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By Roger J. Araujo

A photochromic material is one which undergoes a change of color when exposed to light and reverts to its original color when the light is removed. Review articles carrying extensive bibliographies have been written by Brown and Shaw (1) and by Schwab and Bertelson (2). Organics. Schwab and Bertelson divide the reactions in different organic photochromic materials into some half-dozen categories; Windsor (3) reduces these to the following three main classes of general interest, based on how they work. 1. Stereoisomers. Absorption of light breaks one of the chemical bonds in a. ring molecule, thus allowing the molecule to unwind and form a different geometrical arrangement. The reverse process is a reforming of the bond. Examples of this class are the spiropyrans and the anils. 2. Dyes. A triphenyl methane dye, for example, is oxidized by energetic light; the absorption characteristics of the positive ion so formed are different from those of the original electrically neutral benzene rings. 3. Triplet States. In the class of polynuclear aromatic hydrocarbons, ground-state molecules are excited first to a singlet state by irradiation, and then go, via the lowest triplet state, to an excited triplet state. Visible light is absorbed in the triplet-triplet transition.

Jan 1, 1970

The production of harmful pollutants from coal mines and/or from coal and associated strata has been a recognizable fact in the United States for over two hundred and seventy years. In 1698, Gabriel Thomas observed(l) that the colored water flowing from streams in this country was similar to that which flowed from the coal mines in Wales. Hence, water pollutants such as acid were being produced before any known coal mines were operating in this country. The coal mining industry has contributed to the increase of pollution by exposing large amounts of sulfide materials that enable the reaction of water, oxygen and sulfur containing materials to form acid. A map of the United States coal fields can be seen on Figure 1. The anthracite regions of Pennsylvania, although small when compared to the total reserves, have produced some of the country's major water problems. The map indicates the extent of bituminous reserves of the Appalachian and midwest regions. Also evident are the bituminous, subbituminous and lignite coal reserves in the west which have recently come into greater demand. Acid mine pollution is encountered in numerous states, but the major problem is found in the Ohio, Susquehanna, and Potomac River basins.(2) Most coal beds contain some sulfur which may be in the inorganic, sulfate, or sulfide form, and thus have the potential to produce sulfuric acid. However, much of the strata that overlays the coal beds also contains acid neutralizing materials. Therefore, the amount of acid produced depends upon the amount of both acid and alkali materials that dissolve in the water in any given mine. The common sources of sulfurous material in the seam or surrounding rock are generally called sulfur balls or "nigger heads" by the miners. Sulfur balls that have been observed(3) seem to be equally divided between those containing sulphuritic iron capable of producing sulfuric acid upon oxidation and those that are primarily calcium carbonate. It has been observed in many instances that two types of water, acid and alkaline, are being produced in the same mine. A study of the geological strata and a survey of subsidence, faults and sulfur balls will usually give some indication of why this happens. The reaction of pyrite (FeS2) with oxygen and water to form ferrous sulfate (FeSO4) and sulfuric acid (H2SO4) by a series of complex chemical interactions is well documented but not well understood.(4,5) However, it is well known that the reactions to form the acid cannot occur unless all three constituents are present. Since pyrite is inherent in most coal seams and air is needed to sustain the miner, the most logical answer is to eliminate water infiltration into the mine, or to remove it from the mine before acids can form.

Jan 1, 1970

By A. D. Kennedy

No major breakthroughs in concentration technology were made during the year, but solid advances were made in engineering. Perhaps the most significant was the growing acceptance of the unified or "systems approach" to mineral extraction, processing, refining, transportation and marketing. Under the systems approach, transportation is no longer some- one else's business, but a high cost item within the planning engineer's purview. The Savage River pipeline 1,2 and the Marconaflo process3,4 for land and ocean transport of iron ore slurry, are examples showing that evaluation of transportation as part of a unitized system can lead to innovation, and the determination of the physical location of some of the operations. There is even speculation that the cost reductions possible by ocean transport of iron ore slurry may bring in more plants using direct-reduction steelmaking processes.4 Some perennial problems can be solved by application of the systems approach; for example, under this concept the replacement of three small shovels in the pit with two larger shovels is not permissible on the basis of lower operating costs; the resulting change in ore blending upon metallurgical performance must first be evaluated to prove whether or not the change is economically beneficial to the entire operation (perhaps new storage-blending facilities will be indicated).

