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By Gordon E. Agar, David M. Hopstock

This paper describes the procedures and results of a series of experiments conducted to determine the depressing effect of sodium, calcium and magnesium ions on the amine flotation of quartz. It also presents an analysis of the experimental results by the electrical double layer theory. The flotation of quartz with primary amines has been practiced on a large scale in the phosphate industry for many years. Some glass sand —and recently iron ore — has also been treated by this flotation technique. These applications have been highly successful and demonstrate that a complete mastery of all the details of an operation is not needed to achieve an economic success. There are times, though, when it becomes important to recognize, both qualitatively and quantitatively, the effects of some previously ignored variables. The effects of cations on the amine flotation process, particularly those ions that contribute to water hardness and abound in sea water, are a case in point. In conjunction with the development of a cationic flotation reagent for separating quartz from apatite, it became necessary to quantify the influence of calcium and magnesium on the separation. In order to strengthen and broaden current understanding of the flotation process, the results were interpreted by means of the electrical double layer theory. THEORETICAL BACKGROUND Assume that, given the same equipment, procedure, and time, the recovery of quartz by amine flotation is a function of only the adsorption density of aminium ions in the Stern layer, i.e., that for any given adsorption density there exists only one recovery percentage. By the Stern-Grahame treatment of the electrical double layer,'-' for any ionic species in a solution in equilibrium with quartz,

Jan 1, 1969

By T. L. Iapalucci

To determine the behavior of chlorine in coal combustion, the Bureau of Mines burned 10 chlorine-containing coals, high-, medium-, and low-volatile, in a laboratory-scale pulverized-coal combustor. At carbon-combustion efficiencies of 94 to 98 percent, 1.6 to 7.1 percent of the chlorine or an average of 4 percent of the chlorine in the coal was retained in the ash; the balance, predominantly hydrogen chloride, was evolved in the combustion gas. Sulfur retention in the ash ranged from 2.3 to 10.7 percent or an average of 6.3 percent, Addition of alkali and alkaline earth carbonates to a medium-volatile coal containing 0.27 percent chlorine by preferentially reacting with the chlorine increased the Cl/S atom ratio in the ash, Lithium carbonate addition at 0.43 percent and K2C03 at 1.59 percent increased the C1/S ratio in the ash from 0.2 to 0.6.

Jan 1, 1969

By N. L. Hancox

Previous researchers have used the cutting and rejoining model to represent a porous body when attempting to place Archie's law on a theoretical basis and calculate rock permeabilities (F = Ø-m, where F = formation factor, = - porosity and m = a constant). In using the model, a porous solid is assumed to consist of sections with parallel sides containing straight. continuous pores of total porosity 4 (pore to total volume or, for a homogeneous body, pore to total area). The joining of pores at an interface between two sections is assumed to be random which results in a common pore area Ø2. This reduced area Ø2 is then taken as that area which limits electrical conduction or fluid flow in the body. Agreement between experimental results and results calculated using a model is not always good Because of this, various modifications of the model are presented — for instance, the random nature of the joining is questioned. Formation factor measurements on specially constructed porous specimens are described in this paper. it is concluded that the common pore area limits flow completely only if sections containing straight pores are very thin, and that, in most natural materials, the common pore area at an interface must be greater than that given by random joining. However, the model is still useful in permeability calculations, provided that the fractional area limiting flow is determined from formation factor measurements. INTRODUCTION Two important properties of porous media are permeability k, which describes the ease with which a fluid can flow through a porous medium, and formation factor F, defined as the ratio of the resistivity of a saturated specimen to the resistivity of the saturating liquid which describes the electrical properties of the saturated material. k is defined by Darcy's law,l k= µqL/P Ae . . . . . . . . . . . . . . . [1] where µ = liquid viscosity, q = flow rate, L = length of specimen, p = pressure across the specimen and = - the effective area over which flow occurs, F is given experimentally by Archie's law,2 F = Ø-m ,..............(2) where 4 is porosity defined as the pore to total volume or, for a homogeneous body, the pore to total area; and m lies between 1.3 for loose sand and 2 for cemented sand. Consider a porous body of total cross-sectional area A and length L, saturated with a liquid of resistivity R and with an effective area for conduction of Ae. Then, from the definition of F given previously, F=A/Ae , ................(3) or, from Eqs. 2 and 3, Ae = A Øm ..............(4) Thus, in any attempt to calculate k or F, some assumptions must be made concerning the pore structure of the body and a value derived for A,. To determine Ae, Childs and George3 and Wyllie and Gardner4 suggested an elementary statistical representation often referred to as the cutting and rejoining model of a porous body. The body is assumed to be composed of two or more parallel-sided sections of porosity 4, containing straight, continuous pores with a common pore area of Ø2 at an interface between two sections. The value is given by a random joining of the pores in either section. Two such sections,

Jan 1, 1969

By James J. Scott

Shale formations are the Nemesis of the Mining Engineer. Shales react to changes in environment in the most unusual and unpredictable manner. Increase in temperature may cause spalling, increase moisture and compression induced fractures may occur, and if a full face is exposed it may deteriorate due to atmospheric exposure. Combine only small amounts of shale in layered fashion with hard brittle competent rock and the whole structure may be fractured and fail due to stresses generated in and around the shale. In this paper the author will discuss failure mechanisms encountered under various field conditions and remedial action which may be employed by the engineer.

