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By Bernard G. Carbajal

The dielectric properties and thermal stability of glow-discharge polytnerized films of styrene, chloro-benzene, and other organics and photoresist filrns are presented. Variations in the glow-discharge polymerization procedure are related to thermal stability. Thermal treatwzents to improve the dielectric properties of both positive (A2 340) and negative (KMER) photoresists are given. THIS study of the dielectric properties of thin organic polymer films is part of a program to investigate the electronic applications of organic materials. Thin organic polymer films have been produced in an ac glow discharge,13 with a low-energy electron-beam process,4 and in an rf dicharge. A process has been developed during the course of this program for forming thin organic polymer films in a dc glow discharge. These glow-discharge polymerized (GDP) films exhibit some useful dielectric and insulative properties. Variations in the properties of the GDP films can be induced by changes in the source material (monomer) andor in the conditions of the glow discharge. Thin organic polymer films can also be produced from typical positive and negative photoresists. Some variations in the properties of the photoresist films can be induced by suitable post-application treatments such as thermal crosslinking. The properties of interest in this study are dielectric constant, dielectric strength, resistivity, and thermal stability. POLYMER FILM PREPARATION I) GDP Films. The GDP films were prepared in a dc glow discharge in an atmosphere of organic monomer vapor. The details of the glow-discharge procedure have been presented previously.6 Briefly, under the influence of a dc glow discharge organic vapors can be polymerized in the vapor phase and the resultant polymer (GDP film) deposits on and in the vicinity of the cathode. Substrates placed behind a screen cathode can be uniformly coated over all exposed areas. Pattern definition can be achieved using normal mask stencil techniques. Table I presents the pertinent parameters in the preparation of GDP styrene. Conditions of Forrrzation of GDP Styrene. The rate of deposition for GDP films was monitored using a current-time integrator. The thickness of the deposited film for a given set of experimental conditions was a function of the current-time integral. The fifth row in Table I is a compilation of the deposition rate of GDP styrene films. Other organic monomers behave in a similar fashion. With the exception of the highly halogenated saturated hydrocarbons, all organics subjected to the conditions of the glow discharge form GDP films. 11) Photoresist Films. Photoresists are normally recognized to exist in two forms, a low molecular weight, soluble polymer form (A) and a high molecular weight, crosslinked insoluble form (B). Typical negative photoresists are applied in the low molecular weight form A and converted to the high molecular weight form B by the action of light. (Positive photoresists are applied in form B and converted to form A by the action of light.) Eastman Kodak Metal Etch Resist (KMER) has been chosen as a typical negative photoresist. Polymer film samples were prepared in the same configuration used for GDP films. The KMER was applied in the usual fashion using a 120°C drying step (infrared-lamp heating) and a 180°C post-bake. Care must be taken to completely remove the solvent in the drying step and to properly develop and postbake to exposed photoresist. If the photoresist film is not properly dried and postbaked, severe blistering and peeling will occur during subsequent elevated-temperature exposure. Thickness can be controlled by varying the viscosity of the form A photoresist and the spin rate at application. AZ 340 was chosen as a typical positive photore-

Jan 1, 1967

By D. L. Albright, G. A. Colligan

An investigation has been conducted to determine the nature of the crystallographic substructure of nickel and a 1.0 wt pct Ag-Ni alloy which had been undercooled 105°C prior to solidification. A rotating back-reflection X-ray technique and modified Weissmann diffractometer were used to orient single-crystal sections from these poly-crystalline ingots and to determine the substruc-tural features of these single crystals, The sub-grain size in the pure nickel ingot is 0.5 mm diam while the silver-doped nickel subgrain size is only 0.1 mm diam. The misorientation between adjacent subgrains is approximately 1 deg of arc in both ingots, and the spread of orientation of sub-grains about the mean orientation of the crystal is 5 deg of arc in both ingots. The addition of silver results in a stable impurity substructure which is preserved during isothermal solidification and subsequent cooling to room temperature. In the absence of silver the initial impurity substructure is destroyed by dislocation interactions which produce a secondary substructure which grows to a size five times larger than the initial substructure. THE process of undercooling a metal entails cooling of the molten sample below the equilibrium freezing point without the occurrence of solidification, i.e., by exercising proper constraint over the experimental variables contributing to nucleation in the melt. The current work of walker1 and Colligan Metal reports undercooling large continuous samples of nickel by imposing appropriate restrictions upon the parameters of solidification. The silver-nickel equilibrium diagram3 reveals the presence of a monotectic reaction at 1435°C. At this temperature the maximum solid solubility of silver in nickel is approximately 3 wt pct, but this solubility decreases with decreasing temperature and the solute is rejected as a silver-rich liquid phase at temperatures below 1435°C. Thus, the 1.0 wt pct solute should be held in solution during undercooling and solidification and subsequently precipitate as a silver-rich liquid phase at grain and subgrain boundaries following solidification during cooling below 1435. This assumes no solute segregation sufficient to cause the monotectic reaction. One would expect this second phase to inhibit grain and subgrain growth by retarding dislocation motion after solidification is complete. The effectiveness of silver addition in growth retardation of high-angle grain boundaries has been demonstrated by Colligan and suprenantS4 The principal [l00] dendrite growth directions in a 2 wt pct Ag-Ni alloy undercooled 53 all radiated from the nucleation site. A similar pure nickel ingot undercooled 59°C exhibited a random orientation of [l00] dendrite directions with respect to the nucleation site. Since undoped nickel ingots do not retain any evidence of the casting or solidification texture and silver-doped ingots do retain this texture, it is reasonable to assume that considerable grain growth has taken place in the pure nickel. These particular experiments were performed in order to reveal the differences, if any, in the features of the crystallographic substructure of undoped undercooled nickel and silver-doped undercooled nickel. 1) EXPERIMENTAL PROCEDURE Data are reported on selected specimens from two massive (approximately 260 g) undercooled ingots of nickel. One ingot consisted of electrolytic nickel and the other of this same material with 1.0 wt pct addition of high-purity silver. Powder patterns were taken of both the as-received and as-solidified materials; in all cases the reflections recorded were attributable to the individual elements nickel and/or silver. Fig. 1 is a. schematic diagram of the apparatus employed for the undercooling experiments. The equipment consists in part of a fused silica crucible for containing the charge. A fused silica tube encloses the system, which is covered by a brass cap to permit partial sealing of the inert atmosphere. This cap contains a hole through which a Pt-Pt 13 pct Rh thermocouple is inserted for temperature measurement. The charge is inductively heated under a purified argon atmosphere.

