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By N. D. Shutler

This paper describes a numerical mathematical model of the steamflood process that depends on fewer restrictive assumptions than models previously reported. The solution, however, is obtained economically. Example calculations are presented that, on comparison with experimental results, tend to validate the model. Results that expose certain process mechanics are discussed. The model describes the simultaneous flow of three phases — oil, water and gas — in one dimension. It includes the effects of three-phase relative permeabilities, capillary pressure, and temperature- and pressure - dependent fluid properties. Interphase mass transfer of water-steam is allowed, but the oil is assumed nonvolatile and the hydrocarbon gas insoluble in the liquid phases. The model allows heat convection in one dimension and two-dimensional heat conduction in a vertical cross-section spanning the oil sand and adjacent strata. The hydrocarbon-steam gas composition is tracked, but the effect of gas composition on water-steam phase behavior is neglected. The model is solved numerically in three separate stages. The three-phase mass balances are solved simultaneously using Newtonian iteration on nonlinearities occurring in the accumulation terms. The energy balance is solved separately by noniterative application of the alternating-direction implicit procedure. Separate solution of the composition balance is accomplished by straightforward solution of the finite difference equations. The method of effecting nonsimultaneous, stable solution of the mass and energy balances is the key to the success of the model. INTRODUCTION Mathematical tools as well as laboratory and field experiments are necessary to help us understand the complex steamflood process. A mathematical model can expose process mechanics and show the relative importance of process variables, but this ability is often limited by restrictive assumptions. Most known models of steam processes,l-5 with the exception of the model of Gottfried,6 are "simplified" in that they involve analytic approximations and require many restrictive assumptions. The primary utility of these methods lies in the routine use as an aid in engineering design. By contrast, the comprehensive model presented here is numerical and requires far fewer restrictive assumptions. It finds its primary utility as a research tool. It serves as an aid in understanding the nature of the process, in interpreting laboratory experiments and in evaluating and developing simpler mathematical models for engineering design. The major reason why previously presented models have been confined to the "simplified" class is evidenced by the one published exception. In 1965, Gottfried6 presented a numerical model for the combustion process of which the steam process is a subset. The result is a comprehensive tool (though it neglects capillarity and two-dimensional heat conduction) that is troubled with convergence problems and that requires 2 to 3 hours of IBM 7094 time to complete a calculation. Though our present model does not simulate combustion, it does consider capillarity and two-dimensional heat conduction and it overcomes the convergence and computer-time problems. MATHEMATICAL DESCRIPTION OF STEAMFLOODING FLUID FLOW The equations employed to describe three-phase fluid flow are of a familiar form. Darcy's. law provides expressions for the velocities of the three phases (oil, water and gas), which, when combined with oil, water and gas mass balances, give the partial differential equations governing flow of the

Jan 1, 1970

By Alfred H. Bell

The year 1937 has been outstanding in the history of the Illinois oil industry. During the course of the year the state's daily production has been trebled, increasing from 12,000 bbl. per day at the beginning to 37,000 bbl. per day at the end, and the year's total, 7,426,000 bbl. is 66 per cent above the previous year's production of 4,475,000 bbl. The production in January was 368,000 bbl.; in December it was 1,085,000. Production from the old fields increased slightly. Most of the new production is from fields in the central part of the Illinois Basin, an area that for many years was considered unfavorable to the occurrence of oil and gas. The principal producing horizon of the new fields is the McClosky "sand," an oolitic limestone in the Ste. Genevieve formation of lower Mississippian age. Although development has not yet gone far enough to permit accurate estimates of oil reserves in the new fields, it is believed that they are of the order of 100,000,000 barrels. The following are the oil fields discovered in 1937 listed in order of amount of daily production at the end of the year; Noble (Richland County), Clay City, including Southeast Clay City (Clay and Wayne counties), Patoka (Marion County), New Centralia (Clinton County), Olney (Richland County), Cisne (Wayne County),.Beecher City (Fayette County), and Rinard (Wayne County). One gas field, the Russellville, in Lawrence County, was discovered in 1937. For locations of the new fields see Fig. 1. A generalized geologic column for Illinois, showing producing horizons in the new fields, is given in Fig. 2. The total productive area of the new fields at the end of 1937 was 1712 acres, in which 230 wells were producing. Thisrty-five dry holes were drilled within 1/4 mile of producing wells. At the end of the year there were 19 drilling wells, 28 rigs standing, 18 rigging up and 4 new locations in these fields. In the whole state 447 wells were completed, of which 284 were oil producers and three gas producers. Total initial daily production of