Jan 1, 1969

By M. Metzger, L. E. Hendrickson

Grain boundary attack in 16 pct HCl was found to be substantially the same at low penetrations in zone-refined aluminum (individual impurities 0.1 at. ppm), superior electrolytically refined aluminum (51 at. ppm), and aluminum with various impurities at much higher levels. It was concluded that impurity atom segregation affecting corrosion would have been detected and that the corrosion susceptibility did not originate in this segregation but in the structure of the boundary. It was pointed out that the significance of most previous studies in this system had been obscured by an unrecognized autocatalytic copper reaction. Although general corrosion rate was also impurity-insensitive , there was shallow pitting attributed to iron seg-regation and a hillocked surface texture associated with copper; these were interpreted as due to cathodic damage affecting- cathode distribution. THE grain boundary corrosion suffered by high-purity aluminum in hydrochloric acid has been the object of some interest (the earlier work is summarized in Ref. 1). The central metallurgical question here is whether the corrosion susceptibility of a boundary originates in its structure or in impurity atom segregation. An attempt to study this question revealed large catalytic effects associated with small quantities of the copper impurity in the aluminum, 220 ppm, or in the corrodent, and these magnified the preferential boundary attack and obscured the intrinsic susceptibility question.' After the catalytic effects had been examined,"' test conditions could be designed to avoid them and methods developed for studying the shallow boundary penetrations prevailing when they were absent.= It then became possible to determine whether intrinsic boundary corrosion in aluminum involves impurity segregation. The older work provided no firm information on grain boundary segregation of specific solutes influencing corrosion although several studies suggested iron segregates.4,5 perryman4 found in 10 pct HC1 that the slowly developing (microns per month) grain boundary grooves were deeper in material of higher iron content (range 10 to 550 ppm, with 5 to 80 pprn Cu) but he did not measure the depths of general corrosion, which were probably several times greater, and his reference surfaces may have varied more than did the groove depths. Metzger and Intrater's results for 20 pct HC~,' which yielded higher time-average rates (mm per month) and deeper penetrations, suggested that boundary segregation of iron (range 4 to 230 ppm, with 22 pprn Cu) decreased the penetration rate. However. in the stronger acid the autocatalytic l.E. HENDRICKSON, Student Member AIME ,and M. METZGER, Member AIME, are Research Assistant and Professor of Physical Metallurgy, respectively, Department of Mining, Metallurgy and Petroleum Engineering, University of Illinois, Urbana, Ill. Manuscript submitted March 11, 1968. IMD effect of the copper impurity is greater1,2 and it is now evident that their corrosion rates had been much magnified by this effect and did not provide a proper basis for the analysis of segregation. In exploratory studies of other solutes (made under the same conditions), 1000 ppm additions of Mg, Mn, or Si or 100 ppm Ca were without effect.1 Montariol6 noted that boundary attack in 22 pct HC1 persisted after zone refining although with fewer deep fissures (ranges 0.06 to 4 ppm Cu, 4 to 23 ppm Fe). Autocatalytic effects may have influenced these results also and those of Perryman.4 The present objective was, as a first step, to see whether quantitative tests designed to exclude autocatalytic influences would indicate the existence of low-level impurity effects on intrinsic boundary corrosion. Comparison of electrolytically refined with zone-refined aluminum of lower copper and iron contents revealed no differences in boundary corrosion, but certain impurity-sensitive differences in general corrosion morphology were noted and investigated further at higher impurity levels. I) EXPERIMENTAL PROCEDURE A) Material. A selection from commercially available material was made with the cooperation of several producers. An electrolytically refined lot (III-A, 1 ppm Cu, 2.4 ppm Fe) studied previously3 provided a starting point. Since material of substantially higher copper content could not be used if the autocatalytic corrosion reaction were to be avoided,2,3 a lot (III-B) of about the same purity was added as a check, two zone-refined lots (I-A and I-B) with copper and iron an order of magnitude lower were selected for comparison, and an intermediate lot (11) was included. Analytical data are given in Table I. For copper in I-B and iron in I-A and I-B, the actual concentration is thought to be near the limit given, i.e., about 0.1 ppm. For titanium, vanadium, and chromium in III-B, the actual amounts are thought to be, like those in III-A, substantially lower than in the zone-refined lots (these elements concentrate in the solid on freezing). Data are given later for some additional lots surveved. B) Specimen Preparation and Procedure. one by 3 cm blanks with a notched stem were cut from 1-mm cold-rolled sheet, annealed 24 hr in air at 650°C, and quenched in an air stream (42°C per sec initial cooling rate, 100 sec to cool to 100°C). The high annealing temperature maximized diffusivities and approach to equilibrium impurity distributions. A water quench, in principle more efficient in preserving the distribution established, was undesirable because the boundaries were almost plane and they tended to shear and migrate during the quench and thus to be separated from any existing impurity atmosphere. Test procedures, previously described,3 involved electropolish-ing, etching 2 min in 10 pct HF at 24.0°C, and expos-

