Search Documents

By W. A. Hockings, G. W. Lower, K. A. Smith

The kinetics of dissolution of metallic copper in aqueous cupric ammonium carbonate solutions were investigated. The major variables studied were temperature, agitation, and the cupric, cuprous, ammonia and carbonate concentrations. The rates of copper dissolution from rotating discs were determined by measuring the weight loss. The dissolution rate increased with the square root of the disc rpm and doubled when the temperature was increased from 20°c to 40°C.

Jan 1, 1973

By I. A. Ettlinger

THE formation that the writer has chosen to call "The Central Arizona Batholith" is included in the Globe, Miami, Ray, Pioneer, Troy, and Silver King mining districts. Its extension to the southeast is in the Banner mining field. Basing his argument on what is known of batholithic intrusions, the author offers reasons for considering all these granitic outcrops as parts of a single great mass of plutonic rock. The United States Geological Survey has subdivided this area into three -quadrangles-the Globe, the Ray, and the Florence. Of the first two, geologic atlases1 have been published, but of the last, the topographic map alone is available. These mining districts include such prominent present-day producers as Inspiration, Miami, Old Dominion, Arizona Commercial, Iron Cap, Superior and Boston, Magma, Belmont, and Ray Consolidated. Among those well known in the past are Silver King mine and Gibson mine. Fig. 1 is a geologic map of the Central Arizona Batholith region. F. L. Ransome's excellent work on The Copper Deposits of Ray and Miami, Arizona,' is of great value to all workers in those districts. His geologic map for the Ray and Globe quadrangles has been incorporated in Fig. 1, and the stratigraphic names employed are those first applied and defined by him in his pioneer work in this region. The purpose of this paper is to show that the ores are related to post-Carboniferous granitic intrusions; that while there does not seem to be any adequate explanation for the distribution of all the igneous stocks, a preexisting structure does appear responsible for at least the location of the largest igneous stock of the region; that the principal producing vein mines are located in the sedimentary rocks in the roof of this batholith, while the disseminated copper deposits are found bordering the lower portions of the batholith exposed by erosion; that primary zoning is illustrated not only on a broad (district) scale but also on a small (individual

Jan 1, 1928

By R. D. Daniels, T. G. Oakwood

A study was made of the effects of small quantities of hydrogen on the mechanical properties of colum-bium. Tensile specimens, hydrogenated to concentrations of 20 to 200 ppm, were tested at temperatures of 300°, 191°, and 77°K. Although hydrogen was found to have little effect on the strength of columbium, the ductility of Cb-H alloys was found to be quite sensitive to both hydrogen concentration and temperature. At 300°K, an abrupt loss in ductility occurred at a critical hydrogen concentration, although some ductility was observed beyond the tolerance limit. A similar result was found at a lower hydrogen concentration at 191°K. At 77°K, however, a more gradual loss in ductility with increasing hydrogen concentration was observed. Hydrogenated columbium was thus observed to undergo a ductile-brittle-ductile transition. Metallographic examination of fractured specimens revealed extensive porosity at both 77° and300°K which was a distinct function of hydrogen content. At 191°K, although some secondary cracking was noted, the amount of observed porosity was minimal. These observations are interpreted in terms of hydrogen solubility and mobility as a function of temperature and in the role of hydrogen in promoting growth of microcracks. lHE effect of hydrogen on the mechanical properties of the refractory metals is not, at present, completely understood. A number of studies have shown these materials to be susceptible to hydrogen embrittlement. Roberts and Rogers1 have found that vanadium can be embrittled by hydrogen. It was further demonstrated that fracture undergoes a ductile-brittle-ductile transition as the temperature is lowered from 150° to -196°C; i.e., there is a ductility minimum observed at a certain temperature. The ductility is increased by either raising or lowering the temperature from this point. A more complete study by Eustice and Carlson2 on vanadium containing 10 to 800 ppm placed the ductility minimum at about -100°C with variations reportedly due to hydrogen content and strain rate. Ductility minima have also been found at certain temperatures for tantalum containing 7 ppm H3 and 140 ppm H.4 At hydrogen concentrations above 270 ppm, however, the ductility return at low temperatures was considerably reduced.4 In the case of columbium, some disagreement exists in the literature. Eustice and Carlson,5 Wilcox et al.,6 and Imgram et al.4 failed to find a ductility minimum although a composition-dependent ductile-brittle transition was observed. Hydrogen concentrations in these investigations were 20 ppm,5 1 to 30 ppm,6 and 200 to 390 ppm.4 However, Wood and Daniels7 observed a rather pronounced ductility minimum at hydrogen contents ranging from 19 to 252 ppm. Those theories of hydrogen embrittlement involving the precipitation of diatomic hydrogen which have been applies to ferrous metals8-12 do not seem to be applicable to the case of columbium and other exothermic occluders. Such theories propose that extensive crack formation and propagation occurs by the precipitation and expansion of diatomic hydrogen at internal voids and microcracks. However, photomicrographs of hydrogenated columbium do not show any evidence of damage introduced by the sorption and precipitation of diatomic hydrogen; rather, at high hydrogen concentrations, a hydrogen-rich second phase is precipitated.13'14 In addition, a number of these theories require the development of high hydrogen pressures at voids in the structure.8'10'12 This does not appear to be feasible in the concentration ranges discussed in the aforementioned paragraphs. The possible interaction of atomic hydrogen with microcracks resulting from dislocation pile-ups15,16 remains in doubt since pile-ups have not been observed in bcc metals17 including columbium.18 Wood and Daniels7 have put forth the possibility that a hydride precipitation could be responsible for crack nucleation in columbium. Work by Longson19 has shown that hydrogen embrittlement of columbium parallels the bulk solubility limit; i.e., as the solubility increases, for instance with temperature, the amount of hydrogen necessary to cause embrittlement also increases. Although a hydride precipitation appears attractive as a means of nucleating microcracks in columbium, what require more intensive study are the low-temperature anomalies which have been observed, i.e., the ductile-brittle-d'ictile transition characteristics. Also, the hydrogen concentrations where embrittlement occurs are often below the bulk solubility limits determined by Albrecht et al.13,14 and Walter and Chandler.20 This work is an attempt to determine more definitively the effects of concentration and temperature on the mechanical properties of dilute Cb-H alloys. EXPERIMENTAL PROCEDURE Ultrahigh-purity columbium rods, obtained from the Wah Chang Corp., were cold-reduced by rotary swaging. A chemical analysis is given in Table I. The material was cut into cylindrical blanks 1.50 ±0.005 in. long. Individual specimens were either given a stress relief anneal at 750°C or recrystal-lized at 1200°C. Resulting microstructures were either a "bamboo" structure characteristic of a wrought material or a recrystallized structure with a grain diameter of approximately 100 n. All heat treatments were carried out in a vacuum of 10-5 Torr or less.