Jan 1, 1938

By Philip D. Pearson

CALAND Ore Co.'s dredging program has reached the halfway mark. The goal is to remove more than 160 million cu yd of lake bottom material overlying the iron orebody in Falls Bay of Steep Rock Lake, Ont. Two large dredges were constructed to remove this overburden, a layer of soil about 90 pct varved clay some 400 ft thick. Moisture content of the clay is high-approximately at the liquid limit of the soil. A few years ago, searching for additional reserves of ore, Inland Steel Co. looked toward Canada and the newly developed Steep Rock iron range. To this end an option agreement was signed Dec. 30, 1949, between Steep Rock Mines Ltd. and Caland Ore Co. Ltd., a wholly owned subsidiary of Inland Steel. Several drilling programs were conducted between this date and Jan. 1, 1953, when a 99-year lease was signed covering an area of 1249 acres. This lease calls for ore production to begin in 1960, with full production of 3 million tons per year by 1969.

Jan 8, 1957

By G. L. F. Powell

g samples of Cu-20 wt pct Ag alloy have been mdercooled to a maximum of 197°C by melting under a slag of commercial soda-lime glass in a vitreous silica crucible. No grain refinement of the primary copper was observed in samples undercooled to the maximum of 197°C. When the samples contained a small amount of oxygen, the copper dendrites were partially recrystallized at undercoolings greater than 97°C. In previous papers'-3 reporting the grain structure of undercooled silver and copper, it was observed that grain refinement was dependent on both undercooling and oxygen content. Grain refinement occurred in undercooled silver when the degree of undercooling exceeded the range 153" to 175"C, while in Ag-0 alloys (0.12 wt pct) fine equiaxed grains were exhibited when undercooling was greater than 50°C. Similarly, copper samples undercooled as much as 208°C displayed fan-shaped growth from a single nucleation site, while the grain structure of Cu-O alloys (0.08 wt pct) was fine and equiaxed at undercoolings larger than 150°C. Thus the presence of oxygen greatly reduced the undercooling at which grain refinement occurred. It was also observed that the change in grain size resulted from recrystallization and was not due to an enhanced nucleation rate in the liquid-solid transformation. It is possible that the influence of oxygen on recrystallization is due primarily to its presence as a solute element. walker4,' reported that, although a grain size change did not occur in pure nickel until the undercooling exceeded 150°C, small grains were observed in samples of Ni-Cu alloy solidified at small and large degrees of undercooling. Jackson et al.6 suggested that the fine grained structure of the Ni-Cu alloy resulted from the melting off of dendrite arms during recalescence. This remelting process may occur in alloys as a result of segregation during freezing which causes a variation in liquidus temperature from point to point within a dendrite. It was therefore decided to undercool copper with a metallic alloying element to ascertain whether the presence of a metallic solute would have a similar effect to oxygen in inducing grain refinement. A Cu-Ag alloy was chosen, since both metals had been shown to behave similarly on undercooling. The alloy Cu-20 wt pct Ag was selected since the eutectic constituent outlines the initial growth form of the primary copper, so that the as-frozen grain structure is not obscured if subsequent recrystallization occurs. This paper describes the results of undercooling experiments carried out with Cu-20 pct Ag samples undercooled to a maximum of 197°C and the effect of oxygen content on the grain structure of the undercooled samples. EXPERIMENTAL Melting was carried out in a small cylindrical resistance furnace using "fine" silver granulate and oxygen-free high conductivity copper. The procedure adopted was to melt the required quantity of silver in air in a clean vitreous silica crucible for approximately 15 min, freeze, and add granulated commercial soda-lime glass to form a complete surface slag cover, after which the sample was melted and frozen several times to reduce the oxygen content. The glass slag cover was approximately 3 in. thick. Pieces of copper (=50 g) were added to the crucible until the required quantity to make 350-g samples of alloy had been charged. Each piece was added quickly to the crucible which was held at a temperature slightly above the melting point of silver. The piece was quickly pushed beneath the glass to minimize oxidation and any oxide coating usually decomposed before the piece had settled down into the silver. After the full quantity of copper had been added, the melt was stirred with a silica rod to hasten homogenization and a Pt/Pt 13 pct Rh thermocouple enclosed in a vitreous silica sheath inserted for temperature measurement. Heating and cooling curves were recorded on a potentiometric chart recorder fitted with a zero suppression unit. The milli-voltage range of the recorder was adjusted so that temperatures could be read to 1°C. Heating and cooling curves were taken every hour until three consecutive readings gave the same solidus-liquidus range, consistent with the solidus-liquidus range for this alloy composition by reference to Hansen and Anderko.7 Metallographic examination of samples frozen at this stage, failed to show any variation in composition from bottom to top of the ingot. Consequently, it was considered that the melt was homogeneous at this stage and undercooling experiments were then car-

