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By Milton Williams

It is generally recognized that fluid is lost from rotary drilling muds to permeable strata during normal drilling operations;1,2-3 but that this fluid is the filtrate from the mud, rather than the mud itself, has been shown by various workers.1,4,5 The presence of this filtrate in oil-bearing or gas-bearing strata is undesirable and harmful. The decreased permeability of the stratum to oil effected by the presence of water has been pointed out by several investigators,6,7 and since, in the production of the reservoir fluid, the greatest pressure drop occurs immediately adjacent to the borehole, it follows that infiltered water is particularly objectionable in this region. Again, this filtrate tends to make electrical logs less reliable, since oil in the proximity of the borehole is probably flushed out to an appreciable extent by the water.8 Observation of side wall cores may be misleading for the same reason. Drill-stem tests in low-pressure areas may be of doubtful value where no oil is recovered, unless sufficient time is allowed for production of water lost from the mud. The infiltered water may hinder drilling operations by softening shales and causing sloughing; the ['tight hole" occasioned by excessive deposition of filter cake in the hole is a common occurrence. The filter cake remaining on the face of the producing formation may itself sometimes be detrimental to production.9 In view of these implications of the importance of filtration of mud, an investigation was undertaken to determine the factors involved in the infiltration process, and to correlate these in such a manner that the values obtained in routine filter tests employing a conventional filter of the "wall-building tester" type,10 together with data on size of hole, drill pipe, and rate of mud circulation, could be used to estimate water loss and distance of penetration of the filtrate into strata. Quantitative relations of filter-cake permeability, filtrate viscosity, and rate of filtration have been developed for filtration in the simple laboratory filter.4a,11,12,13 It is obvious, however, that the conditions

Jan 1, 1940

By Milton Williams

It is generally recognized that fluid is lost from rotary drilling muds to permeable strata during normal drilling operations;1,2-3 but that this fluid is the filtrate from the mud, rather than the mud itself, has been shown by various workers.1,4,5 The presence of this filtrate in oil-bearing or gas-bearing strata is undesirable and harmful. The decreased permeability of the stratum to oil effected by the presence of water has been pointed out by several investigators,6,7 and since, in the production of the reservoir fluid, the greatest pressure drop occurs immediately adjacent to the borehole, it follows that infiltered water is particularly objectionable in this region. Again, this filtrate tends to make electrical logs less reliable, since oil in the proximity of the borehole is probably flushed out to an appreciable extent by the water.8 Observation of side wall cores may be misleading for the same reason. Drill-stem tests in low-pressure areas may be of doubtful value where no oil is recovered, unless sufficient time is allowed for production of water lost from the mud. The infiltered water may hinder drilling operations by softening shales and causing sloughing; the ['tight hole" occasioned by excessive deposition of filter cake in the hole is a common occurrence. The filter cake remaining on the face of the producing formation may itself sometimes be detrimental to production.9 In view of these implications of the importance of filtration of mud, an investigation was undertaken to determine the factors involved in the infiltration process, and to correlate these in such a manner that the values obtained in routine filter tests employing a conventional filter of the "wall-building tester" type,10 together with data on size of hole, drill pipe, and rate of mud circulation, could be used to estimate water loss and distance of penetration of the filtrate into strata. Quantitative relations of filter-cake permeability, filtrate viscosity, and rate of filtration have been developed for filtration in the simple laboratory filter.4a,11,12,13 It is obvious, however, that the conditions

