased water viscosity could be economically realized, marked improvements in areal sweep efficiency, as discussed by Caudle and Wittel and others, would be realized in field operations. Similarly, the improved mobility ratio would bring about increased recoveries by correcting permeability distribution problems as discussed by Stiles2 and Dykstra and Parsons,' and improvements in displacement efficiency would be obtained as recognized by Buckley and Leverett4 and Welge.5 LABORATORY STUDIES THE RESISTANCE EFFECT In the course of research to develop a more efficient water-soluble polymer viscosity builder, we discovered that a very few types of water-soluble polymers exhibited a most unusual and very interesting property not previously observed. Among the earliest materials showing such activity were polymers containing acry-lamide. Fig. 1 shows a typical plot of the solution viscosity vs concentration for one of these polymer solutions as determined in an Ostwald viscometer. As usual, such a plot is an approximate straight line on semi-logarithmic paper. Now, an inspection of Darcy's law, shows that a viscosity value can also be determined in a formation sample if the pressure, flow rate and permeability are known. If the core permeability is previously determined with wa- ter or brine, then the viscosity of another aqueous fluid may be determined from the equation. The viscosities so determined for glycerin (glycol or polyvinyl alcohol solutions, for example) agree with the viscometer determinations. However, in the case of the water-soluble polymer solutions in which we are interested, the viscosities measured in the formation sample depart very markedly from the viscometer values. A typical relationship for a polymer solution is also shown in Fig. 1. This unusual departure from the expected response is referred to as a resistance property of the polymer and is quantified as "resistance factor". Since the resistance factor R can best be determined in a core under study, the term has been defined on the basis of the ratio of the brine mobility to the polymer solution mobility at residual oil saturation so that:

Jan 1, 1965

By Jr. Oitto

A polyester-type resin and deformed-steel reinforcing bars (rebars) were used in to strengthen and to stabilize bolted, fractured wall rock along pas 1:'y. in a western gold mine. Reinforcing bars were placed in boreholes drilled into fractured rock and then were surrounded by resin pumped under pressure into the holes and intersecting fractures until the wall rock was thoroughly impregnated. Pumping and injection equipment and infusion procedures are described. Visual examinations for movement in bonded and adjacent unbonded rock were made for 3 years. Fractured walls containing resin-rebar installations were strengthened. The results suggest that resin-rebar support can be used advantageously and economically in repairing fractured or broken rock when compared with rock bolting or timbering.

Jan 1, 1965

By R. V. Lundquist

The specific conductance of solutions of sodium hydroxide and of sodium aluminate was directly proportional to the temperature. The specific conductance of sodium aluminate solutions with identical sodium ion concentration and at constant temperature decreased with increase in aluminum concentration. The aluminate ion population in solution was shown to consist of a mixture of monovalent and polyvalent ions. Aluminate ions did not influence the temperature dependence of pH in caustic solutions containing sodium aluminate. The density and viscosity of a solution was inversely proportional to the temperature and directly proportional to the concentrations of sodium and aluminate ions.

