Search Documents

By M. D. Arnold, P. B. Crawford, P. C. Hall

An experimental study has been made to determine the optimum flooding pressures for four different oils. The oil formation volume factors ranged from 1.08 to 2.13, and solution gas-oil ratios ranged from about 200 cu ft/bbl to 2,250 cu ft/bbl. Viscosities ranged from 0.38 to 0.95 cp at the respective bubble points of the fluids and from 0.7 to 20 cp at atmospheric pressure. Water floods were conducted at various pressure levels from run to run. The recovery as a function of flooding pressure was found to be different for each fluid, with optimum gas saturations ranging from 7 up to 35 per cent. The data indicate that substantially higher recoveries may be obtained if water floods are conducted at an optimum pressure and that this optimum pressure is a function of fluid properties. The same core was used for all tests, and the reproduction of saturations for various runs indicates that wettability in the predominantly water-wet core did not change. INTRODUCTION A paper was presented by Bass and Crawford' which described an experimental study of the effects of flooding pressure and rate on oil recovery by water flooding. This work was conducted using high-pressure models operated in a manner similar to that of an actual reservoir, with gas saturations being obtained by a solution-gas-drive mechanism. They found that the greatest oil recovery was obtained for the system studied by flooding in the presence of a 5 to 7 per cent gas saturation. Another experimental study simulating field conditions was presented by Richardson and Perkins.' They used an unconsolidated sand pack containing kerosene-natural gas fluid and interstitial water. They flooded at various pressures and flooding rates. For their system it was found that the recovery was independent of the pressure level at which the water flood was performed. Kyte, et al," found that oil recovery by water flooding was increased as the free gas saturation at waterflood initiation was increased. However, after the initial gas saturation was increased above 15 per cent, the increase in oil recovery tended to level off. All of their runs were made at the same pressure using a light oil saturated with helium. The desired gas saturation was obtained by injecting helium into the core. Dyes' made calculations which showed that an optimum gas saturation of 12 to 14 per cent may result in an increase in oil recovery of 7 to 12 per cent over that obtained by flooding at the bubble-point pressure. Others have also found that the presence of a free gas saturation may increase the waterflood oil recovery. In each case shrinkage was small and changes in fluid properties with respect to pressure were small. A careful review of the literature reveals that at the present time there is a wide difference of opinion on the factors affecting waterflood recoveries. This diversity of opinion is probably due to the fact that very little research has been done which has taken into account the many variables existing in an actual field being water flooded. Since the literature contains little information on high-pressure waterflooding studies using various types of reservoir fluids, it was believed appropriate that such a study should be made. EQUIPMENT AND PROCEDURE All tests were made using the same consolidated sandstone core. Torpedo sandstone was used to turn a cylindrical core 13.5-in. long and with a 2.92-in. average diameter. The core had a porosity of 28 per cent and a permeability to brine of 146 md. This brine was made up by adding 20,000-ppm sodium chloride and 30,000-ppm sodium nitrite to distilled water. This was used as connate water and flooding water. No fresh water was ever brought in contact with the core, as tests showed the sandstone contained argillaceous material which swelled in the presence of fresh water and plugged the stone. The core was sealed in a section of 6-in. N-80 tubing with Woods metal filling the annulus. The core was mounted horizontally; an injection well was placed in the center of one end and a production well in the center of the other. Pressure control was maintained by placing a back-pressure regulator (upstream control) on the producing well. The "live" oil was stored in a separate bottle and water was injected into this bottle to displace the oil for saturating the core using a two-cylinder standard-proportioning pump. This same pump was used for water flooding the core at a constant rate. This system was enclosed in water jackets and the temperature was automatically main-

By H. E. Cline

Solidification of Pb-Sn alloys ranging in composition from 1.2 to 56 at. pct Pb ws observed with polarized light. Lamellar structures were observed over a larger range of compositions in alloys containing excess tin than excess lead, as expected from constitutional supercooling. The occurrence of pools of supercooled liquid surrounded by lead is explained by the difficulty in nucleating tin. Cells and dendrites weve observed in tin-rich alloys. Evidence was found that the degenerate structure formed at low growth rates, the formation of faults, and abrupt changes in composition and structure can be attributed to non-steady-state growth. The apparent interface shape was observed to have deep grooves at the interphase boundaries. HUNT and Jackson have observed the shape of the interface during growth of organic eutectics. They observed the formation of lamellar faults and shape instabilities upon changes in growth rate. The lamellar structure in these organic eutectics was not restricted to the eutectic composition. Recent work by Mollard and Flemings2 indicated that Pb-Sn alloys from 12 to 26 at. pct Pb could be solidified with a lamellar or rodlike structure if a sufficiently steep temperature gradient was used at a slow growth rate. Observations of the solid liquid interface of the Pb-Sn eutectic were made by Davies3 using polarized light. Photographs were at too low a magnification to determine the interface shape, but he has concluded that tin was the leading phase. In the following experiments, solidification of a range of Pb-Sn alloys from 1.2 to 56 at. pct Pb was observed using polarized light, to determine the factors controlling stability of the lamellar structure. EXPERIMENTAL Procedure. One hundred-gram ingots of alloys prepared from 99.999 pct pure Pb and Sn were cast into graphite molds under argon. The compositions of the alloys were 1.2, 6, 12, 26, 36, 46, and 56 at. pct Pb. Two-gram pieces were melted between two cover glass slides which were squeezed into a 1-mm separation. Samples were then observed under polarized light in a hot stage shown in Fig. 1. A long working distance objective designed for viewing at 500 times was used. Photography was made difficult by the lack of illumination and contrast at these high magnifications. By using an elliptical polarization compensator, as suggested by A. Holik, the contrast and illumination could be optimized. Photographs could be taken only at slow growth rates to avoid excessive interface motion during the 15-sec exposure used. The solidification rate was varied by increasing or decreasing the power to the heater. It was found that insulation was necessary to avoid undesired growth rate fluctuations. The temperature gradient, as measured with two thermocouples 1 cm apart, was 80" ± 20°C per cm during all the experiments reported here. The advantage of this procedure is in being able to observe solidification while it is occurring. However, the observations are restricted to the glass-metal surface and may be influenced by this surface. Also, one has no knowledge of the interior of the sample, in contrast to studies of the freezing of transparent organic eutectics.' Observations. The alloy near the eutectic composition (26 at. pct Pb) solidified in a lamellar structure when the growth rate was uniform. If the growth

