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By R. Schuhmann, J. Th. Overbeek, P. L. De Bruyn

THE technique of concentrating valuable minerals from lean ores by flotation depends upon the creation of a finite contact angle at the three-phase contact, mineral-water-air. If the mineral is completely wetted by the water phase, contact angle zero, there is no tendency for air bubbles to attach themselves to the mineral. However, when the contact angle is finite, the surface free energy of the system, water-air bubble-mineral particle, can be diminished by contact between the bubble and the particle, and if not too heavy the mineral will be levitated in the froth. With a few exceptions, all clean minerals are completely wetted by pure water. Thus the art of flotation consists in adding substances to the water to make a finite contact angle with the mineral to be floated, but to leave the other minerals with a zero contact angle. The contact angle concept and experimental measurements of contact angles have played important roles in flotation research for several decades.'-" Nevertheless, there remain unanswered some basic questions as to the scientific significance of the contact angle and the nature of the processes by which flotation reagents affect contact angles. The contact angle is a complex quantity because the properties of three different phases, or rather of three different interfaces, control its magnitude. Considering the interfaces close to the region of ternary contact to be plane, the relation among the contact angle and the three binary interfacial tensions is easily derived. The condition for equilibrium among the three surface tensions, Fig. 1, or the requirement of minimum total surface free energy leads to Young's equation, Eq. I: ysa — ysl = yLA cos 0 [1] According to this equation, the contact angle has one well-defined value. Actually it is found in many experiments that the value of the contact angle depends on whether the air is replacing liquid over the solid (receding angle) or the liquid is replacing air (advancing angle). The receding angle is always the smaller of the two.4 Two explanations have been offered for this experimental fact. According to some investigators,5-8 roughness of the surface causes apparent contact angles that are different for the receding and the advancing cases although the actual local contact angle may be completely determined by Eq. 1. The other explanation involves the hypothesis that the solid-air interface after the liquid has just receded is different from the same interface when no liquid has previously covered it.1,4 Adsorption of constituents of the air or liquid might play a role here. In this discussion the difference between advancing and receding contact angle will be neglected and plane surfaces where Eq. 1 describes the situation will be considered. But there is still a fundamental obstacle to the application of Young's equation. The surface tension of the liquid (rla) can easily be determined, but the two surface tensions of the solid (rsa and ySL) cannot be measured directly. Eq. 1, however, is not without value. By contact angle measurements it is possible to establish how ysl — ysl varies with the addition of solutes to the liquid phase. Also, Eq. 1 affords a convenient starting point for calculating net forces and energy changes involved in the process of bubble-particle attachment.1,2 . If for the moment surface tension of the liquid (yLa) is considered a constant, an increase in ysa — ysL, will tend to decrease the contact angle. A decrease in ySA — ysl, corresponds to an increase of the contact angle. In cases where ySA — ySL > yLa the contact angle is zero; it will only reach finite values when ysa — ysa has been decreased below YLA. Thus on the basis of Young's equation and contact angle measurements alone, it can be learned how flotation reagents affect the difference Ysa — ysl, but no conclusions can be drawn as to the effects of reagents on the individual surface tensions ysa, and ysL, not even as to signs or directions of the surface tension changes resulting from reagent additions. A quantitative relationship between the surface tension or interfacial tension and the adsorption occurring at a surface or an interface is given by the Gibbs equation, which for constant temperature and pressure reads dy = — 2 T, du, [2] where dy is the infinitesimal change in surface tension accompanying a change in chemical potential

Jan 1, 1955

By Sandford S. Cole, John S. Breitenstein

The recovery of over 80 pct of the vanadium values in titaniferous magnetite from Maclntyre Development,Tahawus, N. Y., was accomplished by an oxidizing roast with Na2O3-NaCI addition. Process description is given for leaching of roasted ore and precipitation of V2O5 and Cr2O8 from leach liquor. THE exploration and development of the Mac-Intyre orebody at Tahawus, N. Y., by the National Lead Co. provided a source of vanadium. Analyses of various composite sections of the drill cores of the MacIntyre orebody were made to establish whether or not the vanadium was constant throughout. Ten drill cores were sampled as 50 ft sections, crushed, and a portion magnetically concentrated. The head and concentrate were analyzed for total iron and vanadium. The results on the concentrates indicated that the vanadium is associated with the magnetite and maintains a close ratio to the iron content. The nominal ratio of 1:25:140 of V: TiO2:Fe was found to exist in the concentrates. Typical value for the vanadium in the magnetite both from laboratory concentration and mill production is 0.4 pct. The recovery of vanadium from the magnetite was investigated in 1942 to 1943. The research program encompassed both laboratory and pilot-plant work on sufficient scale to provide adequate data to establish the feasibility of a full scale plant. The recovery of vanadium from various ores has been reported in the literature and has been the subject of many patents. The literature dealing with recovery from titaniferous ore by roasting is quite limited. Roasting with alkaline sodium chloride, sodium chloride or alkaline earth chlorides, and sodium acid sulphate have been claimed in various processes as effective means.1-8 The reduction of the ore, followed by acid leaching, was another method proposed.'-' "he use of various pyrometallurgical processes for recovery of vanadium in the metal or in the slag has also been extensively investigated, but the results had little application to the problem."-" The separation of vanadium values from subsequent leach liquors and vanadium-bearing solution has been the subject of a considerable number of papers and patents. The most practical is by hydrolysis at a pH of 2 to 3 by acidifying a slightly alkaline solution. Data on solubility of V²O5 and V2O4 in water and in dilute sulphuric acid indicated a solubility of 10 g per liter in water.'" Laboratory Results Magnetite Analysis: Adequate stock of magnetite was provided so that the laboratory and pilot-plant operation was on ore representative of the mill production. The ore was analyzed chemically and examined by petrographic methods to ascertain whether the vanadium was present in combined state or as an interstitial component between grain boundaries. No evidence was obtained which would indicate that the vanadium was in a free state as coulsonite.15 The analysis of the ore was as follows: Fe²O³, 47.4 pct; FeO, 29.1; TiO,, 10.1; V, 0.40; and Cr, 0.2. The screen analysis of the ore on the as-received basis was: -20 +30 mesh, 28.8 pct; —30 +40, 18.9; -40 +50, 9.7; -50 +60, 15.1; -60 4-100, 5.9; -100 + 200, 11.2; -200 +325, 3.7; and -325, 7.2. Roasting Conditions: The prior practice indicated that a chloridizing roast with or without an alkaline salt had been effective on other titaniferous magnetites. On this basis roasts with additions of sodium chloride, sodium carbonate and mixtures thereof were investigated varying the roasting temperature between 800" and 1100°C. Since the ore had shown no segregation or concentration of vanadium, the influence of particle size on the freeing of vanadium by the reagents during roasting was determined. The initial work was on silica trays in an electric resistance furnace with occasional rabbling of the charge. Subsequently, the roasting was carried out in a small Herreshoff furnace to establish the influence of products of combustion on the recovery of the vanadium. The laboratory tests showed that this ore required an alkaline chloridizing roast, in conjunction with a reduction in particle size to less than 200 mesh. When roasted in air at 900 °C with 5 pct NaCl and 10 pct Na2CO³, over 80 pct recovery of the vanadium was attained as a water-soluble salt. The presence of alkaline earth elements gave detrimental effects and care had to be exercised to avoid any contamination of the ore or roast product by such materials. The solubilization of vanadium under the various conditions is given in a series of curves in Figs. 1 to