Jan 1, 1963

To assist the taxpayer of the oil and gas industry in correctly and expeditiously preparing his Federal tax returns, the Bureau of Internal Revenue has prepared a "Manual for the Oil and Gas Industry Under the Revenue Act of 1918." Although the endeavor has been made to anticipate all questions that may be asked, it is recognized that such a manual is only general and cannot cover all cases that may exist. The Manual is based largely upon information gathered during the fall of the year 1918 by a corps of geologists, technologists, and engineers. The investigation was undertaken primarily to furnish a basis for arriving at valuations, and depletion and depreciation deductions in connection with oil and gas properties. All fields in the United States were canvassed. Records of production of thousands of properties were collected and tabulated. These were carefully classified and studied by the most competent and experienced men in the country and the average future production curves and tables of valuation data were produced as a result of this study. Be American! Work and Save. Buy W. S. S.

Jan 7, 1919

By F. D. Rosi

The slip and twinning behavior in extended titanium crystals were studied in some detail. The formation and appearance of coarse kink bands are discussed. Their crystallographic geometry was determined by X-ray analysis. A phenomenological interpretation of the complexities in kink band development is also presented. The critical resolved shear stress, coefficient of shear hardening, and plane of fracture were determined for several crystals extended at room temperature. THE slip and twinning elements observed in the room-temperature deformation of titanium were enumerated in a previous paper1 in which considerations were advanced regarding the nature and selection of these elements and their effect on the known mechanical properties of this metal. The present study concerns the crystallographic, microscopic, and mechanical aspects of flow in relation to the slip and twinning elements, and includes a prediction of slip systems, nature of slip and twin markings, inhomogeneities of plastic flow, and stress-strain characteristics. Unless otherwise noted, arc-melted titanium sponge (99.77 pct) was used in these experiments. The method of production of crystals, their dimensions, and the surface preparation for micrographic examination have been reported.&apos; For obtaining stress-strain characteristics, only those crystals which traversed the entire width of the specimen and were at least 8 mm in length were used. Tensile deformation of the crystals was performed with conventional grips for sheet specimens and a constant-stress loading beam, designed after the method of Andrade and Chalmers.&apos; The specimens were loaded by allowing sand to flow from a reservoir into a bucket suspended from the longer end of a balanced 6:1 lever arm at a rate controlled to load the specimen approximately 2 kg per min. Strain measurements were made using the Baldwin SR-4, bonded, resistance-wire strain gage, Type A-8, which permitted a reading accuracy of 2 microinches per inch. The formulas used in the evaluation of shear stress and shear strain, as in deriving the coefficient of shear hardening, are given by Schmid and Boasv n terms of the original orientation and change in length of the crystal. For calculating the critical resolved shear stress, the standard equation was used. The crystallographic nature of the unpredictable slip observed in a number of specimens was determined by the single-surface X-ray method of analysis as described in ref. 1. Experimental Results Prediction of Slip System: It was reported&apos; that room temperature slip in titanium takes place predominantly on {10i0} and in a <1120> direction, giving three potential slip systems. Hence, it should be possible to predict the operative primary system in the manner used by Taylor and Elam&apos; for alu- minum (i.e., the one with the greatest component of shear stress in the direction of slip). The stereo-graphic construction in Fig. 1 shows that this is true. In all cases, slip was found to occur initially on the (0110) plane and, in a number of cases, in the [21f0] direction. (The direction of slip was not determined for all orientations.) It follows that duplex slip can be expected when two slip systems are geometrically equally favorable for slip, as demonstrated in Fig. 2. In both crystals slip took place simultaneously on the (1700) and (olio) prismatic planes, as indicated by Fig. 2a and b. In the case of crystal B the movement of the specimen axis with increasing extension was toward the (10i0) direction, which represents the stable end orientation resulting from alternate slip on the [2ii0] and [1120] directions. This is analogous to the duplex slip process in face-centered cubic metals." Unpredictable Slip: In a number of crystals whose orientations were well within the operation of a single slip system, secondary slip occurred on planes not predicted by the criterion of maximum shear stress. Examples are shown in Fig. 3. In addition to

