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By Kenneth A. Moon

Kenneth A. Moon (U.S. Army Materials Research Agency)—The authors are to be congratulated for a very interesting and valuable paper. Their discussion of the structural implications of the results shown in their Fig. 5, however, requires a small correction. The model of Speiser and Spretnak with 0 = 1 and z' = 2 is perfectly reasonable for the Ti-O a phase, but Eq. [3] is valid only for solutions sufficiently dilute that the number of empty sites excluded by more than one filled site is negligible. The composition at which intrinsic saturation occurs therefore cannot be deduced from Eq. [3], but but must be decided by consideration of the structural details of the phase in question. In this case, intrinsic saturation is expected not at the composition Ti3O but at Ti2O, because Ti2O has the anti-Cd structurel4 for which each filled octahedral site has two nearby empty sites, one in the hexagonal plane immediately above it, and one in the similar plane below it. The other two models, with ?=1/3 and 1/2, imply a distinction between octahedral sites in pure titanium which is not easy to justify. The problem of extending Speiser's and Spretnak's treatment in a general way to more concentrated solutions will be the subject of a forthcoming publication by the writer. M. T. Hepworth and R. Schuhmann, Jr. (authors' reply)—The authors wish to thank Dr. Moon for calling to their attention the paper by Holmberg which presents the results of X-ray studies of Ti-O solutions ranging from 0 to 33 at. pct 0 and quenched from various annealing temperatures between 400" and 1800°C. Within these ranges, Holmberg found three types of phases: 1) At high oxygen contents (above 25 at. pct) and low annealing temperatures, he found the anti-Cd(OH)2 structure referred to by Dr. Moon. In this structure each titanium atom is in contact with 3 oxygens and each oxygen is in contact with 6 titaniums, the "available" oxygen sites corresponding to every other layer of octahedral sites in the titanium matrix. The limiting composition is Ti2O. However, this anti-Cd(OH)2 structure was not observed for samples containing 25 at. pct 0 or less. 2) For the specimen containing 25 at. pct 0 annealed at 400°C an ordered Ti3O structure was observed. This structure is related to the anti-Cd(OH)2 structure but differs from it by providing only two oxygens adjacent to each titanium atom and thus is consistent with the model represented by Eq. [5] in our paper, with 6 = 1/3, z' = 0. 3) For dilute solutions and for more concentrated solutions annealed at higher temperatures, the structure corresponds to that of the metal with random distribution of oxygens among all the octahedral sites. Thus, it is interesting to observe that the thermo-dynamic indications of ordering in the vicinity of Ti3O can now be supported qualitatively at least by Holmberg's X-ray evidence of the existence of an ordered phase of the composition Ti3O. That is, for solutions with oxygen contents close to that of Ti3O, both the thermodynamic data and the X-ray data are more consistent with models based on the ordered structure of Ti3O than they are with the model which Dr. Moon suggests corresponding to "intrinsic saturation" at Ti2O.

Jan 1, 1963

By J. F. Butler, H. W. Paxton

The vapor pressures of manganese in equilibrium with several alloys in the iron-manganese-carbon system between 1200° and 1275°K have been measured using the Knudsen effusion technique in conjunction with a vacuum microbalance. The effect of orifice area of the effusion cell upon the measured pressure has been determined. The binary iron-manganese system shows small negative departures from ideality, and the system of mixed carbides, (Fe, Mn)7C3, in equilibrium with graphite behaves ideally. THIS work is a continuation of the investigations in which the Knudsen effusion method has been used to determine thermodynamic activities in systems and at temperatures of interest to metallurgists. In a previous publication,' the free energy of formation of Mn7C3 was determined and some preliminary work on the solution behavior of this carbide with the hypothetical "Fe7C3" was reported. The present work deals with this latter topic and also includes data on the binary ir-on-manganese system. EXPERIMENTAL METHOD The Knudsen effusion method was used to measure the vapor pressure of manganese in both the alloy and carbide sections of this investigation. This dynamic method of vapor pressure measurement presents a problem when studying solid alloy systems in which one of the components has a much larger vapor pressure than the others. Over-all depletion of the alloy in the most volatile component will occur during evaporation so that the pressure of that component will decrease. Even more serious than the over-all concentration change is the surface depletion of volatile component in the alloy brought about by the slow rate of diffusion of this component from the interior to the surface of the solid particle. Since knowledge of this surface composition is necessary in order to relate it to the activity determined through the measurements, changes in surface composition from the analyzed bulk composition are to be avoided in dynamic vapor pressure studies of solid alloys. The system under investigation in this study presents the problem of surface depletion of manganese since its pressure at 1230°K is 105greater than iron and 1020 greater than carbon. Since the existence of a volatile manganese carbide had been ruled out previously,' the high manganese pressure relative to iron and carbon insured that the only species leaving the effusion cell was manganese. Therefore, the effusing species required no analysis so that the manganese pressure was determined directly from the weight loss of the effusion cell. In order to detect small weight losses near the beginning of effusion, a vacuum microbalance was used to weigh the cell continually. These initial weight loss data allowed the rate of manganese effusion to be determined before the surface of the alloy became depleted in manganese. The apparatus used in this investigation is shown in Fig. 1. Temperature was measured using chro-