Jan 1, 1952

By P. G. Shewmon

A novel technique for determining the surface energy (?) and its derivative with respect to orientation, (?') is described. Essentially it involves the 'floating" of a wedge on the substrate, said wedge being made of a material which is not wet or only slightly wet by the substrate, i. e., as a greased needle "floats" on water. A thermodynamic analysis of a system in which the wedge is supported entirely by surface energy is given. If the original suyface is not at a cusp orientation, the surface tension is directly measurable from the groove angle formed. If the original surface is at a cusp orientation, there may or may not be a groove depending on the relative value of ?' and the weight of the wedge. Experiments primarily on copper and silver showed that sapphire, quartz and refractory metal wedges were wet while graphite wedges were not. The technique was demonstrated to work using graphite wedges, but the results obtained were not as eccurate as those obtained by other workers using the wire-creep experiments. It is concluded that the technique might prove most useful with non-metals where ?' is large and filament creep experiments would be quite difficult. If an absolute value of the surface free energy (?) of a metal is to be determined, the most reliable methods used to date measure an average over the various orientations exposed on a polycrystalline sample. For example, ? for silver, gold, and copper have been measured by determining the force required to just keep a thin wire,' or foil,' specimen from contracting under the influence of ?. Herring 3 has predicted and experiment confirms, that the sensitivity of this method is inversely proportional to the grain size.' Thus it cannot be used to measure ? for a particular orientation by using a foil single crystal or a very coarse-grained specimen. An accurate value if ? for tungsten averaged over a range of orientations has been determined using a field emission technique. The same techniques cannot or have not been used to measure ? for non-metallic solids, and as a result the values available are much less accurate.4 This Paper resents a means of making an absolute determination of ? for a particular surface orientation on any solid, as long as the given surface orientation does not break up into other orientations during an anneal. Experimentally ? is found to vary with orientation and at a few low index orientations it is found to have a cusped minimum, i.e., the derivative of ? with respect to the orientation of the surface changes discontinuously at the low index orientation, see Fig. 1. The slope of a plot of ? vs orientation (herein designated ?') is called the torque on the surface, since it tends to rotate the exposed surface toward the low index orientation, or if the surface is at the cusp orientation it opposes any force tending to rotate the surface out of the low index orientation. The ratio ?'/? has been determined for a few metals, but in cases where this ratio is high there is presently no means of determining either ?'/? or the absolute value of ?' for the orientations present on an annealed surface. The technique discussed herein also provides a means of determining an absolute value of ?' for those orientations which deviate only infinitesimally from a cusp orientation. It should work best on surfaces where ?'/? is large; that is, for cases where no other technique is available for measuring ?'. Aside from trying to learn more about surfaces through measuring ? and ?', the primary reason for wanting values of ? or ?' is to study adsorption. From measurements of the variation of ? for a particular orientation with the concentration of an impurity, one can obtain the number of impurity atoms adsorbed per unit area (Ti) on that orientation using the Gibbs adsorption equation.' where µi is the chemical potential of the adsorbed impurity. Thus, if absolute values of ? could be obtained for the free surface of a given surface orientation as a function of µi, ri could be determined for the given orientation. Furthermore, by equilibrating a grain boundary with the given surface at various values of ki, one could also determine ri for the grain boundary. Similarly Robertson 6 has pointed out that if y is taken to be a continuous function of and µi, then a2 ?/a @a µ2 = a2 ?/a pi a +. Thus, at all orientations away from cusps the following equation holds From a measurement of ?' vs ki, it is thus possible

Jan 1, 1963

By A. H. Heim

A method and apparatus for measuring gas porosities of rocks are described. The apparatus can be assembled from commercially available components. In principle, measurements are made by volume substitution at constant pressure. The maximum error is not more than 0.3 porosity per cent. Typical results are given. INTRODUCTION Determining the porosity of rock samples is one of the most important and yet most varied types of measurement in core analysis. Among the many techniques devised are the so-called "gas porosity" methods. An old and well known example is the Washburn-Bunting method.' The U. S. Bureau of Mines2-' described and later improved the apparatus for a now widely used method generally known as the "Boyle's law" method. In the present form of the Washburn-Bunting method,' the volume of air in the pores of a rock sample at atmospheric pressure is extracted and then collected in a graduated burette at atmospheric pressure. The volume of air is read directly as the pore volume of the sample. The absolute error in reading the collected volume of gas is independent of the total volume; thus, the relative error is larger when the volume is small, as it is for rocks of low porosity. In addition, the sample after measurement contains mercury, which limits its use for other analyses. The Bureau of Mines (or Boyle's law) method measures directly the solids volume of a sample from which the pore volume and porosity are derived, using a separate measurement of the bulk volume. Gas at a few atmospheres pressure is introduced into a sample chamber of known volume containing the rock sample. The pressure is accurately measured. Following, the gas is expanded into a burette at 1 atm, and the gas volume is read directly. From the initial pressure p, and the final pressure p2 and volume v,, the initial gas volume v1 is calculated using Boyle's law; that is, p1v1 = p2v2. Volume v, minus the volume of the empty sample chamber is the solids volume of the sample. The accuracy of the method is limited, unless corrections are made, by deviations of the gas from the "ideal" gas-law behavior assumed in the simple form of Boyle's law. The purpose of the present paper is to describe a method for measuring the gas porosity of a rock which avoids many of these difficulties. Gas volumes are measured directly with the same accuracy as the bulk volumes. Pressures of at least an order of magnitude larger than those of previous methods are employed to insure rapid penetration of the gas into the sample. While special equipment may be built to apply the method, the porosimeter may be constructed as well from commercially available components. For simplicity, the apparatus described will be referred to as the "Constant-Pressure gas porosimeter". THE CONSTANT-PRESSURE METHOD Fig. 1 shows schematically the arrangement of components comprising the present Constant-Pressure porosimeter. Briefly, the method is one of volume substitution and may be considered a null measurement. Omitting (for the present) some of the operational details, the method of measurement consists of the following three steps. 1. After evacuation, the volume of the measuring system (a ballast chamber, a manifold, two gauges and their connections) up to the sample chamber is filled with gas to a high pressure (- 1,000 psi). A sample of the gas at this pressure is trapped in one side of a sensitive differential pressure gauge to serve as the reference pressure for subsequent steps. 2. The evacuated sample chamber containing the rock sample is opened to the measuring system. As the gas expands into the chamber, the resulting decrease in pressure unbalances the differential pressure gauge. 3. The pressure is restored by means of a mercury volumetric pump. The volume of mercury injected exactly equals the free or void volume of the sample chamber (volume of empty chamber minus the solids volume of the rock within). From the injected volume and the known empty chamber volume, the solids volume is obtained and the porosity calculated. The pressure and the volume occupied by the gas are the same before and after opening the sample chamber. Expansion and compression of the gas are incidental operations and do not enter into the calculation of porosity. By the pressure balancing or nulling, the free volume of the sample chamber is merely substituted by an equal and measured volume of mercury. Since the measurements are at constant pressure, there are no compressibility corrections necessary for the sample chamber.

By G. H. Bishop

The kinetics of the inter granular penetration and embrittlement of [100] tilt boundaries in 99.998 pct pure nickel upon exposure to bismuth-rich Ni-Bi liquids have been determined in the temperature range from 700° to 900°C. The kinetics of penetration are parabolic in time at constant temperature over most of the temperature range. In a series of 43-deg bicrystals the rate of penetration is anisotropic with respect to the direction of penetration into the grain boundaries. In lower-angle bicrystals the penetration rate is isotropic. The rate of penetration decreases with tilt angle at 700°C. The activation energy for penetration in the 43-deg bicrystals is 42 kcal per g-atom independent of direction. It is concluded that the intergranular penetration and embrittlement in the presence of the liquid proceeds by a grain boundary diffusion process and not by the intrusion of a liquid film. This was confirmed by a determination that the kinetics of penetration and embrittlement were the same in the 43-deg bicrystals upon exposure to bismuth vapor under conditions such that no bulk liquid phase would be thermodynamically stable. WhEN solid metals are exposed to a corrosive liquid-metal environment, the grain boundaries are sites of preferential attack. Depending on the temperature, the composition of the liquid, and the composition, structure, and state of stress of the solid, a number of modes of attack are possible. This paper reports a study of the kinetics of intergranular penetration and embrittlement of high-purity nickel bicrystals upon exposure to bismuth which, together with an earlier study by Cheney, Hochgraf, and Spencer,&apos; demonstrates that there are at least two modes of intergranular attack possible in the Ni-Bi system. In the study by Cheney et al., columnar-grain specimens of 99.5 pct pure nickel were exposed to liquid bismuth presaturated with nickel in the temperature range 670" to 1050°C. They found that the majority of the boundaries, which were predominantely high-angle boundaries, were penetrated by capillary liquid films, the attack proceeding by a process which will be termed grain boundary wetting. This process occurs in a stress-free solid when twice the liquid-solid surface tension is less than the surface tension of the grain boundary,* i.e., when 2yLs < YGB In this case the penetration of the grain boundary by the liquid occurs at a relatively rapid rate, resulting in the severe embrittlement of a polycrystalline solid. Grain boundary wetting is a common mode of intergranular attack in systems in which the lower melting component is relatively insoluble in the solid, but the solid has an appreciable solubility in the liquid, for example, the Ni-Bi system, Fig. 1. In systems of this type at temperatures above the range of stability of any intermetallic phases, once the liquid is saturated with respect to the solid so that no gross solution occurs, chemical gradients are small, and surface tensions become major driving forces for attack, provided the solid is stress-free. The results of Cheney et al. appear to be typical of those encountered when grain boundary wetting occurs.&apos; Capillary films were observed in the boundaries after quenching from the exposure temperature. The mean depth of penetration increased linearly with time, and the activation energy for the process was found to be 22 kcal per g-atom. In a study of the Cu-Bi system Yukawa and sinott4 found that the depth of penetration of bismuth into high-purity copper bicrystals of orientations from 22 to 63 deg of tilt about (100) at 649°C ranged from 0.05 to 0.25 in. after a 12-hr anneal. This corresponds to a linear rate of 6 to 15 X 10~6 cm per sec. At the same reduced temperature of 0.68 the rate for the Ni-Bi system&apos; was 7 x lo-&apos; cm per sec. In another study of the Cu-Bi system, Scheil and schess15 determined the kinetics of grain boundary wetting in hot-worked commercial rod. While there were several complicating factors present in this study, there is general agreement with the above results. The kinetics of penetration were linear, the activation energy was 20 kcal per g-atom, and at 650°C the rate of wetting was 2 to 5 x 10-6 cm per sec. The rate of wetting in the A1-Ga system6 is somewhat