Jan 1, 1970

By J. E. Murphy

Purification of samarium metal by sublimation and by vaporization from a low-melting metal flux, at the same temperature, were compared. Vaporization proved more effective for removing impurities such as magnesium, calcium, and manganese. Recovery of samarium, however, is more rapid by sublimation because of its constant rate of distillation.

Jan 1, 1970

By H. Stuart, L. Zwell, N. Ridley

specimen that was subjected to 700°C for 250 hr is shown in Fig. 2(c). The precipitates in this foil appear round and exhibit only very faint strain contrast. From this evidence, along with that described above for the symmetry of the strain field, it may be concluded that this coherent precipitate is spherical, which is generally the favored shape for coherent precipitates when the lattice parameter mismatch is small.12 These observations are consistent with the assumption that this precipitate is the y' (Ni3Al, Ti) phase. y' is known to be spherical in the early stages of precipitation. It is fcc and is similar in composition to the matrix and thus would have contrast similar to that of the matrix as do these precipitates. Direct identification of the spherical precipitate did not prove possible because of its low volume fraction and small size. The results of this investigation suggest that the increases in yield strength and the decreases in elongation observed in 45-Fe 30-Ni 20-Cr alloys containing about 0.4 pct A1 and 0.4 pct Ti on prolonged aging at 550" to 700°C are very likely due to the presence of a coherent, spherical precipitate, thought to be y'. Mi-crohardness measurements indicated that the precipitation of semicoherent M23C6 resulted in some matrix hardening. However, this precipitation process occurs much more rapidly than the changes in mechanical properties at these temperatures. 1C. L. Clark, J. J. B. Rutherford, A. B. Wilder, and M. A. Cordovi: J. Eng. Power, 1962, vol. 84, p. 258. 2 F. A. Comprelli and U. E. Wolff: USAEC Report GEAP-4745, General Electric Company November, 1964. 3C. N. Spalaris: A Monograph, USAEC Report GEAP-4633, General Electric Company, July, 1964. THERE have been many X-ray investigations of the room temperature lattice parameters of austenite which has been retained in quenched steels of various carbon contents. The results of these investigations have been collected by Wrazej,1 Wever et al.,2 and by Roberts3 and are included in Fig. 1 due to Pearson.4 The dashed line in Fig. 1 was considered by Roberts3 to most reliably describe the variation with carbon content of the lattice parameter of retained austenite. This line is given by the equation: a (Å) = 3.555 + 0.044 wt % C and recent unpublished measurements by one of the authors (LZ) support this relationship. The object of this communication is to draw attention to a relationship which describes the variation of the room temperature lattice parameter of 'equilibrium' austenite with carbon content, and which is different from that for retained austenite. The relationship a(Å) = 3.573 + 0.033 wt % C has been obtained from lattice parameter measurements made on equilibrium Fe-C austenites at elevated temperatures, which have been extrapolated to room temperature. The room temperature lattice parameter of 3.555Å which the Roberts' relationship gives for pure y-Fe is no: in agreement with the value of 3.573Å obtained when the high temperature lattice parameter data of Basinski et aL.5 and of Goldschmidt6 is extrapolated to room temperature. A linear extrapolation was

