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By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation' of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,'-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals' force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.' The streaming potential

Jan 1, 1970

By J. A. Putnam, A. D. K. Laird

In laboratory research on the behavior of oil, gas and water in porous materials, no direct method has been devised to measure saturation without disturbing the flow. Indirect methods involving various forms of radiation have been developed for measuring one or two components. The X-ray absorption method for two components has been described previously1-3. The possibility of three component measurement has also been mentioned1. Since two component measurement still requires considerable care to insure accuracy, the fact that three components can be measured satisfactorily is not generally appreciated. The fraction of the energy of an X-ray beam of one wavelength transmitted through a material is given by the transmission factor. in which 1 is the beam's path length through the fluid. p is the fluid density, and 1,. is its mass absorption coefficient. Eq. 1 implies that all parts of the beam pass through equal amounts of the fluid. Practical applications are, therefore, limited to systems in which the fluid is distributed so that I varies negligibly over the cross-section of the beam. Typical variations of the transmission factor with X-ray tube potential arc shown in Fig. 2 from which experimental points have been omitted for clarity. The X-ray absorption of low pressure gases in a core is practically zero so it cannot he distinguished from that a vacuum by instruments that will differentiate between liquids. The transmission factor of a gas in a core is. therefore, unity. Consequently, the saturation of only one gaseous component can be found. If two fluids completely fill a core, their two saturations add to unity and, therefore, only one value of the transmission factor, T, is needed to determine both of them. When two liquids do not completely fill the core, their saturations do not add to unity and transmission factors at two wavelengths must be measured. At one of these wavelengths, 7 for one liquid must be different from T or the other liquid. The change of T for one liquid us the wavelength is changed between the two values must be different from the corresponding change of T in the other liquid. The two values of fluid saturation will also give that of the gas because the three saturations must add to unity. In Fig. 2 it can be seen that there are many large differences of T between various oil solutions and water solutions at any one potential, and between potentials for any one solution. Consequently, conditions for optimum accuracy of measurement of the saturations of a gas and two liquids can be chosen. Once the operating potentials have been selected, however. it is more convenient to cross plot the data from Fig. 2 on transmission factor-solution concentration coordinates for the chosen potentials, as shown in Fig. 3. Fig. 3 was used to plan the experimental procedure for Core N-38-1. Since the voltage control at 45 kv was good, the slopes of the curves in Fig. 2 at this potential would cause little error. At low potentials, however, the voltage control was not good, so 33 kv was chosen because the small slopes of the curves made voltage control less critical. The lowest strength beam that could be measured reasonably at 33 kv corresponded to a minimum T factor of 0.385. Fig. 3 shows that both 4.80 weight per cent of cadmium chloride in water and 24.0 per cent of iodobenzene in crystal oil had this T value, and, consequently, were indistinguishable to the X-rays at 33 kv. Thus, at 33 kv, the liquid saturation was given by the same curve regardless of the relative amounts of oil and water solutions present. This simple calibration curve from which the gas and liquid saturation can be read, is shown in Fig. 4. Fig. 3 also shows that at 45 kv, T for the aqueous solution is 0.610. and that T for the oil solution is 0.220. These values were transferred to Fig. 4 to give the triangular calibration plot from which the brine and oil saturations can be found, after the gas saturation has been determined at 33 kv.