Jan 1, 1970

By Kiyoshi Azuma, Hiroshi Kametani

The variation of the dissolution behavior of a ferric oxide with calcining temperature has been investigated. Samples were prepared by thermal decomposition of ferric hydroxide, nitrate, oxalate, and sulfate at low temperature, followed by the calcination in the temperature range between 600" and 1200°C. The samples of eight series and a fine crystalline sample of hematite were dissolved in 1 N hydrochloric acid at 55.2°C and the results are represented on double-log graphs for convenience. It is confirmed that all dissolution courses follouj either the accelerated process or the parabolic process except in the special case of the crystalline hematite which dissolced in accordance with the uniform dissolution of a particle. Examinations of the physical properties of the oxide powders revealed that the surface area measured by the permeability method is strikingly relevant to the dissolution behavior of the oxide. In the previous paper,' detailed data were presented on the effect of the kind of acid, the solution temperature, and the concentration of acid on the dissolution of two ferric oxides. It was also shown that these sam ples dissolved in strikingly different ways. The present investigation was carried out on the dissolution of various calcined samples prepared from various ferri salts by various methods to ascertain the course of dissolution. Pryor and Evans2 pointed out a change of the dissolution rate at around 700°C for a series of calcined ferric oxides prepared from the hydroxide. Several papers374 reported also the dissolution of ferric oxide samples. It seems, however, that a systematic account of the relationship between the dissolution behavior and physical properties of the oxide has not yet been given. This paper presents the variation of the dissolution of the oxide in relation to the calcining temperature and the change of physical properties of the calcines. EXPERIMENTAL Raw materials were prepared by precalcination of ferric hydroxide, thermal decomposition of ferric nitrate, oxalate, and sulfate, and aerial oxidation of ferric chloride vapor, at as low a temperature as possible. The products were crushed, ground, if necessary, and sieved with a 100-mesh Tylor screen prior to calcination, after which the specimens were dissolved in acid solution. The following is a detailed description of the preparation of the samples. Sample H. About 500 g of ferric chloride (guaranteed reagent) were dissolved in 5 liters of deionized water and filtered. Ferric hydroxide was precipitated by addition of the minimum amount of ammonium hydroxide solution, and the precipitate was washed continuously till chloride ion was not detected by silver nitrate solution, and then filtered. The filter cake was dried at 120°C for a week and ground, and the -100 mesh portion was used. Sample S. Ferric sulfate (guaranteed reagent) was pyrolytically decomposed in a crucible at 700°C for 24 hr and the product was sieved. In this case the following calcination was carried out at temperatures over 700°C. Sample B. Commercial ferric oxide (guaranteed reagent). About 15 kg of ferric nitrate were decomposed in a furnace maintained at 800°C for 2 hr. The actual temperature of the decomposition was not measured. The product was crushed and sieved, and the -100 mesh portion was used. Sample N. About 50 g of ferric nitrate (guaranteed reagent) were decomposed in a beaker in a sand bath until a red-brown dense solid was produced. This product was crushed and sieved, and subjected to complete decomposition at 500°C. The precalcined product was again sieved and used. Sample N2.5. Since the decomposition temperature was not controlled for sample AT, a different sample was prepared in a temperature-controlled furnace. The subscript represents the decomposition at 250°C. The product was treated in the same manner as sample N. Sample Nc. Under atmospheric pressure it is prac-tically inevitable that ferric nitrate hydrate melts to form a brown liquid at about 50°C before pyrolysis. For this reason, the salt was first slowly heated under reduced pressure (about 10-3 mm Hg measured in a trap refrigerated by dry ice-alcohol) to achieve dehydration without melting. About 5 hr were required for the dehydration and the partial decomposition. Then the temperature was elevated to 500° C in air for complete decomposition. The relatively porous product was sieved and used. Sample Ov. About 200 g of ferric oxalate hydrate (extra pure) were dehydrated under reduced pressure (as described above) followed by thermal decomposition at 500°C for 6 hr in air. The decomposition of this salt was accompanied by liberation of carbon monoxide, by which the ferric salt was initially reduced to a black powder. The powder changed in turn into brown ferric oxide as the gas liberation decreased and reoxidation predominated. The product consisted of sparkling fine particles passing through a 100-mesh screen. However it was ground and sieved as for the other samples. Sample D. Commercial fine powder for magnetic tape purposes. The preparation was as follows.5 Ferric chloride vapor and preheated excess air were mixed and passed into a reaction tube where oxidation took place at 450°C. The fine powder formed was collected in a cottrell chamber. The product was vacuum-degassed at 450°C for 1 hr and sieved.

