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By A. K. Mukherjee, J. E. Dorn, J. D. Mole

Investigations were carried out on the effect of polyslip on the strain hardening of aluminum single crystals. The orientations investigated were those lor which the tensile axis was in the [001], [111], [112], and [012] directions plus another for which the Schmid angles for {111}(110) slip were 1 deg. The experimental data were analyzed on a model based on the intersection of dislocations with particular emphasis on the effect of polyslip on the activation volume for inter-section. It is shown that the rate of strain hardening inreases for those orientations wherein attractive dislocation intersections occur and that those orientations which produce the greater number of such intersections exhibit the greater strain hardening. Good correlation of the data is obtained with the concept that attractive junctions, as proposed by Saada, Play an important role in accounting for the rate of strain hardening. EXISTING concepts on the nature and cause of strain hardening in fcc metals have been deduced principally from experiments on the deformation of single crystals under single slip. The effect of crystal orientation on the shapes of the stress-strain curves for single slip have been summarized by seegerl and more recently by Clarebrough and Hargreaves.2 Tensile specimens whose axes fall near the center of the [001]-[011] line of the standard triangle of the stereographic projection exhibit the longest range of easy glide (Stage I) and the lowest rates of linear hardening (Stage 11) whereas specimens whose axes lie near fie [001]-[111] line of the standard triangle have limited or no easy-glide range and exhibit somewhat higher linear strain-hardening rates. Specimens whose axes lie near the [001] or the [ill] poles do not exhibit easy glide and have the highest rates of linear hardening. Kocks3 has shown that the highest rates of linear hardening Occur under Polyslip when the tensile axis coincides with the [111] or the [ 001] pole. Since the rate of strain hardening is sensitive to specimen orientation and the incidence of polyslip, these relationships might help to discriminate between various dislocation models for strain hardening in fcc metals. Previous attempts to analyze the effect of orientation on strain hardening,1"3 however, did not provide a unique answer to this problem. Consequently the present investigation was undertaken wherein additional data, particularly that for the effect of polyslip on the activation volume for intersection, was also determined in order to provide more complete information on the details of strain hardening. Whereas analyses of these data reveal that several recommended models for strain hardening are at variance with the facts, good correlation of the data is obtained with the concept that attractive junctions4 play an important role in accounting for the rate of strain hardening. I) EXPERIMENTAL APPROACH seegerl demonstrated that slip in fcc crystals at low temperatures is dependent on thermally activated intersection of glide dislocations with forest dislocations. This has been confirmed by tests on single crystals of aluminum by Mitra, Osborne and Dorn5 and on polycrystalline aluminum by Mitra and Darn.' Thus in accord with Seeger's theory, the shear strain rate, ?, below a critical temperature, T, is where .V is the number of points of contact per unit volume between forest dislocations and glide dislocations, A is the area swept out per successful intersection, b is the Burgers vector, v is the frequency of vibration of the segment of the glide dislocation undertaking intersection, U is the activation energy for intersection, k is Boltzmann's constant, and T is the absolute temperature. For aluminum, which has an extremely high staeking-fault energy, the constriction energy is negligibly small and therefore the activation energy decreases practically linearly with the stress according to as will be recomfirmed later, where Uo is jog energy at the absolute zero, G and Go are the shear moduli at the test temperature T and O°K, respectively, L is the spacing of the forest dislocations, t is the applied shear stress for slip, and tGo is the stress field that must be surmounted athermally.

Jan 1, 1965

By H. F. Ramstad, F. D. Richardson

The equilibria (a) SiOz +Hz =SiO +H20 and (b) Si + SiO, = 2Si0 have beet1 studied at temperatures of 1425"to 1600°C ad 1310°to 1485°C respectively. The stattdard free energy changes for the tzrro reactions are given by the equatiotts Combination of the results for both equilibria leads to tiotz removes certain anomalies in existing high-terlzperature data for equilibria involving silica and silicon in iron. In many metallurgical processes and in many laboratory investigations silicon monoxide undoubtedly plays an important role. It is unfortunate therefore that wide differences exist between the results obtained by different investigators1-7 in their studies of such equilibria as In an attempt to put our knowledge of SiO on a surer basis, an exhaustive study has been made of equilibria [I] and [2] at temperatures ranging from 1300" to 1600°C. Reaction [I] was studied by measuring the amounts of silica which could be condensed from streams of Hz or Hz + HzO which had previously been brought into equilibrium with silica at temperatures ranging from 1425" to 1600°C. Reaction [2] was studied by measuring the material that could be condensed from streams of Hz or argon which had been brought into equilibrium with mixtures of silicon and silica at temperatures ranging from 1310" to 1485°C. EXPERIMENTAL Materials. The silicon was "superpure" grade and contained less than 0.1 pct impurities. The silica was prepared from pure mineral quartz; this was crushed and treated with concentrated hydrochloric acid to remove particles of iron, washed with water, and finally dried at 120°C. For the hydrogen + silica reaction, the silica was sized to —20+100 mesh. For the silicon + silica reaction, the two materials were ground to a fine powder in an agate mortar. The hydrogen and argon were commercial oxygen-free gases. The gas streams were controlled with capillary flow meters and the volumes were measured by wet gas meters. After passing through the meters, the gases were partially dried by silica gel. The hydrogen for the HZ + SiOz reaction was then passed through palladised asbestos at 300°C and dried with magnesium perchlorate. The efficiency of oxygen removal was checked throughout the experiments by passing the gas over an electrically heated strip of nichrome, used as an indicator as described by Rathman and de itt.' When mixtures of HZ + Hz0 were required, the partial pressures of water vapor (1.8 to 22 mm) were obtained by passing the hydrogen through oxalic acid dihydrateg' lo held at various controlled temperatures, O.l°C, by means of a water bath. The hydrogen for the Si + Si02 reaction was purified by passing it over a mixture of 3 parts of magnesium to 5 of lime heated to 600°."l1 u The argon for this reaction was passed through titanium powder (-3/16 in. + 100 mesh) heated to 900°C. The nitrogen used to prevent the reaction products escaping from the condenser (see later), was deoxidized by copper or iron at 600°C. All these gases were finally dried with magnesium perchlorate. Furnace, Temperature Contr01, and Measurement A molybdenum resistance furnace was used for both sets of experiments. The reactions were conducted inside a high-grade alumina tube, 36 in. long and 1 in. in diam as indicated in Fig. 1. With this arrangement an even temperature zone (2"C) 4 cm long was satisfactorily obtained. The temperatures were kept constant by means of a proportional controller actuated by a Pt-Pt 13 pct Rh thermocouple. This was placed between the two alumina tubes, so that the temperature at the junction was 1400" to 1450°C. Up to 1485"C, the temperatures were measured with Pt-Pt 13 pct Rh thermocouples. For higher temperatures an optical pyrometer was used, this being sighted (through the glass window 1 in Fig. 1) on the end of the alumina tube, that held the SiOz or Si +SiOz mixture, 10 in Fig. 1. The optical pyrometer was recalibrated whenever a change was made in any part of the apparatus situated in the hot zone. Successive readings with the optical pyrometer were reproducible to within 1"C. Equilibrium Apparatus and Procedure. Hydvogen and Silica Reaction. The apparatus is shown in Fig.