Jan 1, 1969

By G. A. Stamboltzis, N. Arbiter, C. C. Harris

Fracture under low-velocity free-fall and double impact and under slow compression have been investigated. The pattern of breakage and the size distribution of resulting fragments of sand-cement and glass spheres have been determined. Photoelasticity methods were used to simulate the stress distributions in free-fall impact in order to explain the observed patterns of breakage. Oblique fracture planes, occurring only in free-fall impact, develop along lines which coincide with the trajectories of maximum compression as determined by mathematical analysis. Breakage efficiencies for different modes of fracture were compared for both types of spheres. For the same specimen and loading system, static loading and low-velocity dynamic loading induce geometrically similar stress fields resulting in reasonably similar fracture patterns and shapes of fragments. This work had its origin in a desire to understand three fundamental processes involved in autogenous comminution: namely; free-fall impact, double impact, and slow compression. To simplify the investigation, it is preferable to reduce the entire multi-stage fracture process to its most elementary form; that is, to study products resulting from a single-stage operation, such as the breakage of a specimen under single fracture conditions. The goal of this research is to study the energy utilization in the single fracture of brittle specimens and to relate the pattern of breakage and the resultant fragment size distribution with the nature of the material, the specimen size, the manner of load application, and the rate of loading. Published works on single fracture have mainly been concerned with tests on large (> 1-in.) irregular mineral pieces, especially coal and coke. These were mainly friability tests employing a single blow on closely sized pieces. More recently, small mineral specimens in the sieve range and glass spheres have been investigated.5-7 Kick8 has reported free-fall and double impact tests with large large cast-iron, cement, and clay spheres. The establishment of a minimum breaking height independent of size in the free-fall impact tests, and the direct proportionality between the minimum work required for fracture and the volume of the specimen in double impact tests were used by Kick as an experimental proof of his classical law of "Proportional Resistances." In the present work, spherical shapes were chosen because of their simple body geometry and consequent impact and stress field symmetry. Because the study involves several physical principles in connection with brittle-fracture, it may be of interest in fields where the strength of materials is of importance. APPARATUS The equipment for the free-fall impact testing is illustrated in Figs. 1 and 2. This consisted of a massive (17 x 17 x 3-in.) hard steel plate onto which specimens were dropped and a specimen release mechanism which could be set at any desired height up to 10 ft above the plate so that the impact velocity could be varied up to about 25 ft per sec. Double impact breakage is characterized by two points of loading situated at opposite poles. For this mode of breakage the apparatus was modified (Figs. 3, 4 and 5) so that a falling mass provided an impact of predetermined magnitude on a specimen resting on the plate. A spring-loaded device operated immediately after fracture to arrest the falling mass and to record its residual kinetic energy. Precautions were taken to avoid secondary breakage. Slow compression tests were performed on a conventional hydraulic testing machine, the specimen being held between two hardened parallel bearing blocks. In the case of glass spheres, carbide bits were used. Photoelasticity studies were performed on two-dimensional models held in a loading frame equipped with a force gauge (Fig. 6). The models were viewed in a polariscope and isochromatic fringe patterns were recorded photographically. SPECIMENS Sand-Cement Spheres: A series of sand-cement spheres were prepared by molding in spherical glass flasks.