Jan 1, 1969

By D. O. Hobson

Zirconium single crystals of various specific orientations were fabricated by rolling or drawing. The resulting textures were determined and are discussed with respect to the deformation modes that produced them. The crystals deformed in a predictable manner by combinations of up to third-order twinning with three twinning modes and by slip. Twinning was found to play a major role in initial texture formation. Texture changes produced by slip occurred only at the higher reductions. The twinning sequences that produced each intensity peak during the initial reductions could be identified. Schmid factor criteria were found useful in predicting which deformation modes to expect for each crystal orientation and fabrication procedure. The possible application of these data to poly-crystalline material is discussed. PREFERRED orientation or texture has a significant effect on the properties of most materials, causing anisotropy in fabricated cubic metals and enhancing the natural anisotropy of noncubic metals. This study evaluates the effects of several fabrication methods on the textures formed from specific starting orientations of zirconium single crystals and, it is hoped, gives an insight into the effects of the same operations on poly-crystalline material. BACKGROUND In fcc and bcc metals, texture changes take place by gradual lattice rotations caused by the operation of one or more slip systems. Deformation twinning plays an insignificant role in the deformation of such metals. In zirconium and its alloys, however, and in many other hep metals the ability to twin allows very rapid texture changes to be made with very small amounts of deformation. The deformation systems found in zirconium and its alloys are prism slip and three twinning modes.1 Slip occurs on the {1010}< 1120) system. There is little or no appreciable basal slip in zirconium. The twinning planes, illustrated in Fig. 1, are {1012}, {ll2l}, and {1122}. Two twinning modes, the {1012} and the {ll2l} operate for a tensile stress along the basal pole. A compressive stress parallel to the basal pole is required for {ll22} twinning. These twinning operations cause a 35- to 85-deg reorientation of the basal pole. The {1012} twin is the predominant tensile twin at room temperature. The twinning shears, S, are shown in the figure. A criterion for predicting which deformation system will operate when a grain is subjected to a known stress state is the Schmid (orientation) factor. This factor gives the fraction of the applied stress that computer program was written2 to calculate the Schmid factors for the four deformation modes in zirconium. It assumed three orthogonal stress axes and considered ninety-one different orientations of the basal pole in one octant of this stress space. At each basal pole position the Schmid factors were calculated for seven positions of rotation at 10-deg increments of the unit cell about the basal pole. Schmid factors were determined for a total of 637 orientations and for twenty-four deformation systems in each orientation. The program listed the Schmid factors for uniaxial stress parallel to each axis and, to approximate rolling, or-thonormal biaxial stress was also considered. Fig. 2 shows the range of orientations over which the various types of deformation would tend to predominate in biaxial plane strain with the stresses, equal magnitude. The exact boundary position between regions of different deformation modes depends, however, on the relative values of the critical shear stress for each deformation mode. Fig. 2 is drawn on the assumption that they are equal and it therefore may be only approximately correct. It is also recognized that the biaxial stress analysis may not be applicable in certain crystal orientations. EXPERIMENTAL PROCEDURE Single crystals of zone-refined zirconium, produced by Wilson of this Laboratory,3 were electrical-discharge-machined to form specimens for rolling, tube-drawing, and rod-drawing studies. Specimens were rolled at room temperature on 2-|--in.-diam hand-powered rolls from three different starting orientations: 1) the basal plane parallel to the rolling plane and the [1120] in the rolling direction, (0001)[ll20]; 2) the (1120) plane parallel to the rolling plane and the basal pole in the rolling direction, (1120)[0001]; and 3)_the (1120) plane parallel to the rolling plane and the [1100] in the rolling direction, (1120)[ll00]. Drawing specimens were cut with the [0001] direction as the drawing direction in the tube blank and [1120] as the drawing direction in the rod specimen. The drawing

Jan 1, 1969

By James V. Luxner

The airflow and methane distribution patterns developed in an equipment-free entry 6.5 feet high and 12 feet wide, ventilated by line brattice operated blowing to or exhausting from the face, were determined by the Bureau of Mines for varying conditions. Results of these studies show that blowing line brattice systems of face ventilation are more effective than comparable exhaust systems. The face ventilating efficiency of any line brattice system is dependent upon the method of ventilation, the face distance, the tight rib distance, the volume of air delivered to the end of the line brattice, and the volume of methane released at the face. Experimental results indicate that maximum face ventilation efficiency is achieved when the inby terminus of the line brattice is installed 5 feet from the face and at a distance less than one-third the entry width from the nearest rib. Analyses of data are based upon the ability of a face ventilation system to dilute methane in the immediate face area.

Jan 1, 1969

By P. R. Jones

A computer program was written for design and cost of a shell and tube heat exchanger in which the total cost, which includes annual fixed charges and annual operating costs, was minimized. The program was written for the type of heat exchanger in which only the tube side pumping costs were significant and for triangular pitch, single or multiple pass, heating or cooling, and no change in phase. Tube diameter was not optimized since the tube dimensions do not affect the cost very much. However, the tube dimensions do affect the shell diameter, number of tubes, and length of tubes; and price optimum design was obtained for four standard tube diameters. Standard heat exchangers having at least the required area are also listed. The program was made adaptable to various fluids and to various tube dimensions by including many of the required data such as physical properties of the fluids, tube data, and standard shell data as input data.