Jan 1, 1968

By D. A. Woodford

In a constant-load creep test, if the density of nlobile dislocations is assumed constant for strains exceeding that corvesponding to the minimum creep rate, it is shown that the creep rate may be approximated by the equation where E is the nominal strain, o0. is the initial stress, and a' the stress fov unit dislocation velocity. The constant C contains the mean density of mobile dislocations and n is a measure of the stress sensitivity of dislocation celocity. This equation is shoum to be applicable to published data on an alloy steel and on nickel. The degree of plastic instability and hence the creep ductility is dependent on the calue of n for these materials. When instability becomes gross and local macroscopic necking occurs, the assumptions are no longer valid. On the basis of this equation, and the strain-time relation derived from it, a method of predicting the creep behavior at different stresses is suggested. MOst analyses of creep data have been concerned with time-dependent transient creep or time-independ- ent secondary creep in constant-stress tests. The far more widely used constant-load test has been neglected in terms of a mechanistic approach. In general, since the strains involved are usually small, the same laws for transient creep may be applied to both types of tests. However, there is no steady-state creep in a constant-load test since the stress increases continuously. Any apparent steady state observed on a strain-time plot is either fortuitous or illusory, and is generally revealed as a continuously varying creep rate on a carefully constructed strain rate vs time plot.* Transient creep may be understood in terms of a simple differential equation representing the change in mobile dislocation density with time:' where p is the density of mobile dislocations. The first term on the right is related to first-order kinetics of dislocation multiDlication and the second to second-order kinetics of exhaustion. On the basis of this equation, several authors2-4 have found good agreement with experimental transient creep curves for a number of materials. When k1p = k2p2, a steady-state creep