By J. W. Downey, S. T. Zegler

A study has been made of the occurrence of Phases having the Cr30-type structure in ternary alloys having the general composition where B cept for iron and copper all the B components are known to form binary compounds having the type structure. The occurrence of the struc-ture type in the ternary alloys was investigated using optical and X-ray metallography. The results indicate that iron can replace virtually none of the cobalt in at 900°C, but substitutes for nickel in up to the approximate composition tually insoluble in V3Ni and 2) and exhibit complete solubility. At 100 nickel can be substituted for cobalt in VSCo up to the composition solubility; and 3) in the system , two solid solutions having the type structure occur. At the same temperature, 1000°C, V3Si exhibits limited solubility for V3Co but is completely mis-cible with V3Ga. Lattice parameters have been determined for all the binary and ternary phases. The solid solutions are discussed in terms of the atomic size and electronic factors which are thought to influence the occurrence of Cr30-type phases. The binary compounds V3Co and V3Ni were found to form peritectoidally from o phases and a vanadium, the former compound at a temperature between 1000" and 1050°C, the latter between 800°and 900°C. The substitutions of nickel and rhodium for cobalt in V3Co were determined not to raise the superconducting transition of VSCo to a temperature as high as 2°K. The occurrence and stability of binary intermediate phases having the Cr30- or A15-type structure (space group o;, Pm3n) have been discussed in several recent papers . Vanadium forms the struc -ture at or near V3B stoichiometry with all the mem -bers of the cobalt and nickel groups in the periodic table and also with Au, Ga, Si, Ge, Sn, P, As, and Sb. This paper describes a survey of the occurrence of the CrsO-type structure in ternary alloys having the general composition V3(B, B') where B and B' are Fe, Co, Ni, Cu, Rh, Ir, Si, and Ga. The purpose of the survey was to clarify the connection between the position of the B partner in the periodic table and its CrsO-type phase-forming tenden~y.~,~ The survey is part of a broader program concerned with the influence of B-partner substitutions on the superconducting transition temperatures of CrsO-type compounds. The transition temperatures, Tc, of some of the ternary Cr,O-type phases found in the survey are also discussed in this paper. EXPERIMENTAL PROCEDURE The alloys were prepared by arc-melting in an A-He atmosphere and were in the form of buttons, weighing approximately 3 g. The metals used in their preparation were received from commercial sources and were in all cases 99.9+ pct pure. The vanadium was spectrochemically pure except for 800 ppm of Si, 200 ppm of Fe, and 200 ppm of Al. For study of each pseudobinary system at least seven alloys were prepared having the general compositions case of alloys containing gallium, melting losses were small, usually less than 0.3 pct of the total weight of the metals charged for melting. Melting losses were somewhat greater for gallium alloys, ranging in general from 0.9 to 5.0 pct. Ternary V-Si-Ga alloys were chemically analyzed and the results are given in Table I. The analyses show most alloys to be within 2 at. pct of the intended composition. Throughout the balance of the paper the intended compositions are used in discussing the alloys. The cast buttons were annealed within evacuated quartz capsules for times ranging from 3 to 6 weeks at temperatures between 800" and 1000°C and water-quenched. The phases present in the annealed and quenched alloys were identified by optical and X-ray metallography. X-ray diffraction photograms were made with powders prepared from the bulk specimens, by the use of a 114.6-mm-diam powder camera with copper irradiation. The lattice parameter of CrsO-type phases and their standard errors