Jan 1, 1955

By Donald A. Corrigan, John Chipman

It is shown that the heat of solution of nitrogen in liquid-iron alloys is Proportional to the interaction coefficient. This proportionality forms the basis for a method of predicting nilrogen solubility at any temperature when the interaction coefficient is knoun at 1600°C ov when the solubility is known at some one temperature. A method for predicting the solubility of nitrogen in liquid steels, including alloy steels, was proposed some years ago by Langenberg.&apos; Since the data available at that time were restricted to temperatures of about 1600°C, his predictions were similarly restricted. More recently, Nelssonz devised an approximate method for estimating nitrogen solubilities at higher temperatures. It is the purpose of the present paper to present a method by which the solubility of nitrogen at any temperature within the steelmaking range may be predicted from the known interaction coefficients at 1600°C. Nitrogen in iron and in all of the alloys to be considered here is known to obey Sieverts&apos; Law; hence the activity of nitrogen in an alloy of fixed composition is proportional to its concentration, here expressed in weight percent. The activity of nitrogen is defined as equal to its weight percent in the binary Fe-N solution at any temperature. Its activity coefficient in any alloy is the comparison being made at equal values of T and PN2. In all alloys the activity coefficient changes with composition, log fN being a linear function of the percent of alloying element at low concentrations. In the following calculations the alloy compositions are restricted to those in which this linear relation is exhibited. For most systems this is a fairly wide range, for example up to 5 pct V and to 10 pct Cr or Ni. For this composition range. complex alloy is the same as that in the Fe-N-j ternary solution. Langenberg&apos;s method of prediction was based on Eq. [3], the values of log fN for various additions being taken from a graph. Instead of using the simple addition indicated in Eq. [3], he used a more complex method suggested for Fe-S-j alloys by Morris and Buehl.3 For the composition ranges in which Eq. [2] is valid the two methods are equivalent. Nelson extended the prediction to other temperatures on the assumption that logfN is inversely proportional to absolute temperature. It may be shown that inverse proportionality would result if the partial molal entropy of nitrogen were unaffected by addition of the alloy element, an assumption which Nelson designated as a "regular" solution. It has been shown recently by the authors4 that this assumption is not a good approximation. The heat of solution of nitrogen (N2) in an alloy may be obtained if the solubility is known as a function of temperature. Measurements of this nature have been reported recently by Beer5 for Fe-Mn alloys, by Nelsson2 for Fe-C, by El Tayeb and parlee6 for Fe-V, and by Pehlke and Elliott7 for many alloys embracing a wide range of compositions. In connection with the work of the last named authors it is noted that their Fig. 22 gives the heat effect per half mole rather than per mole of N2. In using their data we have shifted some of their values slightly by using the best straight line in preference to their curve. Their data, supplemented by others from the literature, are summarized in Table I. In Fig. 1 the heat of solution of nitrogen is shown as a function of composition for the several alloy systems. The difference between the heat effect in the alloy. AH; and that in pure

Jan 1, 1965

By L. Grånäs, B. Aronsson

In a recent study of Fe-Si alloys Walter and Koch&apos; observed pairs of dislocations in Fe-6.25 pct Si crystals rolled to reductions of 10 pct and subsequently annealed for 1 hr at 650°C. They interpreted these pairs as being due to stacking faults. From the spacing of the dislocations a stacking-fault energy of 15 to 19 ergs per sq cm was calculated. These authors did not pay any attention to the order -disorder phenomena in Fe-Si alloys. It is the purpose of this communication to report some preliminary results from a study of ordering and its influence on the plastic deformation of Fe-6.0 pct Si alloys. Our results suggest that the dislocation pairs observed by Walter and Koch may have been due to long-range order rather than to stacking faults. The alloys used in this investigation were prepared from pure electrolytic iron and silicon and were melted in argon. After hot working, strip tensile specimens were machined to a gage length of 70 mm and a thickness of 1 mm. The specimens were heat- treated for 2 hr at 1000°C, furnace-cooled, and subsequently deformed 2 pct in tension at 400°C. The strain rate was 5.6 X lo-&apos; sec-&apos;. Thin foils of the deformed specimens were prepared by means of the Bollman technique and examined in a Siemens Elmis-kop I at an accelerating voltage of 100 kv. In the Fe-Si system long-range ordering occurs at a silicon content of about 6 pct Si. In our alloys evidence for ordering is given by selected-area diffraction patterns which show extra reflections consistent with a super lattice of the D0 9 type. In addition, the dislocation arrangement in deformed specimens indicates that long-range order is present. A typical mi-crophotograph of a thin foil is shown in Fig. l. The dislocations are usually straight and parallel and laying in distinct directions. In the commonly observed (111) zone the projections of the dislocations are close to (113) and (oil). Observation of the image position indicates that the two dislocations in a pair have the same Burgers vector and hence constitute a superlattice dislocation.~ According to theory3 a superlattice dislocation in the DO3 structure consists of four ordinary dislocations connected by two types of antiphase boundaries as shown in Fig. 2. In our specimens only two dislocations in each pair have been observed, Fig. 1. The problem is to decide whether the area between these is a NN or a NNN antiphase boundary. Dark-field images using the (200) reflexion (the indices are defined with respect to the DO3-type superlattice) can