Jan 1, 1965

By J. R. Johanson

With the continuing development of automatic operations, it is important that reliable discharge rates through hoppers and bins be obtained for bulk solids. In most applications a feeder is used to control the feed rate. The selection of this feeder size is usually based on the rated ability of the feeder to move material without regard to the capability of the material to flow through the opening in the hopper onto the feeder. The dis charge rate through a given hopper opening may vary from zero to a theoretical maximum depending on the flow properties of the material. This paper presents an equation for the maximum discharge rate for a bulk material as a function of the hopper shape, the opening size and the flow properties of the material. Discharge-rate tests on various materials indicate good agreement with calculated values for opening sizes from a fraction of an inch to several feet. As part of a program to develop improved design criteria for bulk storage and handling facilities, a specific study of the methods involved in calculating the rate of discharge of bulk solids from hoppers and bins has been made. This study is closely related to earlier work done on the prevention of flow problems through the choice of proper design geometry of hoppers and bins1. The present paper is an extension of this earlier work, and therefore many of the concepts previously derived and explained will be used without explanation. Two types of flow will be considered: plane-strain flow in a wedge-shaped hopper and axial-symmetry flow in a conical hopper. The literature contains many studies on discharge rate for regular-shaped dry particles2*3 such as glass beads, lead shot and coarse dry sand. However, the work is empirical in nature, and it is difficult to extrapolate the given information to apply to moist, sticky materials typical of many industries. Some studies4 have shown a decrease in discharge rate with an increased moisture content of the material. However, no attempt was made to correlate the discharge rate with moisture. The method of calculating discharge rate presented in this paper was derived analytically from the basic knowledge of the flow of frictional, cohesive, granular solids, The equation includes the effect of material cohesion (stickiness), hopper configuration, opening size and bulk density of the material. THEORETICAL WORK The basic assumptions made in deriving the discharge rate equation are as follows: 1) The material is a frictional, cohesive, granular solid. 2) The flow is considered continuous and without significant density change. 3) The material at the hopper opening forms a continuously failing arch that is in dynamic equilibrium. 4) The strength of the material in the arch, which must be overcome for the arch to fail, is caused by the pressure in the flowing mass near the hopper opening. 5) This pressure at the hopper opening can be calculated5. If we consider the dynamic equilibrium of an arch of uniform thickness such as that shown in Fig. 1,

Jan 1, 1965

By Robin O. Williams

Robin 0. Williams (Oak Ridge National Laboratory)— The authors have questioned the degree to which the coherency strains between the iron-rich and chromium-rich phases are isotropic as proposed in Ref. 5 on the basis of the difference between the elastic properties of the two phases. The relative magnitude of the stresses is determined by the moduli as shown by Eqs. [2], [3], and [4] of Ref. 34. However, the moduli of the two phases have no direct bearing on the uniformity of either the stress or strain within either phase. The idea that the strains are isotropic within each phase (but normally of different magnitude and always of different sign) is based entirely upon the experimental observation that X-ray line broadening has not been detected even when the particles become rather large. It has not proven possible to grow the particles sufficiently large that they lose coherency. Based upon this lack of line broadening one can estimate an upper limit for the nonuniformity of the strains within each phase as follows. It is considered possible to detect line broadening if it is as great as 10 pct of the separation of the K, doublet for the (211) line using chromium radiation. The doublet separation would correspond to a total strain of 0.0017 such that the total variation of lattice parameter relative to the average lattice is now k0.05x0.0017 or something less than ± * For the present case the strain in each phase is roughly 0.002 such that the variation of strain within a phase will not exceed 5 pct. It is stated that the expression derived for strengthening for the hydrostatic straining as observed in this system would substantially overestimate the magnitude due to dislocation flexure. This is contrary to the conclusion reached in the original paper34 for the present range of particle sizes. What is the lowest temperature at which a has been observed to form in this alloy? M. J. Marcinkowski, R. M. Fisher, and A. Szirmae (nutlzors' reply)— -Williams' arguments based on X-ray findings for a chromium-rich precipitate and an iron-rich matrix strained to a common lattice parameter are certainly convincing. This being the case, there are no shear components of strain associated with the precipitate-matrix aggregate to interact with the shear components of the dislocation stress fields, contrary to the opinion expressed by the present authors. On the other hand, the present authors, in spite of this error, did not expect the shear interactions to be significant. The chief objection to Williams' model in the present case is that the various segments of the dislocation line are assumed to pass from one potential valley to the next independently of neighboring segments. This is only true for a highly flexible dislocation line, i.e., one whose radius of curvature is something less than the center to center distance between precipitate particles which amounts to about 90A in the present alloy. In order to maintain this curvature, an externally applied shear stress of at least 230,000 lb per sq in. would be required or about four times the observed stress. It is therefore concluded that the dislocation lines move rather rigidly through the lattice. This being the case, the forces on the dislocation resulting from the hydrostatic interaction between the stress fields of the edge-dislocation components and the precipitate particles should average out to zero; that is particles above the below the slip plane produce forces on the dislocation of opposite sign and therefore will cancel when averaged over the entire length of the dislocation. On the other hand, since the dislocation is not perfectly rigid, Williams' model may lead to some strengthening, but far less than that predicted. A second and equally serious objective to using Williams' strengthening model for the present alloys is that profuse wavy slip due to the motion of screw dislocations played a predominant role not only in the unaged alloys but in the fully aged ones as well. Since the screw dislocation has associated with it only shear components of stress the hydrostatic strengthening model no longer applies. In view of these arguments the present authors must reject Williams' model of strengthening as being pertinent to the present alloy system. The present authors have made no detailed study of the lowest temperature at which a forms in the quenched ferritic alloys. None was ever observed n the alloys aged at 500°C so that forma-tion must occur at temperatures higher than this and was therefore not a factor in the present study.