Jan 1, 1962

By R. D. West

Miscible displacenzent recovers all oil in the area contacted by the injected .fluid, whereas water or immiscible gas drives usually leave substantial amounts of oil as residual. However, the Door mobility ratios associated with a gas-driven miscible displacement cause the sweep pattern efficiency to be much lower than that obtained with water flooding. One way in which the sweep eficiency in a miscible displacement process can be increased is by decreasing the mobility behind the flooding front. This can be achieved by injecting water along with the gas which drives the miscible slug. This water reduces the relative permeability to gas in this area and thus lowers the total mobility. The main operating conditions for the simultaneous injection -vrocess are that a zone of gas exists between the miscible slug and the leading edge of the water and that a su,@cient amount of gas be injected with the water to form the pas volume which is being left in the water zone. Laboratory model studies have shown that the ultimate sweep pattern efficiency can be as high as 90 per cent for a five-spot flooding system. If gar alone is used as the driving medium an ultimate sweep-out efficiency of about 60 per cent would be obtained in the same system. I INTRODUCTION The miscible displacement processes are a step towards total oil recovery. Conventional gas or water drives usually leave 25 to 5.0 per cent of the oil as residual in the swept portion of the reservoir. This residual can be eliminated if the oil is driven by a fluid with which it is miscible. At some reservoir conditions natural gas will become miscible with the oil. This is the "high pressure gas process".' More often, the oil does not contain enough light hydrocarbons to cause the gas to become miscible with the oil at reasonable pressures. In these cases a small band of fluid which is miscible both with the oil and gas must be kept between them2. Less than 2 per cent of the reservoir volume of the slug material is needed to keep the displacement miscible. Both processes work in the same manner, recovering all of the oil in the portion of the reservoir contacted by the injected fluids. The only difference is the manner in which the miscibility between the oil and the injected gas is obtained. Previous publications have contained detailed descriptions of these processes.1,2,3,4 However, total displacement of the oil in the swept region does not guarantee an efficient recovery process. The amount of oil to be recovered is also determined by the fraction of the reservoir contacted by the flood. This fraction is largely determined by the mobilities of the fluids. (The fluid mobility is the permeability of the rock to that fluid divided by the fluid's viscosity, k/p). This. dependence of the fraction swept on the mobility ratio has been shown in previous studies. Fig. 1 shows the ultimate fraction swept in a five-spot system as a function of the mobility ratio. The small drawings show the location of the areas left unswept for two different mobility ratios. The ultimate fraction of the reservoir swept is here considered to be attained when the producing stream contains less than 5 per cent oil at reservoir conditions. THE GAS-DRIVEN MISCIBLE DISPLACEMENT Since there is no oil left in the swept region after miscible displacement the mobility in this region is very high. It is often 50 times the mobility in the unswept regions. This means that the fraction of the reservoir contacted by the injected fluid will be less for a gas-driven miscible displacement than for a conventional water or gas drive. For a five-spot injection system, water would contact the entire reservoir volume, and the low pressure gas would contact about 90 per cent of this volume, while a gas-driven miscible displacement would only contact about 65 per cent of the reservoir. This poor sweep efficiency often offsets the benefits obtained through miscible displacement. Fig. 2 shows what the recovery curves for the three processes might look like for a five-spot system. The curves show the fraction of the in-place oil recovered as a function of reser-

By D. A. Elgillani, S. Atak, D. A. Rice, M. C. Fuerstenau, R. B. Bhappu

Quartz and feldspar cannot be floated with sulfonate at any pH; spodumene floats over a narrow acid pH range, while beryl responds moderately over a broad pH range. After wet-grinding in a steel mill, beryl, quartz, and spodumene float well with sulfonate below about pH 7, whereas the improvement in the response of feldspar is not so marked. A mechanism by which iron can be adsorbed on these minerals is presented. Also, the responses of leached, natural, and wet-ground beryl to amine, sulfonate, and oleate flotation are shown and related to the measured zero-points-of-charge of these materials. Earlier work with leached beryl showed that good flotation could be obtained with alkyl aryl sulfonate over a rather wide pH range using a Fagergren flotation cell.' When a similar response was observed with leached quartz, it was decided that unintentional activation was being obtained from the metallic components of the Fagergren cell. To obviate this difficulty, a microflotation cell was designed, and an experimental technique was devised. These have been described elsewhere. Experiments conducted with the small cell showed that leached quartz could not be floated at any pH with any sulfonate addition,3 which is in agreement with the observations of Kraeber and Boppel.4 Similarly, it was also found that leached beryl responded to sulfonate flotation only over a narrow pH range rather than the broad range reported earlier.1 This early work,1 however, revealed the important effect that wet-grinding in a steel mill has on the flotation response of certain silicates. That is, it was found that quartz and especially beryl floated well over an unusually wide pH range after wet-grinding in a steel mill. Microcline, however, floated poorly below pH 4, even though wet-ground under the same conditions. The work of Eigeles6 on adsorption of oleic acid on leached quartz and iron-contaminated quartz at constant pH is in agreement with these flotation data. Other research has shown that ferric iron, added as a salt to the system, functions as an activator in the narrow pH range in which Fe +++ iron hydrolyzes to its hydroxy complexes.3,5 These phenomena indicate that iron functions differently in flotation systems depending on its method of introduction. The object of this paper is to determine the mechanism by which iron is adsorbed on certain minerals, the mechanism of collector adsorption after iron abstraction, and the role that Fe++ and Fe+++ assume in the selective separation of these minerals. EXPERIMENTAL MATERIALS AND METHODS Sodium alkyl aryl sulfonate, mol wt 450,7 pure potassium oleate, and pure dodecylamine were used as collectors. All other chemicals were reagent grade in quality, i.e., n-amyl alcohol as frother; HC1, H2SO4, and KOH for pH adjustment; and ferric chloride as activator. Conductivity water, made by passing distilled water through an ion exchange column, was used in the experimental work. All minerals used in the investigation were hand-picked specimens. Sample Preparation: Each of the minerals was crushed through 8 mesh, and the product was divided into two groups, one to be ground dry and the other wet. Dry grinding was accomplished with an alumina mortar and pestle. The product was dry-screened to 48 x 150 mesh, cleaned magnetically, deslimed in conductivity water, and dried. Preparation of the samples by wet-grinding involved grinding a 200-g charge of the mineral (-8 mesh) at 60% solids with natural water in a mild steel rod mill for four minutes. This charge was then wet-screened immediately with natural water to 48 x 150 mesh, dried, and cleaned magnetically. Some experiments were also conducted with leached beryl and quartz. These products were prepared by leaching the sized sample (48 x 150 mesh) with concentrated HC1 with a percolation technique until no iron could be detected in the leach liquor. Following this step, the sample was rinsed with conductivity

Jan 1, 1967

By B. H. Kear, S. M. Copley

Stress-stvain curves are presented for Ni3Al (y') cvystals in several ovientations, deformed in tension and compression at constant displacement rate, at temperatures from 70° to 2000°F. Both the yield stress and wovk havdening increase with temperature, with the magnilude of the effect dependent on ovientation. The yield stress maximum occurs at 1500°F in [001], at 1400°F in [011], and at 1200°F in [111]. The suppression of the yield stress peak in [011] and [111] orientatiorzs is due to the onset of cube slip, rather than octahedval slip, a1 elerated temperatures. The temperature and orientalion dependence of work hardening in nominal single slip orientations corvelates with changes in the CRSS ratio for octahedral slip and cube slip, in agreement with a model for work hardening based on pinning of screw dislocalions by cross slip from an octahedral plane into a cube plane. It is concluded that the unique plastic properties of y' have a decisive influence on both ductility and strength characleristics of y +y' nickel-base superalloys. It has long been recognized that the strength of y + y' nickel-base superalloys depends on the precipitation of the y' phase [basically Ni3(Al,Ti)]. This paper presents new data on the strength characteristics of single crystals of simple y' (Ni3Al), and forms the first step in a systematic program aimed at elucidating the mechanisms of hardening in the complex commercial alloys. 1) EXPERIMENTAL PROCEDURE Single crystals of off-stoichiometric NiA1 were grown from the melt under vacuum by a modified Bridgman method. The melt was poured into a preheated alumina mold and crystal growth was promoted from one end by gradient cooling. The crystals were homogenized by annealing in hydrogen at 2400° F for 72 hr followed by furnace cooling. Chemical analysis of samples taken from several crystals gave an average composition of 88.2 wt pct Ni. Spectrographic analysis gave as the principal impurities in weight percent— Si (0.02), Mg (0.01), Fe (0.02), Ti (0.002), Cu (0.008), and Co (0.03). Tensile specimens with specifications as in Fig. 1 were prepared by a series of operations involving electrical discharge machining, precision grinding, and electropolishing. Compression specimens with dimensions 1/4 by 1/4 by -3/4 in. were prepared in a similar manner, except for the initial shaping operation using a precision cut-off wheel/two-circle goniometer unit to give selected crystal orientations. Specimens were deformed in a Baldwin-Wiedemann testing machine with furnace attachment, using a strain rate of 5 x 10-4 sec-1. The strain measuring device consisted of extension arms attached to the tensile grips (or compression plattens) at one end and leading out of the furnace to an LVDT at the other. Temperature was controlled by a thermocouple placed in contact with the specimen. According to the known phase diagram for the Ni/A1 system,' when an alloy of the specified composition is cooled from the melt, primary y (nickel solid solution) dendrites grow at the expense of the liquid phase, which becomes enriched in aluminum. At the eutectic composition the remaining liquid freezes as a two-phase mixture of y + y' (Ni3Al). Upon further cooling, a solid state transformation occurs, involving the precipitation of y' in the primary dendrites, and the complete transformation of the eutectic mixture to massive y'. The as-cast structure consists, therefore, of y + y' dendrites with interdendritic regions of massive y', i.e., transformed eutectic, Fig. 2. 2) DISCUSSION OF RESULTS 2.1) Stress-Strain Curves. Fig. 3 shows tensile stress-strain curves for crystals in orientations close to [001] deformed at temperatures from 70° to 2000°F. Both the yield stress and total elongation are strongly temperature-dependent. At 70°F, easy glide is absent, and the work hardening coefficient BIT - G/300. At T > 1500°F, the negative slope of the stress-strain curves is due to pronounced necking in the crystals. The yield stress maximum at 1500° F corresponds with a minimum in the ductility, Fig. 4. The extensive duc-