Jan 1, 1968

By B. C. Allen

The solubility of chromium in liquid silver and that of molybdenum and tungsten in liquid tin have been determined by equilibrating Ike Liquid in a crucible of the solule metal. Generally the weight of solute in solulion was delermined both chemically and from crucible weight losses. The resulting weight percent solubilily of chromium in silver as a function of absolule temperature T is given by log w = -6660/T + 4.02 in the range 960° to 1445°C, and that of molybdenlttrl in tin by log w = —5050/T + 1. 79 in the range 1200° to 2200°C. The values appear unaffected by minor changes in solute composition. Calculations aye made of the parlial molar heal and excess entropy of mixing. The estimated solubility of tungsten in tin is 0.001 pct at 2000°C. Evidence is presented that molybdenwm dissolves in tin without compound for mation and that tungsten and tin form W10Sn. RECENT developments in coatings, heat transfer, and brazing require a knowledge of equilibrium solubilities in a variety of systems at elevated temperatures. Of particular interest are solid-liquid interactions in metal systems involving dilute solutions. This investigation was undertaken since little is known about the phase relations or solubility of chromium in liquid silver or of molybdenum and tungsten in liquid tin.1,2 EXPERIMENTAL WORK As indicated in Table I, high-purity metals or those of known impurity levels were used. Crucibles were machined from chromium, molybdenum, and tungsten bar stock 1.3 cm diam and 2.2 cm long. Chromium rod was prepared by arc melting and extruding iodide process crystals.3 The five chromium impurity alloys were in the form of 0.6-cm-diam swaged rod. A Cr-0.06N* alloy was prepared by exposure to NH3 at 1150°C in a closed quartz capsule for 24 hr. Because significant nitrogen was lost during annealing in argon at 1600°C,4 the estimated level was 0.01 pct N. Chromium and Mo,W crucibles were outgassed at 1200" and 1600°C, respectively, at 3 X 10-5 mm. The solvent was placed In crucibles of the solute metal- 6 g Ag in chromium, 0.4 g Ag in the five chromium impurity alloys, and 4 g Sn in Mo,W crucibles. The silver and tin series were outgassed at 900" and 110O°C, respectively, and held at the desired solution temperature in a tantalum resistance furnace under 1.05 atm 99.995 pct Ar. An equilibration time of 0.5 to 1 hr was chosen since 0.3-, I-, and 4-hr anneals at 1235°C for Cr-Ag yielded similar results. Temperatures were measured optically to +10°C under essentially black body conditions which were checked against the melting point of silver. The Cr-Ag and Mo-Sn,W-Sn series were respectively equilibrated at 990° to 1400°C and 1200" to 2000°C. Vaporization losses were generally held to <1 pct by the argon. In the 1800" and 2000°C anneals for 0.5 hr, the crucibles were placed in tightly sealed tantalum cans which kept tin losses to <5 pct. After the anneals, the specimens were furnace-cooled. One anneal was made on small Mo-0.02 C, Mo-0.5Ti-0.lZr, and tungsten crucibles containing tin at 2200°C. The metals were sealed in an electron-beam-welded tantalum can of minimum volume. After the anneal, tin was still present in each crucible, none of which was severely attacked. After equilibration, the saturated solvent metal was selectively removed from the crucible by acid leaching. Weight losses sustained by the crucibles were determined from the initial weight minus the final blank-corrected weight after acid leaching. Chemical analyses were performed on some of the samples. Hot 1:l HNO3-H2O removed silver from chromium with the blank running <0.1 mg or <0.002 pct on measured solubility. Tin was removed from molybdenum and tungsten by hot concentrated HC1 with the respective blanks amounting to -0.004 and -0.0004 pct in the presence of tin. The insoluble residues were weighed and checked for composition. The leaching solutions contained traces of the solute metals which were analyzed by colorimetric methods, Diphenyl Carbazide for chromium, Thiocyanate for molybdenum, and Dithiol for tungsten. The total of the two percentages found from the residue and leaching solution minus the blank gave the desired solubility values. On the basis of annealing empty molybdenum and tungsten crucibles, weight losses due to MoO3 or WO3 volatilization were found to be generally 10.4 mg and affect measured solubilities by <0.01pct. RESULTS AND DISCUSSION Chromium-Silver . Since no intermediate compounds are reported to form in the Cr-An system,&apos; crucible weight losses and chemical analysis of the entire melt should provide reliable measures of the chromium in solution. Values obtained by the two methods are in agreement as shown by the results for unalloyed chromium in Table II and plotted in Fig. 1. Furthermore, the results are consistent with those previously determined by melting equilibrated silver out of the crucible and analyzing calorimetrically for chromium.&apos; On the basis of limited thermal analysis data, the solubility of chromium in silver has been quoted as 8 pct at the monotectic temperature of -1445°C.1 This investigation indicates an extrapolated solubility of 1.38 pct which is believed to be more reliable. At the eu-

Jan 1, 1968

By A. L. Holley

This process is performed in the Pernot puddling furnace; it removes from 75 to 80 pel. cent. of the phosphorus, most of the sulphur, and practically all the silicon, from crude iron, in from five to eight minutes. It has been in regular use since March, 1877, and has produced over seventeen thousand tons of mashed metal for the openhearth furnace. During two years, nearly all, and lately, all the open-hearth steel produced in these works has been made from about 5 tons of washed pig and 2 tons of scrap per open-hearth furnace heat. There arc 12 open-hearth furnaces, of which 4 to 9 are running, according to the state of orders. A large amount of highly phosphoric iron from France and Belgium has been also washed and then puddled for parties who have taken, or are expected to take, licenses. The mashing of pig for puddling, however, is not a practice at Krupp&apos;s works, because pore pigs are nearly as cheap as impure ones. The author and his assistant, Mr. Laureau, spent, during the last month, three days at Krupp&apos;s works, examining this process. They copied out of the office books characteristic analyses and physical tests, some of which are given berewith. They also brought home many samples of pig, cleaned metal, puddle bar, and steel, which they saw treated. Analyses of some of these samples appear in Table IV. As there are no blast furnaces at Essen, the iron is melted in two Bessemer cupolas with fore-hearths; they melt 124 pounds of iron with 1 pound of coke. The metal is run by a spout from the forehearth into an opening at the side of the main door of the washingfurnace. The The washing-furnace.—This is a regenerative gas furnace. It has a Pernot revolving-hearth of 12 feet external diameter and 3 feet depth. (See Plate.) The four regenerator chambers hare 780 cubic feet capacity, which is about the same as the average regenerator capacity of open-hearth steel furnaces of equal tonnage. The lining is 13 inches thick on the sides and 9 inches on the bottom, thus giving a hearth 9 feet 10 inches by 2 feet 3 inches deep. The lining is composed of lumps of highly refractory ores

Jan 1, 1880

By C. D Looker

Common salt is mentioned in the most ancient writings as an important article of diet. It is fairly certain that it was used by men and animals long before the dawn of civilization. Its presence in natural springs has often been the determining factor in colonization; wars have been fought for possession of salt deposits; trade routes have been established expressly for the purpose of traffic in salt. Naturally this led men into adventures and discoveries that altered history and advanced civilization. In the early days the uses for salt were few and the methods of manufacture were crude and the purity low when compared to salt of the present day. Then the salt came largely from springs, shallow wells or the ocean, while today deep wells must be drilled to the natural brines or beds of rock salt and spacious shafts sunk so that the ancient deposits may be made to yield their supply of stored mineral. Mining and Purification The quantity of available salt seems inexhaustible. It occurs in practically every country of the globe. About 20 million tons is produced and consumed annually in the world. Of this amount about 7 million tons is produced in the United States; 13/4 million tons of rock salt, 2 1/4 million tons as evaporated salt and 31/2 million tons in brine used in the chemical industry. Mined rock salt is used in its natural state without purification. It is classified for the trade by crushing and screening. The average purity of rock salt mined in the United States is about 98.3 per cent pure sodium chloride1. The usual impurities are gypsiferous shale, anhydrite and silica, with traces of potassium, magnesium and calcium compounds. Refined or evaporated salt is made by crystallizing the salt from brine in open pans or vacuum pans. A comparatively small amount of salt is made from ocean water or the brines of inland lakes or seas, sometimes by solar evaporation. By far the larger amount of brine is obtained by drill-