Jan 1, 1970

By W. C. Maurer

A study of bit-tooth penetration, or crater forniation. under simulated borehole condirions has been made. Pressure conditions existing when drilling with air, water and mud have been sirnulated for depths of 0 to 20.000 ft. These crater tests showed that a threshold bit-tooth force must he exceeded before a crater is .formed. This thresh old force increased with both tooth dullness and diflerenrial pressure between the borehole and formalion fluids. At low differential pressures, the craters formed in a brittle manner and the cuttings were easily removed. At high differenlial pressures, the cunings were firmly held in the craters and the craters were formed by a pseudoplas-tic mechanism. With constant farce of 6,500 16 applied to the bit reeth, an increase in differential pressure (sitnulated mud drilling) from 0 to 5,000 psi reduced the crater volumes by 90 per cent. A comparable increase in hydrostatic fluid pressure (simulated water drilling) produced only a 50 per cent decrease in volutne while changes in overburden pressure (simulated air drilling) had no detectable effect on crater volume. Crater tests in unconsolidated sand subjected to differential pressure showed that high friction was present in the sand at high pressures. Similar friction belween the cuttings in craters produces the transition from brittle to pseudo plastic craters. INTRODUCTION The number of wells drilled below 15,000 ft increased from 5 in 1950 to 308 in 1964. Associated with these deep wells are low drilling rates and high costs. High bottom-hole pressures produce low drilling rates by increasing rock strength and by creating bottom-hole cleaning problems. This paper describes an experimental investigation of crater formation under bottom-hole conditions simulating air, water and mud drilling. Although numerous investigators have studied bit-tooth penetration (cratering) at atmospheric pressure conditions, only limited work has been done on cratering in rocks subjected to pressures existing in oil wells. Payne and Chippendale2 have studied cratering in rocks subjected to hydrostatic pressure using spherical penetrators. Garner et aLJ conducted crater tests in dry limestone by varying overburden pressure and borehole fluid pressure independently and using atmospheric formation-fluid pressure Gnirk and Cheathem4,5 have studied crater formation in several dry rocks subjected to equal overburden and borehole pressure and atmospheric formotion pressure. Podio and Gray studied the effect of pore fluid viscosity on crater formation using atmospheric borehole and formation-fluid pressurc and varying overburden pressure. Although these studies have provided useful information on crater formation under pressure, they were limited in that the three bottom-hole pressures could not be varied independently and, therefore, that many drilling conditions could not be simulated. The prersure chamber used in this study allowed visual observation of the cratering mechanism and independent control of the borehole, formation and confining pressures. By using different fluids in the chamber, pressure conditions existing in air, water and mud drilling to depths of 20,000 ft were simulated. The mechanisms involved in cratering at these different pressure conditions were studied for teeth of varying dullness and at different loadins rates. High-speed movies (8,000 frames/sec) and closed-circuit television were used to visually study the crater mechanism under pressure. EXPERIMENTAT PROCEDURE PRESSURE CHAMBER The Pressure chamber in Fig. I was used to simulate bottom-hole pressure conditions. This chamber has been pressure-tested to 22,500 psi and is normally operated at pressures up to 15,000 psi. The chamber contains four lucite windows' used for illuminating and observing the crater mechanism under pressurc. A closed-circuit television and a Fastax camera (8,000 frames/sec) have been used in these studies. Cylindrical rock specimens (8-in. diameter X 6-in. long) were subjected to three independently controlled pressures simulating overburden, borehole fluid and formation-fluid pressures. Overburden pressure, which corresponds to the stress induced by the overlying earth mass, was applied by exerting fluid pressure against a rubber sleeve surrounding the rock. Borehole pressure, which is the pressure exerted by the column of mud in the wellbore, was simulated by applying pressure to the fluid overlying the rock in the chamber. Formation pressure was simulated by applying pressure to the water saturating the rock. The borehole and formation pressures were equal except when mud was used in the chamber, in which case the differential pressure between these fluids acted across the mud filter cake.

Jan 1, 1966

By H. J. Morel-Seytoux

The influence of patten, geometry on assisted oil recovery for a particular dispIacement mechanism is the object of investigation in this paper. The displacement is assumed to be of unit mobility ratio and piston-like. Fluids are assumed incompressible and gravity and capillary effects are neglected. With these assumptions it is possible to calculate by analytical methods the quantities of interest to the reservoir engineer for a great variety of patterns. Specifically, this paper presents (1) very brieily, the methods and mathematical derivations required to obtain the results of engineering concern, and (2) typical results in the dorm of graphs or formulae that can be used readily without prior study of the methods. Results of this work provide checks for solutions obtained from programmed numerical techniques. They also reveal the effect of pattern geometry and, even though the assumptions of piston- like displacement and of unit mobility ratio are restrictive, they can nevertheless be used for rather crude but quick, cheap estimates. ,These estimates can be refined to account for non-unit mobility ratio and two-phase flow by correlating analytical results in the case M = 1 and the numerical results for non-piston, non-unit mobility ratio displacements. In an earlier paper1 it was also shown that from the knowledge of closed form solutions for unit mobility ratio, quantities called "scale factors" could be readily calculated, increasing considerably the flexibility of the numerical techniques. Many new closed farm solutions are given in this paper. INTRODUCTION BACKGROUND Pattern geometry is a major factor in making water-fIood recovery predictions. For this reason many numerical schemes have been devised to predict oil recovery in either regular patterns or arbitrary configurations. The numerical solutions, based on the method of finite difference approximation, are subject to errors often difficult to evaluate. An estimate of the error is possible by comparison with exact solutions. To provide a variety of checks on numerical solutions, a thorough study of the unit mobility ratio displacement process was undertaken. To calculate quantities of interest to the reservoir engineer (oil recovery, sweep efficiency, etc.), it is necessary to first know the pressure distribution in the pattern. Then analytical procedures are used to calculate, in order of increasing difficulty: injectivity, breakthrough areal sweep efficiency, normalized oil recovery and water-oil ratio as a function of normalized PV injected.