Jan 1, 1970

By Robert H. Merrill, Raymond M. Stateham

Recently, the Denver Mining Research Center of the U.S. Bureau of Mines began tests to detect hazardous or potentially hazardous conditions in or around mines with infrared measurement devices. Among the many potential uses of infrared detection techniques are the location of misfires, underground mine fires, combustion in waste dumps, underground water courses and loose rock. However, the primary emphasis has been placed upon the detection of loose rock in roofs, pillars and faces in underground mines. The rock along the edge of an underground opening is subject to two temperature environments: the temperature of the air in the opening, and the temperature of the rock surrounding the opening. Assuming that the rock on the edge of the opening is solid, the rock will reach an equilibrium temperature that depends upon the temperature and flow of the air, the thermal conductivity of the rock and its ambient temperature. Presume that a loose rock exists among this solid rock; because there is a temperature barrier, to some extent, between the loose and the solid, the loose rock will be affected more than the solid rock by the temperature of the air. Therefore, depending upon the temperature differences between the rock and the air, the loose will be warmer or cooler than the solid.

Jan 1, 1970

By G. L. Gates

Five possible sources of water for waterflooding of petroleum reservoirs in the arid San Joaquin Valley of California were considered. Three of them (water produced with petroleum, water from a shallow saline aquifer, and waste irrigation water) were analyzed chemically; laboratory information for one (sea water) had been developed during a previous study. A series of laboratory tests made on the fifth source (fresh water) determined the solubility of calcium sulfate dihydrate in water. Laboratory analyses included the following: Chemical analyses of water produced with petroleum and waste irrigation water; solubility of calcium sulfate dihydrate in water and brines; the effect of excess sulfate on the solubility of calcium sulfate in brines; the presence of sulfate-reducing bacteria; and the permeability of cores from a petroleum reservoir to air, to water from other petroleum reservoirs, and to waste irrigation water. The results showed that most of the waters and mixtures of waters are compatible with petroleum reservoir waters and are generally suitable for injection. The calcium content of some of the formation waters is quite high, and care must be taken to prevent precipitation of calcium sulfate dihydrate. The permeability of the few cores tested was about the same to water and brines as to air, indicating that formation damage due to clay swelling will not be serious. The waters most likely to be available for injection are water produced with petroleum, water from shallow saline aquifers, and waste irrigation water.