Jan 1, 1968

By J. W. Marx, R. H. Langenheim

The authors are to he complimented for a timely presentation of useful information concerning application of heat to oil reservoirs to increase the rate and ultimate recovery of oil. The solution for heated area resulting from constant rate injection of a hot fluid, presented by the authors, and the fluid-flow analogy, solved by Carter,&apos; are particularly interesting in that 110 restriction is placed on the direction of development of the heated area. It is not necessary that the heated area grow radially. Thus the solution could provide useful information for heat injection in any type of well pattern with any specified swept area data. However, it was assumed in the development that the heated region would remain at a constant clevatcd temperature. Vertical heat losses were computed on this basis. Physically. the assumption that the heated region will remain at a constant temperature (independent of distance from the injection point) appears to require that the heat injection medium be stcam, or other condensible gases near the boding point at injection pressure. If a hot liquid below the boiling point or a hot gas considerably above saturation temperature were used, the temperature of the heated region would decrease with distance from the injection well. Lauwerier2 has discussed this problem for a linear system. (See also Jenkins and Aronolsky; and McNiel and Nelson.&apos;) Thus, the authors&apos; solution applies more nearly to steam injection than to hot water injection or hot, non-condensable gas injection. Assuming steam as the injection medium, it appears that steam would pass through the constant-temperature heated region and condense upon contact with the unheated sand. The tempcrature in the condensing region would probably be governed by the release of heat of vaporization required for phase equilibrium at the existing pressure distribution. Temperatures in the region would also be influenced by vaporization of hydrocarbon. Thus, it is doubtful that an expression for radial temperature distribution based on heat conduction only (such as the authors&apos; Eq. 9) would have practical significance. As pointed out by Marx and Langenheim, the growth of the heated area under constant rate steam drive will eventually be limited economically by vertical heat loss. The possibility of continuing to move heat economically by cold water injection or by increasing the steam injection rate appears to be a very important consideration. (Movement of liquids away from the injection well should increase injectivity.) Fortunately, the solution presented by the authors may be generalized to thc case of a variable heat injection rate. The general solution is:

By J. Fageant, W. C. Ellis

All major regions in a progressively solidified germanium ingot were related through successive orders of octahedral twinning. The occurrence of lineage structure and the generation and survival of orientations are discussed. WHEN metals solidify in a temperature gradient a preferred orientation, or casting texture, usually develops. For example, in face-centered and body-centered cubic metals, most of the solidifying crystals have a cube axis, <loo>, aligned approximately in the freezing direction.&apos; In the solidification of diamond cubic metals this is not the case, since there is a natural tendency to form twin orientations.&apos; . In this paper, twinning relationships in cast germanium are described; some conclusions with respect to nucleation and survival of new orientations are discussed. In the first experiment, an ingot of high purity germanium, % in. in diameter and 1 % in. in length, was formed by progressive solidification4 from the bottom. The ingot was cut into 21 slices, each circular and about 0.030 in. thick. The top surface of each slice was polished and etched to reveal the regions of different orientations. Orientations were determined by the Laue X-ray back-reflection method. The uncertainty in the determined orientation relationships was l" or 2" when separate slices and films were involved. Frequently, however, advantage was taken of illuminating across a boundary when the patterns of the two orientations were recorded on the same film. The uncertainty then was less than 1". Often the twin relation was evident from common zones or individual reflections. Twin relationships were recognized through comparison of the values of the nine angles between cube poles of the two orientations with those calculated for successive orders of octahedral twinning. The birth and survival of each region can be reconstructed by visual examination of the etched slices shown in Fig. 1. In slice 21, where solidification began, many regions are present; these regions were found to be twin-related. Solidification appears to have started from one nucleus formed probably at the wall of the crucible.* Subsequent ori- entations were developed by nucleation on existing solid surfaces, and only in the twin relationship. This is an example of a general process of nucleation on a surface of existing solid and may be descriptively termed oriented nuc1eation.t In germanium, and other diamond cubic substances, the orienting habit is that of twinning on an octahedral plane.&apos; " The prevalence of straight traces in the polished surfaces of succeeding slices (Fig. 1) suggests that the twinning observed in the first slice persisted throughout solidification. This was confirmed by X-ray determinations. The schematic diagram of Fig. 2 shows the twinning relationships of the major regions throughout the ingot. Since all observed relationships are describable as twinning, it is reasonable to conclude that no random nucleation occurred in the freezing of the ingot. An alternative possibility would be that nucleation of a random nature occurred, but only those nuclei in twin orientations survived in subsequent growth. This is unlikely for there would be as good a reason for the growth of randomly oriented nuclei as for the growth of the many different orientations present after several orders of twinning. The many twin components contain a wide distribution of orientations, and did grow. In fact, they are the only ones found in the solid. The conditions of solidification of this ingot were such as to discourage nucleation of crystals wholly in the liquid. The rate of solidification was 0.125 in. per min. This slow rate of heat removal afforded but small opportunity for supercooling within the liquid —a condition needed to provide enough decrease in free energy for such nucleation. When nucleation occurs on an existing solid surface, the interfacial energy between the existing and forming regions is important in determining the new stable orientation. The new orientation is expected to be one which minimizes this energy. In the diamond cubic structure, the interface for the