Jan 1, 1940

By E. S. Anolick, Joseph Singer

The magnetic after-effect, in the form of time decay of permeability (l/µ), has been used to obtain independent data on the solubility of' carbon in pure iron. The results differ slightly from the solubilities obtained through internal -friction experiments. The mechanism of the time decay being the magnetic analogue of internal friction, it appears necessary to explain the observed discrepancies, and some suggestions are made. THE purpose of this work was to establish the reliability of the time decay of permeability as a measure of dissolved interstitial in the body-centered-cubic lattice, and further, to establish techniques suitable for such measurements with samples of a form convenient for various other measurements. This particular sample form was the "epstein" strip, i.e., 25 cm by 3 cm by 0.035 cms. While the general conclusions are not limited by this geometry, there are two aspects of the samples that may be relevant: a) texture, and b) grain size, which ranged generally from 1 to 10 mm. Effects due to these two possible parameters were thought to be small and were not investigated. Calibrating the time decay technique and the other experimental procedures by measuring the solubility of carbon in pure iron suggested itself because of the accumulation of data on this subject through the related technique of the internal friction'; The essentials of this report have been published in a somewhat condensed form.5 Since then some additional data have been taken. It is the purpose of this paper to add these data and to provide more complete description of the experimental techniques than was possible then. The time decay of permeability is a form of the magnetic after-effect.6,7 Permeability is measured immediately after demagnetization (µº) and also long after (µ8). The time decay, ?(l/µ), is the difference 1/µ8 - 1/µ0 and has been considered to be proportional to the concentration of a dissolved interstitial6,8,9,12 The relaxation time! 7, is characteristic of a particular diffusion, and affects the permeability as follows: where he being the activation energy for diffusion of the interstitial. Reference is made to the works of snoek6 and Neel7 for a complete discussion. A brief exposition of the principal ideas may be in order here, as follows. On the basis of the simplest model, resistance against domain wall motion increases with time after demagnetization due to the diffusion of interstitials to preferred sites created by the magnetostrictive tetragonolization under the strong magnetic field. Thus permeability, measured with a small field after the abrupt removal of the large field, will continuously fall with the process of diffusion of the interstitials, and the total "time decay" (or "time decrease") should be proportional to the amount of interstitial in solid solution. In the present report, use is made only of the total time decay rather than of the nature of the progress of the decay; the only problem involved in this approach is the need for assurance that only one interstitial is contributing to the effect as used. It is felt that the special use made here of the total time decay warrants the conclusions. Other work has been going on elsewhere on the detailed study of the nature of the time decay.8'9 EXPERIMENTAL A) Materials—12-lb ingots were made in a vacuum furnace from high-purity iron and by a series of hot and warm reductions were brought down to 14-mil strip. This was cut into 25-cm epsteins. The pure iron was decarburized at 750 °C by hydrogen. The time decay measurement for the decarburized iron (see below) indicated a satisfactorily low starting level of interstitials. Grain growth to grain sizes of 1 to 10 mm was produced in the pure iron by a 700" anneal in hydrogen after a critical reduction of about 7 pct as suggested by previous trials. No measurement of texture in the pure iron was made. The grain size was taken to be large enough to be beyond any sharply critical size regarding solubility. B) Infusion of Carbon—Since the permeability measurement required about two dozen epsteins, a special method of carbon infusion had to be developed to ensure homogeneity of infused carbon. This was accomplished by setting the samples edgewise in a

Jan 1, 1961

By F. J. Cuddeback

For low-head pumping of small quantities of water, the water jet, or hydraulic educter, has been used to advantage by Eagle-Picher Mining and Smelting Co. in the Tri-State district. Water-jet pumps are used for draining sumps and pockets up to 15 ft. in depth. They have been used very successfully when only moderate amounts of water are encountered in taking up bottom. A small, easily handled unit is desirable in this work, especially while opening and deepening a new stope. Small air pumps are convenient but can be used only on the day shift, when air is available. Obviously, a jet pump of smaller capacity but operating 24 hr. prevents lost time at the start of each shift. No tests have been made on their power efficiency, but admittedly it is low. However, for certain kinds of work this is offset by their handiness, low initial cost, low upkeep, and reliability. They will handle slime and sand without ill effect, and will continue to pump indefinitely on air. This foolproof 24-hr. performance has led to their continued use at some places even after electric pumps with better power efficiency could have been installed. The success of jet pumps depends largely upon a cheap source of high-pressure water. Owing to mine depths in the Tri-State district, pump pressures range from 100 to 150 Ib. per sq. in. In many mines it is common practice to handle the normal inflow water with triplex pumps ranging in size from 3 to 8 in. The pumps operate 24 hr. per day, and, in order to handle emergency conditions, are speeded slightly faster than necessary to pump the normal inflow. The sump level is governed by controlling the by-pass water with a butterfly valve and float. This method is somewhat wasteful of power, but permits the pumps to operate with a minimum of attention. Such an installation is visited once a day to check lubrication. Hence, if some of this water, normally by-passed to the main sump, were used to operate a jet pump, the power cost could be considered low regardless of efficiency. Figs. I and 2 show two water jets that have done satisfactory work. The one in Fig. 2, made up entirely of pipe fittings, may be of interest partially because of its novelty, but does better work than its appearance indicates. The pipe fittings for this jet as shown cost $2.20. Some improvement in its design may be made by cutting out the 135 by 1¼-in. reducer to a smoother taper as shown by dotted lines. A 3-in. suction pipe is sometimes used in order that the discharge may be as straight as possible. A 2-in. discharge line has been used frequently, but 3-in. pipe is used where several hundred feet of discharge is required.