Jan 1, 1969

By G. R. Love

i\ program has been written which allows fully automatic conversion of data for X-ray intensity, as a function of time, to finished conventional pole figures. The program accepts input data in the serial order in which they are taken and is therefore immediately compatible with automatic data-acquisition devices. From these data taped instructions are prepared for the Calcomp plotter to construct ink-on-paper drawings. Because both Siemens and Norelco pole figure goniometers are used in this laboratory, the program was written for pole figure data obtained from one or more interpenetrating spiral scans during which both the polar angle, @, and the equatorial angle, a, are varied simultaneously and continuously. The reference direction for a scan, that is the point @ = 0 deg, may be chosen coincident with either the normal direction (N.D. figures) or the rolling direction (R.D. figures). In either case the plotted figures are drawn with the transverse direction (a = 0 deg) at the right and the rolling direction at the top. The full, circular, pole figure is drawn as two semicircular figures labeled "front side" and "back side". As presently constituted, the program will also accept data from circular scans taken at constant values of @. In every case the angular coordinates of each intensity entry are generated in the computer from a relatively small number of auxiliary data. The X-ray intensity data are corrected for background scattering by direct subtraction of the intensity measured with 28 set appropriately "off" the Bragg angle. It is possible to enter this correction as an additional spiral scan through the a, @ space; because the background correction does not normally vary rapidly enough to warrant this detailed a determination, the background corrections are entered as one or more auxiliary data. All data are normalized to a multiple of random intensity. The data taken in this laboratory for N.D. figures are normally taken in a reflection geometry from from sheet samples and do not extend beyond <p = 75 deg; for these data random intensity must be determined from separate experiments and entered as auxiliary information. When the auxiliary information is not available, a number is chosen to give intensity values normalized to a scale of 1 to 10. In this laboratory, R.D. figures are based upon hemispherical samples for which data are taken out to @ = 90 deg; for these data random intensity is calculated by direct numerical integration of . sin @ d@ using the trapezoidal rule and the background-corrected values of the input data. Points necessary to the construction of the pole figure are identified by simple linear interpolation between adjacent data points to determine the loci of contour lines. Points lying on a given contour are connected to one another with straight-line segments and the search-calculation-drawing sequence is patterned to assure that different contour lines do not cross, that a single line does not branch, and that lines do not end in space. However, so that there be no ambiguity in the data presentation, all contour lines end at the limits of the input data. Since the curves are constructed of straight-line segments, they are not continuous in their derivatives. However,

Jan 1, 1969

By Paul R. Smith

The theoretical requirements for the flotation d large particles are discussed. A flotation machine is described which has components which meet many of the theoretical requirements for the flotation of large particles. The machine&apos;s salient features include multiple fine-bubble attachment, froth level feeding, quiescence, shallow depth, and short flotation time. Test conditions and results are presented for the laboratory flotation of 10 mesh phosphate, 4 mesh potash, and 1/2 inch coal. In addition, test conditions and results of pilot plant flotation of minus 14 plus 35 mesh phosphate and minus 14 plus 150 mesh phosphate are also presented.

Jan 1, 1969

By G. E. Warner

This paper presents a review and analysis of a highly stratified Burbank sand waterflooding project in Osage County, Okla. Permeability values in this reservoir range from less than 0.1 md to nearly 3 darcys, and 90 percent of the permeability capacity is contained in approximately 26 percent of the reservoir volume. To date, the project has recovered 103 bbl/flood-acre-ft since waterflood initiation, which represents 50 percent of the total preflood cumulative and 12 percent of the original stock-tank oil in place (OSTOIP). The outstanding feature of this project has been the economical recovery of a sizable quantity of oil at water-oil ratios higher than those normally considered prohibitive. Nearly 70 percent of the recovery to date has been achieved at water-cut values greater than 95 percent. An ultimate waterflood recovery of 138 bbl/flood-acre-ft, or 67 percent of the preflood recovery and 16 percent of the OSTOIP, is predicted. The ultimate primary and secondary recovery will be 302 bbl/acre-ft and approximutely 40 percent of the OSTOIP. The actual performance is compared with the predicted performance by both the Stiles and the Dykstra-Parsons methods, and applicabiliry of these methods to this particular reservoir is evaluated. The performance of this project indicafes highly stratified reservoirs can be successfully and economically waterflooded when either reservoir or economic conditions preclude the use of mechanical and chemical means of mdbility control. Introduction The concept of the stratified reservoir has been used by reservoir engineers for many years to describe the vertical variations in permeability within a reservoir. Numerous techniques have been advanced to predict the expected waterflood performance of the stratified reservoir, and in most cases they prove reasonably accurate. The advisability of undertaking a prospective waterflooding project is determined, based on these predictions. This paper presents a review of a waterflood project in a highly stratified reservoir that normally would be considered a marginal prospect, at best, when evaluated with any prediction technique properly adjusted for reservoir conditions. This kind of project can be successful if the predictions are used to design a waterflooding system capable of economically recovering an oil cut of 1 to 2 percent. Experience gained in the early stages of the project&apos;s development was profitably applied in the later development of the entire reservoir and could prove beneficial to other projects with similar reservoir stratification or fracture characteristics. The East Burbank pool waterflooding operations have been developed in three separate stages, each of which has been a separate project: Mid-Burbank Unit, Flood A, and Stanley Waterflood. When referred to collectively, these projects will be called the Composite Project. The Skelly Oil Co.&apos;s Barber lease — the only portion of the pool not included in the three projects — is operated as a separate facility with a cooperative injection-well agreement. It contains less than 80 productive acres and would not significantly affect the over-all performance picture.