Jan 1, 1955

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951

By Tasuku Fuwa, John Chipman, David H. Kirkwood

Fe-C-Si alloys in silica crucibles were held at 1600°C in a controlled atmosphere of CO and Co2 and the approach to equilibrium was obsertsed. Results were not of sufficient precision to establish the activity and interaction coefficients. Observations 012 the equilibrium provided an average value for the standard free-energy change which differed by + 1.1 kcal from the earlier accepted value. The C-SL relation at other temperatures is calculated and shown graphically. IN the refining of steel in an acid-lined furnace, it is well known that, unlike in basic refining, a very significant amount of silicon may remain dissolved in the metal even when the carbon content approaches a final endpoint. Further, it is known that the residual silicon increases with increasing temperature. The quantitative relation between silicon and carbon can be calculated for equilibrium conditions from data already available on the Fe-C-O and the Fe-Si-O systems. Such equilibrium calculations could show us approximately the limitations within which the reaction would be expected to operate in practice. In the oxidation of a bath containing both carbon and silicon it is well known that at low temperatures silicon is preferentially oxidized first. It can be shown by calculation that at high temperatures carbon will be oxidized preferentially. It is the purpose of this paper to record direct observations on the Si-C relation by means of experiments carried out in an atmosphere of carbon monoxide for Fe-C-Si alloys contained in silica crucibles. When such a system is brought into equilibrium, at a fixed temperature, the composition of the liquid metal is governed by the following equations: Both K1 and K2 are known with a fair degree of accuracy, and may be calculated from the tabulated In general the percentage of CO2 is extremely small compared to that of CO and in the experiments to be described the partial pressure of the latter was generally only slightly below 1 atm. EXPERIMENTAL METHOD The induction furnace employed was the same as that described by Rist and chipman&apos; and by Fuwa and chipman.2 It was modified slightly in view of the change from alumina to silica crucibles. The small silica crucible was surrounded by a thin susceptor of molybdenum sheet which in turn rested inside a zirconia crucible. Since the zirconia was subject to breakage, it was supported inside an alumina crucible. The charge consisted of 30 to 35 g of electrolytic iron along with the required amounts of refined silicon and graphite to produce a melt of required composition. Purified carbon monoxide and carbon dioxide were passed into the furnace through carefully calibrated flow meters. Two separate and independent series of experiments were carried out. In Series I (D.H.K.) the melt was held in the furnace at 1600°C for periods of time up to 6 hr. Samples were taken at intervals in silica tubes and were analyzed for carbon and silicon. The results of the last one or two samples taken from each experiment and the direction in which equilibrium appeared to be approached are shown in Table I. In Series II (T.F.) the silica crucibles were of less satisfactory strength and the melts were held at 1600° C for periods of only 2 to 4 hr. In heats number 29 to 45 inclusive, the metal was cooled in the furnace and the ingot itself served as a sample for analysis. In heat 46 and all subsequent heats, samples were withdrawn in silica tubes at the termination of the heat, and these samples were analyzed. The results of all of these experiments in which equilibrium appeared to be approached are listed in Table II.

Jan 1, 1965

By T. M Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the &apos;active masses&apos; of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. dC Thus----— kc [1] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of un-floatable mineral. Hence the first order equation is It has been proposed by various workers1-&apos; that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris- as discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1953

By T. M. Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the &apos;active masses&apos; of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. dC Thus----— kc [1] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of un-floatable mineral. Hence the first order equation is It has been proposed by various workers1-&apos; that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris- as discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1953

By A. E. Powers, J. F. Libsch

THE simultaneous influence of time and temperature upon the tempering process in steel is well known. Hollomon and Jaffe¹ have expressed the effect of time and temperature upon the progress of tempering by a single parameter, T (c + log t); where T is the absolute temperature; t, the tempering time; and c, a constant characteristic of the steel and treatment. It was found that when hardness data for plain carbon and low alloy steels were plotted vs. this parameter, a master tempering curve was obtained which satisfied all the data for a given steel and a given hardening treatment. Roberts, Grobe, and Moersch² successfully applied the tempering parameter to various tool steels, including high speed steel for tempering times ranging from 6 min to 100 hr. The influence of tempering time and temperature upon the physical properties of high speed steel has also been extensively investigated.&apos;" Recently, the use of induction heating for very rapid tempering treatments has received attention. The authors% have shown that tempering treatments of only a few seconds duration may be successfully applied to plain carbon and low alloy steel. However, the influence of such short tempering treatments in high speed steel has not been explored. Since high speed steel is a highly alloyed steel exhibiting physical reactions during tempering that are often relatively slow and large in magnitude, it is an interesting steel for the study of tempering reactions. It was the purpose of the present investigation, therefore, to study the early progress of reactions leading to secondary hardness in high speed steel, type 6-5-4-2, and to determine if induction-tempering treatments of a few seconds duration are able to produce results equal to those of more conventional long-time tempering cycles. Experimental Details The chemical compositions for two different heats of W-Mo high speed steel used in this study are given in Table I. Table II summarizes the heat treatment given various groups of specimens cut 21/2 in. long and centerless ground to ¼ in. diam. Hardening treatments consisted of preheating to 1600°F (870°C) for V2 hr and then oil quenching from 2250°F (1230°C). Heat I was subjected to the high temperature in a salt bath for 3 min, while specimens of heat II were austenitized in a carbon-block muffle furnace for 10 min. Specimens of series E were immediately refrigerated to — 318°F (— 195°C) in liquid nitrogen following the hardening treatment to transform the major portion of the retained aus-tenite. Specimens of series F and G were subzero cooled to — 100°F (-75°C) in a dry ice-alcohol mixture. Induction tempering was performed with a Lepel high frequency converter operating at a frequency of approximately 300,000 cycles per sec. Heating cycles were controlled and recorded for each specimen using a chromel-alumel thermocouple, percussion welded to the surface of the specimen, and a modified high speed instrument with a timer previously used and described.&apos; Temperature oscillation of the specimens, while being held at the tempering temperature, was ± 15°F (8°C). Tempering Treatments: After hardening, specimens were tempered between 900" and 1500°F (480" and 815°C) to study the progress of retained austenite decomposition and secondary hardening. The specimens tempered in salt for 1 hr (series C, G, and I) were considered to represent conventional treatment and are used for comparison with rapid tempering treatments. Several induction-tempering cycles were employed: 1—flash tempering, i.e., induction heating to the tempering temperature and immediately cooling (series A, E, and F); 2—induction heating for 60 sec at temperature (series B); and 3—double-induction tempering by two successive heating and cooling cycles (series D). All specimens tempered by induction were heated at an initial rate of 450°F (250°C) per sec except those of series E, which were heated at an initial rate of 1300 °F