Jan 1, 1967

By Walter Rose, W. A. Bruce

Improved apparatus, methods, and experimental techniques for determining the capillary pressure-saturation relation are described in detail. In this connection a new multi-core procedure has been developed which simplifies the experimental work in the study of relatively homogeneous reservoirs. The basic theory concerning the Leverett capillary pressure function has been extended and has been given some practical application. Some discussion is presented to indicate the relationship of relative permeability to capillary pressure, and to provide a new description of capillary pressure phenomena by introducing the concept of the psi function. INTRODUCTION For the purposes of this paper the capillary character of a porous medium will be defined to express the basic properties of the system, which produce observed results of fluid behavior. These basic properties may be classified in the following manner, according to their relationship to: (a) The geometrical configuration of the interstitial spaces. This involves consideration of the packing of the particles, producing points of grain contact, and variations in pore size distribution. The packing itself is often modified by the secondary processes of mineralization which introduces factors of cementation, and of solution action which causes alteration of pore structure. (b) The physical and chemical nature of the interstitial surfaces. This involves consideration of the presence of interstitial clay coatings, the existence of non-uniform wetting surfaces; or, more generally, a consideration of the tendency towards variable interaction between the interstitial surfaces and the fluid phases saturating the interstitial spaces. (c) The physical and chemical properties of the fluid phases in contact with the interstitial surfaces. This involves consideration of the factors of surface, interfacial and adhesion tensions; contact angles; viscosity; density difference between immiscible fluid phases; and other fluid properties. Fine grained, granular, porous materials such as found in petroleum reser~oir rock possess characteristics which are expressible by (1) permeability, (2) porosity, and (3) the capillary pressure-saturation behavior of immiscible fluids in this medium. These three measurable macroscopic properties depend upon the microscopic properties enumerated above in a manner which defines the capillary character. Systems of capillary tubes or regularly packed spheres may be thought of as ideal and numerous references can be cited in which exact mathematical formulations are developed to show the relationships governing the static distribution and dynamic motion of fluids in their interstitial spaces. The capillary character of non-ideal porous systems such as reservoir rock also is basic in determining the behavior of fluids contained therein; although, in general, the connection is not mathematically derivable but must be approached through indirect experimental measurement. This paper gives consideration to the evaluation of petroleum reservoir rock capillary character. The methods employed may be applied to the solution of problems in other fields, and the conclusions reached should contribute to the basic capillary theory of any porous system containing fluid phases. In this paper, a modification of the core analysis method of capillary pressure is employed and it is intended to show that the capillary character of reservoir rock can be expressed in terms of experimental quantities. A very general method of interpretation correlating the capillary pressure tests with fundamental characteristics such as rock texture, surface areas, permeability, occasionally clay content and cementation is introduced. Eventually an attempt is made for establishing a method of deriving relative permeability to the wetting phase from capillary pressure data. The experimental evaluation of capillary character must be approached in a statistical manner if reservoir properties are to be inferred from data on small cores. This is implied by the heterogeneous character of most petroleum reservoirs, and suggests that considerable intelligence should be applied in core sampling. Finally, this paper supports the view that once the capillary character of a given type of reservoir rock has been established by core analysis, fluid behavior can then be inferred in other similar rock. Although no great progress has been made in establishing what variation can be tolerated without altering the basic fluid behavior properties, evidence will be presented to indicate that certain reservoir formations are sufficiently homogenous with respect to capillary character that the data obtained on one core will be useful in predicting the properties of other cores of similar origin. Tests have shown that cores under consideration can vary widely with respect to porosity and permeability and still be considered similar in capillary character. EXPERIMENTAL METHODS AND TECHNIQUES Various types of displacement cell apparatus for capillary pressure experiments have been described in the literature. Bruce and Welge; Thornton and Marshall; McCullough, Albaugh and Jones3; Hassler and Brunner; Lever-

Jan 1, 1949

By Walter Rose, W. A. Bruce

Improved apparatus, methods, and experimental techniques for determining the capillary pressure-saturation relation are described in detail. In this connection a new multi-core procedure has been developed which simplifies the experimental work in the study of relatively homogeneous reservoirs. The basic theory concerning the Leverett capillary pressure function has been extended and has been given some practical application. Some discussion is presented to indicate the relationship of relative permeability to capillary pressure, and to provide a new description of capillary pressure phenomena by introducing the concept of the psi function. INTRODUCTION For the purposes of this paper the capillary character of a porous medium will be defined to express the basic properties of the system, which produce observed results of fluid behavior. These basic properties may be classified in the following manner, according to their relationship to: (a) The geometrical configuration of the interstitial spaces. This involves consideration of the packing of the particles, producing points of grain contact, and variations in pore size distribution. The packing itself is often modified by the secondary processes of mineralization which introduces factors of cementation, and of solution action which causes alteration of pore structure. (b) The physical and chemical nature of the interstitial surfaces. This involves consideration of the presence of interstitial clay coatings, the existence of non-uniform wetting surfaces; or, more generally, a consideration of the tendency towards variable interaction between the interstitial surfaces and the fluid phases saturating the interstitial spaces. (c) The physical and chemical properties of the fluid phases in contact with the interstitial surfaces. This involves consideration of the factors of surface, interfacial and adhesion tensions; contact angles; viscosity; density difference between immiscible fluid phases; and other fluid properties. Fine grained, granular, porous materials such as found in petroleum reser~oir rock possess characteristics which are expressible by (1) permeability, (2) porosity, and (3) the capillary pressure-saturation behavior of immiscible fluids in this medium. These three measurable macroscopic properties depend upon the microscopic properties enumerated above in a manner which defines the capillary character. Systems of capillary tubes or regularly packed spheres may be thought of as ideal and numerous references can be cited in which exact mathematical formulations are developed to show the relationships governing the static distribution and dynamic motion of fluids in their interstitial spaces. The capillary character of non-ideal porous systems such as reservoir rock also is basic in determining the behavior of fluids contained therein; although, in general, the connection is not mathematically derivable but must be approached through indirect experimental measurement. This paper gives consideration to the evaluation of petroleum reservoir rock capillary character. The methods employed may be applied to the solution of problems in other fields, and the conclusions reached should contribute to the basic capillary theory of any porous system containing fluid phases. In this paper, a modification of the core analysis method of capillary pressure is employed and it is intended to show that the capillary character of reservoir rock can be expressed in terms of experimental quantities. A very general method of interpretation correlating the capillary pressure tests with fundamental characteristics such as rock texture, surface areas, permeability, occasionally clay content and cementation is introduced. Eventually an attempt is made for establishing a method of deriving relative permeability to the wetting phase from capillary pressure data. The experimental evaluation of capillary character must be approached in a statistical manner if reservoir properties are to be inferred from data on small cores. This is implied by the heterogeneous character of most petroleum reservoirs, and suggests that considerable intelligence should be applied in core sampling. Finally, this paper supports the view that once the capillary character of a given type of reservoir rock has been established by core analysis, fluid behavior can then be inferred in other similar rock. Although no great progress has been made in establishing what variation can be tolerated without altering the basic fluid behavior properties, evidence will be presented to indicate that certain reservoir formations are sufficiently homogenous with respect to capillary character that the data obtained on one core will be useful in predicting the properties of other cores of similar origin. Tests have shown that cores under consideration can vary widely with respect to porosity and permeability and still be considered similar in capillary character. EXPERIMENTAL METHODS AND TECHNIQUES Various types of displacement cell apparatus for capillary pressure experiments have been described in the literature. Bruce and Welge; Thornton and Marshall; McCullough, Albaugh and Jones3; Hassler and Brunner; Lever-