Jan 1, 1969

By Forrest T. Moyer

The safety record of the metal mining and milling industries in 1965 is reviewed by the Bureau of Mines. The overall injury-frequency rate of 23.77 per million man-hours was 5 percent lower than in 1964 and was the lowest annual rate in a statistical history beginning with 1931. The injury-severity rate of 3,521 days lost per million man-hours in 1965 represented a 5-percent improvement over 1964. However, the total of 3,825 disabling work injuries comprised 61 fatal and 3,764 nonfatal injuries, one and 92 more, respectively, than in 1964. At primary nonferrous smelters, refineries, and reduction plants, the injury-frequency rate of 8.97 per million man-hours in 1965 was 13 percent lower, but the severity rate percent higher than in 1964. these plants in 1965, 4 more of 1,173 days lost per million man-hours was 17 There were 12 fatal and 971 nonfatal injuries at and 28 fewer, respectively, than in 1964.

Jan 1, 1969

By Verne E. Hooker

In situ stresses, based on isotropic and anisotropic relations, were evaluated using computer techniques from overcoring data obtained in dimension stone quarries along the Appalachian Piedmont, the Ozark Uplift, and the Ouachita Tectonic Belt. Stresses in the horizontal plane near the surface are compressive and range from 100 to 4,500 psi. The direction of maximum compressive stress seems to be alined with the general tectonic structure for most of the determinations. The ratio of the maximum to minimum elastic parameters in the horizontal plane ranges from 1.05 to 2.46 for these competent rocks. Isotropic versus anisotropic stress determinations show differences only as great as 25 percent in stress magnitude and 25° in orientation.

Jan 1, 1969

By Wesley T. Holmes

In this final stage of a three-part investigation of the smelting of titania-bearing iron materials, the Bureau of Mines conducted semicontinuous smelting tests in a laboratory electric arc furnace on four concentrates and one are. The objective was to substantiate the significance of liquidus temperature measurements in predicting satisfactory slag compositions in electric furnace smelting of titaniferous magnetites to produce pig iron. Previously obtained liquidus temperature data were used in determining flux requirements. Self-fluxing pellets of either ore or concentrate plus fluxes and reductants were made to produce pig iron and slags containing 0.2 to 0.6 percent titanium. Individual constituents of the slags generally agreed within 5 percent with the value of the corresponding constituent of target composition. Liquidus temperature of furnace slags generally agreed within 50° C of the value obtained from corresponding nominal synthetic slag. The results of the three phases of the investigation may serve as guide-lines for determining flux requirements in smelting a wide variety of titaniferous magnetites and other titania and iron-bearing materials.