Jan 1, 1969

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.&apos; and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By M. D. Arnold, P. B. Crawford, P. C. Hall

An experimental study has been made to determine the optimum flooding pressures for four different oils. The oil formation volume factors ranged from 1.08 to 2.13, and solution gas-oil ratios ranged from about 200 cu ft/bbl to 2,250 cu ft/bbl. Viscosities ranged from 0.38 to 0.95 cp at the respective bubble points of the fluids and from 0.7 to 20 cp at atmospheric pressure. Water floods were conducted at various pressure levels from run to run. The recovery as a function of flooding pressure was found to be different for each fluid, with optimum gas saturations ranging from 7 up to 35 per cent. The data indicate that substantially higher recoveries may be obtained if water floods are conducted at an optimum pressure and that this optimum pressure is a function of fluid properties. The same core was used for all tests, and the reproduction of saturations for various runs indicates that wettability in the predominantly water-wet core did not change. INTRODUCTION A paper was presented by Bass and Crawford&apos; which described an experimental study of the effects of flooding pressure and rate on oil recovery by water flooding. This work was conducted using high-pressure models operated in a manner similar to that of an actual reservoir, with gas saturations being obtained by a solution-gas-drive mechanism. They found that the greatest oil recovery was obtained for the system studied by flooding in the presence of a 5 to 7 per cent gas saturation. Another experimental study simulating field conditions was presented by Richardson and Perkins.&apos; They used an unconsolidated sand pack containing kerosene-natural gas fluid and interstitial water. They flooded at various pressures and flooding rates. For their system it was found that the recovery was independent of the pressure level at which the water flood was performed. Kyte, et al," found that oil recovery by water flooding was increased as the free gas saturation at waterflood initiation was increased. However, after the initial gas saturation was increased above 15 per cent, the increase in oil recovery tended to level off. All of their runs were made at the same pressure using a light oil saturated with helium. The desired gas saturation was obtained by injecting helium into the core. Dyes&apos; made calculations which showed that an optimum gas saturation of 12 to 14 per cent may result in an increase in oil recovery of 7 to 12 per cent over that obtained by flooding at the bubble-point pressure. Others have also found that the presence of a free gas saturation may increase the waterflood oil recovery. In each case shrinkage was small and changes in fluid properties with respect to pressure were small. A careful review of the literature reveals that at the present time there is a wide difference of opinion on the factors affecting waterflood recoveries. This diversity of opinion is probably due to the fact that very little research has been done which has taken into account the many variables existing in an actual field being water flooded. Since the literature contains little information on high-pressure waterflooding studies using various types of reservoir fluids, it was believed appropriate that such a study should be made. EQUIPMENT AND PROCEDURE All tests were made using the same consolidated sandstone core. Torpedo sandstone was used to turn a cylindrical core 13.5-in. long and with a 2.92-in. average diameter. The core had a porosity of 28 per cent and a permeability to brine of 146 md. This brine was made up by adding 20,000-ppm sodium chloride and 30,000-ppm sodium nitrite to distilled water. This was used as connate water and flooding water. No fresh water was ever brought in contact with the core, as tests showed the sandstone contained argillaceous material which swelled in the presence of fresh water and plugged the stone. The core was sealed in a section of 6-in. N-80 tubing with Woods metal filling the annulus. The core was mounted horizontally; an injection well was placed in the center of one end and a production well in the center of the other. Pressure control was maintained by placing a back-pressure regulator (upstream control) on the producing well. The "live" oil was stored in a separate bottle and water was injected into this bottle to displace the oil for saturating the core using a two-cylinder standard-proportioning pump. This same pump was used for water flooding the core at a constant rate. This system was enclosed in water jackets and the temperature was automatically main-

By Irving Cadoff, Kurt Komarek, Edward Miller

Barium can be purified by equilibration with titanium. The melting point of barium was found to be 726.2° i 0.5 °C. The room-temperature lattice parameters of BaTe and Bask are 7.004 * 0.002A and 6.600 * 0.002A. Melting points for BaTe and Base were found to be 1510° * 30°C and 1830° ± 50°C, respectively. HIGH-purity barium and its compounds are difficult to prepare because of the reactivity of barium with the atmosphere and the large heats of formation of the compounds. Purification of barium by vacuum distillation,&apos; and the preparation and properties of barium oxide2 and barium sulfide3 have been reported. However, little has been done on the homologous compounds barium selenide and telluride. PURIFICATION OF BARIUM Distilled barium obtained from King Laboratories was used as the starting material. The analysis supplied with the metal showed the presence of: 0.4 wt pct Sr, 0.001 pct Mg, 0.02 pct F, 0.003 pct Cu, 0.005 pct Na and less than 5 x 10-3 wt pct of any other metallic impurity. Analyses for oxygen and nitrogen were not available. Since there is evidence4 that any barium nitride present in the starting material may decompose on distillation producing nitrogen which can contaminate the distillate, further purification was performed. At elevated temperatures, any nitrogen and oxygen present in barium should be removed by reaction with titanium. Assuming that the solubility of oxygen in liquid barium is negligible near the melting point of barium, any oxygen present will be in the form of BaO. Removal of oxygen from molten barium is expressed by the equation: BaO(S)+ TixOy(S) = Ba(l)+ TixO(y+1)(s) where Ti,Oy and TixO(y+1) are solid solutions of oxygen in titanium. At 1000°C, the change in free energy for this reaction is negative for (y+1)/x +y+1) x (100) 17.5 at. pct O.5 Since reaction with commercially pure titanium (containing 0.07 wt pct oxygen) results in a free energy change for the reaction of -19 kcal per g-atom, slight solubility of oxygen in barium would not hinder the oxygen removal. Since comparable thermodynamic data are not available to permit calculation of the partition of nitrogen between liquid barium and titanium, a similar quantitative relationship cannot be obtained. However, on the basis of work by Kubaschewski and Dench,5 complete removal of nitrogen from liquid barium can be expected. Since the melting point of barium is depressed markedly by small additions of nitrogen,&apos; the change in melting point during reaction of barium with titanium was used to follow the purification reaction. MELTING POINT OF BARIUM A 50-g sample of barium was sealed by arc welding under argon into an all titanium crucible provided with a thermocouple well. The melting point of the sample was determined by thermal analysis, using a Pt/Pt-10 pct Rh thermocouple which was calibrated according to National Bureau of Standards specification6. The crucible was then heated for 48 hr at 950°C in vacuum and the melting point redetermined. This procedure was repeated until three successive thermal analyses agreed within ±0.5oC, the limits of error of the analysis. The melting point increased from an initial value of 720.0°C to a final value of 726.2°C. Analysis on samples quenched from 950°C gave a solubility value of 0.004 wt. pct Ti. Assuming that the titanium-barium phase diagram is similar to those of titanium-magnesium7 and titanium-calcium,8 the solubility of titanium in liquid barium decreases with decreasing temperature. Therefore, the solubility of titanium in liquid barium should be less than 0.004 wt. pctat the melting point (726oC), and the effect of dissolved titanium on the melting point would be negligible. Addition of up to 3 wt pct Sr does not significantly change the melting point of barium,7 so that the effect of the 0.4 wt pct Sr in the starting material will also be negligible. The value of 726.2" ± 0.5C obtained for the melting point of barium can be compared .with a determination carried out by Keller and coworkers in low-carbon steel crucibles,&apos; who obtained a value of 725± 1C, using barium purified by fractional distillation. The higher value obtained in the present investigation is indicative of the effectiveness of titanium in removing traces of nitrogen. PREPARATION OF BaTe AND Base The compounds were prepared by direct reaction