Jan 1, 1970

By Martin F. Littmann

Inclusions of MnS and Fe3C have been introduced into single crystals of 3 pct Si-Fe to study their effects on recrystallization behavior and textures after cold rolling and annealing. The presence of MnS in (110) [001] and (111)[112] crystals inhibited primary grain growth and promoted secondary recrystallization but did not alter the texture significantly after annealing at 1200°C. The presence of Fe3C in (llO)[OOl] and (100)[001] crystals caused a refinement of the primary re crystallized grain size but did not promote secondary recrystallization. THE texture behavior of single crystals of 3 pct Si-Fe during deformation and recrystallization has been studied by numerous investigators. The early work of Dunn&apos; followed by Decker and Harker2 involved relatively small cold reductions. More detailed studies of Dunn3&apos;4 and of Dunn and Koh5&apos;6 involved a reduction of 70 pct and recrystallization at 980°C for several crystals. Walter and Hibbard7 studied a greater variety of initial orientations and sought to relate the textures to those of polycrystalline material. Attention was focused on the nucleation process during early stages of annealing and on surface energy effects in studies by Walter and Dunn8 and by HU.9&apos;10 One of the most extensive investigations has been reported by T. Taoka, E. Furubayashi, and S. Takeuchi.11 Most of this work has been conducted using relatively pure crystals with minimal amounts of precipi-tate-forming elements such as carbon, oxygen, sulfur, and nitrogen. Recently, however, S. Taguchi and A. Sakakura have observed that AIN precipitates can alter the recrystallization textures of rolled (100)[001] crystals.12 The present studies were initiated to determine effects of MnS and Fe3C precipitates on recrystalli-zation and grain growth behavior of rolled single-crystals of 3 pct Si-Fe. Both of these types of inclusions play significant roles in the recrystallization behavior leading to the formation of the (110)[001] or cube-on-edge texture in commercial grain-oriented silicon iron. It is well known that (110)[001] primary grains are formed by recrystallization of (110)[001] or (11 l)[ 112] crystals after cold reduction of about 60 pct or more. Crystals of these orientations, therefore, were selected for study of the effect of MnS in-clusions on grain growth. On the other hand, a major component of the texture of cold-rolled, polycrystal-line 3 pct Si-Fe is the (100)[011] orientation. The function of Fe3,C inclusions is of interest for this orientation. EXPERIMENTAL PROCEDURE The single crystals used are listed in Table I and were obtained from commercial Si-Fe alloy processed to produce (110)[001] and (100)[001] texture by secondary growth. The cube-on-edge material was 0.59 mm thick. Suitably large (110)[001] crystals 25 mm wide were selected and their orientations were determined using an optical goniometer. Etch pits for texture determination were formed by a ferric sulfate solution. The other crystals used in the study with (100)[001], (100)[011], and (111)[112] orientations were obtained from sheet which contained large grains developed from secondary recrystallization by a surface-energy driving force.13 Most crystals had a (100) plane very nearly parallel to the sheet surface and the rolling direction could be selected readily. The same sheet also contained a few crystals with (111) planes parallel to the sheet surface, these also being a result of growth by surface energy. The crystals selected from the sheet were about 25 mm wide and 0.25 to 0.28 mm thick. As shown in Table 11, the crystals already contained about 0.070 to 0.10 pct Mn. Inclusions of MnS were incorporated into crystal 36 in the following manner. The crystals were first sulfurized by holding them Table I. Initial Orientations of Crystals Crystal No. Initial Orientation Thickness, mm Special Treatment 34 (I10) [00l]* 0.59 None 36s (110) [001] 0.59 Sulfide precipitates added 30,40 (111)[Ti21 0.28 None 43s (III) [Ti21 0.28 Sulfide precipitates added 37 (100) [Oll] 0.30 None 37C (100) [01I] 0.27 Carbon added 41 (100) (01I] 0.25 None 41C (100) [OI11 025 Carbide precipitates added 42 (100) [OOl] 0.25 None 42C (100) [001] 0.25 Carbide precipitates added *Tilted 4 deg to r~ght about R.D. Table II. Compositions of Crystals Special Treatments Base Analysis ~ ______________________£________________Crys- Crystals Pct Si Pct C Pct Mn Pct S Pct N Pct Al tal Pct C Pct S 34.36 2.93 • 0.099 <0.005 - 0.0014 36S 0.011 30.37 to 42 2.78 0.0057 0.070 0.001 0.0008 0.0011 43S 0.022 37C 0.029 -41C 0.028 -42C 0.026 *Estimate 0.004 pct. Oxygen estimated <0.003 pct on all samples