Jan 1, 1969

By S. K. Asunmaa, W. D. English, N. A. Tiner, W. A. Cannon

This paper discusses the reaction of metal surfaces with fluorine. Fluorination reactions result in the formation of metal fluoride films which are "passive" toward further reaction of the metal with fluorine. These films are very adherent, and do not easily detach from the substrate metal by mechanical flexing or thermal shock. Exposure of passive films to a humid atmosphere produces hydrated metal fluorides which cause secondary fluorination reactions upon reexpo-sure of the metal surface to fluorine. The surface films formed range from 10 to 30A in thickness and they pow at the expense of surface oxide films. The apparent film formation is completed rapidly in 15 to 30 min on stainless steel and nickel surfaces. On copper and on Monel surfaces, the film at first grows rapidly, then increases slowly over an extended period of time. Passive films are formed at all fluorine pressures in the range from 0.1 to 1.4 atm at room temperature. ALL metals react when exposed to fluorine. These reactions generally produce surface films which consist of metal fluorides. The rate of reaction is largely determined by the extent to which these films are protective. Although there is an extensive literature concerning reactions of oxygen with metals, there are very few investigations reported concerning fluorine-metal reactions. Brown, Crabtree, and ~uncan&apos; investigated the kinetics of the reaction of gaseous fluorine with copper metal which had been freshly reduced in hydrogen. The reaction rate was independent of pressure over the range from 6 to 60 torr. A logarithmic rate law was obeyed in the temperature range from 25" to 300" ~. There was some deviation at higher temperatures which could have been the onset of a parabolic law. The calculated film thicknesses ranged from about two molecular layers, 10A, for 5 hr exposure at room temperature to thirty-five molecular layers for 5 hr exposure at 200" . The authors concluded that no single mechanism could explain all the observations. O7Donnell and spatkowski2 studied the reaction of fluorine with copper at 450°C at pressures from lo to 133 torr. The reaction was found to be pressure -dependent and followed a logarithmic rate law. It was not entirely diffusion-controlled, and fluorine was thought to be the migrating species in the reaction. Miscellaneous metal-fluorine reactions were investigated by Haendler et ~1.~ Reaction products were identified but no rate data were determined. Air Prod- ucts and Chemicals, Inc., have conducted an investigation of reactions between fluorine and various metal powders at room temperature and 85° C. Fluoride film thickness as a function of time of exposure was reported on the assumption that the reaction takes place between fluorine and metal to form the normal metal fluoride. Surface areas of the powders were only estimated so the relative film thicknesses may not be exact. The data showed reaction rates which were generally logarithmic in character, the rate of film growth virtually ceasing after a few hours exposure time for some alloy powders. The effect of moisture on fluoride films was also investigated by measuring additional reaction with fluorine after exposure of passivated powders to atmosperic moisture. The fluorination of iron was studied by 0&apos;~onnell~ at temperatures from 225" to 525" ~ and at pressures ranging from 20 to 200 torr. In all ranges, the reaction followed a logarithmic rate law and was dependent on the square root of the gas pressure. The author concluded that fluorine gas passes through pores in the film. As the film grows, the blocking of pores leads to a rapid decrease in reaction rate; hence a logarithmic rate law is observed. Jarry, Fischer, and Gunther&apos; investigated the mechanism of the reaction of fluorine with nickel at about 600" to 700°C. On the basis of the metallographic examination of fluoride scales growing on the nickel and from separate radioautographic data, it was claimed that fluorine is the migrating species in the reaction. This is in sharp contrast to the growth of oxide films on nickel where it has been shown that nickel ions migrate through the scale to the gas-solid interface to react with oxygen. Few investigations have been reported of the reaction of fluorine with metal oxides. Such investigations should be of great significance for a better understanding of passivation in view of the ubiquitous oxide films on technical alloys. Haendler et al.3 studied the reaction of fluorine with oxides of copper, tin, titanium, zirconium, and vanadium. Copper (I) oxide reacted as follows in the temperature range 150" to 300"~: temperature above 300" ~ was required for the CuO to react to form additional copper fluoride. Ritter and smith7 also investigated the reaction of fluorine with copper (11) oxide. An oxide powder comprised of spherical particles with a fairly high surface area was reacted with fluorine, starting at room temperature and increasing to 100° C over a period of 3 or 4 hr. The initial reaction was slow until the fluoride film thickness reached about to or 15R at which time the reaction rate accelerated, then decreased again. Most of the kinetic data was obtained during this final phase of reaction. The authors conclude that the film grows slowly at first until the stresses developed in the distorted lattice are sufficient to rupture the initial

Jan 1, 1969

By C. Laird, C. E. Feltner

May different kinds of dislocation structures have been observed in strain-cycled metals and alloys. In order to understand their pattern and causes, an experimental program has been carried out to determine the influence on the dislocation structures of the three variables: 1) slip character of the material, 2) test temperature, and 3) strain amplitude. The results show that at high strain amplitudes cell structures me formed when the slip character is wavy, and that these are progressively replaced by uniform distributions of dislocations as the stacking fault energy is decreased. At lower strains, dislocation debris is formed which consists primarily of dipoles in wavy slip mode materials and multipoles in planar slip mode materials. Temperature merely acts to change the scale of the structure, smaller cells, and clumps of dislocation debris being associated with lower temperatures. It is shown that the results for many metals fit this pattern, which Parallels that occurring in unidirectional deformation. DISLOCATION structures produced by cyclic strain (fatigue) have been examined in a number of metals by transmission electron microscopy. These studies have produced a variety of interesting and often seemingly conflicting results. For example, different investigators have reported such structural features as cells.le4 bands of tangled dislocations,4&apos;5 dense patches or clusters of prismatic dislocation loops, planar arrays,4&apos;10 and various combinations or mixtures of these different structures. Most of these observations have been made on materials which were initially annealed and cyclically strained at low amplitudes resulting in long lives. Recently we have reported observations of the dislocation structures produced in copper and Cu-7.5 pct Al cycled at large amplitudes, resulting in lives of less than 104 cycles.4 These results, examined in combination with those in the literature, have suggested that a common or consistent structural pattern exists. Variations in this pattern appear to be determined chiefly by the three variables, namely, the slip character of the material,4,11 test temperature. and the strain amplitude. To verify this interpretation, we have studied [he influence of the above three variables (in different combinations) on the resultant structures in cyclically strained metals. Copper, fatigued at room temperature, was chosen as a reference state to which all other observations can be compared. The effect of slip character has been investigated by employing fcc metals of different stacking fault energy. Thus aluminum which has a more wavy slip character than copper, and Cu-2.5 pct A1 having a more planar slip char- acter, have been examined. The aluminum samples were fatigued at 210°K thus making their homologous temperature equal to that of copper at room temperature. The influence of temperature has been evaluated by examining the structures in copper at room temperature and 78°K. Finally the effect of strain amplitude was studied by looking at the structures at amplitudes giving lives ranging from 104 to 107 cycles. All of the specimens were examined at the 50 pct life level at which stage the structures have reached a stable configuration.12 I) EXPERIMENTAL PROCEDURE Strip specimens, 0.006 in. in thickness, were prepared from base elements of 99.99 pct purity or greater. Specimens were fatigued by cementing the strips to a lucite substrate which was subjected to reverse plane bending. This method of testing has been described e1sewhere.7 After fatiguing, specimens were thinned and examined in a Philips EM 200 which was equipped with a goniometer stage capable of ±30-deg tilt and 330-deg rotation of the specimen. On the basis of separate calibrations,13 allowances were made for the relative rotation and inversions between the bright-field images and the diffraction patterns. II) RESULTS AND DISCUSSION The life behavior of the materials under different test conditions is shown in Fig. 1 in the form of plots of total strain range vs cycles to failure. Comparisons of structures produced in the different materials were made at amplitudes which produced equal numbers of cycles to failure. The influence of strain amplitude on the structures produced in the reference state material (copper tested at room temperature) is shown in Fig. 2. At the 104 life level the structure produced comprises cells similar to those previously observed.3,4 They are approximately 0.5 p in diam and the cell walls are generally more regular or sharper than those produced by unidirectional deformation.14 At the 10&apos; life level the