Jan 1, 1963

By Carl F. Lutz, Robert F. Mehl

A layer of brass was formed on 0 brass using a vapor-solid reaction technique. The variation in composition with distance within the phase layer and across the a -ß interface was determined by an electron probe. The diffusivities were calculated as a function of concentration; the diffusion coefficient in brass was found to change by a factor of twenty-five over a compositional range of 8 at. pct. An explanation is proposed to account for the large change in the diffusivity, based on possible stresses in the diffusion zone; it is suggested that the concentration dependence of the thermodynamic factor might decrease the activation energy with increasing zinc content. ALTHOUGH the body of data on diffusion coefficients (D- values) in terminal solid solutions and in isomorphous systems is quite large, there is but little quantitative information for intermediate alloy phases. This paper recounts measurements of D-values for the ? phase in the Cu-Zn system. The experimental method employed consists in the forming of alloy layers and determining and analyzing the concentration-distance (c-x) curve. The experimental method employed could have been applied to several systems; the Cu-Zn system was chosen because the D-values in the a and ß phases are well known, and can thus be used for purposes of comparison. The rates of growth, of intermediate alloy layers are known for a number of systems. In nearly all cases the thickness varies parabolically with time, as to be expected if the rate of growth is controlled by the D-values. In a few cases, nonparabolic behavior has been noted.1 Nonparabolic growth may be the result of a) a variation of the composition at the phase interface with time, b) interface-controlled kinetics, c) short diffusion times coupled with long vacancy lifetimes (in vacancy diffusion),2 and d) crystal reorientation during diffusion in anisotropic systems.3 In the Al-Ni system4 and in the Al-u5 system parabolic growth kinetics are slowly approached after an initial transient period. In general those phases stable at a given temperature in a system A-B appear as separate phase layers when A and B are put in contact and given a diffusion he at-treatment. In most cases the compositions at the interface of adjacent phase layers are those read from the phase diagrams for the termini of the respective phases. This discontinuity in concentration is taken as independent of time, and the growth of one phase at the expense of another is assumed to be independent of interface kinetics, i.e., the rate of interface movement is controlled by volume diffusion in the phases concerned. wagner6 has given many solutions for multi-phase diffusion processes, assuming that the chemical diffusion coefficient, D, is independent of concentration, as have others. Jost7 has pointed out that the familiar Boltzmann-Matano solution is as valid for a (c-x) curve exhibiting concentration discontinuities at phase boundaries as for the usual single-phase case. Heumann and associates8,9 have applied this solution to the multi-phase case, but lacking concentration data within the several layers were forced to assume linear concentration gradients, thus calculating only average D-values. The purposes of the present study were: 1) to determine the dependence of D on concentration, 2) to calculate the intrinsic diffusion coefficients D?Cu and D?Zn, 3) to establish the time-law for the movement of the interface, 4) to determine the concentration limits at the ß-? interface, and, 5) to attempt to clarify the mechanism of diffusion. EXPERIMENTAL PROCEDURE The ? phase is exceedingly brittle; conventional solid couples and conventional sectioning methods were thus inapplicable. Vapor-solid couples were accordingly employed. Unfortunately the equilibrium vapor pressures of Zn for the ? phase are unknown; to escape this awkwardness, samples were enclosed in a capsule containing powder of an alloy of known composition, sufficiently large in quantity as to be effectively an infinite source, maintaining the concentration of Zn at the sample surface constant with time. The sources of Zn-vapor which can be employed in reaction with Cu, or a brass, or ß brass, to form a layer of ? brass satisfactorily wide in concentration range, are alloys of the phases ?, or ? + E or ? + d (depending on the temperature).