Jan 1, 1970

By Pedro Bolsaitis, Paul M. Sullivan

The activities of zinc in liquid Zn-A1 alloys in the temperature range of 1000&apos; to 1160°K were determined by means of the isopiestic technique. The results are in reasonable agreement with the previous values determined by the radioactive tracer dew point method. Slightly negative excess entropies of mixing were found. The measured activities suggest that the a function for these alloys is not a constant, as has frequently been assumed, but is better represented by two straight line segments of different slopes. THE thermodynamic data of Al-Z alloys have been the subject of investigation by many authors. However, in the recent compilation of such data by Hult-gren et al.,5 the conclusion is reached that none of the previous measurements are reliable or consistent with each other. Since then two new sets of measurements have been reported,2, 8 both laying claim to good accuracies, yet showing very significant disagreement in the measured activity coefficients of zinc in Zn-A1 alloys and in the magnitude and sign of the excess entropies of mixing. Information on the thermodynamics of the system is of particular interest for interpreting results of the Bureau of Mines research on refining of zinc by distillation of die cast scrap. The present study was undertaken as an independent check on the recent values obtained from dew point measurements 8 and electromotive force measurements.&apos; The isopiestic method, first introduced by Herasy-menko,&apos; was chosen because it is one of the few thermodynamic techniques which, in principle at least, is carried out under perfect equilibrium conditions. The disadvantage of the method is that data are obtained at various random compositions and temperatures, which makes the interpretation somewhat cumbersome. The random errors arising from temperature gradients and fluctuations appear to be comparable to those of other techniques, as evidenced by the magnitude of the estimated uncertainties in the calculated integral thermodynamic quantities. An advantage of the method is that each run provides a relatively large amount of data; thus, it is less time consuming than those methods where samples of each composition must be measured individually. EXPERIMENTAL PROCEDURE The activities of zinc in liquid Zn-A1 alloys were measured by the isopiestic method which uses the principle of the tendency toward equilibrium of a series of samples at various temperatures under an imposed vapor pressure of the more volatile component (i.e., zinc, in this case). The basic apparatus is shown in Fig. 1. The small graphite crucibles that contained the metal samples were 15 mm ID and 13 mm deep with approximately 3 mm wall thickness. Each crucible was notched at the top and bottom to allow easy passage of vapor from one to another. At the beginning of an experiment each crucible was weighed on an analytical balance. Zinc and aluminum of spectrographic purity (99.999 pct) were then weighed into the crucibles. The amounts of each metal added were such that initial compositions varied above and below equilibrium values. One crucible contained only pure zinc. After weighing, the crucibles were stacked with the pure zinc on the bottom (corresponding to the lowest temperature in the furnace) and richest aluminum alloys at the top. The entire stack of crucibles was then placed in the silica glass container "E" which was then sealed under vacuum. Sixteen to twenty calibrated Chromel-Alumel thermocouples were attached by wire along the length of the silica tube, one or more adjacent to each sample.

Jan 1, 1970

Jan 1, 1970

By Peter Soo