Jan 1, 1968

By Charles R. Stewart, William W. Owens

Reservoir performance predictions based on laboratory core test data assume that fluid flow is laminar for the laboratory test. A study has been made to determine the validity of this assumption for laboratory tests on various types of porosity found in producing limestone formation. Data are presented which show that turbulence and slippage can occur during laboratory tests on hetero-geneous-type porosity limestones, thus causing serious errors in measured single-phase permeabilities and two-phase relative permeability characteristics. In single-phase flow tests it is possible to eliminate turbulence and correct for slippage or to eliminate both factors by controlling test conditions. It is not always possible to control test conditions and thereby eliminate turbulence and slippage in two-phase .flow tests. A correction method is presented which can be used to calculate the true two-phase laminar flow relative permeability characteristic even though furbulence and slippage exist. .INTRODUCTION It is customary to make use of Darcy's law and modifications of this law, together with laboratory data on formation core samples to predict the performance of producing reservoirs. Such predictions are based on an assumption that fluid flow is in the laminar or streamline region for the laboratory test. It was the purpose of this inves- tigation to determine the extent to which turbulent flow may occur in laboratory fluid flow tests on hetero-geneous porosity limestones. Considering that turbulent flow conditions might exist in some laboratory fluid flow tests, additional emphasis was placed on the development of a method to correct for turbulence when laminar flow conditions could not be attained. FLUID FLOW CONCEPTS FOR POROUS MEDIA The Influence of Pore Geometry on Fluid Flow One of the more important factors influencing fluid flow in porous media is the geometry of the pore space which includes such characteristics of the pores as size, shape, distribution, roughness, uniformity, etc. In general, oil- and gas-producing formations can be divided into two broad types on the basis of pore geometry. One has been called sandstone-type porosity media, which is characterized by a small range in pore size, uniformity in shape of the pores, smooth pore surfaces and a regular and uniform distribution of pores. The other type has been called heterogeneous porosity media and is usually limited to the dolomites and limestones. This type is characterized by a wide variation in the size, shape, and distribution of the pores and rough, irregular pore surfaces. It is therefore apparent that conditions are much more favorable for turbulent flow* in heterogeneous-type porosity media than in sandstone-type porosity media. Interrelationship Between Turbulence and Gas Slippage In studying the problem of turbulent flow in laboratory tests on porous media, it is necessary to be aware of the interrelationship between slippage and turbulence for gas flow. As a result of slippage or the Klinken-berg effecta, apparent perrneabilities to gas are greater than the true value because there is no stationary layer of gas in contact with the walls of the flow channels. Gas slippage decreases as the mean free path of the gas molecules decreases. Since the mean free path of any gas decreases with increasing density, increases in static pressure result in lower apparent gas permeabilities. However, a reduction in gas permeability can also be due to turbulence. Therefore, in studying only turbulent flow in porous media, it is necessary to hold gas density, and slippage, constant or to reduce slippage to a negligible value by operating at high static pressures. Presentation of Laminar and Turbulent Flow Data A graphical relationship between permeability and a pseudo-Reynolds number, N,, will be used to show the two types of fluid flow, i.e., laminar and turbulent. The usual graphical method for such a description has been the use of friction factor-Reynolds number charts4. On such a logarithmic diagram, the laminar region appears as a straight line having a slope of 45 degrees. As the friction factor decreases and the Reynolds number increases, the turbulent region is reached and appears as a deviation from the 45-degree slope line. However, in petroleum engineering literature resistance of por-

By J. H. Waxweiler, L. C. Ikenberry, R. J. Bendure

Carbon which is present as insoluble carbides in austenitic stainless steels can be measured quantitatively by dissolving the steel in iodine-methanol and analyzing the residue for carbon. Severe sen-sitization was observed in Type 302 due to precipitation of only 0.003 pet carbon. Both cold work and the presence of delta ferrite caused a marked acceleration in rate of carbide precipitation. Carbide precipitation rates in 17-7 PH were stzulied for the austenite conditioning and also the aging heat treatment. CARBON and its compounds exercise a major influence on the properties of stainless steels and their response to thermal treatment. Sensitization in 18-8 type stainless steels has been the subject of numerous investigations throughout the years. Bain, Aborn, and utherford," and Binder, Brown, Frankss all studied the effects of heating austenitic stainless steels in the temperature range of 1000° to 1500°F. The primary purpose of most of these studies was the investigation of susceptibility to in-tergranular attack in acids due to these sensitizing heat treatments. Intergranular precipitation of carbides was always associated with intergranular attack but it was recognized2 that severe attack could occur with but minute quantities of precipitated carbide. Mahla and ielsen utilized the electron microscope to make a significant contribution in illustrating the appearance and method of growth of chromium carbides during sensitizing heat treatments. However, as they stated, their studies of residues could not be used to obtain a quantitative measurement of the amount of carbon which was actually precipitated. The aim of the present investigation was to devise a relatively fast, simple method for the quantitative measurement of carbides in stainless steel. EXPERIMENTAL WORK The initial investigations were made to determine the best means of separating carbides from the matrix. A number of dissolving media were tried using both chemical and electrolytic attack. Qualitative examination of the extracted residues by X-ray diffraction indicated that solution in iodine-methanol would furnish a good means of separation. Consequently, further work was pursued along this line. The method is quite simple. The sample in the form of millings or nibblings is dissolved in iodine-methanol solution at room temperature (6-g iodine, 25-ml methanol per g of sample). The insoluble residue containing the carbides is separated by suction filtration through an ultra-fine glass filter disc. This is a very fine filter medium that will retain particles as small as 0.1 to 0.2 p in diameter. After washing with methanol and drying, the filter disc and residue are placed in a conventional combustion carbon-tube furnace and the carbon determined gravimetrically. Using this technique it was found that reproducible insoluble carbon values were obtained. However, since such small amounts of insoluble carbon were obtained on Type 302 after sensitizatipn at 1250°F and 1500°F, the values were confirmed by a second method. In the second method the sample was dissolved with copper potassium chloride and filtered through a millipore paper. This treatment dissolves the matrix but leaves undissolved practically all of the carbon irrespective of how it is present in the steel. The amount of insoluble carbon present as chromium carbide is determined by calculation from the analysis of the residue for chromium and iron. The derivation of the formula used for this calculation is discussed later. The values obtained by the indirect copper-potassium-chloride method were in agreement with those obtained by the iodine-methano1 method. See Table I. It should be pointed out that the sensitivity of the direct combustion method is not too high when the amount of carbide present is small. This is due primarily to inherent blanks and to analytical errors such as weighing. For this reason it cannot be stated with any degree of certainty that there is a significant difference between values of 0.002 and 0.005 pct. Having confirmed that the iodine-methanol extraction gave a quantitative measurement of the precipitated carbides in Type 302, exploratory tests were conducted on Armco 17-7 PH stainless steel. Samples from commercial Heat 54807 were solution annealed at 2000°F, water quenched and heated at 1250" and 1500°F, and water quenched. The analysis of Heat 54808 is as follows:

Jan 1, 1962

By R. J. Burgess, A. R. Ramey, A. R. Adams

During interpretation of pressure buildup tests on gas wells in a tight dolomite gas reservoir, peculiar behavior was noticed. Two straight lines were apparent. Effective permeability to gas taken from either straight line was about the same, and the Miller-Dyes-Hutchinson dimensionless time check for the straight line was proper for both straight lines. Geological data indicated the likelihood of scattered trending fractures in the reservoirs. Since the first straight Iine yielded permeability values close to the geometric mean permeability from core analyses, it was postulated that the reservoir model was that of an acidized well completed in the tight dolomite, but that widely scattered hairline fractures caused the mean permeability of the reservoir distant from the well to be higher than the matrix permeability. Because all other studies of fractured reservoirs to the authors' knowledge assumed that the fracture matrix was dense enough to communicate directly with the well, no interpretative methods were available. The Hurst line-source solution for a radial change in permeability for interference between oil reservoirs was adapted to pressure buildup testing. The result indicated that the first straight line should yield the proper matrix permeability and wellbore skin effect. The second straight line may be extrapolated to obtain static pressure. The time of bend between the straight lines was used to estimate distance to a fracture. Application to field test data is shown. It is believed that the methods developed and the case history presented will add to present tools available for pressure buildup interpretation. Introduction Since the pioneer studies by Miller, Dyes, and Hutchin-son1 and Horner' in 1950 and 1951, well test analysis has become recognized as one of the most powerful tools available to both production and reservoir engineers. Well test analysis serves as a logical basis for well stimulation and completion analysis, and for long-term reservoir engineering. Since the early 19501s, much effort has been placed on the development of well-test analytical methods. Reservoir and well conditions of increasing complexity have been considered systematically to provide the analyst with a catalog of causes and effects. Matthews and Russella state that some 200 papers dealing with this subject have been published in the last 35 years. Developments in well test analysis appear to have originated in one of two ways. Either a physically realistic field condition was anticipated and analytical solutions for the condition achieved, or anomalous field test behavior was recognized and interpretative methods sought for the anomaly. In recent years, it has appeared that the latter has inspired an increasing number of studies. The analyst today finds an increasing number of known cause and effect studies available for well test analysis, the classic of which is that of finding the specific flow problem that generated the answer — the well behavior. Although it may be impossible to achieve this goal uniquely, the analyst often is able to select a useful interpretation that combines all known performance and geologic data — or to show that various logical alternatives would not significantly affect the interpretation. During a recent reservoir study, we observed gas well test behavior that did not appear to fit behavior described previously. Although it cannot be said that we have found a unique interpretation, we shall present in this paper the peculiar behavior observed, and describe the reservoir and interpretative methods developed. Reservoir Description The subject gas reservoir is a 9-mile-long, narrow dolomite reservoir lying within a limestone of Ordovician age. (See Fig. 1.) The dolomitized rock in the field consists of dark brown to buff, dense to coarsely crystalline, vugular dolomite containing numerous hairline fractures, many of which may have been closed in the reservoir and parted when cores were brought to the surface. Larger fractures are also apparent in core, but usually are filled and sealed with euhedral dolomite crystals. Portions of the north flank of the reservoir are known to be cut by a sealing fault downthrown to the north. Gas wells located near the fault have higher open flow potentials than those more distant from the fault. This is believed to be a result of higher permeability near the fault due to more extensive and open fractures. Detailed coring and core analysis have been performed on several of the wells in this reservoir. Fig. 2 presents permeability variation' plots for both horizontal and vertical

Jan 1, 1969

By W. R. Hibbard Jr., R. W. Guard, N. G. Ainslie

Evidence is presented that copper-base solid solutions of different solutes having equal grain sizes, no preferred crystal-lographic orientation, equal electron-atom ratios, and, within experimental scatter, identical initial yield strengths, need not have identical stress-strain curves at strains larger than about 0.04. The stress-strain behavior is rationalized in terms of the proposed Suzuki chemical interaction between solute atoms and extended dislocations using what is thought to be a somewhat different means of representing stress-strain data. ALTHOUGH the effect: of alloying element upon the strength characteristics of sold solutions is a subject which has received considerable attention in the past, the exact relationships between the common deformation parameters and certain common variables are not really known in some cases. As a result some of the experiments reported in the literature in which these variables are inadequately controlled lose some of their persuasion regarding underlying principles. Nonetheless, facts are known which bear pointing up: When the true stress, a, and true plastic strain, E, of tensile deformatic~n are plotted on a double logarithmic coordinate system, one may observe a straight-line relationship at strains greater than 0.02. The form of the curve in the linear region is given by a = Ken! where a represents true stress, E, true strain, and K and tn, constants. If the relationship holds, K and m define the flow characteristics of the material being tested. m and K, however, may vary with other parameters. Hollomon found that in a-brass, m is influenced by grain size. French and HibbardZ found in alloys of copper that inverse relationships existed between m and 1) the solute concentration for a given solute, 2) the 0.01 yield strength, and 3) the constantK. Lacy and Gensamer3 observed (du/d~) (= U/Em) to increase with increasing values of K in systems of alloyed ferrites (although with considerable scatter of data which may be attributed to uncontrolled grain size). Brick, Martin, and Angier* deduced in copper-base alloys a straight-line relationship (with some scatter) between the change in the Dph number due to solid-solution strengthening and the change in the Dph number due to work hardening which suggested that copper-base alloys having equal yield strengths might have identical stress-strain curves in the plastic flow regions. French and HibbardZ concluded that the yield strength of copper-base solid solutions is the proper basis for comparing the effects of solute elements. Also, Allen, Schofield, and ate' showed that, within their experimental variation, copper-base alloys of zinc, gallium, germanium, and arsenic having the same electron-atom ratios have the same true-stress true-plastic strain curves. Dorn, Pietrokowsky, and ~ietz' also found that with aluminum-base alloys the stress-strain curves in the flow regions are approximately the same if "equivalent" concentrations of alloying elements are used. Solute valence and lattice parameter distortion were the parameters used to determine equivalency. The present report describes an investigation in which an attempt was made to obtain copper-base solid-solution alloys of four solute elements having within close tolerances equal grain sizes and yield strengths, and to see if the level of yield strength does indeed define the flow curve regardless of solute type. During analysis of the data certain unexpected features of the stress-strain curves became apparent which gave rise to some speculation and are discussed at length in the paragraphs that follow. EXPERIMENTAL PROCEDURES Alloy Preparation—Using the data of French and HibbardZ as a first approximation, four different binary copper-base alioys were designed so as to have the same yield strength. In addition, other alloys were prepared in which the solute aoncentrations varied slightly from those calculated above so as to span a range of yield strengths, see Table L The yield strengths of all alloys prepared except the copper-tin alloys were subsequently found to Lie fairly close to one another. The copper used in the alloys was produced by the American Smelting and Refining Co. and was of very high purity (99.999 pct). The alloy additions and their initial purities are as follows:

Jan 1, 1960

By R. D. Burlingame, T. L. Joseph, Gust Bitsianes

DESPITE almost fifty years of commercial practice, the sintering of iron ore has received little fundamental study. Much of the theoretical work1-'has dealt with the constitution of sinter produced under widely varying conditions. While these studies have broadened our knowledge of the changes that occur in the sintering zone and in the freshly formed sinter during the early stages of cooling, they provide little insight into the changes that precede the formation of sinter. These preliminary changes merit study as a part of the overall process. Hessle. working with beds of Swedish magnetite concentrates, was one of the first investigators to study the sintering process in its entirety. On the basis of temperatures observed at various levels of the bed during sintering, he postulated a number of distinct reaction zones to account for the chemical changes leading to the formation of sinter. A more direct method of attack is that of arresting the sintering zone after it has progressed part way through the bed. A study of a vertical cross section through such a quenched bed provides direct information on the changes taking place at various levels. This method was used by McBriar et al.' to show that several well-defined zones of chemical change existed within beds that were typical of British sintering practice. The same general method of attack was developed independently in the present investigation to study partially sintered beds typical of American practice. Experimental Sintering Equipment The sintering operation was carried out on an experimental scale with the equipment shown in Fig. 1. The refractory-walled sintering chamber A was 11 in. deep and averaged 9 in. in diameter. Air was introduced through a tapered flow section B, which contained the orifice C for accurate metering of the incoming air. This section was located directly above the square ignition housing D, which in turn rested upon the sintering chamber A. The bed was ignited with burner E. The required suction for the operation was furnished by a fan F, which had an air capacity of 500 cfm (stp). Hot exhaust gases from the sintering chamber were cleaned in the dustcatcher G before entering the exhaust fan. In the study of partially sintered beds, it was essential to find some technique for removing the entire charge from the sintering pot without disarranging the unsintered bottom portion. This problem was finally solved by sintering the charge in a removable basket, which snugly fitted the sintering chamber. This basket was constructed of two thicknesses of window screen and was lined with a 3/16-in. layer of asbestos paper. The bottom of the basket consisted of two thicknesses of wire screen, which were fastened to the basket wall. For high fuel mixtures, additional insulation was provided by a somewhat thicker layer of asbestos cement. Preparation of Partially Sintered Mixtures The moist feed was carefully placed in the sintering basket, to prevent segregation of the particles, which varied widely in size and composition. A thermocouple was placed in the center of the basket with the hot junction halfway down, and the mixture was evenly distributed around it. During ignition and throughout the sintering of the upper half of the bed, the hot junction temperature increased very little. When the sintering zone reached the halfway point, as indicated by the sudden increase in the hot junction temperature, the charge was quenched. During quenching the suction was turned off and the orifice was tightly stoppered to prevent further influx of air. At the same time, nitrogen was admitted to the sintering chamber through the orifice tap. As soon as the nitrogen had displaced the air and products of combustion, the charge was removed from the sintering pot for immediate dissection. It is impossible to preserve the exact zone structure of the bed at the instant that combustion is arrested unless the downward transmission of heat is also immediately stopped. Fortunately, heat transfer is very slow in beds containing a stationary fluid, especially if the particle size is small. It follows that the minimum quantity of nitrogen should be used to displace the air and that static conditions be established as soon as possible. A very steep temperature gradient across the combustion zone for some time after the quench was evidence of in-

Jan 1, 1957

By Peter Tegart

The discovery of gold in the Toodoggone River area is credited to Charles McClair who mined placer deposits in 1925, reportedly valued at $17,500. After he and his partner went missing in 1927, efforts to relocate their workings resulted in the formation of Two Brothers Valley Gold Mines Ltd. in 1933, in which the legendary Grant McConachie (first president of CP Air) played an active role. This was the age when the prospector first utilized the airplane to reconnoitre remote areas. What greeted the observer from the air was an area rich in orange and yellow colours characteristic of gossans formed by the oxidation of sulphides. However, Samuel Black, a Hudson Bay Company fur trader, had also noted in his diary as early as 1824, the unusual and many gossanous colours in the headwaters of the Finlay River. These gossans, coupled with white limestone bluffs and the presence of placer gold, attracted the first reconnaissance of the area by Cominco in 1929. Cominco was ever active in remote areas at this time. They staked and worked several base-metal showings hosted by limestone at the margins of intrusive stocks. These early workers also obtained erratic high gold assays from chalcedony float samples found in creeks draining into the Toodoggone River. However, because the samples gave inconsistent assays, no concerted effort was made to locate their source. Except for the occasional horse-supported prospecting party of the late 1940s and early 1950s, the area did not receive much attention until 1968. Work until this time focused on the base metal lead-zinc showings which contained attractive silver credits. Gold was not an attraction because of the set price established by the US government. The late 1960s saw the northward expansion of porphyry copper exploration into the Toodoggone. A program of gossan soil sampling (gossans which had attracted the early workers) was carried out by Kennco Explorations (Western) Ltd. in 1966-1967. They analysed for base metals in the field, using a cold extraction method. The Kemess copper- gold prospect was staked as a result of anomalous copper values from this early geochemical program. In 1968, Kennco continued the program of silt traversing and field geochemical testing. The samples were further subjected to multielement analysis consisting of copper, molybdenum, lead, zinc, cobalt, nickel, and silver at Kennco's North Vancouver laboratory. Several anomalous creeks, high in combinations of copper, molybdenum, and silver, were outlined. Some initial soil grids were also established. The fall of 1969 saw the return of Kennco prospector Gordon Davies and geologist Bob Stevenson to check out a well-defined molybdenum, scattered copper and silver anomaly in soils from a grid on the Chappelle claims. The subsequent analysis of several selected quartz felsenmeer floats yielded one assay which ran in the order of 0.25 kg/t (8 oz per st) gold and 2.2 kg/t (70 oz per st) silver. Subsequent trenching on the Chappelle claims exposed the source of float in a 4- m (134) wide vein of high grade gold-silver mineralization. These results led quickly to the realization that the district had precious metal potential. Subsequent exploration in the period 1969-1974 by Kennco resulted in the discovery of most of the gold and silver occurrences on the Chappelle and Lawyers properties. Several other gold and silver occurrences were found in this district by Cordilleran, Cominco, and Sumitomo, working the district during this period. Conwest optioned the Chappelle in 1973 and explored underground by adit entry as part of a one-year program. In 1974, Du Pont of Canada Exploration Ltd. optioned the Chappelle claims and in March 1980, using reserves developed on the A vein, placed the Baker mine into production at a rate of 90.7 Vd (100 stpd). The Amethyst zone on the Lawyers property, 8 km (5 miles) north of Chappelle, was found in 1973 by Kennco using continued, persistent followup prospecting of silver silt geochemical anomalies. A silt anomaly in the order of 3.4 ppm silver occurred in a stream flowing 300 m (984 ft)

Jan 1, 1985

By A. S. Odeh

This paper analyzes the effect of limited entry to flow at the wellbore on the steady-state productivity of a well. Wells that have been opened to flow along a fraction of their productive interval are termed wells with limited entry. Previous work treated the cases of a partially penetrating well, a well producing from the central portion of the productive interval and a well in which several intervals equally spaced were open to flow. In this paper the open interval can be located anywhere within the productive interval. Thus, in a sense, it generalizes previous work. The finite cosine transform was used to arrive at a solution for steady-state flow of a slightly compressible fluid. The solution was programmed for a CDC 1604 computer. Numerical vaIues for rd = 660 ft, r, = 1/4 ft, and range of sand thickness of 20 to 200 ft are presented in graphical form. The effect of rd and r, values on the result is shown in a table. The correct calculation of skin and damage ratio in the presence of limited entry to flow is explained and illustrated by examples. Moreover, the paper shows how to calculate the net decrease in productivity due to the combined effect of limited entry and perforations. INTRODUCTION In some wells only a fraction of the productive interval is open to flow. Location of this fraction is usually dictated by formation characteristics and reservoir behavior. For instance, if a gas cap exists, the open interval is located away from the gas-oil contact to prevent any possible gas coning. Wells that intentionally have been opened to flow along a fraction of their productive formation are tened wells with limited entry. Obviously, unintentional completions of this type also exist. Limited entry to flow decreases well productivity. Magnitude of the loss depends on the fraction of the formation open to flow, on the thickness of the sand, on the location of the open interval and on the ratio of rd /r, where r , is well radius and rd is the drainage radius of the well. The use of pressure buildup data on producing wells to calculate the condition of the formation around the wellbore is an accepted practice. van Everdingenl and Hurst2 introduced the concept of she skin factor s considered to be due to a thin layer of different permeability immediately around the wellbore. These authors dealt with the case of a well of complete radial geometry, i.e., a well with open-hole completion that completely penetrates the formation. The presence of a low-permeability skin results in a loss of productivity, as does limited entry. Therefore, if pressure buildup data obtained on a well with limited entry are used to establish the presence or absence of skin (i.e., formation damage), and a correction is not made for this loss of productivity, the calculations would result in an erroneous skin value. They might indicate the presence of formation damage when in reality there is none, or they might indicate a value larger than the true value. This could lead to an incorrect basis for planning remedial measures. Muskat3 studied the problem of partially penetrating wells for the case of incompressible flow. He presented equations and figures which allow estimation of loss in productivity. Brons and Marting,4 using equations based on Nisle's work,5 studied the loss of productivity for three cases. The first was for a partially penetrating well; the second was for a well producing from only the central portion of a productive interval; and the third was for a well in which several intervals equally spaced were open to flow. Their work was for steady-state depletion-type reservoirs wherein the well radius of drainage is established and the fluid is considered to be slightly compressible. Considered in this paper is the problem of wells with limited entry in which the open intervals are located anywhere within the productive sand. The finite cosine transform is used to arrive at a