Jan 1, 1952

By N. K. Chen, R. Maddin

THE textures of straight-rolled and of cross-rolled molybdenum were first determined with the aid of pole figures by Custers and Riemersma.&apos; These authors have shown that for straight-rolling, the main texture was (100) [0111 with a considerable spread about the rolling direction. After cross-rolling a second texture was obtained in which there was a [111] axis perpendicular to the rolling plane, possessing a rotary symmetry. Recently Semchy-shen and Timmons2 in their study of preferred orientation of arc-cast molybdenum sheet obtained similar pole figures. In these two investigations, polycrystalline materials were used. In the main, the textures of molybdenum in these cases are qualitatively consistent with rolling textures of other body-centered cubic metals, such as iron and Fe-Si alloys." In the present investigation, single crystals of molybdenum were deformed by rolling with respect to specific crystallographic planes and directions. Since the deformation textures of polycrystalline aggregates have been related intimately to the behavior of individual grains,4 a study of possible correlations of final textures with respect to the initial orientations of the single crystals might conceivably lead to a better understanding of the textures. Annealing treatments were carried out after deformation in order to study the recrystallization characteristics as well as the recrystallization texture. Rolling of Single Crystals Single crystals of molybdenum (about 1/8 in. in diarn x 1-in. long), grown by the method previously described,5 were cold-rolled without intermediate anneals. Except for specimens MR-1 and MR-2, which were rolled at random in the preliminary test in order to find a proper rate of reduction, all other specimens were carefully documented as to their respective orientation before deformation by means of X-ray Laue back-reflection methods. A stereo-graphic projection was constructed from which it was possible to determine a particular plane and direction to be considered for rolling. Parallel flat surfaces were then polished metallographically with respect to a reference scratch on the specimen which was mounted in sealing wax. These flat surfaces contained the plane chosen for rolling. After etching, a Laue back-reflection photogram was again made of one of the flat surfaces to determine the exact plane of rolling. The initial orientations of all the specimens (specified by two elements for each crystal, direction of rolling and the pole of the rolling plane) are summarized in Fig. 1. The specimens were mounted in plasticene between two hardened Si-Fe plates. The sandwich was then rolled down, keeping the direction constant in the case of straight-rolling. In cross-rolling (MR-10, MR-11, and MR-12) the sandwich was rotated 90" after each pass so that every first and third pass contained the same rolling direction. Specimens MR-14, MR-15, and MR-16 were compression-rolled following the manner of Barrett." In these cases the direction of the sandwich through the rolls was changed by 3" to 5" for each pass until the specimens were rolled to the desired reduction in thickness. It was found that if extreme care was exercised in rolling, i. e., the amount of deformation per pass was extremely small, the specimens could be rolled to a large reduction in thickness. The rate of reduction used, with a single exception of MR-1. was generally 0.001 in. per 10 passes. Thus, it took about 800 passes to reduce a specimen to a final reduction in thickness of 87 to 98 pct. The results of rolling are shown in Table I. Cold-Rolling Textures The final orientations were determined by the conventional Laue transmission method," using molybdenum radiation, with or without a zirconium filter. Pole figures were plotted from (1101 and (200) reflections in which three degrees of intensity— heavy, medium, and light—were determined visually. Three main types of textures have been observed from the deformed single crystals. These are: 1—a

Jan 1, 1954

By W. C. Leslie

W. C. Leslie (Edgar C. Bain Laboratory for Funda mental Research)—This investigation, with its com bination of high-purity metal, calorimetry, and metallography, will serve as a model for annealing studies for a long time to come. The evidence for a competition between recovery and recrystalliza-tion is particularly convincing. The demonstration of edge-nucleated recrystallization was so clear that it may obscure the necessity for other types of "nucleation" sites; otherwise, single crystals of aluminum could not be recrystallized after cold work. At least three types of sites have been found to operate in iron: 1) high-angle boundaries, probably in the same manner as in aluminum, 2) matrix sites, 3) inclusions or second-phase particles. In each instance, the cells developed during cold work and perfected during recovery are the "nucle for recrystallization. Observations by ourselves and others of the dislocation structure of cold-worked metals and of the structural changes that occur during annealing have led us to doubt the validity of the basic assumption of the Lucke-Detert theory, and of the modification developed by Gordon and Vandermeer, that during recrystallization of a metal containing foreign elements in solid solution a high-angle boundary is ad vancing into a cold-worked matrix having a random distribution of solute atoms. We contend that an es sential part of the cold-working and annealing of solid solution alloys is the trapping of solute atoms by the low-energy "wells" afforded by individual dislocations and by dislocation arrays. If cells are formed during cold work, the cell walls are stabilized by this concentration of solute atoms. Thus, solutes inhibit recrystallization not only by decreas-ing the rate of high-angle boundary migration, but also by preventing the formation of high-angle boundaries by subgrain growth or coalescence, i.e., solutes can inhibit both "nucleation" and growth. In addition to stabilizing the dislocation Structure, the solute-dislocation interactions may produce clusters of solute atoms which are not as readily assimilated into the recrystallized grains as are individual solute atoms. There is an additional complication. The dislocation structure formed upon cold working a dilute solid solution may not be the same as that formed during cold working of the pure solvent metal. The solute can either enhance or minimize the formation of cells during cold working. Both effects have been observed in binary alloys of iron. The annealing process is inextricably connected with the mechanisms of strain hardening and solid solution hardening. Although the correlation between experimental boundary migration rates and the predictions made from the theoretical equations are impressive, it should be mentioned that in at least four other instances (Pb-Ag and pb-Au,15, Fe-Mn,16, Fe-Mo)17 the agreement was rather poor. In brief, while it is probable that the migration of high-angle boundaries is held back by solutes in the manner described, this is only a partial explanation of the total effect of solutes upon recrystallization of cold-worked alloys. Paul Gordon and R. A. Vandermeer (author&apos;s reply)— The authors first wish to thank Dr. Leslie for his compliments of this work. It is perhaps worth pointing out that some of Dr. Leslie&apos;s remarks are directed toward subject matter covered in two earlier papers in our work.18,19 We agree with Dr. Leslie&apos;s main contention that the exact nature of the metal structure in the vicinity of a boundary should have an effect on the boundary migration. The theory of Lucke and Detert does not take such detail into account, nor does it account for orientation effects on the migration rates. We assume that since our data checks the theory so well, the effects of detailed structure are statistically averaged out by the polycrystalline techniques used just as are the effects of orientation factors.