Jan 1, 1962

By K. R. Evans

The yield and fracture characteristics of a Ti-8 pct A1 alloy have been examined at room temperature as a function of exposure temperatures to 1700°F. Em-brittlenzent of the alloy is observed to occur following exposures below 1280°F, the critical temperature for formation of ordered Ti3Al particles. Presence of Ti3Al particles results in an increase in the yield and flout stresses which, for a given exposure time, are a maximum at the critical temperature. Embrittlement is attributed to the occurrence of plastically induced fracture controlled by the increase inflow stress. This interpretation is compatible with the decreasing ductility and increasing crack popagation rates observed with increasing exposure time below the critical temperature. Slip line observations and measurements of the gain size dependence of the yield stress indicate that the slip character of the alloy is not influenced by exposure treatments below the critical temperature. ThE potential usefulness of Ti-A1 alloys in structural applications has prompted considerable interest in studies of their microstructure and mechanical characteristics. The relatively recent surge of interest in the system and at the same time its complexities are indicated by the fact that despite numerous recent efforts14 there has not even been general agreement upon a phase diagram for the system. However, most of the Ti-A1 alloys of commercial interest range in aluminum content from 5.0 to 8.5 wt pct where most investigators achowledge the existence of the ordered Ti41 phase. Goldak and parrs confirmed the existence of Ti41 from X-ray diffraction analysis of the stoichiometric composition while Blackburn6 has determined its presence in commercial Ti-8 pct A1 alloys by electron diffraction analysis and dark field transmission microscopy. The embrittlement of Ti-8 pct A1 alloys was initially reported by Crossley and carew7 who showed that aging in the temperature range of 750" to 1110°F resulted in extreme brittleness. This behavior was later confirmed and correlated by Soltiss to the presence of long-range order in the commercial Ti-8 pct Al-1 pct Mo-1 pct V alloy (Ti-8-1-1) which exhibited anomalous creep and yield strength behavior at 950°F. This investigation was designed to study the mechanical characteristics of a binary Ti-8 pct A1 alloy in order to further examine the nature of the embrittlement behavior reported for the alloy system. EXPERIMENTAL PROCEDURE A Ti-8 pct A1 binary alloy was obtained from the Wah Chang Co. in the form of 0.050 in. sheet. The chemical composition of the alloy is given in Table I. Heat-treatment of the alloy was conducted in evacuated vycor capsules for the tensile sDecimens (1.25 bv 0.25 in. gage section) and in evacuated stainless steel jackets for the crack growth-rate panels. All specimens were annealed at 1700°F for 24 hr and water quenched before an exposure at elevated temperatures. Tensile testing was conducted at room temperature in an Instron testing machine equipped with a pushbutton control for instantaneous control of the cross-head motion. In this manner the change in stress, Aa, accompanying an increase in strain-rate by a factor of 10 was measured immediately after yielding. The crack growth-rate panels used were 3 by 18 in. with a precrack 0.33 in. long cut into the center of the panel. The panels were cycled at a maximum gross stress of 40,000 psi at a maximum to minimum tension stress ratio of 20. Cycling of the specimens was continued until the crack propagated the width of the panels. The crack length was intermittently measured during slow crack growth. EXPERIMENTAL RESULTS Correlation of Embrittlement to the Critical Temperature for Ordering. Blackburn6 has found that the critical temperature, T,, for the formation of Ti41 in a Ti-8 pct A1 alloy with an interstitial content on the order of that given in Table I is approximately 1245°F. The relationship between the ductility of the binary alloy used in this investigation and T, was estimated from tensile tests on specimens which were exposed for 24 hr at various temperatures followed