Pvestrained Ferrovac E iron has been neutron-irradiated at approximately 90°C to an integrated flux of 1020 nut (E > 0.82 mev]. The irradiation was found to produce an incveased temperature dependence of the flow stress in addition to a greatly increased athemal stress. Measurements of the flow stress and stress relaxation, from which the activation volume and activation energy for slip were deduced, show that neutron irradiation changes the rate -controlling slip process to one based on dislocation interactions with tetragonal distortions which are Produced around submicroscopic interstitial loops in the lattice. The study indicates that without prestraining prior to irradiation the chances of detecting a change in the rate -controlling slip process are greatly reduced because in the initial stages of slip a substantial fraction of the radiation defects are swept out of the slip plane by gliding dislocations. Thus, activation parameters which are subsequently measured are representative of a greatly reduced defect density and would not differ appreciably from those for unirradi-ated material. The large increase in the athermal component of the flow stress is probably connected with the presence of depleted zones in the lattice which are introduced by irradiation. ALTHOUGH fast neutron-irradiation has not been observed to markedly alter the activation parameters for slip in bcc metals,&apos; small but significant changes do occur. Most experimenters agree that irradiation predominantly increases the athermal component of the yield stress.&apos;-= In addition to this, Laidler and smidt7 have shown that in iron irradiated to 5 X 10" nvt and molybdenum irradiated to 10" nvt, changes occur in the activation volumes for slip. A similar conclusion has been reached by Milasin and Malkin8 for irradiated iron. Work by Ohr et a1.5 shows that for Ferrovac E iron, irradiated to 1.2 X 1016 nvt, small increases in the activation energy for slip also occur. So far these changes in the activation parameters have not been explained on a firm theoretical basis. One important factor which would minimize the chances of detecting a change in the slip mechanism upon irradiation is the presence of "channeling" which has been observed in molybdenum,9 niobium,10 and iron.11These channels are formed by gliding dislocations which sweep irradiation defects out of the active slip planes and thereby create zones in which continued dislocation motion is encouraged. The activation parameters for the dislocations gliding in the defect-free channels would, therefore, be similar to those for unirradiated iron and a change in the rate-controlling slip process would be difficult to detect. In the present work, an attempt has been made to reduce the effect of uneven deformation on the measured activation parameters for slip in neutron-irradiated Ferrovac E iron polycrystals, so that a more realistic assessment of the effects of neutron-irradiation could be made. Primarily, the experiments involve the irradiation of specimens which had been prestrained to 9 pct elongation at room temperature prior to insertion into the reactor. It was hoped that the introduction of a large number of evenly distributed dislocations would substantially decrease any channeling effect which might otherwise occur. MATERIAL AND EXPERIMENTAL PROCEDURE The starting material was vacuum-melted Ferrovac E iron, an analysis of which is given in Table I. The standard tensile specimen had a gage length of 1.125 in., a cross-sectional diameter of 0.120 in., and a re-crystallized grain size of 1.2 x 10-3 in. All tensile tests were conducted on a floor model "Instron" tensile machine at a strain rate of 3 x 10-4 per sec. The irradiation of the prestrained specimens was performed in the Brookhaven High Flux Beam Reactor to an integrated flux of 1020 nvt (E > 0.82 mev) at a temperature of about 90°C. All specimens were excap-sulated in high-purity aluminum sheaths which were lightly swaged around the samples to ensure good thermal contact. Subsequent measurements on the irradiated specimens showed that within experimental accuracy the swaging had not deformed them. EXPERIMENTAL RESULTS Fig. 1 shows the flow stresses for a series of unirradiated control samples. In order to produce a comparable dislocation substructure throughout the test sm range, all specimens were prestrained