Jan 1, 1946

By J. D. Exner

With the introduction of rotary drilling in the Gulf Coast area, some thirty-two years ago, and its subsequent spread to other producing localities in the United States, there has been a constant change in the design of equipment. Only the general features remain, namely the rotating drill stem and the circulating mud. Only recently have the properties of mud and their behavior received attention from petroleum engineers, but circulating problems in present deep drilling demand further study and understanding. It is the purpose of this investigation to determine the relative changes in the apparent viscosity of muds with changes in temperature and to discover other physical effects due to heat. Very little information has been published regarding the effects of temperature on the viscosity of drilling muds. Maustl states: "The viscosity of most muds is decreased on heating, but the interesting thing is that the degree of flocculation is also increased on heating. There will be a greater tendency to seal off formations at high temperatures than at low temperatures." With regard to the effect of temperature on viscosity and yield point, Herrick2 states: "The variation of yield point and viscosity of mud with temperature.....is not very clearly brought out by the data available. Both appear to decrease slightly with increasing temperature up to 200' F." The experimental results presented in this paper further emphasize this point. Two types of viscosimeters are available for measuring the apparent viscosities of drilling muds: the efflux tube type as used by Herrick3 and Marsh, and the torsional type such as the McMichael or the Stormer viscosimeters. Because of its extensive use in measuring the apparent

Jan 1, 1933

By Walter S. Weeks

THE process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case 1 If compressed air is allowed to expand to the atmospheric pressure through an orifice in an sir line that is supplied by a running compressor, no cooling results except the negligible one due to the Joule-Thompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. Cv Specific heat of air at constant volume, B.t.u. per lb. per deg. F. Cp Specific heat at constant pressure, B.t.u. per lb. per deg. F. T1 Absolute temperature of air in pipe, deg. F. T3 Absolute temperature of air outside after expansion and mixing and coming to rest. J Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By Walter S. Weeks

The process of cooling air by allowing it to expand and do work in an engine is well known, but the theory of obtaining cold air by free expansion without the aid of an engine operating with cutoff has been little discussed. Case I If compressed air is allowed to expand to the atmospheric pressure through an orifice in an air line that is supplied by a running compressor, no cooling results except the negligible one due to the JouleThompson effect, which will not be considered in this discussion. The effect of moisture will also be neglected. Symbols P1 Absolute pressure in pipe line, lb. per sq. ft. P3 Atmospheric pressure, lb. per sq. ft. V1 Volume occupied by 1 lb. air in pipe. V3 Volume occupied by 1 lb. air at P3. C, Specific heat of air at constant volume, B.t.u. per lb. per deg. F. C, Specific heat at constant pressure, B.t.u. per lb, per deg. F. T1 Absolute temperature of air in pipe, deg. F. T8 Absolute temperature of air outside after expansion and mixing and coming to rest. j Mechanical equivalent of heat (778 ft. lb.) R Gas constant for air, ft-lb. per deg. F. = 53.3. Formulas Consider 1 lb. of air moving out of a pipe. The air behind it does work on it to the extent of P1V1 ft-lb. This work is really done by the thrust of the piston of the compressor and does not come from any energy that exists in the air in the pipe. The pound of air contains

Jan 1, 1937

By H. Margolin, E. Ence

In order to understand the effect of zirconium on properties of Ti-Cu-A1 alloys, Ti-Zr alloys were examined for the presence of ordering or compounds at the following compositions in weight percent: 24.1 pct Zr (lZr:GTi), 32.2 pct Zr (lZr:4Ti), 38.8 pct Zr (lZr:3Ti), 49.0 pct Zr(1Zr:ZTi). Alloys were prepared as 15-g buttons by non- consumable arc melting under argon atmosphere from Bureau of Mines titanium (Bhn 63) and Reactor Grade zirconium (Bhn 150). Weight losses during melting did not exceed 1 pct of the initial button weight. Prior to heat treatment, buttons were hot-rolled at 600" to 700°C to rods of about 6 mm diam. Contamination after hot-rolling was found to extend to a depth of less than 0.5 mm. Specimens for heat treatment were wrapped in molybdenum sheet, annealed in argon-filled quartz capsules, and quenched by breaking the capsules under iced brine. Annealing times were as follows: 700°C — 7 days; 600°C— 14 days; 575°C-1 and 2 months; 525°C-2 months; 500°C-2 months. Prior to heat treatment, all Ti-Zr alloys were vacuum annealed at 900°C to remove hydrogen. The reanneal of 575°C specimens for an additional month produced no observable microstructure changes. The results obtained by microstructure and X-ray diffraction are shown in Fig. 1, together with data of Hayes et al.' No other phases than a or P were found. Small amounts of retained P were detected by X-ray in the 49 pct Zr alloy. The data of the present investigation suggests that ß and a transus boundaries are at considerably lower temperatures than those of Hayes et al. The work of Hayes et al. is based on sponge titanium and Bureau of Mines zirconium, both of which contained 0.15 pct 0. Since melting was performed in