Jan 1, 1949

By D. N. Seidrnan

In the present note we present thermal-analysis data for the liquidus curve from 0 to 76 at. pct Se and for the selenium-rich monotectic reaction in the Pb-Se system. We have previously reported that no expey-imental eviderzce was found for a lead-rich monotectic reaction, at -860°C with a monotectic composition of -20.5 at. pct Se, as found by Nozato and Igaki.&apos; Our additional data substantiated this earlier finding and extended the composition range studied. The alloys were prepared from semiconductor -grade lead and selenium purchased from the American Smelting and Refining Co. Both elements were 99.999+ wt pct pure as determined by the supplier. The impurities for lead were Fe (1 ppm) and Cu & ppm) while for selenium the impurities were Cu (< 1 ppm), As (< 1 ppm), Te (1 ppm), and C1 (<1 ppm). The general procedures used for thermal analysis were those specified by the National Bureau of Standards. A Pt/Pt-10 pct Rh thermocouple calibrated against the freezing points of zinc and copper purchased from the National Bureau of Standards and antimony (99.985 pct pure) purchased from A. D. Mackay, New York, was used for all the thermal analysis. The thermocouple electromotive force was measured with a Rubicon Type B potentiometer used in conjunction with a galvanometer with a sensitivity of 0.5 pV (mm) -&apos;. The absolute accuracy of this thermal-analysis system was *0.5"C. One-hundred-gram alloys of the desired composition were sealed in quartz crucibles, with a central thermocouple well, at a pressure of less than 10"1 Torr. The alloys were initially heated well above the liquidus curve and shaken vigorously to insure homogeneity. Cooling curves were then taken by the direct method at cooling rates ranging from -0.5" to 1.5"C (min)-&apos;. The phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis is shown in Fig. l.* An extrapolation of the selenium-rich portion of the liquidus curve to the monotectic reaction isotherm (678.3"C) gave a value of 76.1 at. pct Se for the monotectic composition. A tabulation of all the thermal-analysis data is given in Table I. As we previously reported no experimental evidence was found Fig. l—The partial Pb-Se phase diagram from 0 to 76 at. pct Se as determined by direct thermal analysis. For the sake of clarity the points for the 49.00 and 49.16 at. pct Se alloys were not drawn on this phase diagram, see Table I. for the lead-rich monotectic reaction found by Nozato and Igaki.&apos; This result was further substantiated by the fact that none of twelve lead-rich alloys, see Table I, examined for this monotectic reaction exhibited a thermal arrest in the temperature range (849" to 863°C) cited by Nozato and Igaki for the lead-rich monotectic reaction. Hence, our results tend to support the earlier qualitative work of ~elabon&apos; and Friedrich and ~eroux" in the 0 to 50 at. pct portion of the phase diagram, though the selenium-rich monotectic composition and reaction isotherm temperature were in agreement with the approximate values (75 at. pct Se and 672" to 680°C) given by Nozato and ~~aki. &apos;

Jan 1, 1967

By O. D. Gonzalez

Existing measurements for the steady-state permeation of hydrogen in a iron above 100°C have been examined for contribution of determinate errors. The analysis leads to a recommended equation for the permeability of hydrogen in a iron: o= (2.9 ±0.5) x 10-3 exp - (8400 ± 400)/RT cu cm (ntp H2) cm-1 sec-1 atm-1/2 THE permeability of a iron to hydrogen has been the subject of numerous investigations over the past 40 years, and at present there are thirteen sets of published results for the rate of steady-state permeation of hydrogen in a iron above 100°C. The numerical values in each set of results are entirely self-consis-tent, but the spread among the sets is too large to be attributed solely to experimental error, i.e., to error other than in the specimen itself. Several reasons have been advanced to explain the disparities, but to date the relative importance of experimental inaccuracy to the spread remains uncertain. The purpose of this report is to examine in detail the sources of determinate errors inherent in the experiments and to assess as far as possible the contribution of the errors to the results. The ultimate goal is the selection of values for the permeability and heat of permeation most nearly representative of hydrogen in a iron. The analysis is limited to those experiments in which the permeation rate was observed at steady state—a condition in which traps for hydrogen within the metal are filled to a fixed level15 so that the trapping mechanism is not reflected in the rate of passage of the gas. Furthermore only data are examined in which surface processes are judged to have little or no influence on the flow. It is hoped with these restrictions to obtain values of the permeability and the heat of permeation which will be as closely related as possible to the mechanism of lattice diffusion. I) DEFINITION OF TERMS; UNITS In this report the data for permeation are given in terms of a coefficient oj permeability, ?, which is defined by the equation: jt=?A/?x{p1/2-po1/2) [1] where jt is the total flow of gas normal to the surface of a membrane of planar geometry, e.g., a disc, of area A and thickness ?x; pi and po are the pressures in the input and output sides, respectively. For flow radial to the walls of a membrane of cylindrical geometry, e.g., a tube, the corresponding equation is: where 1 is the length of the cylinder, and ri and ro are the inner and outer radii, respectively. The flux normal to the surface is given by Fick&apos;s law: j= -D(dc/dx) [3] At steady state the concentration gradient will be constant, and integration of Eq. [3] gives for the total flow through a disc of area A and thickness Ax: h =-DA(co - ci) [4] where c, and ci are the concentrations of solute at the output and input surfaces, respectively. When surface control is absent, co and ci are given by Sievert&apos;s law c = Kp1/2, and substitution therewith into Eq. [4] gives directly Eq. [I] where ? = DK. Integration of Fick&apos;s Eq. [3] in cylindrical coordinates will give Eq. [2] where again ? = DK and is thus shown to be independent of geometry (provided that surface control is negligible). The coefficient of permeability, or simply the permeability,* must be expressed in proper units. In *The term permeability will refer in this report always to the coefficient defined above; permeation will be used to specify the general phenomenon of gas passage through a membrane. this report ? will be expressed in the units of cu cm (ntp H2) cm-1 sec-1 atm-1/2. The variations of D and K with temperature are given by D = Do exp(-Ea/RT) and K = KO exp(-?Hs/RT) where E, is the activation energy for diffusion and AH, the heat of solution, each usually expressed in calories per mole of solute. The variation of permeability with temperature will thus be given (for conditions where surface control is negligible) by ? = ?o exp(-?Hp/RT) where ?0 = DoKo and ?Hp = Ea + ?Hs. The units of ?0 are the same as those of 6, and??Hp will be expressed in calories per mole H. 11) SUMMARY OF PERMEABILITY RESULTS Table I gives the values reported to date for the permeability of H2 in a iron in terms of ?o and ?Hp. Except where noted the parameters listed were taken directly from the numbers reported by the various investigators with only a change in units. The temperature limits within which the listed ?o and ?Hp hold are given in column 7; the limits marked in parentheses in this column indicate the entire temperature range covered in each investigation. The listed values of ?o and ?Hp are those giving a linear plot of ln? against T-1 at the higher temperatures in each set of measurements, and thus presumably represent the case for which surface control was negligible. Column 6 gives values of 9 at a representative tem-