Jan 1, 1938

By C. D. Looker

Common salt is mentioned in the most ancient writings as an important article of diet. It is fairly certain that it was used by men and animals long before the dawn of civilization. Its presence in natural springs has often been the determining factor in colonization; wars have been fought for possession of salt deposits; trade routes have been established expressly for the purpose of traffic in salt. Naturally this led men into adventures and discoveries that altered history and advanced civilization. In the early days the uses for salt were few and the methods of manufacture were crude and the purity low when compared to salt of the present day. Then the salt came largely from springs, shallow wells or the ocean, while today deep wells must be drilled to the natural brines or beds of rock salt and spacious shafts sunk so that the ancient deposits may be made to yield their supply of stored mineral. Mining and Purification The quantity of available salt seems inexhaustible. It occurs in practically every country of the globe. About 20 million tons is produced and consumed annually in the world. Of this amount about 7 million tons is produced in the United States; 13/4 million tons of rock salt, 2 1/4 million tons as evaporated salt and 31/2 million tons in brine used in the chemical industry. Mined rock salt is used in its natural state without purification. It is classified for the trade by crushing and screening. The average purity of rock salt mined in the United States is about 98.3 per cent pure sodium chloride1. The usual impurities are gypsiferous shale, anhydrite and silica, with traces of potassium, magnesium and calcium compounds. Refined or evaporated salt is made by crystallizing the salt from brine in open pans or vacuum pans. A comparatively small amount of salt is made from ocean water or the brines of inland lakes or seas, sometimes by solar evaporation. By far the larger amount of brine is obtained by drill-

Jan 1, 1938

By W. O. Philbrook, A. H. Jolly, T. R. Henry

In the course of a study of slag-control methods, the authors devised a laboratory technique by which the basicity of basic open-hearth furnace slags could be estimated with sufficient accuracy to make the method of possible interest for slag-control purposes. The process consisted of measuring the slight basicity of an extract of the powdered slag in water. The procedure was presented, for the benefit of those who might care to experiment with it, in a paper submitted in the 1944 McKune Award Contest and presented at the 1944 Open-hearth Conference in Pittsburgh.&apos; Interest expressed at that meeting and favorable operating experience with the method at a neighboring plant, as described in a related paper by Michael Tenenbaum and C. C. Brown,; have encouraged us to present further details of the development, technique, and pitfalls of the method and some additional data not included in our first report. At the outset it must be admitted that this method of estimation of slag basicity is not perfect; neither is any other that we know of. It is subject to somewhat greater errors than would be desirable, but compares favorably with other techniques in this respect. It has the disadvantage that it places the final determination of slag basicity in the hands of a laboratory technician rather than the furnace oper- ator, although it can be operated in a control laboratory adjacent to the furnaces. It requires close attention to certain details, as do most laboratory procedures. On the favorable side, it eliminates the "human factor" of personal judgment inherent in estimation from pancakes or powdered samples. The procedure can be placed in practice much more rapidly and presents much less of a training problem than visual methods of estimation. The principle and operation of the method are so simple that it would not be surprising if others have experimented with the same or similar procedures, but we are not aware of any prior publication of details. Our own shop has been operating fairly successfully for several years with the aid of slag pancakes. Since the past year or two have not been favorable for the expenditure of time and energy where the need was not urgent, we have not introduced the new practice for actual slag control and hence do not have extensive operating data. In presenting this method, therefore, we make no claims as to theoretical justification nor guarantees as to practical applicability, but offer it as an empirical observation. We believe it has sufficient merit to warrant its investigation by those just instituting a slag-control program or in search of supplementary methods for judging slag basicity Principle of the Method It is well known that when burnt lime or slaked lime is shaken up with water it

Jan 1, 1945

By Harold S. Morgan

INTRODUCTION The Waste Isolation Pilot Plant (WIPP) is being developed in southeastern New Mexico by the United States Department of Energy as a research and development (R&D) facility to demonstrate the safe disposal in salt of radioactive wastes resulting from defense activities. As part of the WIPP R&D program, a series of in situ tests will be performed to determine the behavior of drifts and storage rooms in the creeping salt medium (Matalucci, et al. 1982). Data obtained in these tests will be used to evaluate and improve numerical models used to compute the structural response of these drifts and rooms. Stress has been proposed as one of the parameters to be measured in the tests, and borehole inclusion stressmeters have been included in the instrumentation package. Cages of this type provide an indirect measurement of stress change in that they actually monitor borehole displacements which are then related to changes in the in situ stress away from the borehole. The relationship between stress and displacement is highly dependent upon the constitutive behavior of the rock in which the gage is emplaced. This relationship is well understood for rocks with linear stress-strain behavior (Fossum, et al, 1976), but, for creeping rocks like salt, the relationship has yet to be determined. Thus, inclusion gage response in salt must be investigated fully before stress measurements from the WIPP in situ tests can be used for comparisons with computed stresses The calculations presented in this paper were performed as part of an investigation of inclusion stressmeter performance in salt. They focus on the strain gaged stressmeter (SGS) (Cook and Ames, 1979) and on a hypothetical solid cylindrical inclusion with variable stiffness Issues addressed include the effects of creep and the effects of gage stiffness on stressmeter output for various loading conditions. The