Jan 1, 1970

By C. S. Matthews, M. J. F. Rosenbaum

The purpose of thir work wax to lcarn it~lzut infori~lation could he obtained from various typs of pilot water floods and to attempt to find the optunum pilot patter11, for a revervoir which had previously been depleted by a solution gas drive. The study was made in the laboratory with mathemetical methods a dynamic analog and a potentiotnetric analog. Results werp tested against the field llistorics of a nrrnlber of pilot water floods. At a reasonable valrre of currzulative injection, the total production rate for the one-injector five-spot should reach about 6.5 per cent of injection rate, and for a four-injector five-spot, about 9 per cent. Accurate estimates of ultimate recovery cannot be made on the basis of such snzall prorluction rates. However, with a pilot composed of nine ir1jector.s and 16 producers the production rate is approximately 50 pcr cent of injection rate at a reasonable value of camulative injection. Sonle inforn~ation for extended performance predictions might he obtained from such a large pilot. These conclusions were drawn on the basis of results obtained for unit mobility ratio, and a sturly using tlre potentiometric analog was made of the effect of other mobility ratios to determine the range of applicability of these predictions. For the four-injector, five-spot pilot with the ratio of production to injection rate (before water breakthrough) is about twice that for with it is about two-thirds; and with M0= 10, it is about one-third For high mobility ratios, it was found that the production rate increased considerably as water-cut increased. These result can be used to modify, qualitatively, the inter.pretntions based on curves for the unit rnobilit\. ratio CaSeS. It was found that the maximum ratio of production rate to injection rate obseriled in field pilot floods was of rhe scime order as that prerdicted by these methods. The time required to reach thisr maximum did not generally agree with the time predicted for a homogeti~orir reservoir. The differcrlce between predicted and observed time of response gives an indication of the permeability profile and of the condition of the producin,g wells. Pilot water floods of the pattern type are generally carried out in reservoirs which have been depleted by solution gas drive and are at low pressure. Under these conditions, oil and water can be considered incompressible. It is assumed that, as the water is injected, an oil bank forms ahead of it and that there is a distinct interface between the water zone (or bank) and the oil zone (or bank) and between the oil zone and the region ahead of the oil zone. It is further assumed that only gas is mobile in the unflooded (gas) region, only oil is mobile in the oil bank and only water is mobile in the water bank. The saturations and the mobilities associated with each zone are assumed uniform. We idealize our reservoir to be homogeneous, horizontal and of constant thickness. Effects of gravity within the producing layer are assumed negligible. If the actual time-dcpendent flow problem is approximated by a acries of steady-state problems. the potential and stream function in the oil bank and water hank satisfy Laplace&apos;s equation in two dimensions. We can therefore use a poteiitiometric analog of this system. Potentiometric models have yielded uscful results in this laboratory&apos; and clsewhere in the study of a variety of secondary recovery problems. For the case where M = I, we generally prefer to use theoretical mcthods as well as a simpler dynamic analog. Except where otherwise noted, the ratio, side of five-spot/wellbore radius. is taken to be 3,600. a figure which corrcsponds to a normal-size wellbore in a 10-acre well spacing. THEORETICAL EVALUATION OF VARIOUS PILOT PATTERNS, Mw0 = 1 <&apos;he theoretical models which we used to examine the performance of various pilots are shown in Fig. 1. Image theory was used to determine the ratio of production rate to injection rate as a function of the volumc of the flood. The ratio of production rate to injection rate was chosen because this is an easily measurable quantity which is characteristic of a pilot

By Raymond L. Orr

Calorimetric measurements have been made of the heats of solution of gold axd indium in a number of liquid tin-rich alloys at a temperature of 705°K. Relative partial molar enthalpies of gold were determined as a function of dilute solute concentrations in the binary Au-Sn system and in the ternary Ag-Au-Sn and Au-In-Sn systems. Relative partial molar enthalpies of indium were determined for dilute solute concentrations in the In-Sn, Ag-In-Sn, and Au-In-Sn systems. Through application of the interaction coefficient concept introduced by Wagner and more recently extended by Lupis and Elliott, ualues have been obtained for the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. The results are inte@reted in terms of solute atom distributions through comparisons with the predictions of dilute solution models. INTEREST in the thermodynamic behavior of dilute liquid alloys stems from two primary sources. From a practical viewpoint, it is often of importance to know or to be able to predict the effect that one solute will have on the thermodynamic properties of the other solutes in a multicomponent system. Studies of dilute solutions may also be rewarding from the theoretical point of view. Some of the difficulties arising from the more complex interactions possible in concentrated solutions are avoided, leading to easier interpretations in terms of solutibn models and bonding energies. For example, in a binary alloy the limiting values of the partial molar properties of the solute represent the case for which each solute atom is completely surrounded by atoms of the solvent, and no other interactions are possible. Solute - solute interactions in dilute solutions are conveniently treated by the interaction coefficient concept of ~agner.&apos; Using a Taylor series expansion for the logarithm of the activity coefficient, In yi, of a component, i, in a solution consisting of dilute solutes with atomic fractions xi, xj, xk, and so forth, in a solvent, s, and neglecting the second- and higher-order terms, Wagner obtained the expression: Where Wheyz is the limiting value of yi in the pure solvent, s. The interaction coefficients, e:, e:, and so forth, are defined by: Since yi is related to the excess partial molar Gibbs energy of component i by GfS = RT In yi, E: is re- ferred to as the "Gibbs energy interaction coefficient". Lupis and Elliott~ extended Wagner&apos;s treatment to the relative partial molar enthalpy, aHi, and the excess partial molar entropy, qS. They defined the enthalpy interaction coefficient as: and the excess entropy interaction coefficient as: leading to expressions similar to Eq. [I]: The three interaction coefficients are related by? The self-interaction coefficients, E:,qf,and at, represent the effects of interactions between atoms of component i in solvent s; €3, q{, and 03 represent the effects of interactions between i and j atoms in solvent s; and so forth. From the Maxwell-type relationships between partial molar quantities, it may be shown1&apos;2 that e{ = ej, r}\ =tj), and ai - crj. Experimental determination of the interaction coefficients requires extremely precise measurements of the appropriate properties as functions of solute concentrations in very dilute regions. Few such data exist for intermetallic alloys, even for binary systems, because of experimental difficulties. This is especially true with respect to enthalpy data for dilute alloys. Examination of the compilation of data for binary alloys by Hultgren, Orr, Anderson, and ~elle~~ reveals that determination of limiting values of &fii(Xi =0) often requires extrapolations to infinite dilution from xi = 0.05 to 0.10. Direct measurements of the enthalpy interaction coefficient, qi, for multicomponent systems are virtually nonexistent. This quantity is of course subject to direct calorimetric measurement, but its determination must be limited to cases where high experimental precision is possible. The heats of solution of gold and indium in liquid tin can be measured with relatively high precision, which makes determinations of 73 involving these metals as the measured solutes experimentally attractive. This paper presents the results of such determinations of the Au-Au, Ag-Au, Au-In, and Ag-In enthalpy interaction coefficients in liquid tin. MODELS FOR DILUTE-SOLUTION BEHAVIOR Random-Solution Behavior. In the quasi-chemical treatment of solutions, only nearest-neighbor bonds are considered, and a composition independent value