Jan 1, 1963

By T. M. Morris

THE rate of flotation of solid particles determines the percentage recovery of these particles which can be obtained during a given time interval. It is an established fact that the recovery is greatest in the fine sand size range and falls off on either side of this size range. It is also a fact that the history of the development of concentrating devices has been marked by a desire to recover the small particles: tables were developed to treat material too fine to recover in jigs; flotation recovers material too fine to be recovered on tables. As our ores become more complex and require finer grinding, a greater proportion is in the slow-floating size range. It is therefore of economic importance that the effect of size of particle upon rate of flotation be studied. Many studies have been made along this line. The present investigation attempts to quantify the rate of flotation by means of a rate equation, and then compares the effect of size upon the rate of flotation. It was found that the flotation rate constant increases with increase in diameter of particle in the size range smaller than the optimum size particle. The flotation rate constant decreases with an increase in diameter of particle in the size range coarser than the optimum size particle. This suggested two different actions taking place, and these are discussed. Suggestions for further work in order to improve the flotation rate of both fine and coarse particles are made. The usual method of expressing rate is to plot cumulative percent recovery vs time. If we knew the equation of this kind of curve we could replot it as a straight line, and the slope of the line would be an index of the magnitude of the flotation rate. It is easier to compare straight lines than curves. The basis used for obtaining the equation of the recovery vs time curve is the law of mass action. This law states that the "rate of a chemical reaction is proportional to the `active masses&apos; of the reacting substances present at any given time." This, of course, implies a constant temperature. We can modify this for our use by using the term flotation reaction instead of chemical reaction and the term floatable particle instead of active masses. [ ] where C denotes concentration of particles, t denotes time, k denotes a proportionality constant. If the exponent of C is 1, then we have a first order rate reaction. If the exponent of C is 2, then we have a second order rate reaction. For a first order rate reaction, we obtain, after integration, [ ] where k is again a proportionality constant and has the dimension of the reciprocal of time. C, is the original concentration or weight or percentage of floatable particles. C, is the concentration or weight or percentage of floatable particles remaining in the flotation cell after time t. If all particles of the mineral to be floated were capable of floating we could take C, as 100 and C, would be 100 - R, where R is the cumulative percentage recovery of mineral at time t. But it is not usual for all of the particles to be capable of floating, because of surface oxidation, etc. Therefore, we must introduce a factor x which is the percentage of unfloatable mineral. Hence the first order equation is [ ] It has been proposed by various workers1-3 that this equation describes the flotation rate. More recently N. Arbiter4 states that a second order rate equation fits the recovery vs time curve more closely than does a first order rate equation. Morris&apos; has discussed the evidence presented for this statement. It has been concluded that the first

Jan 1, 1952

By Frederick Laist

THE past year has witnessed no radical changes in methods for the reduction and refining of copper. The Carson litigation was finally brought to a close ant1 the copper smelter is again free to introduce charge into his reverberatory furnaces in whatever manner suits him best. This litigation naturally led to much experimentation with various methods of charging and with various types of bath. In some cases the charge was introduced more or less centrally on a relatively dry hearth and in other cases into a bath of greater or less depth. The results of these furnaces were meticulously compared with the results obtained in side-charger furnaces, and it was apparent that it made little, if any difference how a given furnace \\.as charged so long as care was taken that there was always something in the furnace for the flames to work on. So long as this requirement was complied with, consumption of fuel per ton of charge smelted and tonnage smelted per furnace day remained substantially the same regardless of the method of charging or the depth of bath employed. In some instances the center-charged deep-bath furnaces gave slightly better results than the side-charged particularly with respect to copper losses. The slags of the deep-bath furnaces are generally a little cleaner