Jan 1, 1984

By P. A. Larssen, P. R. Gage, R. W. Bartlett

The kinetics of formation of intermediate sili-cide compounds from MoSi2/Mo and WSi2/W couples were studied using a cylindrical sample configuration. Concentration profiles of the constituent metals were deter mined from electron-microprobe analysis of cross-sectioned samples after isotlzernzal diffusion annealing. These data also yielded hand widths of phases. Growth of intermediate phases depends on diffusionin them and obeys a parabolic rate law. The rates of formation of the intermediate phases decrease in the order Mo5Si3 > W5Si3 > Mo3Si. Crowth rates. for the isomorphous phases Mo5Si3 and W5Si3 had the same activation energy. 43 kcal per mole. SILICIDE coatings employed to protect refractory metals from high-temperature oxidation are usually formed by a diffusion process requiring concurrent transfer of silicon to the refractory metal surface. For a simple binary system and a coating thickness of one or two mils, the coatings on molybdenum and tungsten are primarily the disilicides WSi2 and MoSi2, respectively. During use of the coated re- fractory-metal system at high temperatures, in the absence of the silicon source, further diffusion causes growth of lower silicide compounds and depletion of the disilicides. Recent investigations have shown that the lower silicides are less effective than the disilicides in forming a glassy oxide film which impedes oxidation.&apos; Consequently, failure of coatings at high temperatures may coincide with complete conversion of the disilicide phase. The purpose of this part of the study is to investigate the growth kinetics of the intermediate compounds in the W-Si and Mo-Si systems. There are three intermetallic compounds in the Mo-Si system: MoSi2 with a tetragonal structure

Jan 1, 1964

By John H. Smith, Michael B. Bever

Pure gold was deformed by wire drawing at room temperature and 78°K. After deformation at room temperature, the stored energy and the resistivity increment reached nearly constant levels at high strains, whereas the yield stress continued to increase with strain. After deformation at 78K, the stored energy, the reszstivity increment, and the yield stress were larger than after deformation at room temperature mzd increased continuously with strain. Annealing at THE stored energy and the changes in properties resulting from cold working of Au-Ag alloys by various processes have been the subject of a series of investigations in this laboratory.&apos;-&apos; The work reported here room temperature after deformation at 78°K did not affect the yield stress appreciably. The stored energy, resistivity increment, and Lncrease in yield stress after deformation at room te-lnperature can be explained primarily in lerrns of dislocations while point defects, as well as dislocations, contribute to the changes in these properties after deformalion at 78°K. extends this research to pure gold. The stored energy, the resistivity increment, and the tensile properties after deformation by wire drawing were measured as functions of the strain at room temperature and at 78°K. The effect of the testing temperature and the effect of intermediate annealing at room temperature before testing at 78°K on the tensile properties of gold deformed at 78°K were also investigated. wire drawing made it possible to use a large range of strains, which was desirable because previous work on the deformation of gold had been carried out mainly at relatively small strains.&apos;-l2 Also, wire specimens

Jan 1, 1969

By M. Paulus

It is known that multicomponent powders are mostly nonhomogeneous. This paper investigates the effects of nonhomogeneity of composition and grain size on the melting point and the sinterability of compact taking into account homogenization mass transport and the length of the diffusion path in solid state sintering, and the kinetics of liquid phase formation in liquid phase sintering. After a discussion on the ideal characteristics of a powder for sintering and low temperature reaction, the main conventional processes are compared. Finally we develop the freeze-drying technique and demonstrate the capabilities and the limits of the process by some examples, mainly in the ceramics field.