Jan 1, 1962

By Reginald S. Dean

THE widespread occurrence of manganese in low grade oxide and carbonate ores not amenable to mechanical concentration has led to extensive investigations of hydrometallurgical methods for producing a pure manganese compound suitable for further treatment. Manganese carbonate is the preferable compound. This product when fully crystalline and of not too fine crystal size is easily filtrable and stable in air. It can be converted to other compounds such as the oxides by heating in air or can be reacted with acids for producing salts. A useful hydrometallurgical process must produce relatively concentrated solutions that can be purified easily, reagents must be cyclically used, and heat requirements must be small. Neither the ammonium sulphate nor sulphur dioxide leaching processes that have been tested extensively fulfill these 'requirements. Other hereto-fore proposed processes have obvious limitations and have not been tried on a large scale. The present process is based on the discovery by the writer of a new group of aqueous manganese-ammonia complex solutions highly concentrated in ammonia, which permit rapid solution of manganous oxide to concentrations of 80 to 100 g Mn per liter and from which a fully crystalline, easily filterable manganese carbonate is precipitated by the addition of carbon dioxide and partial ammonia removal. Although the process may be carried out with many ammonium salts, commercial advantages dictate the use of ammonium carbamate, which is obtained when CO2 is passed into concentrated aqueous solutions of ammonia. If the carbamate is used, the only reagents, ammonia and C02, are volatile and may therefore be recovered from solutions and residues by heating, thus eliminating washing and extensive evaporation. Impurities are controlled easily as most metal oxides are either insoluble in the lixiviant or fail to precipitate with the manganese carbonate. Others are controlled by sulphide addition. The process has been tested extensively on a small scale on a wide variety of ores; including Three Kids, Artillery Peak, Cuyuna, and Chamberlain; as repre-

Jan 1, 1952

By John Dorn

THE phenomenon of diffusion, according to the most prevalent conceptions at the present time, undoubtedly played an important part in the formation and distribution of metals and minerals in the earth's crust. Apparently there is good evidence that in the geological rate of cooling diffusion caused numerous materials to separate into individual masses or into duplex structures. As is well known, the early steels were made by cementation; that is, by heating wrought ferrous metal in contact with carburizing materials so as to produce a relatively high carbon content on the surface. If the process was continued long enough, the carbon diffused throughout the piece. A more homogeneous product depended upon further heating and forging, so that the carbon diffused to a fairly uniform concentration throughout the metal. In the modern metallurgical industry, diffusion is the basis for many operations; for example, the production of hard surfaces oil steels by carburizing, nitriding, cementing with chromium, silicon, boron and beryllium. Castings or ingots as they solidify do not have homogeneous structures, but these structures are made largely homogeneous by suitable process of heat-treating and the resulting diffusion. It is in modern physical metallurgy, however, that we become greatly concerned about the mechanism of the phenomenon of diffusion. The rates of diffusion, effect of temperature and time on diffusion, and the relation of diffusion to the many properties of the parent metal and the diffusing metal have become important; also, we are concerned with the diffusion of a single metal into a complex alloy. For example, what is the mechanism whereby carbon and nitrogen travel into steel? What is the effect of alloying elements in the ferrous material on the rates of diffu-sions? What is the effect of simultaneous diffusion of carbon and nitro-gen? How does chromium, beryllium, boron, or the like, diffuse into the steel, and what are the effects of alloying elements in the steel previous to the cementation process? These inquiries are by no means limited

Jan 1, 1937

By John E. Dorn, Oscar E. Harder

The phenomenon of diffusion, according to the most prevalent conceptions at the present time, undoubtedly played an important part in the formation and distribution of metals and minerals in the earth's crust. Apparently there is good evidence that in the geological rate of cooling diffusion caused numerous materials to separate into individual masses or into duplex structures. As is well known, the early steels were made by cementation; that is, by heating wrought ferrous metal in contact with carburizing materials so as to produce a relatively high carbon content on the surface. If the process was continued long enough, the carbon diffused throughout the piece. A more homogeneous product depended upon further heating and forging, so that the carbon diffused to a fairly uniform concentration throughout the metal. In the modern metallurgical industry, diffusion is the basis for many operations; for example, the production of hard surfaces on steels by carburizing, nitriding, cementing with chromium, silicon, boron and beryllium. Castings or ingots as they solidify do not have homogeneous structures, but these structures are made largely homogeneous by suitable process of heat-treating and the resulting diffusion. It is in modern physical metallurgy, however, that we become greatly concerned about the mechanism of the phenomenon of diffusion. The rates of diffusion, effect of temperature and time on diffusion, and the relation of diffusion to the many properties of the parent metal and the diffusing metal have become important; also, we are concerned with the diffusion of a single metal into a complex alloy. For example, what is the mechanism whereby carbon and nitrogen travel into steel? What is the effect of alloying elements in the ferrous material on the rates of diffusions? What is the effect of simultaneous diffusion of carbon and nitrogen? How does chromium, beryllium, boron, or the like, diffuse into the steel, and what are the effects of alloying elements in the steel previous to the cementation process? These inquiries are by no means limited