Jan 1, 1930

By C. E. Birchenall, G. Derge

IN studying the kinetics of slag-metal reactions, it has become increasingly apparent that a complete knowledge of all aspects of interface phenomena will be required to clarify these processes adequately. A part of the data required for all oxidizing slags used in the refining of impure iron to steel is the rate of exchange of iron between the slag and metal phases. The simplest equilibrium of this type is that between liquid iron and iron silicate slag when both phases are equilibrated with the silica crucible containing them. In this study, the exchange of iron between the two liquid phases has been measured by using radioactive Fe as tracer. The observed high exchange rate indicates the ease with which such interfaces may be crossed in refining processes. The experiments required for this study involved relatively minor and normal modifications of well established techniques. Melting was accomplished by induction heating in heavy walled, fused silica, rotating crucibles." Rotation was used to minimize dilution of the slag by crucible erosion. The melting stock was ingot iron. Slags were prefused in iron crucibles using chemically pure grade oxide reagents. The special conditions applying to the active iron additions will be described for individual experiments. Suitable precautions were observed with regard to protection against radiation hazards.&apos; Identification of Activity This particular study was initiated several years ago, but held in abeyance because the radioactive iron available at that time contained a foreign activity which concentrated in the slag so as to mask the iron activity and render the results unin-terpretable. With the benefit of experiences from other studies, radioiron of suitable purity can now be prepared. As received from the Isotope Div. of A.E.C., the unit appears to contain Fe + Fe50 and a high activity cobalt. The cobalt and iron are separated by repeated ether extractions, and the purified iron stored for sufficient time for the Fe&apos;7 44 day half-life) to decay to negligible activity, leaving only Fe as the active isotope. This was confirmed by the absorption curves for slag and metal samples from heat No. 1. In Fig. 1 the experimentally measured points for the absorption curves of slag and metal are fitted by the calculated slope of 5.8 mg per sq cm in aluminum, which corresponds to the Mn K doublet emission resulting from the capture of an orbital electron of Fe" by the nucleus. This shows that the radioactive species are the same in both slag and metal and identifies it as Fe55 Description of Individual Heats For the first heat, the radioactive iron was contained in the prefused slag. The active Fe55 had been precipitated with carrier and was added as Fe2O3 during fusion in the iron crucible. The charge of 500 grams of ingot iron was melted, the protective iron sleeve added, rotation started, and a prefused, inactive slag was added to allow the system to approach equilibrium. After about 5 min at temperature, the wash slag was skimmed and the active slag added. Initial slag and metal samples were taken as soon as the slag was molten. Additional samples were taken at indicated intervals thereafter. Slag samples were dipped with a small iron spoon and metal samples were sucked into 1/4 in. ID silica tubes. The slag and metal samples were pulverized and mounted for radioactive counting. The slag samples were analyzed chemically for FeO. Temperature was read after the last slag sample by immersion of a Pt-Pt-Rh thermocouple protected by a fused silica sheath. Since no significant variation of rate with temperature was observed

Jan 1, 1954

By Ronald J. McGregor, Anton R. Hendriksz

INTRODUCTION The NIMCIX contactor was developed in the late sixties at the National Institute for Metallurgy in South Africa, for the main purpose of extracting uraniuy from relatively low-grade uranium solutions. &apos; The concept was sufficiently developed by 1974 to permit the operation of a 1500 litre per minute column to treat unclarified urgnium-bearing solution under industrial conditions. The plant operated so successfully that several large-scale units have subsequent18 teen constructed and are operating efficiently. &apos; Total resin consumption figures as210w as 3 per cent per annum have been reported, and the extraction efficiencies of the installations have been exceptionally good. All the solutions treated have been acidic in nature and in every case have been of such a nature as to significantly depress the maximum uranium loading on the resin beads. The chemical constituents of the leach solution fed to the loading column determines the ease with which the soluble uranium can be absorbed by an ion exchange resin. The concentration of competing ions and various resin foulants define the nature of the continuous ion exchange equipment required for efficient extraction performance. The basic NIMCIX concept is retained in these various alternate designs, but batch or continuous elution methods with fully automated or manual control systems may be selected for the different process solution conditions. BRIEF DESCRIPTION OF THE NIMCIX CONTACTOR The NIMCIX ion exchange column is a multi-stage fluidized bed contactor which is designed to permit a counter-current flow of solution and resin in order to maximize extraction efficiency. The flow o resin is periodic, based on the Cloete and Streat 5 principle of reverse flow. The basic operating cycle can be divided into five periods, as illustrated in Figure 1. For the purposes of describing the cycle, the loading column is considered; how- ever, a similar sequence may be applied to the operation of a NIMCIX continuous elution column. S&apos;I&apos;EP 1: During the forward flow period, Solution flows up through the column and fluidizes the resin contained in each stage. The uranium depleted solution overflows the upper flared-section of the column as the tail solution. Step 2: The flow of solution to the column is temporarily stopped and the resin is allowed to Settle onto the plates in the column. STEP 3: During the reverse flow period, a fixed volume of solution is drained from the column to the transfer vessel. This flow causes resin transfer to occur from stage to stage and also out of the bottom stage. At the end of this period, which expires when the low level switch (LS) is actuated, some of the resin is left in the conical section of the column and the pipe interconnecting the column and the vessel. STEP 4: The cone flush period ensures that all the resin left in the cone of the column and the pipe is transferred to the transfer vessel before forward flow commences. STEP 5: The loaded resin in the transfer vessel, which has been isolated from the column, can either be hydraulically transferred to the top of the elution column or eluted in the vessel before being transferred to the top of the loading column. The major advantages associated with the NIMCIX concept are: (i) Simple method of operation (ii) Contactor can readily be scaled up to large diameters. (iii) Because the resin does not pass through pumps or airlifts, and valves cannot be closed on resin beads at any time, the resin losses are exceptionally low. (iv) Operating costs are low. (v) Relatively few valves in the system. (vi) Stable operation is achieved over a wide range of feed rates and concentrations.

Jan 1, 1980