Jan 1, 1961

By Lawrence A. Shepard, Richard H. Krock

A series of ductile, two phase W-Ni-Fe composites, sintered in the presence of a liquid phase, were tested in tension. Identical room temperature stress-strain curves were obtained for specimens containing from 80 to 92 wt pct W (58 to 75 vol pct W particles). The composites exhibited a maximum elongation of 29pct at room temperature, and 10.7 pct at 77 °K. The tungsten particles in the composite elongated by the same amount at these temperatures. Single-phase alloy specimens matching the composition of the composite matrix showed about one half the flow stress of the composites. The test results demonstrated that the mechanical properties of W-Ni-Fe composites are determined by the tungsten particles alone and are independent of matrix volume fraction or mean free path over the composition range studied. A general prediction of the plastic behavior of two-phase alloys or composites from a knowledge of the properties, size, shape, and dispersion of the individual components is not, at present, possible. The excellent theoretical and experimental exposition of the dispersion-strengthening problem applies only to cases where the stronger phase is present as fine particles and in volume fractions of a few percent. Materials in which the stronger phase constitutes a significant fraction of the volume, although of broad engineering interest, have received comparatively little analytical attention. This important group of materials is the concern of the present study. The degree of deformation of each phase during the plastic working of a ductile two-phase alloy has been established by Boas and Honeycombe,1 Clare-brough,2 and Clarebrough and berger.3 These workers empirically correlated the recrystallization temperature of the individual phases with the degree of cold work sustained by each. It was shown that the deformations of both phases are equal and therefore the same as that sustained by the composite whole when the volume fraction of the stronger phase exceeds 35 pct. At yielding, however, deformation begins in the weaker phase. A direct correlation of composite strength, as a function of deformation, with the strength of the individual components cannot be made. In the presence of stronger phase particles, the flow stress of the weaker matrix phase is enhanced by an additional hydrostatic component. The development and potential magnitude of matrix strength promotion upon straining has not even been experimentally established. Quantitative work in this field has been confined to ceramic-metal composites. These materials fracture at strains considerably below 1 pct by cracking of the ceramic particles.4-6 An indication of the potential constrained matrix strength capacity is given by the observation by Nishimatsu and Gur-land4 that the maximum tensile strength of a WC-Co composite is almost double the bulk strength of the cobalt matrix. The relationship between composite strength and geometry is ordinarily expressed in terms of the mean-free matrix path (referred to subsequently as MFP) between the stronger particles.* This factor takes into account both the volume fraction of matrix phase and the average size of the particles. unke17 concluded that composite strength varied directly with the decreasing log MFP, following the Gen-samer8 relationship. However, Gurland and ~radzil~ reported a strength maximum at an MFP of the order of 1 p in WC-Co composites. A ductile two phase metallic composite was chosen for the present investigation of composite mechanical properties with the view of avoiding the difficulties and ambiguities noted above. The W-Ni-Fe heavy alloy of Green, Jones, and pitkin9 contains 80 to 94 wt pct W, and nickel and iron in a weight ratio

Jan 1, 1963

By J. F. Smith, J. R. Ogren, N. J. Magnani

The uapor pressrcres of magnesium over binary alloys of magnesium with twelve of the yare-earth eletnetzts have been measured by the Knudsen effuion method in the temperature range 675° to 910°K. These vapor-pressure measurments were combined with data concerning the tevtrlitzul magnesium solubility and the vapor pressure of pure magnesinm to evaluale the standuvd free energies of pluase jormation. These free-etzergy values indicate that the CsCl structures of the heacy rave earths tend to be somewhat less stable than those of the light rare earths. This dif-]eying- behaviov covrelates with differences which have been obsevz~ed in other alloy systetns wherein a phuse appeurs, disappeavs, or changes crystal stvucture as the atomic number of the rare-earth com-ponent is changed. This behauior also appears to correlate with the struclurul rariations within the rare-earth elements themselves, and it is speculated that cariations in the spatial extent of the 4f orbitals are responsihle. STUDIES of the phase relationships and crystal structures in the binary systems between rare-earth metals (lanthanons) and magnesium are extensive but far from complete. However, the currently available information1-10 does produce a rather interesting pattern. This is illustrated in Table I. If one excludes europium and ytterbium from consideration because of their generally atypical behavior, it can be seen from the table that the phase relationships in the magnesium-rich regions show a distinctly different pattern for the lighter lanthanons as compared to the heavier lanthanons. For the lighter lanthanons, LnMg2 phases occur from lanthanum to gadolinium with the cubic MgCu2 structure, LnMg3 phases occur from lanthanum to terbium with the BiLi3 structure, and magnesium-rich phases occur from lanthanum to gadolinium with stoi-chiometries between Ln5Mg42 and LnMg12. In contrast, for the heavier lanthanons, those LnMg2 structures which have been examined have the hexagonal MgZn2 structure, LnMg3 phases have not been observed beyond terbium, and the magnesium-rich phases occur with the a manganese structure near a stoichiometry of Ln5MgZ4. The heavy lanthanon-magnesium systems thus appear to be analogous to the Y-Mg system""2 wherein YMg has the CsCl structure, YMg2 has the MgZn2 structure, and the region Y4Mgz5-Y5Mg24 has the a manganese structure, and no other intermediate phases are observed. Similarity in alloying behavior between yttrium and the heavy lanthanons occurs commonly, and on this basis it seems likely that LnMg2 phases will be found with the MgZn2 structure in the binary systems of dysprosium, thulium, and lutetium with magnesium when the appropriate investigations are made. In the case of the magnesium-rich phases of the lighter lanthanons, only the Ce-Mg phase relationships have been investigated thoroughly and in detail, and until similar investigations are made for the other systems there will remain questions as to which magnesium-rich stoichiometries represent equilibrium phases and what systematic variations occur in the sequence from lanthanum to gadolinium. Thus the data in Table I show that only the LnMg phases occur with the same crystallographic structure throughout the sequence from lanthanum to lutetium. It was speculated that the relative stability of these LnMg phases might vary from one lanthanon to the next in such a way as to presage the differences which occur among the more magnesium-rich lanthanon-magnesium phases. On this basis the present investigation of the thermodynamics of phase formation was Gndertaken for the LnMg phases. PROCEDURE AND RESULTS A generalized phase diagram for the lanthanon-rich portion of a lanthanon-magnesium alloy system is shown in Fig. 1 where ß represents a high-temperature bcc

Jan 1, 1968

By B. B. Rath, Hsun Hu

In wedge-shaped bicrystals of zone-refined aluminum it is observed that (111) pure tilt boundaries migrate under the driving force of their own inter-facial free energy. The boundary velocity is a power function of the driving force. The driving force exponent decreases with decreasing angle of misorien-tation. For example, at 64O°C, the exponent decreased from 4.0 for a 40 deg to 3.2 for a 16 deg tilt boundary. An evaluation of the driving force acting on the boundaries during their motion indicates that for low driv-forces, up to about 2 x l03 ergs per cu cm, the velocity is relatively independent of misorientation, whereas at higher driving forces a 40 deg tilt boundary exhibits the highest velocity. The measured activation energy for boundary migration approaches that for bulk self-diffusion at low driving forces, decreasing from 33 to 27 kcal per mole as the driving force is increased from 1 x l0 to 5 x l03 ergs per cu cm. These results are compared with current theories of grain-boundary migration. In previous experimental studies of grain boundary migration the driving force has been limited to a difference in stored energy across the boundary. This stored energy has been introduced into the crystal either by prior deformation1-3 or by grown-in lineage structure. A part of the energy stored in the deformed crystal is released by recovery either prior to or concurrently with grain boundary migration, thus introducing an uncertainty as to the magnitude of the driving force responsible for grain boundary migration. The grown-in lineage structure, though thermally stable during annealing, neither provides conditions under which different levels of energy may be stored in the imperfect crystal nor provides a control of orientation difference across the migrating boundary of a growing grain. Furthermore, because of variation in the lineage structure, it is difficult to determine accurately the energy stored in the imperfect crystal. Several investigations of grain boundary migration during normal grain growth have also suffered from difficulties in estimating the driving force because of uncertainties in the principal radii of curvature.~ In the present investigation the velocity of pure tilt boundaries in zone-refined aluminum bicrystals of selected orientation (40, 30, and 16 deg around the [Ill] tilt axis) has been measured in the absence of a dislocation density difference across the moving boundary, thus eliminating the previous experimental difficulties. The driving force for boundary migration is derived from a gradient of the total interfacial free energy of the migrating boundary in wedge-shaped bicrystals. A similar method was attempted by Bron and Machlin in a study of grain boundary migration in silver. However, they found that one of the crystals was deformed and consequently the motion of the boundary was partly due to a difference of stored energy across the boundary. The observed behavior of boundary velocities as affected by the driving force is examined in the light of the predictions of the current theories of grain boundary migration.7"10 The effect of boundary misorientation on velocity is compared with the theory of " which is based on a dislocation core model for high-angle boundaries. EXPERIMENTAL METHOD Seed-oriented bicrystals of zone-refined aluminum, 2.5 cm wide, 0.5 cm thick, and 12 cm long, containing tilt boundaries with a common (111) axis, were grown from the melt in the direction of this axis. Spectro-graphic analysis, reported earlier,&apos;&apos; indicated the purity of the crystals to be 99.999+pct. Three such bicrystals containing 16, 30, and 40 deg tilt boundaries were used. Wedge-shaped specimens were prepared from these bicrystals by spark cutting followed by electrolytic polishing. The angle of the wedge was usually 40 deg and the specimens were usually 0.25 cm thick. The intercrystalline boundary was located within 0.2 to 0.5 cm from the tip of the wedge. Fig. 1 shows a section of an oriented bicrystal containing an outline of a wedge-shaped specimen. The crystallographic directions shown in Fig. 1 represent the orientation of one of the crystals (the larger section of the bicrys-tal); the orientation of the other crystal differs only by rotation around the common [lil] axis. The parallel faces of the wedge always corresponded to the common (171) planes in both crystals, whereas the orientation of the side faces varied, depending on the misorientation angle. The bicrystal orientations were determined