Jan 1, 1969

By Donald S. Colby

This Bureau of Mines report is essentially a handbook, or manual, for making the type of mineral resource valuation commonly required for such public policy problems as mineral leasing. The principle of resource valuation through the capitalization of cash flow is well established. A mathematical procedure, based on a simplified accounting system, is detailed for calculating cash flow from revenue, plant costs, and operating expense. Variations of procedure cover cost depletion, percentage depletion, and depletion limited to 50 percent of net income. The influence of the depletion provisions of the tax regulations on the value of a resource to an owner and to an operator is analyzed. The relationship of royalty, bonus payments, and sales price to resource value is also described, and methods for approximating resource values using these payments as input data are developed.

Jan 1, 1969

By T. S. Lundy, R. A. Padgett

The fact that cobalt diffuses in silver at a much slower rate in a region near a free surface than in bulk material has been demonstrated in a variety of experiments. Various possible mechanisms of this near-surface effect (NSE) are examined in light of experimental evidences. The tendency for surface segregation of some solute atoms appears to be a likely mechanism to explain the effect. UNIDIRECTIONAL and isothermal diffusion from a plane source of radioactive tracer into an isotropic, homogeneous medium follows the Gaussian solution to Fick&apos;s second law, or: where A(x,t) is the position and time-dependent concentration of the diffusing species, M is the quantity of diffusant per unit area initially at x = 0, and D is the diffusion coefficient. For a given time, say t = tl, one can easily see that: d In Aixji)_____1_ r2] d(x2) 4Dti Thus, if diffusion data obtained by serial sectioning are plotted as In A(x,tl) vs x2, the diffusion coefficient is obtained from Eq. [2]. The ideal behavior seldom is observed in real systems. Deviations from ideality generally occur either at small or large values of penetration distance. The overall picture is shown schematically in Fig. 1 where Regions I, 11, and 111 are due, respectively, to some near-surface effect or effects (NSE), volume diffusion, and short-circuiting effects. For different systems and conditions of specimen preparation and analysis, the relative importance of Regions I, 11, and I11 may be drastically different. Region I is completely absent in many systems and there is no NSE. In others, however, there may be considerable difficulty in determination of volume diffusion coefficients due to the overshadowing influences of Region I. Such is particularly true when indirect techniques such as the surface concentration decrease or the Gruzin method&apos; are used to find D. In this paper several experiments which had as their goal a better understanding of near-surface effects are reported. Specifically, it is well-known that unusual penetration behavior results for the diffusion of several impurities in ilver- and that considerable controversy exists with regard to interpretation of the published diffusion data. We chose to examine those unusual results which occur for cobalt diffusion in monocrystalline silver395 primarily because knowledge of experimental procedures and materials were readily available. Both radioactive co60 and co5&apos; could be utilized to offer a wide range of available concentration of the diffusing species. Experiments were also performed on the diffusion of AgnO in silver. They gave base-line data for the system—both for technique evaluation and for examination of the vacancy distribution near the surface. I) PROCEDURES Cylindrical-shaped specimens 1.25 cm diam and 1 to 1.25 cm long were cut from 99.999 pct Ag single crystals obtained from Monocrystals Co., Cleveland. One end surface of each specimen was polished flat and etched with a mixture of 20 ml saturated Cr03 solu-tion-20 ml H20-3 ml concentrated HC1. Radioactive tracer (co60 or co5&apos; or Ag&apos;lO, each having a radio-chemical purity of greater than 99 pct) was deposited onto the prepared surface either dropwise with evaporation to dryness of the solution containing the tracer (0.5 N HC1 solution for the co60 and co5&apos; and 0.6 N HNO3 solution for the A"&apos;), by electroplating, or by evaporation from a tantalum or tungsten filament in an evacuated bell jar. The amount of deposited cobalt was varied from many atomic layers of cobalt containing the co60 to approximately one co5&apos; atom per lo6 surface atoms of silver. This large variation in amount of deposited cobalt yielded information about both the influence of a thick-source layer of tracer and solubility effects on the NSE. Such variations were possible because of the large differences in half-lives,