Jan 1, 1969

By A. Andreas

New Mexico, after several years as the sixth ranking oil-producing state, was surpassed by Illinois and for 1939 ranks seventh in the United States. Oil production for 1939 was 36,746,840 bbl. Production for 1938 was 35,510,176 bbl., a gain of 0.033 per cent. Production for the year would have been greater had there been a pipe-line outlet for the Vacuum field. The complete shutdown during the latter part of August covering a period of 15 days meant a production loss of over 1,500,000 bbl. of oil. Daily production allowable as set by the Oil Conservation Commission has followed very closely the recommendations of the Bureau of Mines. It has been found that the recommended allowables as quoted by the Bureau of Mines do not always reflect the actual demand, as there is a considerable lag hetween the recommended amounts and the current demands. During the year the various operating companies have done considerable remedial work in setting packers to reduce the gas-oil ratios in the various fields. Six new fields were discovered in New Mexico during 1939; three in Lea County, two in Eddy County and one in Chaves County. In the early part of 1939 a committee composed of the various engineers and geologists recommended subdividing the old Artesia area into various producing pools. This division was accepted, therefore the total number of producing fields in New Mexico is considerably greater than the number of fields in 1938, but does not represent new fields discovered during the year. The southeastern area continues to he the largest producer of oil. During the year 2,716,551 bbl. were produced in Eddy County and 33,690,996 bbl. in Lea County. Total production ill the northwestern part of the state, which includes San ,Juan and McKinley Counties, was 338,293 bbl. At the beginning of the year the daily average nonmarginal well allowable for Lea County was 48 bbl. At the close of the year it was 49 bbl. The daily average production for the year was 97,313 bbl. During the year, 659 wells were drilled in the state, of which 565 were producing oil wells, 15 gas wells, 6 carbon dioxide gas wells and 73 dry holes. Summarized at meeting; manuscript received at the office of the Institute March 18, 1940. * State Geologist, member of New Mexico Oil Conservation Commission, Santa Fe, New Mexico.

Jan 1, 1940

By A. Andreas

New Mexico, after several years as the sixth ranking oil-producing state, was surpassed by Illinois and for 1939 ranks seventh in the United States. Oil production for 1939 was 36,746,840 bbl. Production for 1938 was 35,510,176 bbl., a gain of 0.033 per cent. Production for the year would have been greater had there been a pipe-line outlet for the Vacuum field. The complete shutdown during the latter part of August covering a period of 15 days meant a production loss of over 1,500,000 bbl. of oil. Daily production allowable as set by the Oil Conservation Commission has followed very closely the recommendations of the Bureau of Mines. It has been found that the recommended allowables as quoted by the Bureau of Mines do not always reflect the actual demand, as there is a considerable lag hetween the recommended amounts and the current demands. During the year the various operating companies have done considerable remedial work in setting packers to reduce the gas-oil ratios in the various fields. Six new fields were discovered in New Mexico during 1939; three in Lea County, two in Eddy County and one in Chaves County. In the early part of 1939 a committee composed of the various engineers and geologists recommended subdividing the old Artesia area into various producing pools. This division was accepted, therefore the total number of producing fields in New Mexico is considerably greater than the number of fields in 1938, but does not represent new fields discovered during the year. The southeastern area continues to he the largest producer of oil. During the year 2,716,551 bbl. were produced in Eddy County and 33,690,996 bbl. in Lea County. Total production ill the northwestern part of the state, which includes San ,Juan and McKinley Counties, was 338,293 bbl. At the beginning of the year the daily average nonmarginal well allowable for Lea County was 48 bbl. At the close of the year it was 49 bbl. The daily average production for the year was 97,313 bbl. During the year, 659 wells were drilled in the state, of which 565 were producing oil wells, 15 gas wells, 6 carbon dioxide gas wells and 73 dry holes. Summarized at meeting; manuscript received at the office of the Institute March 18, 1940. * State Geologist, member of New Mexico Oil Conservation Commission, Santa Fe, New Mexico.

Jan 1, 1940

A professional and special section of the United States Employment Service, Department of Labor, has been created for the purpose of aiding officers and men who have been discharged from military service, but who, for various reasons, cannot resume their former positions, to place themselves in industry without loss of time. Its work is carried out in conjunction with the Engineering Societies Employment Bureau. The machinery of this new professional section is being set up as rapidly as possible, and an office is already in operation at 16 East 42c1 St., New York. The work in the New York State district is under the direction of Mr. Henry Bruere, formerly City Chamberlain of New York City. Dr. Thomas T. Read, Chairman of the A. I. M. E. Committee on Industrial Organization, has charge of the clearance between the State offices of the Eastern States. This service is designed for the purpose of placing not only men in the engineering professions, but for all other kinds of professional and highly trained, skilled men. Full details regarding the qualifications desired in a man should be given, so that employers may be put in touch only with such available men as will fully qualify for the positions.