Jan 1, 1970

By A. B. Cook

Gas cycling is generally considered a much less efficient oil recovery mechanism than water flooding. HOWever, recoveries from some fields have been exceptionally high as a result of gas cycling. Recovery from the Pick-ton field, for example, was calculated to be 73.5 perceni of the stock-tank oil originally in place. In evaluating pressure maintenance projects, determining how much of the recovery is due to displacement by gas and determining how much is due to vaporization of the imrnohile oil in the flow path of the cycled gas is very difficrilt. Even though most of the oil is recovered by displacetr~ent, the success of a project may depend on the amount of oil vaporized. A limited number of experiments have heen performed with a rotating model oil reservoir that simulates gas cycling operations and allows a separation of the oil from, tile free gas flowing into the laboratory wellbore at reservoir conditions, thus revealing which is displaced oil and which is vaporized oil. It Iras been determined that the amount of varporizatio&apos;n is .significant if proper conditions exist These experiments show that oil vaporization depends on pressure, temperature, volatility of the oil and amount of gas cycled. Increases in each of these conditions increase the volume of oil vaporized. Data from six experiments affecting vaporization are presented to illustrate reservoir condition that range from favorable to unfavorable. 111 these eaperitnenis recovery by vaporization ranged from 73.6 to 15.3 percent of /he immobile oil (oil not produced by gas displacerrlt). INTRODUCTION Between 1930 and 1950, gas cycling was a popular. oil recovery practice. especially for the deeper reservoirs. Later, with many case history-type studies published for both gas cycling and waterflooding, it was generally believed that waterflooding was far superior to gas cycling, even when gas cycling was conducted as a primary production procedure by complete pressure maintenance. A good example illustrating the advantage of water-flooding over gas cycling is given in a paper by Matthews&apos; on the South Burbank unit where gas injection was followed by waterflooding. The author concluded in part that "Early application of water injection, without the intervening period of gas injection, would have recovered as much total oil as ultimately will be recovered by waterflooding following the gas injection, and total operating life would have been shortened". This appears to be a logical conclusion. However, it should not be applied to all fields. Pressure maintenance with gas in the Pickton field, as reported by McGraw and Lohec;&apos; will result in a much larger percentage of oil recovery than was obtained in the South Burbank unit. The great success in the Pickton field resulted partly from vaporization of the immobile oil in the flow path of the cycled gas. The amount of vaporization is related to the following conditions: volatility of the oil as reflected by the APT gravity of the stock-tank oil; reservoir temperature; reservoir pressure during gas cycling; and the amount of gas cycled. Therefore, the U. S. Bureau of Mines is investigating these effects on vaporization in a research project using a model oil reservoir. Three different stock-tank oils having 22, 35 and 45" API gravities are being used as base stock to synthesize reservoir oils. Experiments are being performcd to determine vaporization at 100, 175 and 250F and at 1,100, 2,600 and 4,100 psia. This is a progress report showing the results from six experiments. Other Bureau of Mines reports"- concerning vaporization are listed. LABORATORY EQUIPMENT AND PROCEDURES The equipment &apos; consists of an internally chromium-plated steel tube packed with finely sifted Wilcox sand. The tube is approximately 44 in. long and has an ID of 13/4 in. The sand section contains approximately 570 ml of voids, has a porosity of 32 percent, and a permeability to air of 4.3 darcies. A unique feature of the laboratory reservoir (Fig. 1) permits the tube part to rotate at 1 rpm while the outlet and inlet heads are held stationary. The outlet end contains diametrically opposed windows to permit observatlon of the flowing fluids, and two valves, one on the top and the other at the bottom. Oil and free gas. when being produced simultaneously, can be separated by manipulating the two valves to keep a gas-oil interface in view through the windows. Thus, only gas is produced through the top valve and only oil flows through the bottom valve. The laboratory equipment was designed to study vaporization. Therefore, a uniform reservoir was made using dry sifted sand as opposcd to using a consolidated sand core with interstitial water. Furthermore. the reservoir was tilted to minimize fingering of gas. This tilting also in-

By W. F. Chiao, R. B. Gordon

Tile sharp-yield point found in magnesium crystals in the solulion-treated and aged condition is studied by dislocation internal-friction experiments. The results show that the sharp yield is not file to the sudden release of pinned dislocations hut is movc likely due to the rapid multiplication of an initially small number of dislocations. Recovery or the dislocation internal friction after deformation is also studied. This yecovery results from the re-pinning of dislocations by a solute, presumably nitrogen, which moves with a relatively small activation energy. SHARP-yield points, when they occur, are a striking feature of the stress-strain curve generated during a tensile test. Although commonly associated with steel, sharp yielding has been found in a variety of metallic and nonmetallic crystalline materials. In particular, sharp-yield points have been found in zinc"&apos; and cadmium3 containing nitrogen. With this background, Geiselman and Guy4 investigated the tensile properties of magnesium single crystals containing nitrogen to see if sharp yielding also occurs in this system. They found that sharp yields did indeed occur in solution-treated and aged specimens tested at elevated temperature but were not able to give conclusive proof that the sharp yield was caused by nitrogen, a yield drop being observed even in their purest crystals. Sharp-yield points have also been found in various polycrystalline magnesium alloys.7&apos;8 In the study of the sharp-yield phenomenon it is desired to observe the behavior of dislocations in the earliest stages of the deformation process. Internal-friction experiments are useful for this purpose because dislocation damping is sensitive to the mobility of free-dislocation segments. At low strain amplitudes the damping, A, due to the the forced vibration of dislocation segments of average length L is ? =KAL4 [1] where A is the dislocation density and K, if the applied frequency is well below the resonant frequency of the dislocation segments? is a constant for the sample under observation.5 Dislocation damping, because of the fourth-power dependence on L, is particularly sensitive to the creation of free-dislocation segments during deformation. Since sharp yielding is associated with the sudden release of pinned-dislocation segments, marked changes in the dislocation damping are expected at the yield point.6 The use of the dislocation-damping observations to help elucidate the incompletely understood mechanism of yielding in magnesium is the primary objective of the experiments reported here. PROCEDURE Many investigations have shown that very marked and rapid changes occur in the dislocation damping of of a deformed material as soon as the straining is stopped.5 It was quite essential, then, for the purpose of this investigation, to make the damping measurements during the deformation of the samples. This can only be accomplished through the use of the ultrasonic-pulse method. In this method traveling sound-wave pulses are used and, in contrast to resonating-bar methods, only the sample ends are set in vibration. Thus, the sample can be gripped along its sides in the tensile-test machine without disturbing the damping measurements. In the pulse method, the decrease in the amplitude of a sound pulse is measured as it travels back and forth through the sample. If A is the amplitude after traversing a distance x and A. is the initial amplitude, A=Aoe-ax [2] and a is called the attenuation. It is commonly measured either in units of cm-I or as db per µ sec. The observed attenuation in a metal sample is due to a number of causes. These include scattering by grain boundaries and impurity particles, thermo-elastic damping, diffraction effects, stress-induced ordering of solute atoms, and dislocation damping. The total observed attenuation in a given sample usually cannot be resolved into these various components, but changes in a due solely to changes in dislocation damping can be accurately determined, provided the experiment is arranged so that all other sources of damping are held constant. It is desired to reduce the extraneous sources of attenuation to a minimum and for this reason the experiments are done on single crystals of high purity. Magnesium crystals offer the further advantage that, when properly oriented, only a single set of slip planes is active during deformation. Crystal Preparation. The method of sample preparation is similar to that of Geiselman and Guy.4 The starting material was high-purity, sublimed magnesium rod supplied by the Dow Chemical Co. Melting under Dow 310 flux was used to reduce the nitrogen content of the starting material: the fluxing was done under an argon atmosphere and the