Jan 1, 1938

By Oscar E. Harder, John E. Dorn

The phenomenon of diffusion, according to the most prevalent conceptions at the present time, undoubtedly played an important part in the formation and distribution of metals and minerals in the earth's crust. Apparently there is good evidence that in the geological rate of cooling diffusion caused numerous materials to separate into individual masses or into duplex structures. As is well known, the early steels were made by cementation; that is, by heating wrought ferrous metal in contact with carburizing materials so as to produce a relatively high carbon content on the surface. If the process was continued long enough, the carbon diffused throughout the piece. A more homogeneous product depended upon further heating and forging, so that the carbon diffused to a fairly uniform concentration throughout the metal. In the modern metallurgical industry, diffusion is the basis for many operations; for example, the production of hard surfaces on steels by carburizing, nitriding, cementing with chromium, silicon, boron and beryllium. Castings or ingots as they solidify do not have homogeneous structures, but these structures are made largely homogeneous by suitable process of heat-treating and the resulting diffusion. It is in modern physical metallurgy, however, that we become greatly concerned about the mechanism of the phenomenon of diffusion. The rates of diffusion, effect of temperature and time on diffusion, and the relation of diffusion to the many properties of the parent metal and the diffusing metal have become important; also, we are concerned with the diffusion of a single metal into a complex alloy. For example, what is the mechanism whereby carbon and nitrogen travel into steel? What is the effect of alloying elements in the ferrous material on the rates of diffusions? What is the effect of simultaneous diffusion of carbon and nitrogen? How does chromium, beryllium, boron, or the like, diffuse into the steel, and what are the effects of alloying elements in the steel previous to the cementation process? These inquiries are by no means limited

Jan 1, 1938

By William L. Fink, E. H. Dix, L. A. Willey

The results of a preliminary investigation of the aluminum-iron-manganese system showed that small amounts of iron (0.10 per cent) substantially reduce the solid solubility of manganese in aluminum. This is clearly shown in the photomicrographs of three alloys, Figs. 1 to 3. Fig. 1, of an alloy containing 1.04 per cent manganese after a heat treatment at 626° C. for 45 hr., shows only solid solution. This alloy contained less than 0.008 per cent iron. Fig. 2 shows the abundance of a constituent (which undoubtedly contains aluminum, manganese and iron) in an alloy containing 1.00 per cent manganese and 0.11 percent iron after a solution heat treatment at 625" C. for 63 hr. For comparison, Fig. 3 is included to show the relatively small amount of constituent (FeA13) in a similarly heat-treated aluminum alloy containing 0.10 per cent iron but no manganese. These data necessitated a reconsideration of the binary aluminum-manganese diagram that was previously presented,' inasmuch as the alloys used in that work contained from 0.02 to 0.05 per cent iron. This paper is the fourteenth of a series from the Research Laboratories of the Aluminum Company of America reporting the results of investigations of equilibrium relations in aluminum-base alloys of high purity. The purpose was to determine the phase relations in aluminum with aluminum-manganese alloys containing the smallest amount of iron that could be realized with the purest material available at the present time (less than 0.01 per cent iron). Since the previous publication from these laboratories, five investigations of the aluminum-manganese system have been reported. Krings and Ostmannz assigned the formula MnA14 to the compound at the aluminum end of the syst,em, and found a eutectic between this compound and aluminum at 649" C. and 3 per cent manganese.

Jan 1, 1933

By Douglas M. Dwosh

Inland Steel Coal Co.'s system of applying a gypsum/fiberglass rib and roof sealant with standard rock dusting equipment will be outlined. The criteria for use included acceptability of results, flexibility of equipment, ease of application, and economics. Material is conveyed dry until the gypsum, fiberglass, and water are combined at the discharge end of the rock dust hose.