Jan 2, 1919

By Leon Y. Sadler

Three new transfer functions relating the time response of the amount of floatable mineral in the under flow to time-dependent changes in the amount of floatable mineral in the feed to the cell are presented. Using experimental stimulus-response data obtained from the flotation of -200+325-mesh glass spheres in a rotor-stator-type cell, the new transfer functions are compared to the only transfer function to be presently found in the literature by nonlinear least-squares fitting in the frequency domain. The new mathematical model based on the amount of available bubble surface area and its rate of introduction is quite promising. The transfer function which allows for a distributed first-order flotation rate constant also gives good results. Simultaneous sodium chloride tracer and glass bead stimulus-response tests show that the mixing conditions in the cell were nearly ideal. It is felt that the new transfer functions presented offer excellent alternatives for use in the design of automatic process control equipment for the continuous mechanical froth flotation cell.

Jan 1, 1974

By Robert W. Zimmerman

POROUS SOLID COMPRESSIBILITIES There are four different compressibilities associated with porous solids, each relating the fractional change in either bulk volume or pore volume with the change in either pore pressure or confining pressure. These will be referred to as Cbc, Cbp, Cpc, and Cpp, with the first subscript denoting the relevant volume, and the second subscript denoting the relevant pressure. They are defined as: [ ] Note that minus signs are included in two of the definitions so that each of the compressibilities will always have a positive value. In general, each compressibility depends on the elastic moduli of the matrix material, the porosity, and the exact geometry of the pores. Taking the latter factor into account calls for separate analysis for each different pore shape, which of course can only be attempted for a few relatively simple cases. But lower bounds for each of the four compressibilities can be found, independant of pore structure, in terms of only the porosity (0) and the elastic moduli of the matrix material (any pair chosen from K, E, G and V). The first step is to find relationships between the four compressibilities, starting with the following observation: If a porous solid made of a linear elastic, isotropic and homogeneous matrix material is subjected to uniform hydrostatic pressure of magnitude P on its external and all of its internal (pore) surfaces, the state of stress in the solid will be exactly the same as that which would occur

Jan 1, 1982

(This list includes only those who have entered military service within the past month, or whose entry has only recently become known to us; it also includes a few names of those whose titles or assignments have been changed within the month. The last complete list was printed in Bulletin No. 131, November, 1917. A complete Honor List is maintained in the reception room at the office of the Institute:) AARONS, J. BOYD, Captain, 4th Reinforcements, 11th Infantry, Australian Imperial Force. AHBE, F. R., Captain, 33d Engineers. AMBLER, HARRY A., 30th Infantry, Camp Greene, Charlotte, N. C. ALFORD, NEWELL G., Sergeant, Headquarters 84th, 9th Division, Camp Zachary Taylor, Ky. ANDERSON, ALEXANDER, Lieutenant, Royal Garrison Artillery. ANDREWS, CLARENCE W., 1st Infantry Co., Officers' Training Camp, 83d Div., Camp Sherman.

Jan 2, 1918

The personnel of the. Naval Advisory, Board on Inventions, of which Thomas A. Edison is to, be Chairmen, has- been announced. by' Secretary of the Navy Daniels, as follows: W. R. WHITNEY L: H. BAEKELAND American Chemical Society. FRANK JULIAN SPRAGUE, American Institute of Electrical Engineers. B. G. LAMME ROBERT SIMPSON WOODWARD ARTHUR GORDON WEBSTER American Mathematical Society. ANDREW MURRAY HUNT American Society of Civil -Engineers. ALFRED CRAVEN MATTHEW BACON SELLERS American Aeronautical Society. -HUDSON MAXIM PETER COOPER HEWITT Inventors' Guild. THOMAS ROBINS . HOWARD COFFIN ANDREW L. RIKER J American Society of Automobile Engineers. WILLIAM. LAWRENCE SAUNDERS American Institute of Mining BENJAMIN BOWDITCH THAYER Engineers. ? JOSEPH WILLIAM RICHARDS American Electrochemical Society. LAWRENCE ADDICKS WILLIAM LE. Roy EMMET American Society of Mechanical Engineers. SPENCER MILLER HENRY ALEXANDER WISE WOOD American Society of Aeronautic ¬ELMER AMBROSE SPERRY Engineers. ?