Jan 1, 1965

By J. F. Enrietto

Internal friction measurements were used to determine the effect of manganese on the solubility and precipitation kinetics of nitrogen. Manganese, in concentrations up to 0.75 pct, has little effect on the solubility at temperatures above 250°C. On the other hand, at Concentrations as low as 0.15 pct, manganese inhibits the formation of iron nitrides, especially Fe4N, even though it may not form a precipitnte itself. The precipitation and solubility of carbides and nitrides have been extensively investigated in the pure Fe-C and Fe-N systems.1-3 In recent years, some effort has been ispent in studying the influence of substitutional alloying elements on the behavior of carbon and nitrogen in ferrite.4 -7 In particular Fast, Dijkstra, and Sladek have investigated the effect of 0.5 pct Mn on the internal friction and hardness during the quench aging of Fe-Mn-N alloys.&apos;, &apos; They found that at low temperatures (below 200°C) the presence of 0.5 pct Mn greatly retarded quench aging. For example, after 66 hr at 200°C very little precipitation had taken place in the iron alloyed with manganese, whereas precipitation was complete after a few minutes in a pure Fe-N alloy. The effect of varying the manganese content and the details of the precipitation process were not mentioned in these papers. Fast&apos; postulated that manganese causes a local lowering of the free energy of the lattice with a resulting segregation of nitrogen atoms to these low energy sites. The segregated nitrogen atoms are bound so tightly to the manganese atoms that they cannot form a precipitate. The internal friction measurements of Dijkstra and Sladek tended to confirm the concept of segregation of nitrogen around manganese atoms, and the increase in free energy on transferring a mole of nitrogen atoms from a segregated to a "normal" lattice site was computed to be - 2800 cal. Dijkstra and Sladek9 distinguished between two types of precipitates: ortho, a nitride of appreciably different manganese content than that of the matrix, and para, a nitride with a manganese content essentially that of the matrix. With each type of precipitate a solubility, again designated ortho or para, can be associated. Since the internal friction maximum in alloys which were aged several hours at 600" C dropped almost to zero, Dijkstra and Sladek9 concluded that the ortho solubility must be very low. The effect of temperature on the ortho and para solubilities has no1: been investigated. There are obviously several gaps in our knowledge concerning the influence of manganese on the behavior of nitrogen in a-iron. It was the purpose of the experiments described in this paper to determine the following: 1) The ortho and para solubilities of nitrogen as a function of temperature. 2) The details of the precipitation process at elevated temperatures. 3) The effect of varying the manganese concentration on the above phenomena. EXPERIMENTAL PROCEDURE Internal friction is conveniently employed in studying the precipitation of nitrides and/or carbides from a -iron because it is one of the few parameters, perhaps the only one, which is not affected by the presence of the precipitate itself. For this reason, internal friction techniques were heavily relied upon in the present experiment. A) Preparat of -. All specimens were prepared from electrolytic iron and electrolytic manganese. Alloys containing 0.15, 0.33, 0.65, and 0.75 wt pct Mn were vacuum melted and cast into 25 lb ingots. After being hot rolled to 3/4 in. bars, the ingots were swaged and drawn to 0.030 in. wires. The wires wen? decarburized and denitrided by annealing at 750° C for 17 hr in flowing hydrogen saturated with warer vapor. To obtain a medium grain size, - 0.1 mm, the wires were then heated to 945oC, allowed to soak for 1 hr, furnace cooled to 750°C, and water quenched. Subsequent internal friction measurements showed that this procedure reduced the nitrogen and carbon concentrations of the alloys to less than 0.001 wt pct. The wires were nitrided by sealing them in pyrex capsules containing anhydrous ammonia and annealing them for 24 hr at 580°C, the nitrogen being retained in solid solution by quenching the capsule into water. Immediately after quenching, the wires were stored in liquid nitrogen to prevent any precipitation of nitrides. By varying the pressure of ammonia in the capsule, it was possible to produce any desired nitrogen concentration. B) Internal Friction. The internal Friction measurements were made on a torsional pendulum of the Ke type,&apos;&apos; a frequency OF 1. or 2 cps being used. For

Jan 1, 1962

By L. Delisle

This work represents the first step of an attempt to test the applicability of the electron microscope to the study of subgrain structures in copper. Observations on annealed and deformed single crystals and polycrystalline samples of copper are described. IN the course of study of the structure of fine tungsten wires and tungsten rods with the electron microscope, well defined subgrain structures were observed. The size, size distribution, and orientation uniformity of the etch figures varied widely in different samples. Figs. 1 and 2, electron micrographs of a tungsten wire and of a tungsten rod, respectively, are illustrations of the difference in size and size distribution of the etch figures in different samples of the same metal. The observed differences, as pointed out in a previous paper,&apos; appeared to be related to the heat and mechanical treatments of the samples. They were also consistent with the results reported in the literature on the mosaic structure of metals.&apos; For that reason a program of research was initiated in an effort to obtain more systematic evidence of the possible relation of heat and mechanical treatments to the subgrain structure of metals as observed in the electron microscope. The purpose of this paper is to present observations made on the effect of cold work on the subgrain structure of copper. Procedure Starting Materials: Copper was the metal studied because it can be obtained in a high degree of purity, much information is available in the literature on its properties and its response to cold work and heat treatment, it shows no allotropic change, and it is sufficiently hard to be handled without great difficulty. Two groups of specimens were used: 1—single crystals cast from spectroscopically pure copper and 2—polycrystalline samples of oxygen-free high conductivity copper. Single crystals were studied because it was hoped that the elimination of a number of variables, such as grain boundaries, orientation differences, degree of purity, would simplify the problem and perhaps permit a better understanding of the phenomena that would be observed. The polycrystalline samples were designed to give a general picture of the changes considered. The single crystals were made of copper which analyzed spectroscopically to better than 99.999 pct Cu. They were cast in vacuum, by the Bridgman method, in crucibles made of graphite with a maximum ash content of 0.06 pct. The mold design is shown in Fig. 3. It permitted casting crystals of the size and shape required for the experiments, so that the danger of introducing cold work in the original samples by cutting or other machining would be eliminated. The polycrystalline samples were pieces, 3/4 in. long, cut from a rod of oxygen-free high conductivity copper, % in. in diameter. A flat surface, 1/4 in. wide, was milled along the rods, polished, and etched. The samples were then annealed in vacuum at 850°C for 1 hr. Polishing and Etching: Work previously done on tungsten,&apos; polished mechanically and etched chemically," had shown that: 1—the general appearance of the etch figures of a given sample was not altered by repeated polishings and etchings under similar conditions; 2—variations in the time of etching and the concentration of the etchant changed the definition of the etch figures, but did not alter their general size nor orientation distribution within the limits of observation. Further work confirmed the reproducibility of the subgrain structures observed in, 1—single crystals and polycrystalline samples of copper when polishing and etching were repeated under similar conditions, and 2—specimens of tungsten and polycrystalline copper when electrolytic polishing and etching were substituted for mechanical polishing and chemical etching, respectively. On the strength of these observations, it was felt that, if conditions of polishing and etching were kept constant, changes observed in the subgrain structure of a sample upon deformation and annealing would be attributable to such treatments. For that reason the conditions of polishing and etching were kept as constant as possible. The single crystals were polished electrolytically in a bath of orthophosphoric acid in water, in the ratio of 1000 g of acid of density 1.75 g per cc to 1000 cc of solution, under a potential drop of 1.6 to 1.8 V. Electrolytic polishing was selected to prevent the formation of distorted metal in polishing. The same samples were etched by immersion in a 10 pct aque-