Jan 1, 1970

By C. G. Brennecke, R. T. Gallagher

This paper is the result of a research program entered into cooperatively by the General Reinsurance Corporation and Lehigh University in January 1944. The research program was instituted to find a more positive method to determine the presence of hazardous roof conditions in , mining operations. The co-authors, together with Mr. R. D. Currie, Engineer for the General Reinsurance Corporation, started working on the project in January 1944, first undertaking a library search; second, a preliminary study based on some existing equipment; third, the design of new and more suitable equipment; and finally, the field testing of equipment and methods. Purpose Any study of the accident statistics of mining operations will disclose the rather startling fact that approximately 50 to 60 per cent of all fatal underground accidents in the anthracite and bituminous mines are caused by falls of roof and coal, the metal and nonmetal mines showing only a slightly smaller percentage. Advancements in safety engineering have produced definite results in the decrease of accidents due to blasting, haulage, electricity, and explosions but no such decrease is shown in those caused by falls of roof, coal, or ore. Table Il,2 is a compilation of statistics as published by the United States Bureau of Mines, showing the percentages of fatal accidents caused

Jan 1, 1947

By R. T. Gallagher, C. G. Brennecke

This paper is the result of a research program entered into cooperatively by the General Reinsurance Corporation and Lehigh University in January 1944. The research program was instituted to find a more positive method to determine the presence of hazardous roof conditions in , mining operations. The co-authors, together with Mr. R. D. Currie, Engineer for the General Reinsurance Corporation, started working on the project in January 1944, first undertaking a library search; second, a preliminary study based on some existing equipment; third, the design of new and more suitable equipment; and finally, the field testing of equipment and methods. Purpose Any study of the accident statistics of mining operations will disclose the rather startling fact that approximately 50 to 60 per cent of all fatal underground accidents in the anthracite and bituminous mines are caused by falls of roof and coal, the metal and nonmetal mines showing only a slightly smaller percentage. Advancements in safety engineering have produced definite results in the decrease of accidents due to blasting, haulage, electricity, and explosions but no such decrease is shown in those caused by falls of roof, coal, or ore. Table Il,2 is a compilation of statistics as published by the United States Bureau of Mines, showing the percentages of fatal accidents caused

Jan 1, 1947

By J. L. Bruce, G. W. Nicolson

THE country rock of the Mavrovouni mine of the Cyprus Mines Corp. is hydrothermally altered, disintegrated pillow lava, with very little tensile strength ("short" ground). In places, especially when wet, it is heavy ground, though not extremely heavy except where movement has been caused by underlying or nearby stoping operations. Damage by caving from roof or sides of galleries is not sudden but progressively faster when the size of the cave increases as a result of the fall of small pieces. CEMENT AND CONCRETE LININGS During early operations, galleries in the country rock were supported by customary mine-timbering methods. Available timber, however, was of poor quality and of relatively high price, and replacements were frequent and expensive. Furthermore, the massive sulphide ore bodies required large volumes of fresh air for ventilation and cooling, and it was therefore desirable to provide smooth-lined galleries with low resistance for the introduction of air to the ore bodies. It was also desirable to eliminate hazards of fire in shafts and underground workings insofar as this would be practical. Cement and concrete were relatively cheap, and plans for using these in support of shafts, underground galleries, raises, and chutes, were developed steadily. Circular shafts with diameters ranging from 10 to 15 ft were adopted for all permanent shafts and airways. In places these were lined with concrete poured behind sectional pressed-steel forms especially constructed for this purpose. In other places, they were lined with precast-concrete blocks. It was found that such precast concrete of good quality could be produced on mass production scale and delivered at the mine from most favorable point of manufacture, at a cost of about 25 cents per cubic foot of concrete. This refers to prewar costs. As the use of concrete blocks in circular lined galleries was developed, it was found that there were very great advantages in the reduction of air resistance as compared with customary timber supports. After best methods had been developed, it was found that breakage and replacements were extraordinarily low, averaging only about 1 ½ pct per year during a period of about 15 years. Furthermore, it has been possible to reclaim for re-use a very large percentage of the concrete blocks from abandoned galleries. During the history of the operations precast-concrete blocks have been used for lining shafts, raises, ore chutes, galleries, and shaft stations, ranging from 3 to 16 ft id. The thickness of lining has varied from 5 to 10 in.; with I2 in. thickness in a few cases. Junctions of two galleries at angles ranging from about 30 to 60° are usually made of poured concrete behind sectional forms, or of a combination of poured concrete and precast blocks. In nearly all cases it has been found advisable to make the point of the wedge at the junction, of