Jan 10, 1915

Wyoming State Geological Survey, Capitol bldg , Cheyenne, Wyoming. John G Marzel, State Geologist. Unfortunately, most of the publications of the Wyoming State Geological Survey are now out of print In particular should be mentioned Bulletins describing the various oil fields of Wyoming, and Bulletin 17, Bibliography and index (1918), all of which are out of print State geologic and topographic maps are also not available. A list of publications will be sent upon request Still available are: Bulletin 18, Mining laws, state and federal (1921), 19, Mineral hot springs of Wyoming (1926), 20, Atlantic City-South Pass gold mining district (1926), Circular 5, Operating regulations to govern the production of oil and gas on state and patented lands (1929). The last two Biennial Reports, issued 1928 and 1930, are still available. The bulletins and reports listed are distributed free.

Jan 1, 1933

US 4,192,851-Recovery of elemental sulfur and the metal values from a complex sulfide ore containing two or more of the metals zinc, lead, copper, silver, gold and/or other metals. A mixture of ore and sulfuric acid and/or spent electrolyte is flowed at optimum temperature and pressure in a quiescent zone to dissolve selected metals and sulfur and coalesce the sulfur. The coalesced sulfur and unreacted sulfides are separated by flowing the leach slurry with an upward velocity component The separated materials are discharged and further processed by conventional methods as war- ranted. H.E. Hirsch, J F. Higginson, EG. Parker, and G M Swinkels, assigned to Sherritt Gordon Mines Ltd. Mar. 11, 1980. 6 pp. (423-28) Filed. 3-14-78 (886,368). Priority. United Kingdom, 3-15-77 (10800/77).

Jan 1, 1982

Dr. Healy's paper presents a concise state-of-the-art description of mechanistic, thermodynamic models available today for design, interpretation, and trouble-shooting flocculation processes and problems. Coagulation by manipulation of inorganic electrolyte concentrations is controlled largely by adjustment of electrostatic repulsive forces, guided by well understood theory. For simple solids in simple electrolytes, existing models are capable of predicting the influence of potential determining ion and one dominant, non-reacting, symmetrical electrolyte concentration on floc stability quantitatively. Concentration changes required to coagulate and disperse can be estimated. Convenient, easily understood means are available for summarizing the effects of key variables, (e.g., pH, ionic strength) on dispersion stability, and estimating tolerance to unintentional changes (Matijevic coagulation domain diagrams). These models have not been developed to the point that mixed unsymmetrical electrolytes can be easily handled. They are capable of describing two- solid heterocoagulation, but not “n-solid” heterocoagulation. In combination with recently developed computer codes for simultaneous computation of solution equilibria, ion exchange and electrical double layer properties (1,2), these models .should be capable of describing simple clay coagulation systems. This has not been done. Models developed for polymer flocculation are valuable interpretive tools, have some qualitative predictive value, but are less potent in quantitative needs. Most real systems probably involve more than one mechanism of floc stabilization. Little has been done toward developing combined models, even in the simplest systems.

Jan 1, 1979

By M. C. Fuerstenau, A. M. Gaudin

A homogeneous suspension is viewed by X-rays. The radiation density seen, affords a measure of the extra absorption due to the solids contained. This radiation density, at a predetermined depth, varies with time. The chart of this relationship gives the desired determination. s it is frequently necessary to know the distribu-rt tion of particle sizes in various products used in industrial applications, a number of means have been devised for these determinations. Some of them include direct microscopic measurement, screening of product, extraction of samples from a settling slurry, air and liquid elutriation, adsorption of gases and liquids, and light absorption. The absorption of light as a means for particle size analysis has been known and employed for some time. X-ray absorption has not received the attention that light has enjoyed primarily because of the complex and costly instrumentation involved with X-rays. In 1954, Brown and Skrebowskil suggested the use of X-rays for this type of determination but did not supplement their suggestion with experiment. In 1958, the authors conducted size analysis experiments on suspensions of quartz with the Trans-viewer: an X-ray unit specifically adapted for sedimentation research, and Rossa conducted experiments in a similar manner in 1959 with a stable gamma emitter, AmZ4l, on suspensions of uranium oxide. To illustrate the applicability of X-ray absorption for analyzing particle size distributions, an essentially mono-energetic and well collimated X-ray beam was used as a source. The beam was made mono-energetic by placing a zirconium filter before the counting window together with feeding the pulses from the proportional counter into a reverter, a device capable of discriminating against pulses of various heights. The sketch in Fig. 1 shows the collimation arrangement in more detail. As shown, the X-ray beam was collimated by inserting a 3/8-in. ID pipe into one of the ports of the X-ray tube and further by two small steel plates with slits 3/32-in. wide and 1/2-in. long placed in front of the window of the Geiger-Mueller (G-M) tube. One of the plates was located 1/2 in. and the other 2 1/2 in. from the window of the counter; both plates were contained in an aluminum holder mounted on the box containing the G-M tube. This type and degree of collimation should eliminate any intensity due to scattered radiation; the transmitted intensity would then be solely a functior. of the absorption by the suspension at that level. Experimentally, homogeneous suspensions of finely ground quartz were prepared, Daxad (a sulfo-nated compound made from wood) was added as dis-persant, and the transmitted X-ray intensity measured as a function of time at a fixed depth in the suspension. In more detail, the experimental procedure involved the following: 1) measuring the transmitted X-ray intensity through the Daxad solution at a predetermined position or settling depth in the absence of solids, 2) placing a known amount of dry solids into the vessel and agitating thoroughly, 3) measuring the transmitted X-ray intensity at time zero (i.e., immediately upon cessation of stirring), and 4) measuring the transmitted X-ray intensity as a function of time (a 10-sec counting interval being chosen and counting being started 5 sec before the desired time). Since a linear relationship exists between percentage solid in a slurry and the logarithm of transmitted intensity for a homogeneous material, the cumu-