Jan 1, 1967

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&apos; 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&apos; 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&apos; plots for both horizontal and vertical

Jan 1, 1969

By F. G. Miller

Earlier studies of the mechanism of flotation showed that coal flotation products are contaminated by composite coal and mineral particles. The mineral matter of these particles has the dual effect of increasing the specific gravity and decreasing the coal surface of the particle available for bubble attachment. The present study showed that these particles are more loosely held in the froth column than the high grade coal particles, especially in the coarser sizes. Consequently, it is possible in the laboratory to produce a secondary concentration of the product by sprinkling the froth product with water to wash these loosely held particles from the froth during formation and recovery. To improve coal flotation, Bethlehem Steel Corp.&apos;s research department has been working on a number of related problems based on both physical and chemical factors. The ideal is of course full understanding of the interrelated effects of both sets of factors. However, detailed studies1 of each physical factor have produced immediately usable results in commercial coal flotation and are providing the basis for our current work on the effect of chemical factors. Since these detailed studies provided the basis for the present investigation of froth sprinkling, their key results are highlighted here. For example, for a highly floatable bituminous coal, particle floatability was shown to be directly related to the percentage of coal surface available for bubble attachment and inversely related to particle mass. The data also underscored that in a given size range the addition of mineral matter to a particle makes flotation more difficult both by adding to the mass of the particle and by decreasing the amount of coal surface available for bubble attachment. Size also affects particle floatability in that as the size of particles of a given specific gravity increases, mass increases and the ratio between coal surface area and mass of the particle decreases. Flotation tests showed that any recovery of the coarsest particles in a coal feed is accompanied by progressively higher recovery of finer and finer particles. Consequently, fine high-specific-gravity particles are recovered with the coarse good coal. As a result, when the entire 14 mesh x 0 size range is processed by froth flotation, the good coarse coal is contaminated with high-specific-gravity fines. It is the small quantities of these fines that must be rejected from the froth product if flotation efficiency is to be increased above its present level. These principles and findings, together with work by Professor V. I. Klassen,&apos; led to the froth sprinkling investigation reported in this paper. Working with Russian coals, Klassen had shown that froth sprinkling washes loosely held refuse particles from the froth and compensates for the water lost in the upper froth layers and increases its stability. As a result, the coal particles are retained in the froth and the loss of coarse coal from the froth is prevented. Decreases in ash of 0.1% to 1.5% were reported by Klassen. Working with a 28 mesh x 0 American coal, the author of the present paper found that single-stage flotation coupled with froth sprinkling produced a product comparable to that obtained by the more expensive method of roughing and cleaning.3 The investigation reported in the present paper expanded study of the effect of froth sprinkling to include each of the standard size fractions of a bituminous coal. The main findings are as follows: (1) For those size fractions between 48 mesh and 150 mesh, froth sprinkling produces a marked reduction in both sulfur and ash. In the case of those sizes coarser than 48 mesh, while this reduction is not as significant, the additional benefit of shorter retention time is still a plus for froth sprinkling. Furthermore, when froth sprinkling is coupled with normal fast flotation, the product purity approaches that obtained by starvation reagent feeding, i.e., gradual feeding of flotation reagent to float the recoverable coal from the pulp slowly in several increments. The specific results for these two size groups are: (a) 14 x 48 Mesh. By using froth sprinkling with fast flotation, product sulfur can be reduced to a level