Jan 1, 1978

By R. Simon, D. J. Graue

This paper presents correlations for predicting the solu-lility, swelling and viscosity behavior of CO2-crude oil sys8i.m~. The correlations were developed from experimental data obtained by the authors. These data are also presented. The data were determined by measuring the properties of mixtures of CO, and nine different oils. Experiinental conditions covered a range of 100 to 250°F and pressures up to 2,300 psia. Properties predicted by the correlations have average deviations, expressed as per cent of experimental value, of 2 per cent for solubility, 0.5 per cent for swelling and 12 per cent for viscosity. INTRODUCTION Interest in CO2 injection as an oil recovery process has led to the development of performance prediction methods which can be applied to specific reservoirs.1 iS To use these performance prediction methods, it is necessary to know the solubility, swelling and viscosity properties of CO2-crude oil mixtures at reservoir conditions. Some information on these properties has appeared in the literature; however, this information did not cover the range of different oils and conditions needed to prepare generalized correlations for reservoir engineering purposes. Consequently, an experimental program was undertaken to collect the data needed. The data obtained and the correlations developed from the data are described in the following sections of this paper. SOLUBILITY OF CO2 IN CRUDE OILS CO2 solubility data in the literature come from six principal sources. The solubility prediction method of Welker and Dunlop3 is limited to 80F. The information in Ref. 4 is of two types: the first includes binary and ternary mixtures of CO, and light hydrocarbons (C1 to C6), and the second gives data for CO1 and heavy hydrocarbons for a temperature range of 40 to 90F. Ref. 5 contains a KCO2 chart for systems whose convergence pressure is 4,000 psia. The KCO2's are based mainly on CO2-natural gas mixtures. Poettmann's work covered CO2 solubility in one condensate and one crude oil6,7 Ja-coby and Rzasa measured CO? solubilities as a function of pressure and temperature for two natural gas-absorber oil mixtures and two natural gas-crude oil mixtures.'8 CO, concentration in these four systems was fixed at 5 mol per cent. The work reported in this paper extends CO, solubility data to a variety of different crude oil types in a temperature range from 110 to 250F and pressures up to 2,300 psia. The experimental procedure used by the authors to obtain the solubility data consisted of combining known amounts of pure CO, and crude oil in a visual cell at a fixed temperature and measuring the bubble point of the mixture. Measurements were made for a total of 40 different CO2-oil mixtures and the results are shown in Table 2. The mixtures included nine different oils (seven crude oils and two refined oils) whose properties are listed in Table 1. All nine oils had vapor pressures less than 1 atm at the experimental temperatures. Consequently, analysis of the bubble-point vapor showed a CO, concentration over 99 mol per cent. At no time during these experiments was a second, more dense, liquid phase observed. The solubility correlation which was developed from the data in Table 2 is presented in Figs. 1, 2 and 3. In these figures, solubility is expressed as xco2 the mol fraction of CO, in the CO2-oil mixture. Fig. 1 shows solubility as a function of CO2 fugacity6 and temperature. Fig. 2 shows the same solubility data expressed as a function of saturation pressure and temperature. The solubility shown in Figs. 1 and 2 is for an oil whose UOP characterization factor is 11.7. UOP characterization factors of crude oils can be determined from Ref. 10 if the viscosity and APT gravity of the oil are known. Fig. 3 gives the solubility correction factor for oils whose UOP characterization factors differ from 11.7. The solubility correlation in Figs. 1, 2 and 3 predicted

Jan 1, 1966

By R. Maddin, N. Ujiiye

ALTHOUGH the cold-rolled texture for body-centered-cubic metals and alloys is well known (see, e.g., Barrett'), the pole figure representing the texture may be interpreted in two ways. It may be regarded as consisting of several ideal preferred orientations with an associated spread (a view which is shared among several investigators2), or it may be regarded as consisting of two sets of continuous preferred orientation also with an associated spread."." Recently, Chen and Maddin7 noted a stable (001) [loo] end orientation for molybdenum single crystals rolled at low rates of reduction provided the initial rolling. orientation" was close to the cube ori-