Jan 1, 1969

By N. J. Grant, Per Knudsen, J. T. Blucher

The fatigue behavior of three SAP alloys was studied in ternzs of strain rate and temperature, at high strains. The k values in the modified Manson-Coffin equation, Nk4 = C, were less than 0.5 under all test conditions, and change with strain amplitude for the lower-oxide alloys at about 2 pct strain. Lowest k values were near 0.25. Strain rate had no effect on life at 80 F, but had an increasingly greater effect with increasing temperature above 500". Life decreased with decreasing strain rate, above 500"F, and with increasing temperature. Ductility at fracture in a tension test was indicated to be an important factor in determining 1ife in these big+-strain tests with the SAP alloys. INEVITABLY, in the course of mechanical tests at elevated temperatures, particularly if significant time at temperature is involved, there are large changes in structure; these changes make it difficult to relate behavior patterns over ranges of temperature or strain rates at high temperatures. Such changes are to be expetted in low cycle fatigue at low strain rates and high temperatures. Accordingly, it was of great interest to examine the low cycle fatigue behavior of SAP / an aluminum oxide dispersion-strengthened aluminum, a type of alloy which had shown unusual structure stability to temperatures as high as 1000" to 1150°F and resisted recrys-tallization essentially to the melting temperature.&apos;j3 Since the matrix is pure aluminum, there are no complications of averaging, agglomeration, or phase solution. It was also desirable to check the Manson-Coffin equation4?&apos; for the SAP alloys, namely N~E~ = , where ep is the total plastic strain amplitude, k and C are constants, and N is the number of cycles to failure. Here, too, was an opportunity to check the roles of temperature and strain rate with a very stable material. Tavernelli and coffin6 had concluded that k had a value of about 0.5 for many alloys and C was equal to ~/2, where E is the fracture ductility determined from a static tension test. The results were obtained from low-temperature tests where creep and diffusion processes are unimportant. Manson7 found k = 0.6 fitted his data reasonably well; however, in later analyses of a large amount of low cycle fatigue data generated at room temperat~re@"~ he found k to vary from 0.6 for short lives to 0.21 for long-life fatigue tests. In the latter studies,89g Manson separated the total strain range into elastic and plastic components when he found that k was influenced by the nature of the strain. The use of EL (total strain) instead of EP (total plastic strain)4&apos;5 makes a difference in the resultant k value. The ratio of changes with temperature, strain rate, and strain; further, there are the problems in the determination of the elastic strain. Based on these considerations, and the improved fit of points in a plot of by Wells and Sullivan,&apos; is also utilized in these studies. Anderson and wahl,14 using commercial 1100 aluminum, and Blucher and Grant,15 using 99.99 pct pure aluminum, found an increase in life with increasing test temperature. Anderson and Wahl were the first to report low cycle fatigue results from SAP materials. With increasing temperature, the role of strain rate becomes more important. In this regard, care must be exercised to differentiate between frequency (wherein strain rate may vary from zero to a maximum in each cycle, sinusoidally, for example), and constant strain rate, as used in the present study, in a saw-tooth type cycle; in the latter case, the frequency is not specified but can easily be calculated from the strain and strain rate data. It has generally been found that life in low cycle fatigue tests decreases with decreasing frequency16 or with decreasing strain rate at elevated temperatures.15 Coffin,17 reviewing Eckel&apos;s work,16 also reported that k increased with decreasing frequency for acid lead, yielding values from 4.0 at a frequency fo 6.6 cycles Per day to 1-46 at a frequency of 7440 cycles per day; the value of k decreased to 0.58 at a frequency of 2.38 x lo6 cycles per day. EXPERIMENTAL PROCEDURE Three SAP alloys, of two nominal compositions, were tested. Alcoa supplied XAP 005 as 2-in.-diam extruded bar, of nominal composition A1-7 wt pct A1203. The Danish Atomic Energy Commission supplied SAP 930 (A1-7 wt ~ct Ala3) and SAP 865 (A1-13 wt pct Al&) manufactured by Swiss Aluminium Ltd., in the form Of $-in.-diam extruded rod. Metallographic comparison of the structures of XAP 005 and SAP 930 showed the former to have a more uniform oxide distribution. Button-head specimens were machined in the longitudinal direction of the bar with 0.4 in. gage length by 0.2 in. diameter, with a fillet radius of j-B in. After machining, the specimens were electropolished in a 1 to 4 mixture of perchloric acid to methanol to remove all machining marks. All test bars were in the as-extruded condition. The fatigue tests were performed on a hydraulically activated, axial strain machine, with complete reversal of strain.15 Test conditions were:

Jan 1, 1969

By Ronald J. Roman

A mathematical model was developed for the grinding and flotation section of Union Carbide&apos;s Bishop mill and this model was used to indicate how variations in grind, retention time, and calcite and fluorite content effects the mill capacity, tungsten units produced, and the grade and recovery of the scheelite concentrate. A model such as this is a starting point in determining the economic optimum running condition for a mining and milling operation and an example of this is given.

Jan 1, 1969