Jan 1, 1970

By Rex B. McLellan

A simple model for dilute interslitial solid solutions is set up which enables a solubility equation for the equilibrium between the solid solution and the gaseous solute to be deduced. This solubility equation is used to estimate the partial thermody -namic functions of Ag-O and Fe-N dilute interstitial solid solutions from the measured equilibrium between these solutions and the gas phase. It is shown that the partial excess entropy of the solute atom in solution is a vibrational entropy which is due Principally to the oscillation of the interstitial atom and does not arise from electronic or elastic interaction between the solute atoms and solvent matrix. In this work measurements of the equilibrium between dilute solid interstitial solutions and a gaseous phase are used to deduce the important thermody-namic functions of the solid solution with the aid of a theoretical solubility equation formulated from a knowledge of the thermodynamic functions of the gas and a simple model for the solid solution. The quantity of principal interest which is deduced from the equilibrium data is the change in vibrational entropy occurring when a solute atom (u) is placed in an interstial site in the solvent (u) lattice. This paper forms part of a more general study in which the properties of condensed phases are deduced from measurements of the equilibrium between the condensed phase and a gas. Previous investigations have dealt with the equilibrium between krypton and liquid metals,&apos; a pure metal and its vapor,&apos; and dilute substitutional alloys and the vapor,3 and the subject has been popularly reviewed by McLellan.4 In the latter investigation3 the vapor pressures of very dilute Cu-Ag and Cu-Au alloys were measured with a Knudsen cell technique over a large range of temperatures and the analysis of the vapor-pressure data showed that the relative partial excess entropies were large and positive [ds= -Sudk = 30 for Au-Ag alloys and 150 for Cu-Au alloys; these values should be compared to unity, the value assumed for these exponentials in the quasi-chemical theory of solutions]. For many interstitial solutions experimental data is available for the equilibrium between the solution and a gaseous phase, and this can be used to deduce the vibrational entropies of the solute atoms in solution. The general method employed is to calculate the chemical potential of the solute atoms in the gas and equate this to pi, the chemical potential of solute atoms in the solid, which is deduced from a simple model set up for the dilute interstitial solution (in which the solute atoms act as bound oscillators in interstitial sites). This enables a theoretical solubility equation to be set up. In the case of Ag-O and Fe-N solid solutions the solubility c, is found to vary with temperature according to a relation of the type, where PU2 is the pressure of the O2 or Np molecules. Essentially, the theoretical solubility equation enables the parameter A(T), which gives the vibration entropy, and the parameter AH, which gives the energy of solution of a solute atom, to be estimated from the measured variation of solubility with temperature. The solutions treated are dilute enough to enable solute-solute interactions to be neglected so that the partial energy and excess entropy of solution E, and GS are not functions of composition and the configurational entropy is that of a random solution. Large positive values have been found for sxSu this quantity has not been given sufficient consideration in recent work on interstitial solutions and it is felt that the partial thermodynamic quantities of very dilute solutions should be understood before the thermodynamics of concentrated solutions can be fully appreciated. EXPERIMENTAL DATA 1) The Silver-Oxygen System. The measurements of Steacie and Johnson,= using silver foils, indicate that there is a pronounced minimum in the solubility vs temperature curve for O-Ag solutions. Eichenauer and Miiller6 have recently redetermined the solubility of oxygen in silver using a method developed in the investigation of metal-hydrogen systems.7 The solubility determinations were carried out on compact specimens of differing shapes and sizes and the results indicate a much lower solubility than was obtained by Steacie and Johnson with no minimum at 400°C. Subsidiary experiments showed that the erroneous results of Steacie and