Jan 1, 1961

By Klaus Detert

Fifteen and 18 pct Ni maraging steel and several binavy and ternary alloys of the iron-rich corner of the Fe-Co-Ni system have been studied. After annealing in the austenite range, these alloys were deformed slightly by cold rolling and subsequently aged. Compavison of experimental measurements at various processing stages indicates that small degrees of deforn~ation (5 to 10 pct reduction in thickness) do not influence hardness and strength or the aging kinetics. Electrical resistivity and ductility are somewhat redu]ced and the coercive force is substantially lower when compared to identical samples which were not deformed. The results are explained in terms of retained austenite which transforms into martensite with the small amount of deformation. RECENTLY there has been increasing interest in maraging steel for applications in electric power generators requiring a high ratio of power to weight.' Fifteen pct Ni maraging steel has been investigated to evaluate its properties and performance for application as high-strength magnetic rotor steel,' and a thorough investigation of the precipitation and transformation processes in this alloy has been conducted in this laboratory.3 The influence of deformation, which preceded the aging treatment, was also studied. It was found that a small deformation in the order of 5 pct has a rather striking effect in reducing the coercive force. Other interesting effects on the properties caused by such deformation have led to the more detailed studies reported herein. EXPERIMENTAL METHOD The methods used to produce the samples from 15 pct Ni maraging steel have been described elsewhere.3 The general procedure of hot forging and cold rolling to sheet has been followed. The composition is included in Table I which also contains the composition of the 18 pct Ni maraging steel grade 250 studied. More data about the material and the processing of the 18 pct Ni maraging steel have been recently reported.4 The experimental alloys of binary and ternary Fe-Ni-Co alloys were made by levitation melting in an argon atmosphere and casting into rod-shaped ingots 7 mm thick weighing 20 g. From these ingots 25-mm-long rods were machined to study the phase transformation by a dilatometer. These rods were then cold-rolled to strips, 2.4 mm thick. Annealing for austenitizing was done in tube furnaces in an argon or helium atmosphere followed by cooling in the water-cooled portion of the tube. Aging was done in a salt bath containing a neutral blend of Alkali nitrates and nitrites. Vickers hardness was measured using a load of 50 kg for 15 sec. Tensile tests were carried out on a hard beam tensile tester at a strain rate of 5 X lo-' per sec using flat samples with a gage length of 37.5 mm and a cross section of 1.25 by 6.25 mm. Estimated sensitivity was 5 K x strain and 0.35 kg per sq mm stress. Magnetic saturation was determined on small cylindrical samples, 2.5 mm in length and diameter, by measuring the force exerted by the gradient of a magnetic field of 1000 oe per cm in a mean field of 11,500 oe. The measured values could be reproduced within *1 pct. Coercive force was measured by a precision-type magnetic field probe in a magnetic coil as described by Foerster.5 The magnetizing field was 1300 oe. The samples were 5 cm long, 1 cm wide, and 2.4 mm thick. he coercive force was measured to within +0.1 oe. Electrical resistivity was measured by using a potentiometer on flat strips with a gage length of 100 mm and a cross section of 2.5 by 0.5 mm. The accuracy of the measurement was 0.1 pct but the reproducibility of the measured specific resistivity among different samples was in the order of 1 pct. The method used to prepare the samples for electron transmission has been reported elsewhere.3 RESULTS Fig. 1 shows the influence of deformation after annealing on the resistivity, hardness, and coercivity. The samples were annealed for 30 min at 1000"C,