Jan 1, 1969

By F. Bonaccorso, G. Venturello, C. Antonione

A study of the effect of small amounts of interstitial impurities on recovery and re crystallization in high-purity iron (99.995 pct) has been undertaken. This paper gives results on the effect of carbon, introduced in small-dosed amounts @om 0.0005 to 0.0086 wt pct) by heating iron specimens of high purity m a static atmosphere of CO + ,. The materials prepared in this way, cold-worked 80 pct and subjected to a series of isochronal and isothermal annealings, were submitted to examinations by X-rays, micrographs, and hardness tests. It was observed that effect of carbon is remarkable in the sense of blocking recovery of mechanical properties up to the temperature at which re crystallization begins. On the contrary, carbon has a negligible effect on primary re crystallization temperature, when compared with the known effect of substitutional impurities. This is in agreement with the high mobility of interstitials. In effect, only a slight decrease, -20 pct, of the grain-boundary motion rate was noted, due to the interaction between the grain boundary and the carbon atoms. On the other hand, in the samples in which the carbon content is above the solubility limit at the temperature at which re crystallization occurs, a slight increase of nucleation frequency is noted due to the presence of precipitated carbides. ThE effect of purity on recovery and recrystalli-zation phenomena has been known for a long time; however, recently, new attention has been given to the problem since new methods for obtaining metals with extremely low impurity contents have become available. Most of this research work essentially concerns the effects of impurities which cause precipitates or give rise to substitutional solid solutions. The works of Bolling and winegard1 and Aust and utter' on lead, and Vandermeer and orddon' on aluminum, 01sen4 on nickel, and Abrahamson and Blakeney on iron should in particular be referred to. On the effect of this type of impurities a quantitative theory has been formulated by Detert and Lucke6 and has lately been discussed critically by Cahn7 and Gordon and vandermeer.' Interstitial solid solutions in iron have not as yet been studied. As the study of the effect of interstitials is of great interest both from a theoretical and practical standpoint, it was deemed useful to examine the effects of carbon, nitrogen, and boron on recovery and primary recrystallization of iron. There already is some work by Chaudron et al.,1-" on the effect of interstitials on iron; their work, however, mainly concerns secondary recrystallization. The present paper refers in particular to the effect of carbon. EXPERIMENTAL PART Preparation of Materials. The pure iron used for this research was obtained from FeCIS recrystal-lized and purified by extraction with isopropylic ether. From the ferric chloride purified in this manner, hydroxide was precipitated with a solution of very pure ammonia, and, by calcination in pure sintered alumina crucibles, oxide was obtained. Reduction of the oxide to iron sponge was performed in sintered alumina tubes with very pure hydrogen at 650°C; at the end of the operation temperature was increased to 900°C. Specimens for the experiments were obtained by sintering the sponge at 1480°C in pure Hz after a pre sinter ing treatment at 900° C. It is important to note that the treatment at 1480°C in Ha produces a further purification from more volatile elements such as zinc, cadmium, arsenic, lead, and tin. Details on the preparation and characteristics of this type of very pure iron are given in a previous work.'' Only the complete analysis performed by neutron-activation methodsz3 is given here, Table I. Some of the specimens prepared in this way were carburized in the 0 region with very low amounts of carbon by treating them at 700°C in a static atmosphere of Ha containing a definite amount of CO. The set-up used is described in Fig. 1. A gas-tight quartz tube containing the specimen to be carburized and an internal friction control specimen, after being evacuated, was filled with Hz

Jan 1, 1963

By N. Brown, R. Kossowsky

Plain carbon steels with 0.48 and 0.95 pct C were quenched and tempered at 705°C to produce carbide dispersions with spacings on the order of 1 p. The morphology of the structure consisted of a carbide-dislocation network. The strengthening due to the dispersion was found to vary linearly with M-½ where M is the mean free-ferrite path determined by the entire network. No preyield microstrain preceded the upper yield point. After prestraining, the lowest stress at which dislocation movement could be detected was 104 psi; this frictional stress was independent of the dispersion and prestrains up to 6.5 pct. The Cottrell-Petch equation for grain-size strengthening was used to discuss the dispersion strengthening in this investigation. The results support an impurity mechanism for the upper yield point rather than one based on the Johns ton- Gilman theory. IT was pointed out by Gensamerl that the mean free path in the matrix is the important variable which controls the degree of dispersion strengthening. Gensamer's data on steels showed a linear relationship between the yield point and the logarithm of the mean free-ferrite path. The first theory was by Orowan,2 who suggested the mechanism of dislocations bowing between particles, with the resulting relationship that where a is the yield point, P is the distance between particles, and G is the shear modulus. The Orowan equation applies to that range of dispersion where P is large compared to the particle size and the particles are not coherent, so that the matrix is essentially free of internal stresses. As was pointed out by Orowan, there are different degrees of dispersion which, in turn, will influence the strength-controlling mechanism. However, in this investigation, we wish to confine ourselves to the region of coarse dispersion, where the Orowan mechanism should, intuitively, be applicable. It was soon evident that the data, which existed at about the time that the Orowan theory was proposed, did not agree with the Orowan equation in that the actual strengthening was always greater than the theoretical predictions. Thus, Fisher, Hart, and pry3 modified the Orowan theory by suggesting that the Orowan process took place in the microstrain region preceding macroscopic yielding and the subsequent, rapid work hardening in the form of residual dislocation loops around the particles largely determined the observed macroscopic yield point. The F-H-P theory stated that the increment of strengthening due to the work-hardening mechanism was proportional to f3/2 where f is the volume fraction of the precipitate. F-H-P used data by Shaw, Shepard, Starr, and Dorn4 on A1 3-5 pct Cu to support their theory. Roberts, Carruthers, and Averbach5 were the first to make a microstrain study of dispersion strengthening, and they found that for steel the Gensamer relationship was obeyed. Hayman and Nutting6 suggested that in the case of tempered steel 1) the ferrite grain boundary was the primary obstacle and 2) the carbide particles simply formed part of the grain boundary obstacles. They found that the strength varied as G"" where G is the ferrite grain size. Turkalo and LOW' determined the structure of quenched and tempered plain carbon steel using a replica technique; they concluded that the carbide particles did not necessarily lie in the ferrite grain boundaries. When they defined the mean free-ferrite path as being determined by both particles and the ferrite path boundaries, their data obeyed the Gensamer relationship. Meiklejohn and skoda8 showed that the strengthening from iron particles in mercury was a function of the particle size and the distance between particles. Dew-Hughes9 explained the Meiklejohn and Skoda results by the following theory: 1) grown-in dislocations which surrounded the particles were produced by the thermal stresses during the time the material was cooled to the testing temperature, and 2) the observed strengthening was associated with the cutting of the grown-in dislocations by the glide dislocations. Ansell and Lenel10 proposed a theory in which the glide dislocations pile-up or surround the particle until the number of dislocations in the pile-up is sufficient to yield or fracture the particle. The resulting theory says that the yield point varies as p-1/2, where P is the distance between particles. The Ansell-Lenel theory is almost identical to the