Jan 1, 1964

Plans are now being made for the formation of the American Meteorological Society, which has for its object the advancement and diffusion of the knowledge of meteorology and climatology said the broadening of their applications in public health, agriculture engineering, industry and commerce. Information regarding the society may be obtained from Charles F. Brooks, Weather Bureau, Washington, D. C.

Jan 12, 1919

"Acta Metallurgica" Dennis Carney, &apos;59 Alfred Noble Joint Prize Committee F B Foley, Dec &apos;61 American Association for the Advancement of Science F T Agthe, Dec &apos;59, William L Fink, Dec &apos;60 American Geological Institute Arthur Montgomery, Oct , &apos;59, F C Kruger, Oct &apos;60 American Power Conference J P Weir, T D Hess American Society for Testing Materials

Jan 1, 1959

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made. his gift ?for the erection of a suitable home? for the engineering societies,

Jan 1, 1943

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made. his gift ?for the erection of a suitable union home? for the engineering societies,

Jan 1, 1941

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made. his gift ?for the erection of a suitable home? for the engineering societies,

Jan 1, 1944

The Institute conducts jointly with the American Society of Civil Engineers, American Society of Mechanical Engineers and American Institute of Electrical Engineers, certain activities as listed below, and is joint owner with them of certain properties. United Engineering Trustees, Inc. When Mr. Carnegie made. his gift ?for the erection of a suitable home? for the engineering societies,

Jan 1, 1942

By Charles H. Jacoby

Solution-mined salt cavities are being used for storage of liquid petroleum gas, natural gas, and other hydrocarbons; waste disposal or storage; storage of radioactive wastes; and as a surge vessel for air compressed by an electric utility during off-peak hours. Examples of each use are given. Other contemplated uses of salt cavities are noted.

Jan 1, 1973

By V. K. Karra, A. J. Magerowski

An overview of the scope of a computer program meant for aiding the design of crushing circuits is presented. Effect of circuit variables like the screen separation size and the crusher setting is illustrated. For a better understanding of the logic behind the circuit sizing, a detailed commentary in the case of a starting example is given.

Jan 1, 1982

By E. P. Pfleider, C. A. Dufresne

The problem of mooing open-pit ores over large vertical distances is increasing in importance because of the immense deposits being mined. Gravity fall of ore through transfer raises to central haulage points underground has advantages for certain open-pit operations, and this method is being seriously considered for the Carol Project now underway in Canada.

Jan 6, 1961

By Reynold Q. Shotts

Nitric acid oxidation rate analyses of three coals, previously studied microscopically by the Bureau of Mines, revealed three components. Relative quantities agree with those found for the four components given by the Bureau and results are consistent with current ideas of coal constitution. Possible multi-component composition for bright coal and a reactivity-rank relation are suggested.

Jan 5, 1953