Jan 1, 1947

By R. Al-Hussainy, P. B. Crawford, H. J. Ramey

The effect of variations of pressure-dependent viscosity and gas law deviation factor on the flow of real gases through porous media has been considered. A rigorous gas flow equation was developed which is a second order, non-linear partial differential equation with variable coeficients. This equation was reduced by a change of variable to a form similar to the diffusivity equation, but with potential-dependent diffusivity. The change of variable can be used as a new pseudo-pressure for gas flow which replaces pressure or pressure-squared as currently applied to gas flow. Substitution of the real gas pseudo-pressure has a nrtmber of important consequences. First, second degree pressure gradient terms which have commonly been neglected under the assumption that the pressure gradient is small everywhere in the flow system, are rigorously handled. Omission of second degree terms leads to verious errors in estimated pressure distributions for tight formations. Second, flow equations in terms of the real gas pseudo-pressure do not contain viscosity or gas law deviation factors, and thus avoid the need for selection of an average pressure to evaluate physical properties. Third, the real gas pseudo-pressure can be determined numerically in term of pseudo-reduced pressures and temperatures from existing physical property correlations to provide generally useful information. The real gas pseudo-pressure was determined by numerical integration and is presented in both tabular and graphical form in this paper. Finally, production of real gas can be correlated in terms of the real gas pseudo-pressure and shown to be similar to liquid flow as described by diffusivity equation solutions. Applications of the real gas pseudo-pressnre to radial flow systems under transient, steady-state or approximate pseudo-steady-state injection or production have been considered. Superposition of the linearized real gas flow solutions to generate variable rate performance was investigated and found satisfactory. This provides justification for pressure build-up testing. It is believed that the concept of the real gas pseudo-pressure will lead to improved interpretation of results of current gas well testing procedures, both steady and unsteady-state in nature, and improved forecasting of gas production. INTRODUCTION In recent years a considerable effort has been directed to the theory of isothermal flow of gases through porous media. The present state of knowledge is far from being fully developed. The difficulty lies in the non-linearity of partial differential equations which describe both real and ideal gas flow. Solutions which are available are approximate analytical solutions, graphical solutions, analogue solutions and numerical solutions. The earliest attempt to solve this problem involved the method of successions of steady states proposed by Muskat.&apos; Approximate analytical solutions&apos; were obtained by linearizing the flow equation for ideal gas to yield a diffusivity-type equation. Such solutions, though widely used and easy to apply to engineering problems, are of limited value bemuse of idealized assumptions and restrictions imposed upon the flow equation. The validity of linearized equations and the conditions under which their solutions apply have not been fully discussed in the literature. Approximate solutions are those of Heatherington et al.. MacRobertsl and Janicek and Katz.&apos; A graphical solution of the linearized equation was given by Cornell and Katz. Also, by using the mean value of the time derivative in the flow equation, Rowan and Clegg&apos; gave several simple approximate solutions. All the solutions were obtained assuming small pressure gradients and constant gas properties. Variation of gas properties with pressure has been neglected because of analytic difficulties. even in approximate analytic solutions. Green and Wilts8 used an electrical network for simulating one-dimensional flow of an ideal gas. Numerical methods using finite difference equations and digital computing techniques have been used extensively for solving both ideal and real gas equations. Aronofsky and Jenkins"I " and Bruce et al.11 gave numerical solutions for linear and radial gas flow. Douglas et al." gave a solution for a square drainage area. Aronofsky 13 included the effect of slippage on ideal gas flow. The most important contribution to the theory of flow of ideal gases through porous media was the conclusion reached by Aronofsky and Jenkins" that solutions for the liquid flow case&apos;" could be used to generate approximate solutions for constant rate production of ideal gases. An equation describing the flow of real gases has been solved for special cases by a number of investigators using numerical methods. Aronofsky and Ferris 10 onsidered linear flow, while Aronofsky and Porter 17 considered radial gas flow. Gas properties were permitted to vary as linear functions of pressure. Recently, CarteP 18 proposed an empirical correlation by which gas well behavior can be estimated from solutions of the diffusivity equation using instantaneour values of pressure-dependent gas

Jan 1, 1967

By Ernest Kirkendall

The amount of research done in the last fen years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Deschl in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl&apos;s paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for it? review and bibliography is an article by 14. I. Krynitsky.~ While considerable material lias appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined :it three temperatures. Procedure The method used consisted of plating copper on a beta brass, heating it, to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the tem perature at which diffusion takes place the beta brass is saturated wit11 copper. Thus, while the beta brass supplies thc zinc, no diffusion takes

Jan 1, 1939

By Ernest Kirkendall

The amount of research done in the last fen years on the subject of diffusion in solid metals is significant of the importance of this problem. To review the literature dealing with diffusion is unnecessary here. Deschl in 1912 reviewed the work that had been done on diffusion in solids and gave a bibliography of the literature published before that time. Mehl&apos;s paper in 19362 is an excellent review of diffusion in metals and contains a large bibliography. Of importance also for it? review and bibliography is an article by 14. I. Krynitsky.~ While considerable material lias appeared in the literature on diffusion in brass, the amount of information is not great compared to that pertaining to some of the other alloys. Most of the information published is of a qualitative nature; that which is quantitative varies considerably. Thus the quantitative determination of the rates of diffusion of copper and zinc in alpha brass by a new method appeared worth while. In the present investigation the rate of diffusion of zinc in approximately the same composition alpha brass has been determined :it three temperatures. Procedure The method used consisted of plating copper on a beta brass, heating it, to allow diffusion to take place, and measuring the concentration of copper by determining the lattice constant of the alloy. This method is unique in that it uses a beta brass of such a composition that at the tem perature at which diffusion takes place the beta brass is saturated wit11 copper. Thus, while the beta brass supplies thc zinc, no diffusion takes