Jan 1, 1965

By T. P. Papazoglou, N. A. D. Parlee, W. C. Phelps

PRACTICAL designs for good "home made" molybdenum furnaces are hard to find in the literature. The one described briefly below left something to be desired but was good enough to operate as a rather long (30 in.) two-zone furnace for periods of over 2 months at temperature (1400° to 1600°C) without shutdown. The principal problem in our application was to establish a temperature profile with two distinct constant-temperature zones and no dip between the zones. This and other problems mentioned below would not arise, however, if both zones were operated at the same temperature and if a shorter furnace were acceptable. Since molybdenum windings oxidize very rapidly when heated in air, impervious refractory tubes were used for both the furnace core and the outer jacket tube shown in the accompanying figures. A protective atmosphere of forming gas (10 pct H2, 90 pct N2) was continuously passed through the gas-tight annular volume between the core and outer jacket. The water-cooled copper ends shown in Figs. 1 to 3 sealed the ends of the tubes. Annealed molybdenum wire (40 mil) was wound on the recrys-tallized alumina core (35.5 mm OD by 28.5 mm ID by 30 in.) at a spacing of 0.36 in. The spacing was reduced to 0.29 in. close to the ends to partially compensate for end heat losses. Fig. 2 shows two molybdenum-ground lead taps off the center of the winding to produce the two independect temperature zones. The ground lead was insulated with 1/4-in. alumina tubing and connected to the grounded copper end by passing the wires through the gas port tube and crimping each wire into notches cut at the mouth. To prevent sagging of the core at high temperatures, refractory "troughs" were cut from alumina and mullite tubing to cradle the core. The support "troughs" which were 6 in. long and located about 5 in. from each end of the annular volume also served as radiation shields. In view of the different expansion coefficients and operating temperatures of the core and outer jacket (3.5 in. OD by 3 in. ID by 30 in.), the ends of the tubes were smoothed and squared to produce good sealing surfaces, and the core was ground 1/32 in. shorter than the outer tube. The power terminals were passed through their respective conductor ports which were internally lined with alumina tubing and sealed with Armstrong adhesive A-6 leaving about 1 in. of protruding lead wire for external connections. (Adhesive A-6 is a two-component system consisting of an epoxy-type resin with a mineral fibrous filler and an amine catalyst.) Figs. 1 and 3 show the entire assembly of concentric refractory tubes, copper ends, and sealing o rings, held together with two brass flanges and 3/8-in. bolts with heavy springs for dimensional flexibility. The furnace shell (19 by 19 by 30 in.) consisted of a steel frame with sheets of transite forming a box. The copper ends protruded through two 3.75-in. circular holes cut at the center of each transite square end. Thermal insulation next to the transite exterior was effected by K-23 B&W bricks alld in a central volume of approximately 9 by 9 by 30 in. a row of K-30 bricks was lined up to support the hot assembly. The rest of the volume around the outer

Jan 1, 1965