Jan 1, 1957

By H. Doi, Y. Fujiwara, K. Miyake

In order to throw light on the mechanism of plastic deformation of WC-Co alloys, compressive tests of WC-(7 to 43) vol pct Co alloys have been carried out at room temperature, and stress-micro strain relation has been investigated in detail. The analysis of the factors affecting the yield stresses reveals that the yield stresses can be predicted by modified Oro-wan's theory if one properly estimates the planar in-terfiarticle spacings. Conzpressive straining of some of the alloys by 0.066 to 0.17pct increases the decrements by a factor of as much as 3.4 to 14, whereas the corresponding increase in the electrical resistivities is less than 10 pct. The analysis of the decrement data in terms of -Gramto and Lücke theory shows that the marked increase is attributed to increased dislocation darnping itt the binder (cobalt) phase. By cornbilling the decrement data and the conzjwession duta, one obtains the relation between flow stress in shear (?t) and increase in dislocation density (p): At = const . v6 . This is interHeted to mean that the mechanism of strain hardening of CirC-Co alloys is essentially sarne as the one for dispersion strengthened alloys. The possible effect of bridge formations between the carbide particles has also been examined. OWING to the combination of hardness, strength, and other physical and chemical properties, WC-Co alloys have opened the way for unique fields of applications, the recent ones being, for instance, anvils for super-high-pressure generation apparatuses. In such applications, the alloys are frequently subjected to very high compressive stresses: these stresses may cause the alloys to deform plastically and eventually to fail. However, much remains obscure regarding the nature of the plasticity of the alloys. Evidently, the alloys owe their high strength to the hard carbide particles which frequently occupy as much as 80 to 90 pct in volume fraction, whereas the ductility required for practical applications is provided by the small amount of the binder phase between the carbide particles. When the volume fraction of the carbide phase is not very large, deformation behavior of the alloys may be described by some of the current dispersion strengthening theories. However, greatly increasing the carbide phase is thought to lead to some carbide skeleton structure or bridge formations owing to the increased chances for direct contacts between the carbide particles;1,2 this may appreciably affect the plasticity of the alloys. Regarding the effect of formation of the carbide skeleton structure, it is interesting to note the work by Ivensen et al.3 on compression tests of the alloys containing somewhat large carbide particles; they observe extensive generation of slip bands in the carbide particles after application of some preliminary compressive stresses. They interpret the results in terms of plastic deformatiot: of the carbide particles which are supposed to have formed a skeleton structure; the binder phase plays only a passive role, at least in the early stages of the deformation. That carbide crystals exhibit microplasticity at room temperature is apparent from the work of Takahashi and Freise4 and French and Thomas5 on indentation of WC single crystals. On the other hand, Dawihl and coworkers6-10 maintain that even when volume fraction of the carbide phase is very large (for instance, more than 90 pet), a very thin binder layer generally exists between the carbide particles. They interpret the results of the extensive mechanical tests in terms of the plasticity of such a layer. Gurland and Bardzil11 point out that decrease in ductility of the alloys with increase in the carbide phase is caused by the effect of plastic constraint exerted by the dispersed carbide particles. Drucker12 further develops this concept from a continuum-mechanics approach on an assumption that a continuous thin binder layer separates the carbide particles. A common feature of the studies reported so far on the plasticity of the alloys is that the information deduced is invariably qualitative in nature. Thus, very few systematic experiments for obtaining reliable and sufficiently detailed stress-strain curves of the alloys varying widely in the microstructural features have been carried out. In particular, it may be of special interest to investigate in detail the early stages of the plastic deformation of the alloys in order to shed light on the strengthening mechanism. However, such work appears to be extremely rare. Doi et al.13 recently reported a first brief account of the results of some quantitative analysis of the plasticity of the alloys in terms of dislocation theory. Their experiment was rather limited in the composition range covered (volume fraction occupied by the carbide phase: 79 to 83 pct), and thus they could not necessarily elucidate the controlling mechanism of plastic deformation of the alloys of a more general composition range. Consequently, in the present investigation, deformation behavior and some other physical properties of the alloys were investigated and discussed in more detail over a much wider composition range. SPECIMEN PREPARATION WC-Co alloys used in this experiment were prepared in cylindrical or rectangular form by sintering in vacuo compressed mixtures of tungsten carbide and cobalt

Jan 1, 1970

By H. L. Brunjes, G. B. Gould

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By G. B. Gould, H. L. Brunjes

The softening temperature of coal ash, as determined in the laboratory, has been used for years as an indication of the tendency of coal to form clinker and slag. It has not, however, provided an index of unfailing and complete reliability for forecasting the relative performance of different coals, even in the same plant and under the same conditions of operation. A large amount of investigation has been done in attempts to account for this, but practically all of this has been in the direction of studying the chemical constitution of coal ash. Much has been learned, but without much progress toward a better practical application of knowledge to the selection of coal. There has always seemed to be an important factor that eluded discovery. It has long been recognized that the ash-softening temperature as determined in the laboratory had one weakness, in that it represented the temperature at which a thorough mixture of the whole ash of the coal would melt, the mixing having taken place before the heal was applied. This does not, of course, simulate what takes place in practice. With certain exceptions, which will be noted later, almost all of the investigations that have been made, especially the chemical studies of coal ash, have likewise dealt with a mixture of the whole ash in the coal. The present investigation differs from these fundamentally in its approach to the problem. It started from the observation that some clinkering and slagging obviously takes place in a boiler furnace at temperatures below the laboratory-determined ash-softening temperature of the coal. Knowing that coal as it is shipped to market is a heterogeneous mixture of diverse mineral substances, each of which may act independently of the others in the initial stages of clinker and slag formation, it seemed logical to investigate separately the softening temperature of the ash in physically separable portions of the coal, and to determine the relative quantities of ash contributed by each portion. While the data are far from complete, covering as they do only a few coals, and while the conclusions to be reached from the data at this stage arc, in some measure, speculative, they are presented at this time because