Jan 1, 1965

By D. A. Elgillani, M. C. Fuerstenau

In this paper, oxidation potentials measured in the presence of various concentrations of cyanide, ferro-cyanide, and ferricyanide and ethyl xanthate at various values of pH are related to flotation response. Eh-pH diagrams are presented to show that the formation of surface ferric ferrocyanide is probably responsible for depression when cyanide is added. The influence of cyanide on the depression of pyrite with xanthates as collector has been the subject of a number of investigations,'-6 and several theories on the mechanism of depression have evolved from these studies. Wark and Cox7 and Gaudin8 have suggested that the depressing effect is due to a competition of cyanide ion with xanthate ion for the surface. Cook and his colleagues9-11 have explained this phenomenon in terms of competition between hydrocyanic acid and xanthic acid. Sutherland 12 has shown that although both of these theories accurately describe the relation between pH value and cyanide addition at constant collector addition, they fail to describe the relation between pH value and the amount of collector required to cause flotation. Taggart 13 suggested that depression in these systems is due to the formation of a reaction product between ferric ion at the pyrite surface and ferrocyanide ion derived from solution. Majumdar4,6 has attempted to prove this hypothesis by measuring the contact angles of pyrite in the presence of 25 mg per liter ethyl xanthate and different concentrations of potassium ferrocyanide and ferricyanide. In all cases the contact angles were quite high up to pH 10. These results indicate that pyrite should not be depressed by either potassium ferrocyanide or ferricyanide. In view of these facts, Majumdar has assumed that the compound Fe(CN)2 forms at the surface. Gründer and Bornl4 have stated that depression may be due to the formation of the compound K2Fe(II)Fe(CN)6 at the pyrite-solution interface. This compound is thought to be an interaction product between the K2Fe(CN)6-2 ion from solution and the Fe++ ion at the pyrite surface and, accordingly, K4Fe(CN)6 should depress pyrite at least as effectively as KCN. This was proven experimentally, but there was no simple relation between the depression of pyrite and the concentration of either KCN or K4Fe(CN)6 in solution. In view of the many mechanisms that have been proposed for pyrite depression by cyanide, it is apparent that a clear understanding of the phenomena occurring in these systems is lacking. One reason for this may be the fact that the species responsible for pyrite flotation in the presence of xanthate is not the xan-thate ion but rather dixanthogen.15 Since the oxidation of xanthate to dixanthogen is dependent on the oxidation potential of the solution, it would seem that knowledge of these potentials would be a requisite to understanding the pyrite-xanthate-cyanide system. It is the object of this paper to measure both the oxidation potential and pH of the pyrite systems in the presence of various concentrations of cyanide, ferrocyanide, and ferricyanide and xanthate and to relate these values to flotation response. EXPERIMENTAL MATERIALS AND 'TECHNIQUES In the experiments discussed here, pure potassium ethyl xanthate was used as collector, and reagent grade potassium cyanide, potassium ferrocyanide, and potassium ferricyanide were used as depressants. Reagent grade HC1 and KOH were added for pH adjustment. Conductivity water, made by passing distilled water through an ion exchange column, was used in all experimental work. Two natural samples of pyrite were used in the investigation. Sample preparation for flotation included dry grinding with a mortar and pestle and sizing the product to 100 x 200 mesh. Prior to flotation, a 0.75-gm sample of pyrite was added to a solution containing a known amount of depressant at the desired pH value, and the system was conditioned for 4 min. Following this, a known amount of collector was added and the system was conditioned for another 4 min. The pH — termed flotation pH - was measured; the pulp was transferred to a Hallimond cell, and flo-

Jan 1, 1969

By Richard O. Y. Breese

Geologically and commercially, the term diatomite is applied to the nearly pure sedimentarv accumulation of diatom frustules- the microscopic skeletons of unicellular aquatic algae belonging to the class of golden brown algae, bacillariophyceae. The sediments are fine-grained, siliceous, and consist primarily of amorphous opaline silica with only minor amounts of organic residue, secondary minerals, and co-deposited non-diatomaceous or crystalline clastic debris. In the geological sense, the name diatomite implies sedimentary accumulations that have reached appreciable thickness and when thick enough, such accumulations consequently may have possible commercial potential. Although the term diatomite is popularly and inappropriately applied to any sediment in which there is an abundance of diatom frustules, alternative terminology is more correctly employed to describe the less pure diatomaceous sediments, for example: clay-bearing diatomite or diatom-bearing clay. Synonyms in current usage include diatomaceous earth and kieselghur. More antiquated and obsolete terminology includes tripoli-powder, tripolite, and infusorial earth. Worldwide, diatomites occur within Tertiary to Recent lacus- trine and marine sedimentary facies. Although diatomite is wide- spread throughout the world, deposits that contain high purity, commercially versatile ore are uncommon. Physical properties of the diatom and of processed diatomite that provide unique commercial value in a broad spectrum of market end-uses include ornate fine structure, low bulk density, and high porosity and surface area. Properties of equal importance are mild abrasiveness, high absorptive capacity, insulating ability, relative inertness, and high brightness. End-use markets are diverse and range from insulating brick and absorbents through quality sensitive filter aids and premium quality functional fillers. Notwithstanding both the economic attractiveness of the specialty markets and the commercial versatility of the high purity deposits, deposits of lesser purity are mined in nearly all parts of the world for less demanding uses. Mining costs are minimized through open pit quarrying, but in Europe, Asia, Africa, and South America underground mining methods are also employed. Blasting is not required because diatomite is soft and easily broken loose with mechanized equipment. Following gentle crushing, the ore is dried, milled, and processed into one of three broad categories of products: naturally milled, straight calcined, and flux calcined grades. Each of these principal categories is further subdivided into additional grades through particle size adjustment of the powders. Agglomeration of particles, alteration of fine structure, and color change are achieved through calcination. Flux calcination further accentuates these changes. Production throughout the world is dominated by the United States, followed by Romania, the former Soviet republics, and France. Other major producers include Spain, Mexico, Iceland, Korea, Japan, and Germany. Denmark is a major producer of Moler earth products, which consist of a diatomite-clay mixture. HISTORICAL BACKGROUND The first industrial use of diatomite can be traced back some 2000 years to the Greeks and to the use of diatomaceous earth as a component in lightweight building brick and in ceramic pottery. It was not until the mid-1800s, however, that the unique properties of diatomite were first recognized and the market end-uses explored and developed. One of the most important of the early uses followed the development of dynamite by Alfred Nobel in the mid-1860s, whereupon diatomite was used as a component of the explosive to improve stability and safety. Other early uses included low temperature insulating and refractory bricks and as a component in insulating and fireproofing construction panels. During the 1920s, processing technology underwent a very rapid evolution with the development of calcination, flux calcination, and air classification technologies. Through these technologies, innumerable different size and grade classifications could be made for market applications and for rapidly diversified end- uses. Today, the application of processed diatomite for filter aid is the largest of the quality sensitive end-uses. Specific filtration uses include the clarification of beer, wine and liquor, vegetable oil, syrup and sugar, pharmaceuticals, and swimming pool water, to name a few. As a functional filler and extender, processed diatomite is ideally suited for application in paint, rubber, and plastic formulations. Other filler applications include use as an anti-blocking agent in plastic film, anti-caking agent for fertilizer, thermal insulating material, catalyst carrier, polish, abrasive, pesticide and fertilizer carrier, and chromatographic supports. Throughout much of the world diatomite is still used as a component of insulating brick and as an absorbent.

Jan 1, 1994

By M. Yoshinuga, S. Watanabe

Some iron ores, sinters and pellets occasionally show abnormal behavior during reduction which makes them undesirable as blast furnace burden. These may be divided into the following three types: (1) decrepitation of iron ore, (2) swelling of iron ore and pellet, (3) size degradation of sinter. In this paper reduction experiments and microscopic examinations were made to clarify the mechanisms and causes of these abnormal phenomena. Decrepitation occurs mainly when compact hematite ores containing small amounts of limonite are heated to about 500°C. Abnormal swelling of ores and pellets is caused by the rapid growth of fibrous metallic iron from the surface of wustite grains during rapid reduction and is fundamentally related to their original microstructure. Size degradation of sinter occurs through the development of cracks in the reduction stage from hematite to magnetite. About 80% of the iron ore used in Japan's blast furnaces comes from abroad, and the iron and steel industry must import this raw material from distant overseas places at high freight rates. The blast furnace operators, therefore, have made strong efforts to cut costs under these restrictive raw materials conditions by increasing productivity and simultaneously decreasing coke consumption. If, however, a high proportion of the ore burden consists of unsuitable materials furnace irregularities often result, establishing the need for detailed investigations of the basic natures of the ore constituents and their reactions during the reduction process. Recent investigations '-' of various ore burdens suggest that some iron ores, sinters and pellets are occasionally abnormal in appearance and behavior during reduction studies and may prove to be undesirable for use in the blast furnace. In the present study reduction experiments and microscopic observations were made to clarify the causes and the mechanisms of the abnormal behavior observed in some constituents of the burden and their effect on blast furnace performance. REDUCING APPARATUS The four kinds of reducing apparatus used in this investigation were the following: 1. The JIS* (Modified Gakushin') apparatus shown in Fig. la is most commonly used in Japan to evaluate the reducibility of ores under static conditions. It consists of a stainless steel tube of 60 mm inside diam suspended from a balance. 2. Linder's Reduction Test apparatus (Fig. lc) has a reducing barrel 130 mm diam and 200 mm long which rotates at 30 rpm. Some modifications were made in test procedures. 3. Gakushin Standard Test apparatus for determining the reducibility of granular ores (Fig. Id) consists of a horizontal silica tube 32 mm diam, 370 mm long and a movable electric furnace which enables rapid heating and cooling of the specimens. 4. The test apparatus for reduction under load (Fig. lb) gives a comprehensive evaluation of the behavior of ores under conditions simulating the static loading and the chemical reduction conditions encountered in. a blast furnace stack. A stainless steel tube of 50 mm diam and a carbon rod of 35 mm diam were used as the sample container and the support for the weight, respectively. In each investigation care was taken to select the most suitable method and apparatus to distinguish the abnormal nature of the ore in question. SIZE DEGRADATION OF SINTER DURING REDUCTION Sinter makes up the major portion of the blast furnace burden and its behavior during reduction should bear a close relationship to the iron productivity. Recently, some of the sinter was found to show serious size degradation during reduction at a relatively low temperature range. Because this phenomenon was thought to be a possible source of furnace irregularities, tests were made to clarify the phenom-