Jan 1, 1939

By E. H. Roberts, L. G. Swenson, F. C. Nix, R. A. Morgen

The binary system lead-antimony has been the subject of comprehensive investigations in these laboratories by Dean1 and his associates. The effect of a third constituent on this system, particularly on the lead-rich alloys in which dispersion hardening was found, has a commercial value as well as an academic interest. This paper covers the effect of the addition of copper, bismuth and tin, all of which are likely to be found in commercial lead-antimony alloys, and is divided into three parts, as follows: I. The System Lead-A~ili~r~ony-Copper II. The System Lead-Antimony-Bismuth III. The Lead Corner of the System Lead-Antimony-Ti11 These three systerrls are of three different types, and hence may be considered as covering three general kinds of additions. Bismuth forms no compounds with either lead or antimony and forms solid solutions with both. Copper forms several compounds with antimony as well as solid solutions but with lead it forms a two liquid layer system and no appreciable solid solution. Tin is soluble in both lead and antimony in the solid state and also forms a compound with antimony. The effect of small amounts of bismuth on the lead-antimony alloys is small, having no appreciable effect on the solubility of antimony. The temperature of the solidus floor is lowered appreciably by the presence of bismuth, cutting down the range of heat treatment. Copper, on the other hand, due to compound formation, increases the apparent solubility of antimony. The excess antimony is tied up with the copper finally and so is not available for dispersion hardening. The net result of addition of small amounts of copper is to shift the dispersion hardening peak of the

By C. E. Sims, C. A. Zapffe

AN investigation of the behavior of inclusions in steel several years ago1 led to the conclusion that some of the commonly occurring inclusions in steel have appreciable solubilities, particularly in liquid steel. In the belief that further study and clarification of this matter was warranted, a laboratory study of oxides in liquid steel was started. These oxides are generally the result of deoxidation treatment, and the basis of an understanding of their behavior must be, therefore, the behavior of the deoxidizer in liquid iron. The Fe-Si-O system was selected for the first study, and the apparatus used and experiments conducted are described herein. APPARATUS The apparatus is shown in Fig. I and the system is shown by diagram in Fig. 2. Furnace Atmosphere Commercial hydrogen (1) passes through an orifice (2) into a manometric system that measures the tankside pressure (3) and the back pressure (4) in the system. A water trap (5) guards against excess tankside pressure. A by-pass with stopcocks (6 and 7) is provided, so that the hydrogen can be routed directly from the tank to the furnace if desired. When stopcock 7 is closed and stopcock 6 is open, the gas proceeds through the conditioning train, of which the first unit is a furnace (8) that contains platinized asbestos at 350°C. The temperature is measured by a thermo-couple and potentiometer (9) and is controlled by a slidewire resistance (10). In [ ] this furnace free oxygen is converted to water vapor. The exiting gas passes over a water bath (11) kept slightly below boiling temperature by an auxiliary heating unit (12). This unit also heats a surrounding copper coil (13) containing water, and the heated water rises through a collar (14)

Jan 1, 1942

By S.H. Ash, P.S. Miller

Extensive and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past I0 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the Succdeding face, constituting a round. Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons" tunne1ing is more hazardous than mining in any branch of the mineral industry. On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. The Delaware Aqueduct The new Delaware aqueduct is a Manhattan project of some magnitude; when regular it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1943

By P. S. Miller, S. H. Ash

Extensive and diversified resources justify large populations and great industries. To carry on the business of commerce and meet the demands of large populations, the utilization of tunnels in some form for transportation purposes constitutes an important link in modern civilization. The driving of tunnels has been appropriated by the tunneling branch of the heavy-construction industry, and the progressive steps taken by modern tunnel builders were not even dreamed of 50 years ago. Great strides have been made toward more rapid progress in tunneling in the United States during the past I0 years. Tunneling consists of a definite cycle of operations developed from ideas that are crystallized and translated into action programs through various engineering phases that begin with the first preliminary survey and do not end until the job is completed. Once the line of the bore is established and a time set for the completion of the work, the face must advance according to estimates prepared before the work commences. This schedule must be followed in regular sequence from the moment the drills start against a new face of rock until they are ready again to drill the Succdeding face, constituting a round. Mining is largely tunneling carried on under conditions often more inherently hazardous than actual tunnel construction, but for various reasons" tunne1ing is more hazardous than mining in any branch of the mineral industry. On the other hand, obstacles are sometimes encountered in heavy-construction tunneling projects that when met in mining enterprises do not offer comparable tasks to avoid or overcome them. One is the existence of water under high pressures. In mining enterprises, various alternatives offer a solution in driving a tunnel, even to the extent of its discontinuance or the abandonment of the mine, but a "construction" tunnel usually must go forward because some important project depends largely if not entirely upon it. This paper describes an unusual method of driving a water-supply tunnel through rock carrying water under pressures and conditions that did not permit the use of ordinary tunneling methods. The Delaware Aqueduct The new Delaware aqueduct is a Manhattan project of some magnitude; when regular it will contain what probably will be, for some time to come, the longest tunnel in the world. Various features in its construction are currently described in the trade journals of the construction industry, and informative engineering details are given in the Delaware Water Supply News, published twice a month by the Board of Water Supply of the City of New York. Work was begun on this project on March 24, 1937. The tunnel will convey water from reservoirs at the headwaters of the Delaware River to the City of New York.

Jan 1, 1943