Jan 1, 1940

By C. E. Brukl, E. Rudy, St. Windisch

The ternary-alloy system Nb-Mo-C was investigated by means of X-ray, melting point, DTA, and metallo-graphic techniques; a complete phase diagram for temperatures above 1500°C was established. Above 1960°C, niobium monocarbide and the cubic (Bl) high-tenzperature phase in the Mo-C system form an uninterrupted series of solid solutions. The ternary range of the pseudocubic q MoCl-, is very restricted. Dimolyb-denum carbide dissolves up to 44 mol pct Nb2C (2240°C), whereas the maximum solid solubility of MO2C in Nb2C does not exceed 5 mol pct. The order-disorder transformation temperatures in Mo2C and Nb2C are lowered by the mutual metal exchanges. Six invariant (p = const) reactzons occur in the ternary system; three correspond to class 11-type four-phase reactions involving a liquid phase, one to a class I (eutectoid)-type, and two further isotherms are associated with limiting tie lines. The results of the Phase diagram investigation are discussed, and the thermodynamic interpretation identifies the low relative stability of the binary sub-carbides in conjunction with the large stability diflerences between niobium and molybdenum carbides as the cause for the formation of a stable equilibrium between the monocarbide and the metal phase in the ternary reson. Due to their refractoriness, the carbides of the high-melting transition metals have received increased interest in recent years as base materials in composite structures for aerospace applications at high temperatures and for the development of self-bonded cutting tool materials; other novel fields of application include power reactors, where operation at high temperatures becomes essential for attaining high power efficiencies. In these applications, the increased reaction rates at high temperatures require a close consideration of the chemical interactions between the alloy constituents. As a consequence, a detailed knowledge of the phase relationships in the alloy systems is required in order to provide a sound basis for developmental -type work. Partly as a result of the considerable experimental difficulties associated with the investigation of this high-melting alloy class, no complete studies of ternary metal-carbon systems have been performed until recently. Even the high-temperature phase relationships in the binary transition metal-carbon systems have been delineated only during the past few years to a degree of accuracy required for a more detailed study of ternary or higher-order alloys. In recent investigations of binary and ternary systems of refractory transition metals with carbon, boron, and silicon,&apos; alloys from the ternary systems Nb-Mo-C became of interest because of the demonstrated possibility2,3 of obtaining compatible composites based on metal + monocarbide combinations. In the meantime, however, studies in other, but related, ternary metal-carbon systems, such as Ta-W-C, have shown that the solid-state equilibria may change significantly toward higher temperatures (>2000°C), and that extrapolations based on low-temperature equilibrium data are, in general, not very reliable. Although the lower-temperature (<2000°C) phase relationships in the Nb-Mo-C system are similar to those found in Ta-W-C, a cursory thermodynamic analysis of the equilibria indicated4 that complete solid-solution formation between Mo2C and Nb2C should not occur at higher temperatures. The present work was conducted in order to experimentally verify these expectations and, in addition, to provide phase equilibrium data in the melting range of the alloys. In the boundary systems, niobium and molybdenum are known to form a continuous series of solid solutions.576 The continuous solubility was also confirmed by Kornilov and Polyakova,7,8 who also observed a minimum melting point at 22 at. pct Mo and 2345°C. The phase diagram investigations of the Nb-C system by Storms and Krikorian9 and Kimura and Sasaki10 were recently supplemented by Rudy et al.11,12 The system contains a high-melting monocarbide with the B1 structure, Table I, and a subcarbide, Nb2C, which exists in at least two different states of sublattice order at low temperatures47"-&apos;3 and a disordered state above approximately 2500°C.11,12 The melting-point measurements by Rudy et al .11,14 are in close confirmation of the data by Kimura and Sasaki.10 The rather complex phase relationships in the Mo-C system were only recently Clarified.15,18 The system is characterized by three congruently melting, intermediate phases, MozC, ? MoC1-x and a Mol-,, Table I, of which only Mo2C is stable at temperatures below 1650°C. Substoichiometric MozC exists in several states of sublattice order which interconvert in homogeneous phase transitions. Hyperstoichiometric compositions cannot exist in the ordered state. Upon cooling through a critical temperature range, the

Jan 1, 1968