Jan 1, 1980

By P. Niessen, W. C. Winegard, C. J. Beingessner

DURING the last 10 years, several grain-growth studies have been made using zone-refined metals with controlled amounts of solute to elucidate the interaction of solute with moving boundaries. In all these studies, it was more or less implicitly assumed that the alloys used were, after recrystallization and grain growth, homogeneous within the grains with respect to solute and lattice defects. This note deals with observations made on microstructures originating from solidification of dilute alloys and from grain growth. Briefly, the experimental procedure used in these studies was the following: zone-refined cadmium and master alloys were melted and cast in Pyrex under vacuum to produce bars 14 mm in diam and about 150 mm long. These bars were cut into 8-mm-thick slices which were mechanically and chemically polished. The specimens were then deformed 30 pct in compression and given a 1-week anneal at 260°C in argon. After this anneal, a second deformation produced completely recrystallized samples 4 mm thick. The time-temperature controlled anneals were carried out in a bath of silicone oil. After the grain-growth anneal, the specimens were polished in Gil-man&apos;s&apos; solution (33 g CrOs, 6 g NazSO, in 100 ml of water). Several etches were used depending on the alloy investigated, but mostly a mixture of concentrated HC1 and HNOj (98:2 vol) was employed. In all the alloys examined, the ease with which substructures could be revealed depended strongly on the crystallographic orientation of the surfaces of the grains. However, very frequently the microstructures to be discussed here etched up over broad areas comprising several grains. Fig. 1 is a micrograph of a Cd-0.05 at. pct Mg alloy annealed for 100 sec at 270°C. Different substructures are seen in this photograph. A denotes the now existing grain boundaries. The well-defined lines and points marked B are the remains of a solidification substructure. The lines are boundaries between cell colonies, and the points are nodes located on regular two-dimensional cells. This cellular structure has the same appearance as that found by weinberg2 for rapidly quenched Zn-Au alloys. The "ghost boundaries", marked C, are very similar in appearance to a grain boundary array in a polycrystalline sample. Repeated polishing and etching showed that all the substructures observed were three-dimensional. To date, the ghost boundaries have been clearly observed in all samples containing 0.005, 0.01, 0.05, and 1 at. pct Mg, and in samples containing 0.01 at. pct Zn. Attempts to outline these ghost boundaries in cadmium alloys containing 0.01 at. pct Ag and Au were only partially successful. In these alloys, parallel lines, having a resemblance to the ghost boundaries in the Cd-Mg and Cd-Zn alloys, were observed, but it was not possible to obtain complete arrays of ghost boundaries which extended over several grains. It is possible that a different etch than that presently employed would reveal the ghost boundaries in the Cd-Au and Cd-Ag alloys as clearly as in the Cd-Zn and Cd-Mg alloys. A close examination of the ghost structure showed that it consisted of linear etch-pit arrays, Fig. 2. The ghost boundaries were resolvable even in grains which showed over-all faceting due to the etching, as seen in the corner of Fig. 2. The general appearance of the ghost structure suggests that it originated during grain growth. This is supported by the observation that the mesh width in the ghost-boundary array generally increased with increasing final grain size. To test whether the ghost structure was formed during the long homogenizing anneal or during the grain-growth anneal, some as-cast samples were deformed and given a grain-growth anneal. This anneal was terminated by air cooling or

Jan 1, 1967

By M. E. Wadsworth, A. S. Peck

Infrared spectra disclose that oleic acid will not adsorb on the surface of pure beryl unless the mineral is first activated with HF. The adsorption of oleic acid on HF activated beryl is attributed to the hydrogen bonding of oleic acid monomers to F-surface bridging sites. These sites are formed as a result of the reaction of HF with chemisorbed water or surface hydroxyl. Characteristic infrared spectra of physically adsorbed oleic acid are correlated with flotation at different pH at temperatures of 25°C and 75°C for colloidal and -60-mesh particles. The usual mode of occurrence of the beryllium mineral beryl, Be3A12Si6O18, is in granite pegmatites as pale green, white, or yellow crystals. A dark green gem variety, emerald, may be found in the wall rock of pegmatite veins or in mica schist. The most important beryl deposits in the United States are in the Black Hills District of South Dakota, and several mountain ranges of central and west-central Utah contain potential commercial sources of this mineral. Several papers have been published concerning the flotation of beryl with different conditioning reagents. Kennedy and O&apos;Meara1 reported on the essential use of HF in the flotation of beryl from different ores. The use of calcium hypochlorite to separate HF activated beryl from feldspar after flotation with an amine collector was made by Runke.2 A report on the activation of beryl with different cations using sodium oleate collector was presented by Viswa-nathan and co-workers.3 Flotation of beryl with sulfonate collector and different activating salts was employed by Fuerstenau and Bhappu.4 The role of the surface charge or zeta potential in the flotation of beryl with different collectors and salts was also extensively investigated.5"7 Previous infrared investigations by the authors8 disclosed that the orthosilicate beryllium mineral, phenacite, reacts with oleic acid to form a chemisorbed oleate monolayer on the mineral surface. Thus, chemisorption is the effective mode of adsorption in the phenacite-oleate acid flotation system. In contrast, neither chemisorption or physical adsorption of oleic acid occur on the surface of pure beryl as evidenced in this study. Efforts were subsequently made to determine the mechanism of activation and collector adsorption for HF pretreated beryl. EXPERIMENTAL PROCEDURES Large, white, terminated crystals of beryl were obtained from Madagascar through Ward&apos;s Co., Monterey, Calif. The crystals were broken into -60-mesh fragments in a porcelain mortar. Part of this prepared material was ground to a powder with a Fisher Grinder using an agate mortar and pestle. The powder was transferred to a graduated cylinder and mixed with 500 ml of distilled water. After 5 min, the colloidal suspension was separated from the settled particles by decantation and used as a stock for infrared test determinations. Adsorption tests were performed by first transferring 20 ml of colloidal suspension to 50 ml glass centrifuge tubes. The solids were then centrifuged out and the liquid was discarded. Then, the solids were pretreated with one molar HC1 or one molar HF. After 15 min, the solids were again centrifuged out. The mineral solids were washed free of residual acid by repeated centrifuging and water washing operations. Then, 20 ml of distilled water was added to the solids, and the resultant suspension was used for test purposes. In the preparation of mineral for flotation tests, 1.5 g of -60-mesh beryl was deslimed by removing the colloidal fraction by three successive water washes and decantations. Then, the coarse particles were pretreated with either one molar HCl or one molar HF for 15 min. The mineral was next washed free of acid with distilled water, and 20 ml of distilled water was added to the beryl prior to collector conditioning. The conditioning of mineral with collector was performed in 50 ml centrifuge tubes to which either NaOH or HC1 was added for pH modification. One drop (6.0 mg) of U.S.P. reagent grade oleic acid or 2 ml of 0.01 molar sodium oleate was added to the pulp and stirred at about 1500 rpm for 3 min at a