Jan 1, 1969

By R. F. Jones, N. E. Truitt, M. Prats

In most published discussions and theories of in situ combustion, the combustion fronts are assumed to be vertical. However, evidence from field tests leaves no doubt that combustion fronts often advance more rapidly along the top than near the bottom of a formation as a result of difference in density between injected air and formation liquids. The approximation proposed in this paper to determine the movement of the resultant tilted combustion surfaces states that the vertical rate of movement of combustion surfaces is proportional to the horizontal oxygen flux. Where self-ignition is possible, the proposed method demands that a secondary combustion surface exist around production wells which produce some oxygen. These secondary combustion surfaces may be formed long before the primary combustion surface can advance from injection to production wells. Heat liberated near production wells at these secondary combustion surfaces can contribute to an early increase in production rate. Results indicate that significant oil recoveries cannot be obtained from the usual flood patterns (five-spots, seven-spots, etc.) without producing large volumes of unused oxygen. Ideally, to increase oxygen- consumption efficiency, well patterns should allow oil production from a first line of production wells and gas production from more distant lines of producers. However, it may be desirable to produce some gas at all wells to support (and benefit from) active secondary combustion surfaces. Results indicate that the well spacing through which combustion can be advanced is larger than that predicted by other methods. A large number of production wells may still be desirable to take quick advantage of gravity drainage. From a comparison with results at South Belridge field, California, it appears that this method adequately describes oxygen concentration and temperature histories and combustion-front shapes. However, this method does not accurately locate the most advanced point of the combustion surface. There is some field evidence to substantiate the actual presence of secondary combustion surfaces at South Belridge. Use of the proposed method appears warranted at this time when lay-over of the combustion surface can be anticipated. INTRODUCTION The assumption of vertical combustion fronts has been embodied in all previous publicationsl-6 which use the movement of combustion fronts away from injection wells to determine the temperature and fluid distributions in the reservoir. The only paper concerned with a mathematical model of the combustion process in which a nonvertical combustion front is used was written by Gottfried.11 Actually, nonvertical combustion fronts have been observed in most in situ combustion field tests for which adequate data are available.7, 8, 6 In practice, the typical vertical extent of the burned zone decreases with distance from the injection well, and this burned zone is at or near the top of the sand body. In some cases, such as at South Belridge field near Taft, Calif., the combustion surface is almost horizontal over a very large area.8 Thus, for some years an obvious and serious gap has existed between theory (vertical fronts) and practice (tilted fronts). This is indicated in Fig. 1. Tilted combustion fronts such as observed at South Belridge8 sometimes result from the natural tendency of injected gases to rise to the top of an oil sand. An initially present gas cap, even if thin, would make apparent the effect of gravity segregation from the first, particularly since formations considered for in situ combustion field operations are generally selected for their

Jan 1, 1969

By Robert G. Page

"Stabilization" of copper differs from sin in at least one respect - no one seems to be against it. Every time a tycoon in the producing industry pontificates on the economic history of copper, or prophesies its future, he is likely to praise the virtues of "stabilization". Consumers of copper constantly bemoan fluctuations in the supply and price of the metal. Governments in some producing countries, to a greater or lesser degree dependent upon exports of copper for foreign exchange and upon taxation of copper profits for substantial parts of their budgets, are perhaps more eager than any other group for "stabilization".

Jan 1, 1962

By A. Y. Bethune, W. G. Woolf

THE hydrometallurgy of special high-grade zinc as practiced by the Sullivan Mining Co. at its electrolytic zinc plant, Kellogg, Idaho, involves an important filtration step immediately following the leaching process. By means of the filtration the heavy zinc sulphate solution is separated from the residual products which remain after the zinc calcine has been dissolved in the sulphuric acid electrolyte. Because this plant uses the so-called high-acid, high-density process' for the production of First, the strength of the electrolyte (270g H,SO, per liter) results in a saturated zinc sulphate solution, having a specific gravity of 1.510 to 1.540, which must be kept warm during filtration because of its property of "seeding out" small crystals if allowed to drop much below 60°C. Second, the action of the "high" acid on zinc calcine under the temperature conditions of the leach (80" to 102 "C), although favorable to good zinc extraction, causes a considerable quantity of iron to be dissolved (8 to 18. g per liter) along with variable quantities of alumina and silica, depending on the grade and type of original zinc concentrates roasted. These three, iron, alumina, and silica, are almost completely precipitated during the neutralization of the leach (only a few. milligrams per liter of each remain in solution), so that the resulting pulp, instead of being a granular, sand-like product having a particle-size distribution dependent on the fineness of the zinc calcines leached, is in reality a slimy, chemical precipitate whose filtration characteristics constantly change depending on the amounts of iron silica, and other impurities, which are dissolved and reprecipi-tated. Third, the combination of supersaturated solution of high specific gravity plus a dense, semi-gelatinous residue creates a difficult washing problem requiring a positive displacement wash to liberate the zinc sulphate entrapped in the pulp. In a closed-cycle hydrometallurgical operation, such as practiced in this plant, the extent of washing is determined by the volum,e limitations imposed on the intermediate wash waters by the amount of "fresh" (or process) water which may be added. The volume of fresh water used for makeup purposes is limited to the amount which is lost during the closed cycle by evaporation in the leach, sulphate content of the calcines leached, moisture content of the residue, and spillage. The Burt filter as modified and improved by the Sullivan Mining Co. has successfully met and overcome these difficulties under a variety of zinc plant operating conditions since 1928. It might have many interesting applications to metallurgical fields other than that of electrolytic zinc, and its possible usefulness to hydrometallurgists in general warrants its description and discussion. The Burt filter is so named from its inventor who originated it in Mexico for pulp filtration in the cyanide process for gold and silver ores. While retaining the basic principle of Burt's earlier revolving pressure-type filter with internal filtration media, a number of modifications and improvements have been made in Sullivan Mining Co.'s installation. The Burt filter may be classified as a batch-type pressure filter in contradistinction to either the conventional vacuum-type filter, which depends on atmospheric pressure to force solution through a cloth medium, or to the filter-press, which employs whatever pressure is imparted by the pump delivering the liquid being filtered. The Burt consists essentially of a hollow steel cylinder about 40 ft long, 5 ft in diameter, resting horizontally, and capable of rotation about its long axis. It is supported on one end by a hollow trunnion and near the other end by a riding-ring and roller combination. The cylinder is lined with filter units each fastened against the inside of the shell and parallel to the long axis so as to form a hollow cavity into which pulp may be charged. A specific amount of pulp is admitted to the filter and a unique valving arrangement prevents the loss of pulp while air pressure forces the solution through a canvas medium to the discharge port of each filter unit. The residue is left on the surface of the canvas inside the cavity. The remainder of the filter cycle is concerned with washing the residue free of zinc sulphate, discharging it from the Burt, and preparing the filter for the next charge. A more detailed description of Burt filter construction, a typical filter cycle, and its operating characteristics when employed on material encountered in this plant will be given in that order. Description of the Filter: Fig. 1 shows a side elevation view of a filter with riveted shell construction. Since this drawing was made shells have been fabricated by welding, instead of riveting, with complete success. Shells are lagged on the outside to retain heat. Fig. 1 shows a side elevation and plan view of a Burt filter in operating position. The 1/2-in. steel shells are lined with 3/16-in. copper sheet as protection against the corrosive action of the solution (containing about 500 mg Cu per liter) on iron, and the copper is given a thin protective coating of plastic-base paint. Fig. 2 is a view from the discharge end of the filter, with head removed, before filter units are fastened to the periphery. It shows

Jan 1, 1951