Jan 1, 1970

By W. E. Horst

In Part I of this paper we describe two techniques that were employed in the development of mathematical descriptions of the size reduction process which takes place in a ball mill. In Part II we show how the comminution model was imbedded in a process model to effect steady-state and dynamic simulation of a closed-circuit grinding operation. Increasing emphasis is being placed on development of approaches whereby the essential characteristics of a process can be succinctly represented in terms of a mathematical description of the relationships that exist among important process variables. This activity, commonly known as mathematical modeling, predates modern electronic computers: however, these computers with their tremendous computational capability have given new impetus to the whole field. Although the computer is quite helpful in the development of mathematical models, the real value to the engineer lies in the fact that computers represent such a powerful tool for simulating systems described by mathematical models. As a consequence, engineers may simulate and thereby study the behavior of complex. interacting, systems over a broad range of process variables and configurations once appropriate process models have been developed for the sequence of steps comprising the process.

Jan 1, 1970

By W. G. Davenport, M. Paneni

Experiments in sheets of mercury and water have confirmed that the dynamics of bubble rise are simi-lur in Liquid metal and aqueous systems. RECOGNITION that bubble/metal interactions are important in pyrometallurgical refining processes (e.g., steelmaking, vacuum degassing, deoxidation of copper) has led to a number of investigations into the dynamic behavior of bubbles rising in liquid metals. Terminal velocities of bubbles rising in mercury (20°C)&apos; and silver (1000" to 1050"c)1,2 have been measured. Good agreement between aqueous and liquid metal systems has been obtained. Shapes of air bubbles rising in mercury have been determined experimentally by Davenport, Bradshaw, and Richardsonl who used a system of electric probes to measure maximum horizontal and vertical dimensions, Fig. 5. In the present work the motion and shape of nitrogen bubbles rising in a thin sheet of mercury (i.e., a "two-dimensional" environment) have been studied with the view of confirming dynamic similarity between aqueous and metallic systems. The use of thin sheets of liquid permitted direct visual and photographic comparisons of bubble behavior in clear liquids and in mercury. EXPERIMENTAL METHOD The thin sheets of mercury or water were held in a clear acrylic plastic container, Fig. 1. The sheets of liquid were 80 cm high by 30 cm wide and 0.47 cm thick. Single bubbles were formed by injecting the desired volume of nitrogen into an inverted semicircular cup (stainless steel). The cup was then rotated into the upright position using an external handle thus releasing a single bubble of measured volume. Nitrogen was injected into the cup from a nitrogen cylinder through the external handle and a hollow rotating axle. The volume of a bubble (volume range 0.01 to 10 cu cm) at any instant was obtained by connecting a soap film meter to a small gas space above the liquid. By this technique any change in the volume of a gas bubble in the liquid (i.e., during cup filling or during rise) produces an equivalent displacement from gas space A into the buret B. This displacement is determined by measuring the movement of a horizontal soap film in the buret. Bubble shapes were determined using single-frame photography. Rising velocities were determined by cinephotography with a 1/100-sec stopwatch in the field of view. In both cases dimensions were referenced to a rule attached to the container surface, also in the field of view. Linear dimensions were measured on projections of the single-frame negatives. Rising velocities were calculated from measured heights of rise (10 to 20 cm) and times of rise. The effects of disturbances caused by cup rotation and by bubble release were minimized by photographing bubbles at a point not less than 25 cm above the cup. MATERIALS Mercury: Technical-grade purified: minimum 99 pct Hg; Johnson Matthey and Mallory Limited, Toronto. Nitrogen: Technical-grade purified nitrogen: 99.99 pct Nz, 0.01 pct 02, trace argon; Air Liquide Canada Limitee, Montreal.

Jan 1, 1970

Jan 1, 1970

By Garrett R. Hyde

Sintered yttria and sintered dysprosia can be used to make single-component thermistors having typical thermistor geometries and operable in the temperature range 500° to 1,200° C. However, at these temperatures, instability of platinum electrodes can contribute a slight aging effect if the thermistor is kept near 1,200° C for long periods. Typical characteristics at 500° C for an yttria disk thermistor 12 mm in diameter and 2 mm thick are a resistance of 12.4 megohms and a temperature coefficient of resistance of -3.8 percent per degree C. Typical characteristics at 500° C for a dysprosia thermistor of the same dimensions are a resistance of 1.84 kohms and a temperature coefficient of resistance of -1.6 percent per degree C.

Jan 1, 1970

By T. R. A. Davey

A Survey of current and recent research and developmental work is supplemented by predictions for processes which should be developed over the reminder of this century.

Jan 1, 1970

By E. B. Brauer, W. Hurst, J. D. Clark

Because of drilling, completion, and workover practices, the permeability around a wellbore generally is different from the permeability of the formation. The zone with the altered permeability is called "skin" and its effect on the pressure or flow behavior of the well is called "skin effect". Hawkinsl has shown that the radius and the permeability of this zone are related to the skin by: If the permeability in the skin zone is less than that of the formation, the skin is positive; if it is more than that of the formation, the skin is negative. If the two permeabilities are equal, s is zero; that is, there is no skin. Van Everdingen2 and Hurst3 have given mathematical solutions to the case of a zone of reduced permeability around the wellbore. This skin effect is illustrated in Fig. 1. They treat the positive skin as a zone of reduced permeability of infinitesimal thickness around the wellbore. When applied to a well with negative skin, however, their solutions lead to the calculated flowing well pressure which is smaller than the formation pressure, i.e., an injection situation. This is a physical contradiction. In this paper, it is shown that this mathematical difficulty can be overcome by assuming an effective wellbore radius larger than the actual wellbore. Existing solutions2"4 are modified to include the effect of an enlarged wellbore radius, and thus enable the engineer to deal with negative as well as positive skins. Theoretical Development Van Everdingen and Hurst,4 through the use of Laplace transformation, obtained the following expression for transient fluid influx into a wellbore: The values for QtD, reported extensively by van Everdingen and Hurst,4 are obtained from the following integral:

Jan 1, 1970

The principal activities of the Bureau of Mines Explosives Research Center (now Safety Research Center) during fiscal year 1968 (July 1, 1967, to June 30, 1968) are reviewed in part 1. Part 2 presents short abstracts of the publications issued during this period in the Bureau series and in other media. Part 3 describes a short study on the thermal decomposition of RDX and HMX not destined for publication elsewhere. ACKNOWLEDGMENTS The Bureau gratefully acknowledges the support received through cooperative agreement in fiscal year 1968 from The Manufacturing Chemists Association.