Jan 1, 1968

By C. W. Lawr

The ores mined by the Santa Gertrudis Co. at Pachuca, Mexico, arc mainly silver-bearing; they also yield some gold and carry a little copper. Strong cyanide solutions are used to dissolve the silver and gold, and the mechanical loss of cyanide at the tailings filter has been considerable. Prior to the year 1923, the pulp, after agitation, was given a 35 to 37-min. wash with barren solution in a Butters-type leaf filter; the discharged slime cake was repulped and pumped into eight Merrill self-sluicing slime presses in which the slime was given a further wash with barren solution for 25 to 35 min., followed by a 10-min. water wash. At that time the barren solution titrated around 0.350 per cent. free KCN and 0.500 per cent. total KCN. (Aero brand cyanide is used.) It can readily be seen that a 10-min. water wash would leave considerable cyanide in the filter cake, which of course was a total loss. This averaged 0.522 kg. (1.15 Ib.) KCN per ton of solution. As the daily discharge to the dam was 1600 tons&apos; of slime of a 2:1 ratio of liquid to solid, the value of this mechanical loss of cyanide was an important item and it&apos;s recovery held alluring possibilities. Principle of Cyanide-recovery Process As it had acquired the patent rights to theLayng (H. R.) and Halvor-sen (A. L.) processes, also those of Mills (L. D.) and Crowe (T. B.) after considerable experimental work in its own laboratory and at Tonopah, Nev., The Merrill Company of San Francisco early in 1923 notified the Mexican Corporation and compania de Santa Gertrudis of its process for the recovery of cyanide from weak wash solutions, or for the transference of cyanide from a foul mill solution to a clean alkaline solution. This method is known as the Mills-Crowe process, the principle of which is as follows: The solution from which the cyanidc is to be removed is made acid by bringing it into contact with sulfur dioxide (SO2). The acidified solution is the; transferred to a closed tank in which air and solution are brought into intimate contact. The air leaving the tank charged with HCN is then passed to another tank in which it is mixed with an alkaline solution,

Jan 1, 1930

By William P. Blake

In view of the present exposition at Atlanta, and the timely meeting of the Institute in that city, and the expressed desire of the Council for contributions to the knowledge of the mineral resources of the Southern States, I may be permitted to offer some desultory notes upon the subject, chiefly in the form

Jan 1, 1896

By B. C. Craft, T. J. Johnson, H. L. Kirkpatrick

Petroleum engineers are displaying considerable interest in the problems of cementing oil wells, especially in the Gulf Coast and California areas, where steep temperature gradients are encountered and where wells are being drilled to greater depths. Deep drilling, that is, at depths in excess of 7000 ft., has been undertaken in these areas only in the last few years and with this trend oil-well cementing requires more technical treatment. It is not the purpose of this paper to describe the scope and application of cement operations in the oil industry or to give the standard specifications, methods of sampling and testing of portland cement. The various testing methods have been described by the American Society for Testing Materials1, Uren2, Tickell and Wankowski3 and Rakestraw and Parsons4. The latter authors (pp. 50-58) have also described in detail the methods of cementing. The authors realize that it is impossible to reproduce in the laboratory the scale of forces and dimensions that exist at great depths, but an attempt has been made to scale down these dimensions proportionally. The selection of problems to be studied was based largely upon the practical questions asked by several of the largest operators in these fields. All cements used in these experiments met the specifications of the American Society for Testing Materials.

Jan 1, 1935

By Roy A. Koski

INTRODUCTION Cleveland-Cliffs Iron Company, and its subsidiary companies, operate and manage mining, beneficiation, and pelletizing operations in the Upper Peninsula of Michigan, the province of Ontario, Canada, and the State of Western Australia, Australia. The concentrates and natural ores vary mineralogically, physically and chemically. This paper describes the techniques employed in pelletizing the various concentrates and ore fines. The plant operations described are the Republic, Humboldt, Tilden, Empire and Pioneer in Michigan, the Adams and Sherman in Ontario, and the Robe River in Western Australia. Table 1 contains further details regarding design and operating capacities, commissioning dates, and participant ownerships. Allis-Chalmers grate-kiln systems are utilized in Michigan and Ontario, and Dravo straight-grate systems in Western Australia. Currently, the Empire and Tilden operations are being expanded. At Empire the additional pelletizing unit, identified as Unit IV, will have a design capacity of 8 996 metric tonne/d and is scheduled for startup May 1, 1979. The Tilden operation is being doubled with the additional pelletizing unit, identified as Unit 11, having a de- sign capacity of 12 599 metric tonne/d. Startup is scheduled for January 1, 1980. MINERALOGY OF CONCENTRATES AND NATURAL ORES In the Upper Peninsula of Michigan, the operations process ores from the Negaunee iron formation of the Marquette Range. The