Jan 1, 1954

By E. F. Poncelet

Forty years ago A. A. Griffith developed a theory explaining why brittle materials displayed such low tensile strengths.&apos; He based his views on two points. First, he found himself compelled to assume that all brittle materials are replete with flaws, cracks, and other defects that act, although quite invisible, as large stress raisers. Second, he applied the "theorem of minimum potential energy," which says that the total potential energy of a system must pass from the unbroken to the broken condition by a process involving a continuous decrease in potential energy. By this means he satisfactorily accounted for the noted low strength of such solids and also for the wide spread obtained in experimental measurement of these strengths. So successful has the theory been that it is favored by some to this day. Unfortunately this theory is of limited use beyond the explanation of these two noted phenomena and it is keenly felt that a better theoretical insight into the physics of the fracturing process is needed as the volume of experimental evidence accumulates. The author proposes in the following to build on the fundamentally sound concepts of Griffith and, with the help of increased theoretical knowledge over that available to Griffith, develop a mechanism for frac-ture which will provide far greater understanding of the experimental evidence accumulated to date than is possible from the original Griffith idea. THE GRlFFlTH THEORY Very little progress indeed can be made without accepting the first postulate of Griffith which supposes all brittle solids to be full of microcracks. It would be difficult indeed to find a better mechanism for the small strength of such brittle materials, in conjunction with the fact that the energy that must be expended for comminution is by no means small. The postulate of the existence of the microcracks permits the breakup of the various bonds a few at a time by concentrating the stress at the tip of the progressing crack, while the total energy expended is the same as if they all had been ruptured simultaneously. The only flaw in the argument is that no reasonable explanation has been proposed to account for the genesis of such cracks. Indeed their very presence is in violation of the Griffith second postulate, the potential energy theorem. This theorem is straightforward for isothermal processes, and, in spite of Griffith, there is some doubt that treating the problem isothermally is legitimate. The surface energy of bodies is a free energy, not a potential energy as stated by Griffith, and the production of new surface free energies is not necessarily an isothermal process. There is ample evidence to the contrary. Generally speaking, if heating a body increases its surface area, then, by virtue of Le Chatelier&apos;s principle, any increase of that area by other means will tend to lower its surface temperature. Lord Kelvin calculated the actual cooling that resulted in drawing out a film of liquid.2 R. A. Houston calculated the surface cooling that resulted in stretching a metal wire.3 These calculations were made by applying the Carnot cycle to the process and evaluating the thermodynamics thereof. IRREVERSIBILITY OF THE FRACTURING PROCESS While Griffith was very careful not to say so, the impression gained from studying his papers is that he considered the fracturing process as reversible, that is, a succession of quasi-equilibrium states. There is ample evidence that it is not. The indication that the new surfaces produced by the propagation of a crack are cooler than the original body points to an irreversible heat flow from the interior to the new surfaces to equalize the temperatures. If the process be reversible, any crack accidentally formed should immediately close up as, in the absence of any strain energy, the potential energy would thereby be lowered. The fact that they do not, constitutes a paradox. Such paradoxes are nothing new where certain phenomena that propagate from minuscule nuclei are assumed to be reversible. Such is, for instance, the condensation of a pure saturated vapor that is suddenly chilled by adiabatic expansion. At the beginning the tiny droplets that are formed should be only a few angstroms in size, but the vapor pressure at such droplets is so high that they should evaporate at once. A similar situation arises if a saturated pure solution becomes super-saturated upon cooling; the first tiny crystal nuclei should dissolve as fast as

Jan 1, 1964

By John S. Crandall

THE mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sandpaper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where Occurrence: Garnets in the Emerald Creek area occur as disseminated crystals in beds of micaceous schists of the Belt Series, which in this section are estimated to be close to 4000 ft thick. The schists are high in alumina and silica with iron, manganese, and magnesium. Subjection of the original sediments to high temperatures and pressures caused metamorphism to take place with the resultant re-crystallization of high alumina-silica minerals such as garnet, mainly spessartite and almandite varieties, cyanite, sillimanite, chlorite, actinolite, tourmaline, biotite, and muscovite, with minor amounts of ilmenite and magnetite. Quartz is also present in considerable amounts. Fast erosion of the soft mica schists on exposure to weathering has created extensive alluvial deposits containing up to 10 pct garnet having a maximum grain size of 3/16 in. These alluvial sands and gravels are now being treated for the recovery of garnet sands. Treatment: Overburden of 1 to 4 ft must be stripped to expose the garnetiferous gravels. This operation and the subsequent feeding of the gravels to a trommel-screen washing plant are performed by a % yd dragline. The trommel-screen openings are 3/16 in., thus allowing a separation and concentration based on grain size, since over 95 pct of total free garnets are minus 3/16 in. All plus 3/16-in. material is wasted at this point. The minus 3/16-in. material is further concentrated in a sand-drag classifier, where the slimes and silts are washed out and wasted. The sand product from the classifier varies in garnet content from 20 to 60 pct according to the particular section of ground being worked. This sand product is trucked to a jig plant where two sized fractions are made in a trommel-screen. The minus 3/16-in. plus 10-mesh portion is fed to a Pan-American two cell 42-in. jig. The minus 10-mesh portion is treated in a Bendelari three cell 42-in. jig. The jig concentrates are combined to form a 98 pct garnet sand. The jig tailings contain 3 to 5 pct garnet which is mainly flat crystals and chips which will not settle into the jig hutch. Subsequent treatment of these tailings in a scavenger jig followed by drying and electromagnetic separation will, according to tests, reduce the garnet losses in the tailings to something around 1 pct. Jig treatment of this feed approaches ideal as the major portion of the garnet crystals are the natural dodecahedrons and so are, in general, close to spherical. The specific gravity of pure garnet is 4.2, while the next heaviest mineral in the feed is cyanite with a specific gravity of 3.6, then quartz with specific gravity of 2.6. The garnet concentrate is practically free of quartz. The predominant impurity is cyanite which amounts to about 1.5 pct. The rod-like crystals of cyanite appear to up-end in the jig and go into the hutch with the garnets. Some ilmenite and magnetite appear in the concentrate but in very minor amounts. Subsequent washing in a sand-drag classifier removes fine silts and iron oxides. The gravel feed to the washing plant will average 8 pct recoverable garnet content. Concentration ratio in this plant runs about 2.5 to 1. Washing-plant concentrate as fed to the jigs will average 45 pct garnet by weight. Concentration ratio of jigging runs about 2.2 to 1. The garnet concentrate is dried in a rotary oil-fired drier and then fed to vibrating screens in closed circuit with crushing rolls. Practically any grit from 10-mesh down to 150-mesh grain size may be graded to specifications in two 3-deck vibrating screens. The present production, however, is approximately 75 pct No. 36, 15 pct No. 60. and the balance No. 80 and No. 100. Metal-screen cloth is used for sizes down to 36 mesh. From 36 mesh and finer, silk-screen cloth is used since it has less tendency to blind. All garnet sand is bagged in 100 lb self-sealing, sleeve-type paper bags. Practically all shipments are made in carload lots. Car loading is convenient since the plant is in Fernwood on the tracks of a branch line of the Milwaukee railroad. Truck shipments can and are made occasionally.

Jan 1, 1951

By John S. Crandall

THE mineral garnet, while ordinarily considered a semiprecious gem stone or a second-grade industrial gem, has also proved itself in the field of industrial abrasives. Its use is well known as a sandpaper grain, and as a sandblasting sand its qualities are rapidly becoming recognized in more and more industries. Production of garnet as an abrasive is confined chiefly to two areas in the United States, North Creek, N. Y., where the Barton Mines Corp. operates, and Emerald Creek, Benewah County, Idaho, where Occurrence: Garnets in the Emerald Creek area occur as disseminated crystals in beds of micaceous schists of the Belt Series, which in this section are estimated to be close to 4000 ft thick. The schists are high in alumina and silica with iron, manganese, and magnesium. Subjection of the original sediments to high temperatures and pressures caused metamorphism to take place with the resultant re-crystallization of high alumina-silica minerals such as garnet, mainly spessartite and almandite varieties, cyanite, sillimanite, chlorite, actinolite, tourmaline, biotite, and muscovite, with minor amounts of ilmenite and magnetite. Quartz is also present in considerable amounts. Fast erosion of the soft mica schists on exposure to weathering has created extensive alluvial deposits containing up to 10 pct garnet having a maximum grain size of 3/16 in. These alluvial sands and gravels are now being treated for the recovery of garnet sands. Treatment: Overburden of 1 to 4 ft must be stripped to expose the garnetiferous gravels. This operation and the subsequent feeding of the gravels to a trommel-screen washing plant are performed by a % yd dragline. The trommel-screen openings are 3/16 in., thus allowing a separation and concentration based on grain size, since over 95 pct of total free garnets are minus 3/16 in. All plus 3/16-in. material is wasted at this point. The minus 3/16-in. material is further concentrated in a sand-drag classifier, where the slimes and silts are washed out and wasted. The sand product from the classifier varies in garnet content from 20 to 60 pct according to the particular section of ground being worked. This sand product is trucked to a jig plant where two sized fractions are made in a trommel-screen. The minus 3/16-in. plus 10-mesh portion is fed to a Pan-American two cell 42-in. jig. The minus 10-mesh portion is treated in a Bendelari three cell 42-in. jig. The jig concentrates are combined to form a 98 pct garnet sand. The jig tailings contain 3 to 5 pct garnet which is mainly flat crystals and chips which will not settle into the jig hutch. Subsequent treatment of these tailings in a scavenger jig followed by drying and electromagnetic separation will, according to tests, reduce the garnet losses in the tailings to something around 1 pct. Jig treatment of this feed approaches ideal as the major portion of the garnet crystals are the natural dodecahedrons and so are, in general, close to spherical. The specific gravity of pure garnet is 4.2, while the next heaviest mineral in the feed is cyanite with a specific gravity of 3.6, then quartz with specific gravity of 2.6. The garnet concentrate is practically free of quartz. The predominant impurity is cyanite which amounts to about 1.5 pct. The rod-like crystals of cyanite appear to up-end in the jig and go into the hutch with the garnets. Some ilmenite and magnetite appear in the concentrate but in very minor amounts. Subsequent washing in a sand-drag classifier removes fine silts and iron oxides. The gravel feed to the washing plant will average 8 pct recoverable garnet content. Concentration ratio in this plant runs about 2.5 to 1. Washing-plant concentrate as fed to the jigs will average 45 pct garnet by weight. Concentration ratio of jigging runs about 2.2 to 1. The garnet concentrate is dried in a rotary oil-fired drier and then fed to vibrating screens in closed circuit with crushing rolls. Practically any grit from 10-mesh down to 150-mesh grain size may be graded to specifications in two 3-deck vibrating screens. The present production, however, is approximately 75 pct No. 36, 15 pct No. 60. and the balance No. 80 and No. 100. Metal-screen cloth is used for sizes down to 36 mesh. From 36 mesh and finer, silk-screen cloth is used since it has less tendency to blind. All garnet sand is bagged in 100 lb self-sealing, sleeve-type paper bags. Practically all shipments are made in carload lots. Car loading is convenient since the plant is in Fernwood on the tracks of a branch line of the Milwaukee railroad. Truck shipments can and are made occasionally.