Jan 1, 1968

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,' based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.' This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- '. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By T. G. Nilan

Steels containing 0.4 and 0.8 pet C have been transformed isothermally at pressures up to 34 kbuv. Decomposilion mechanisms are so intimately related to phase equilibvia that, as the equilibria shift under high pressure, the microstruclures of the decomposition producls change, maintaining at pressure the same correspondence between a given phase equilibrium and a given microstructure as a1 1 atm. A bainitic unicvo-structure occurs in these steels at high pressure that IS observed only at 1 aim abole 1.4 pct C. This strrrcl111,e 1s ruliorzalized in terms of the effect of pressure on the transformation to lower bainite. The pressuve depetlderlce of the kinetics of pearlile formation is descrihed by an absolute rule theory amalysis. The activation volume for the transformation is 7 cu cm per mlole, which is indicative of a phase-interface transformation-rate cotntrol mechanism. This fortmulation, when expressed in terms of known solule effects on the energelics of tvansformation, gives promise of explaining the effects of alloying elemenls on hnrden-abilily, particularly that of 'coball. KINETIC processes in solids are functions of the primary thermodynamic variables of state: composition, temperature, and pressure. Until the development of high-pressure techniques' that permitted the generation of sustained high pressure at high temperatures, metallurgical studies of such reactions were largely limited to isobaric conditions at atmospheric pressure. The data so obtained, and theoretical deductions based on these data, were necessarily incomplete For the particular case of austenite decomposition, a knowledge of the phenomenology of the reaction in terms of all the state variables should lead to a clarification of the process. This deeper understanding should facilitate a decision between conflicting theories that have been proposed to rationalize these phe- nomena. An analysis, derived from an understanding of the transformation mechanisms, may aid in the optimization of alloy steel development. The first studies of the effect of pressure on transformations in steel were made by Kulin et al. in 1952.' In a study of the influence of applied stress on mar-tensite formation in a 30 pct Ni steel, they found that the martensite start (M,) was depressed 8°C per kbar* by hydrostatic pressure. Jellinghaus and Friedewold3 were apparently the first to investigate the effect of pressure on isothermal transformations above the Ms. They found that the bainite transformation rate in a 1.2 pct C, 3.8 pct Mn steel was reduced by a factor of 3 by a hydrostatic pressure of 4 kbar. In both of these investigations,2,3 the M, of the steels studied was below room temperature. Austenitizing and quenching were done at atmospheric pressure, followed by the decomposition of the metastable austenite under pressure. The maximum temperature at pressure in the bainite study3 was 350°C. Until the advent of the present high-pressure devices, it was not possible to conduct isobaric high-pressure heat treatments from austenitizing through isothermal decomposition and quenching. The exploitation of high pressure as a variable in metallurgical studies was greatly advanced by the apparatus and techniques developed by Hall4 and co-workers. Utilizing these techniques, Radcliffe et a1.5 and Hilliard6 etermined the pressure dependence of phase equilibria in the Fe-C system. Hilliard and cahn7 examined the pearlite transformation rate in an AISI 1080 steel and also in a high-purity 0.92 C Fe-C alloy at 1 atm and at 34 kbar and found a 700-fold reduction in rate at pressure in the 1080 steel but only a fivefold reduction in the high-purity alloy. In agreement with the shift of phase equilibria under pressure, the microstructures were hypereutectoid at 34 kbar pressure, whereas they are eutectoid at 1 atm. Determination of the effect of pressure on carbon diffu-

Jan 1, 1968

By O. M. McRae. Discussion by R. W. Jones

R. W. Jones (Senior Exploration Geologist, Standard Oil Co. of California, Box 250, Seattle, Wash.) -Mr. McRae6 and his colleagues are to be congratulated for providing a more coherent structural synthesis of the complex structure in the Courtland-Gleeson area, Cochise County, Arizona, than the "gigantic thrust breccia" concept of Gilluly. 4 However, a few problems of interpretation remain. It is the intent of this note to point out some of these problems, and, drawing on my own work in the area as well as the work of McRae6 and Gilluly, 4 to suggest some interpretations which differ from those previously published. GRAVITY SLIDES In an unpublished manuscript (Jones5) I previously argued that most of the complex structures in the Courtland-Gleeson area can be most reasonably interpreted in terms of gravity sliding caused by uplift and eastward tilting of Jurassic intrusives and associated Paleozoic rocks. Although the field work and drill hole data described by McRae6 provided excellent documentation for two important gravity slides, McRae6 interpreted the basic structure in the Courtland-Gleeson area in terms of major eastward directed thrusting. I continue to disbelieve the

Jan 1, 1967