Jan 1, 1977

By D. H. Turner, F. A. Crossley

The titanium-rich corner of the system Ti-Al-Si has been studied to determine the phase relationships in the temperature interval 600° to 1200°C. Metallographic examination of long time isothermally annealed specimens was the means of investigation. PART of a program on phase relations and transformation processes of titanium alloy systems included the study of the titanium-rich corner of the Ti-Al-Si system. The investigation covered ternary compositions in the range 2 to 8 pet A1 and 0.1 to 2 pet Si and binary compositions in the range 0.2 to 2 pet Si. Temperatures were in the range of 600" to 1200°C. Alloys containing 6 pet A1-0.1 to 0.5 pet Si were investigated down to 400°C. Partial vertical sections are presented for 2, 4, 6, and 8 pet Al. The Ti-Si system has been reported by Hansen et al.&apos; It is characterized by a eutectoid decomposition, ß = ± a + Ti3Si3, at 860°C. The maximum solubility of silicon in a is reported to be about 0.5 pet at the eutectoid temperature. The solubility of silicon in 0 increases from 0.9 pet at the eutectoid temperature to approximately 3 pet at the eutectic temperature, 1330°C. Several investigations in the composition range of interest have been reported for the Ti-A1 system."&apos; These investigations are in agreement on the phase fields, but differ to small extents on boundary positions. However, very recent, and as yet unpublished, findings" " indicate that there are perhaps two phases which occur at lower aluminum contents than the ? (TiA1) phase, and that the solubility of aluminum in a titanium is less than 6 pet. In the present investigation phase relations found are in agreement with the published literature exemplified by the work of Bumps et al.3 Therefore, it is probable that the partial system reported herein is metastable and does not represent true equilibrium. Experimental Procedure High purity Bureau of Mines titanium sponge of 103 Bhn hardness, granulated aluminum shot of 99.7 pet purity, and silicon powder of 99.8 pet purity were used in making the alloys. For the work in the range from 600" to 1200°C, 100 g ingots were prepared by arc melting. Melting losses were negligible and spot checks by chemical analysis showed good agreement between nominal and analyzed results. Nominal compositions are used throughout this paper. Ingots were forged to 3/8 in. rounds and cut into specimens for heat treatment. Isothermal anneals in the range from 600" to 900°C were preceded by solution treatment at 1000°C for 1 hr, followed by furnace cooling to the annealing temperature. Samples were sealed in evacuated Vycor bulbs for heat treatments up to 1000°C. Higher temperature anneals were done with the samples sealed in quartz bulbs under a partial pressure of argon.

Jan 1, 1959

By R. W. Snyder, W. H. Guilinger, B. S. Gottfried

Two numerical methods are presented JOT solving the equations Jor one-dimensional, multiphase /low in porous media. The case oF variable physical properties is included in the Formulation, although gravity and capillarity are ignored. Both methods are analyzed mathematically, resulting in upper and lower bounds for the ratio of time step to mesh spacing. The methods are applied to two- and three-phase waterflooding problems in laboratory-size cores, and resulting saturation and pressure distributions and production histories are presented graphically. Results oJ the tuo-phase flow problem are in agreement with the predictions of the Buckley-Leuerett theory. Several three-phase flow problems are presented which consider variations in the water injection rate and changes in the initial oil-and ujater-saturation distributions. The results are different physically from the two- phase case; however, it is shown that the Buckley-Lez~erett theory can accurately predict fluid interlace velocities and displacing-fluid frontal snturations for three-phase flow, providing the correct assumptions are made. The above solutions are used as a basis JOT et~aluuting the numerical methods with respect to machine time requirements and allowable time step for a fixed mesh spacing. INTRODUCTION Considerable progress has been made in recent years in obtaining numerical solutions of the equations for two-phase flow in porous media. Douglas, Blair and Wagner2and McEwenll present different methods for solving the one-dimensional case for incompressible fluids with capillarity (the former using finite differences, the latter with an approach based upon characteristics). Fayers and Sheldon4 and Hovanesian and Fayers8 have extended these studies to include the effects of gravity. West, Garvin and Sheldon, l4 in a pioneer paper, treat linear and radial systems with both capillarity and gravity and they also include the effects of compressibility. Douglas, Peaceman and Rachford3 consider two-dimensional, two-phase, in compressible flow with gravity and capillarity and Blair and Peaceman1 have extended this method to allow for compressible fluids. No one, however, has examined the case of three-phase flow, even for the relatively simple case of one-dimensional flow of incompressible fluids in the absence of gravity and capillarity. In obtaining a numerical technique for simulating forward in situ combustion laboratory experiments, Gottfried5 has developed a method for solving the one-dimensional, compressible flow equations with any number of flowing phases. Gravity and capillarity are not included in the formulation. The method has been used successfully, however, for two- and three-phase problems in a variable-temperature field with sources and sinks. This paper examines the algorithm of Gottfried more critically. Two numerical methods are presented for solving the one-dimensional, multi-phase flow equations with variable physical properties. Both methods are analyzed mathematically, and are used to simulate two- and three-phase waterflooding problems. The numerical solutions are then taken as a basis for comparing the utility of the methods.

Jan 1, 1967