Jan 1, 1970

By J. M. W. Mackenzie

Recent successful applications of emulsion flotation suggested that a detailed study of some of the physicochemical aspects of the process was warranted. The objective of the current research was to provide general information on the electrokinetic properties of emulsion drops of the type commonly used in oxide mineral flotation. Combinations of the parafin oil Nujol and several long-chain reagents in water were studied with respect to the effect of pH on the surface and zeta potentials. It war concluded that for emulsion drops in the presence of a long-chain reagent but in the absence of any other electrolyte which is adsorbed at the oil-water interface, the surface potential will be some two to four times the value of the zeta potential. During the last decade there has been a revival of interest in the so-called agglomeration, or emulsion flotation (in this paper the term emulsion flotation will be used), process. In this flotation technique, a neutral hydrocarbon oil, together with longcnain reagents, usually of a polar-nonpolar structure, are added to the pulp to function as collectors for specific minerals. The combination of oil and longchain reagent is either emulsified prior to addition to the pulp, or in the pulp itself, and the resulting collector species is an oil-in-water emulsion of a neutral hydrocarbon oil emulsified by polar-nonpolar long-chain reagents. Emulsion flotation has been used successfully in the treatment of ores containing iron, manganese,&apos; and titanium oxides. 2 Two other major and long established applications of emulsion flotation are the flotation of coal and Florida phosphate ores. In recent years, emulsion flotation has been particularly successful in the treatment of ores containing oxide minerals which slime readily and, consequently, are difficult to treat by conventional flotation processes. The recent successful

Jan 1, 1970

By T. T. Field, M. Gell

MUCH has been learned about plastic deformation behavior in crystals through the use of dislocation and slip band etchants. Slip in nickel and nickel-base alloys has previously been revealed by various etching techniques.l-5 The techniques for nickel-base super-alloys4,5 were successful only in the Udimet 700 composition in specific heat-treated conditions. The objective of this work was to develop a more generally applicable slip-band etching procedure. The nominal compositions of the alloys used in this study are listed in Table I. The low carbon Mar-M2OO alloy referred to in the text is the same as listed in Table I with the exception that the carbon content is less than 100 ppm. Mar-M200 and Udimet 700 were solutionized at 2250" and 2150°F, respectively. The aging treatment for both cast alloys was 32 hr at 1600°F and for wrought Udimet 700 was 4 hr at 1975"F, 24 hr at 1550°F, and 16 hr at 1400°F. The new slip-band etching technique consists of a chemical etch followed by a short electropolish, Table 11. Fig. l(a) shows the best result obtained on an internal section of a plastically deformed single crystal of Mar-M2OO when using a conventional slip-band etching procedure which consists of electropolishing followed by etching. Ghostlike traces corresponding to planar slip bands are observed, but the contrast between the bands and the background is weak. Fig. l(b) shows the same field using the new slip-band etching technique. After the etching step of this technique, the same ghostlike traces of Fig. l(a) are observed, but the subsequent electropolishing accentuates the slip bands and the subgrain boundaries while the rest of the matrix is being polished. Longer electropolishing obliterates the slip bands. The new slip-band etching technique makes use of the etchants and electrolytes that are normally used for a given material. Because of this, it should be possible to slip-band etch other nickel-base superal-loys by using existing etchants and electrolytes for a material and following the procedures outlined in the "Comments" section of Table 11. All the illustrative examples given below show internal plastic deformation in single crystals of regular and low carbon Mar-M200 in the solutionized and

Jan 1, 1970