Jan 1, 1951

By A. L. Labbe

SOON after the Cottrell treater was placed in operation in the Murray plant in 1918 to treat combined lead sinter and Wedge roaster smoke, it was noticed that the power flowing through the treater did not remain constant. This was indicated by the varying milliamperes and also by the total amount of power consumed by the rectifiers. At times, for then unknown reasons, the treater current fluctuated through a wide range of from 40 to 300 milliamperes. Fortunately, these variations in power did not affect the treater&apos;s overall recovery, as this installation consisted of three independent units in series, a feature which made the Murray Cottrell an outstanding installation over many years of operation. Water conditioning of the smoke as a means of improving recovery was already known, but was not adaptable to this installation for reasons of excessive corrosion, which had been the case with other treaters using water as a conditioner exclusively. Tests conducted on the smoke had proved conclusively that water vapor played no part in the fluctuation of power, and the same was true of the SO2 contents and dust burden of the smoke. Neither did temperature variations of from 150 to 400°F have any effect on the power. Finally it was noticed that the variation in power taken by the treater, and the efficiency of recovery, had some definite relation to the number of Wedge roasters operating, and particularly to the sulphur contents of the charge. This observation soon led to the discovery that free sulphuric acid was the conditioner for Murray smoke and that variations in acid contents of smoke accounted for fluctuations of treater power. Analysis of recovered dust revealed that only a few hundredths of a per cent free acid was necessary to maintain a very efficient recovery. Once this knowledge was available, the roaster charge was adjusted as to sulphur contents to produce the necessary acid conditioner. For a number of years this practice was followed, but with improvements in the field of flotation, excess pyrites were eliminated from the smelting picture, so with a change in metallurgical practice we were confronted with the problem of providing the deficiency in acid by some other means. The situation was aggravated and our problem of acid conditioning made more difficult by the increase in the lead contents of concentrates roasted resulting from better flotation methods. The first step towards introducing acid vapors into the smoke stream by accessory means was accomplished by boiling sulphuric acid in cast iron pots placed in an open fire box. Acid fumes evaporated from the pots together with the combustion gases from the fire box were discharged into the flue through a cast iron pipe. Capacity of the iron pots was quite limited because of the comparatively slow rate of evaporation and the use of lump coal as a fuel, which did not lend itself to practical temperature control. This method of firing resulted in frequent pot failures due to overheating. In spite of these incidental difficulties, encountered in any new venture, the pot evaporator demonstrated the practicability of fuming sufficient acid to make up the deficiency in that naturally evolved in the Wedge furnace operation. As time progressed, less and less high sulphur material was available for Wedge roasting, and the necessity for accessory acid conditioning reached a climax when the supply of this material was entirely eliminated. Since the cast iron pots could only evaporate a few hundred pounds of acid per day, and were costly to replace, the logical thought presented itself of spraying the acid in a heated chamber. This new type of acid evaporator was simpler and more economical to operate and had sufficient capacity to fume several thousand pounds per day. The attached fig. 1 presents the outstanding features of the new furnace. A is the vaporizing drum, which is heated by the combustion gases of coal stoker fire box, B. Acid is sprayed into the hot gas stream within the drum through a number of air-acid atomizers, C, and the acid vapor, together with combustion gases, is introduced into the smoke stream through two cast iron pipes extending to different points in the flue. The operation of this type of furnace requires control of temperature inside the drum to prevent overheating, which dissociates the acid vapor to SO, and eventually to SO2, with resulting loss of acid. The dissociation to SO, at elevated temperatures is comparatively high, and in some cases accounts for as much as 60 pct of the acid sprayed into the drum. To reduce the loss of acid, through dissociation, some Cottrell plants, where the rate of acid sprayed reaches at times 9 ppm, use two evaporating units. Fuming the acid into the smoke stream is only

Jan 1, 1951

By A. M. Turkalo

IT is a well-known fact that martensitic steels show a greater resistance to brittle fracture than do pearlitic and bainitic steels. It was, therefore, thought worthwhile to investigate the mode of brittle fracture with respect to structure by studying the effect of various austenite decomposition products on the propagation of brittle fracture in steel by means of electron microscopy. Newly developed replication techniques together with the advantages of the electron microscope such as great depth of field, available high magnification and easy adaptation to stereophotography make electron microscopy very suitable for fracture studies. EXPERIMENTAL PROCEDURE An essentially plain carbon steel containing 0.56 pct C, 1.30 pct Mn, 0.02 pct P, 0.03 pct S and 0.22 pct Si was used in this investigation. The following table gives the heat treatments used to obtain the various austenite decomposition products: The resulting austenite grain size from the 870°C austenitization treatment was about an ASTM No. 7 grain size. The specimens which were 2 in. long, 1/4-in. diam bars were austenitized in a tube furnace through which argon gas was blown. The tube was not, however, air-free and the specimens were not completely oxide-free. Isothermal treatments were done in a lead bath. With the exception of the fully hardened specimen and the one as-isothermally transformed at 300°C the heat treated specimens were notched in the following fashion with a jeweler&apos;s saw. A cut about 0.08 in. deep was made perpendicular to the length of the bar. The specimen then was rotated about 45 deg and another cut about 0.08 in. deep was made. In the case of the hard martensitic and bainitic specimens, only one cut was made and the depth was not controlled. The design of the two-cut notch caused fracture to initiate at the point of intersection of the two saw cuts. The specimens were broken at -196°C in a Charpy impact testing machine. In order to hold the specimens securely in the impact machine two square pieces of mild steel were made about 5/8 in. long having the same cross section as that of a standard Charpy specimen but containing a hole 1/4 in. diam through the center of the cross-section. These adapters were slipped over the ends of the test specimen which was then secured tightly by means of set screws in the adapters. The specimen with the adapters was cooled to -196°C in liquid N,, then placed in the impact machine and broken within 3 sec. One half of the broken specimen was used for the electron microscope study of the actual fracture surface. The other half was nickel-plated and a cross section through the notch and fracture was polished for electron microscope examination. Carbon replicas of the fracture specimens for the electron microscope study were made essentially according to Bradley&apos;s evaporation technique.&apos; Both direct carbon and two-stage carbon replication techniques were used. In the case of the direct carbon technique, a thin layer of carbon was evaporated first at an angle of about 45 deg to the mean fracture surface and then another film of carbon was evaporated normally to the fracture surface. The carbon replica was freed electrolytically.2 The specimen was made an anode in a 10 pct Nital polishing solution. It was etched intermittently by shutting off the power now and then. The freed replica was washed in 40 to 50 pct water solution of nitric acid for 10 min or so, then washed in water and picked up on a screen for examination. The two-stage carbon replication technique involved first making a primary replica of cellulose * acetate from which a carbon replica was then made. One side of a strip of cellulose acetate wet with acetone was pressed lightly against the surface of the specimen, allowed to dry and then stripped. Prior to the deposition of carbon, which was done at 90 deg to the cellulose acetate replica surface, chromium was evaporated at 45 deg. After the carbon evaporation the cellulose acetate was dissolved in acetone according to the Jaffe method3 leaving the carbon replica preshadowed with chromium for examination.

Jan 1, 1961