Jan 1, 1962

By P. E. Fitzgerald, J. C. Gindlesperger

1. The Acidizer (Trade Publication of Dowell Inc.): No. 1. Aspects of Acidizing. No. 2. Inhibited Acid. No. 3. The Value of Acidizing. No. 4. The Chemistry of Acidizing. No. 5. Jelly Seal in Acidizing. No. 6. Loosening Stuck Drill Pipe. No. 7. The Geology of Acidizing. 2. J. C. Albright: Acid Is Being Used for Cleaning Intake Wells in Water-flooded Areas. Oil Weekly (Sept. 23, 1935) 24. 3. D. H. Bancroft: Acid Tests Increase Production of Zwolle Wells, Miller County, Arkansas. Oil and Gas Jnl. (Dec. 22, 1932) 42. 4. A. H. Bell: Possible Areas for Acid Treatment in Illinois. Pub. of Illinois- Indiana Petr. Assn. and lllinois Geol. Survey (1934) 49. 5. N. A. Best: Treating Limestone Formations Consists of More than Pouring Hydrochloric Acid in the Well. Oil and Gas Jnl. (April 5, 1934) 54. 6. L. G. E. Bignell: Sealing Off Salt Water from Oil-bearing Formations. Oil and Gas Jnl. (Jan. 30, 1936) 59. 7. L. G. E, Bignell: Acidizing Upper Limestone Formation Facilitated by the Use of Jelly Seal. Oil and Gas Jnl. (March 5, 1936) 30. 8. L. G. E. Bignell: Bailing, Shooting, Tubing and Acidizing Have All Been Tried in Deep Test at Binger, Oklahoma. Oil and Gas Jnl. (May 10, 1934) 38. 9. L. G. E. Bignell: Dowel1 Incorporated Increasing Its Field Service for Acid Treatment of Wells. Oil and Gas Jnl. (June 7, 1934) 62. 10. L. C. Chamberlain, Jr. and P. E. Fitzgerald: Oil Well Acidizing in Michigan. Mich. Acad. Sci. Papers (March 1937). 11. M. E. Chapman: Some of the Theoretical and Practical Aspects of the Acid Treatment of Limestone Wells. Oil and Gas Jnl. (Oct. 12, 1933) 10. 12. C. E. Clason and J. G. Staudt: Limestone Reservoir Rocks of Kansas React Favorably to Acid Treatment. Oil and Gas Jnl. (April 25, 1935) 53. 13. W. F. Cloud: Cleaning and Reconditioning Oil Wells—Reconditioning by Use of Acid (Petroleum Production 1937), 389. University of Oklahoma Press, 1937,' 14. K. A. Covell: Developments in Eastern Production Practice. Acid Treatment of Michigan Wells. Amer. Petr. Inst. Prod. Bull. 213 (1934) 77; Oil and Gas Jnl. (May 31, 1934) 89; Oil Weekly (May 28, 1934) 17. 15. B. A. Cunningham: Acid Treatment of Lime Formations. Amer. Petr. Inst. Paper 901 (1933) 9D, 1-7. 16. 0. I. DeSchon: Pondera Production up 22,000 Barrels. Montana Oil & Min. Jnl. (Jan. 26, 1935) 1.

Jan 1, 1937

By Robert Bakish, William D. Robertson

AFTER more than fifty years of investigation and continuing failure in service, a satisfactory mechanism to explain stress corrosion cracking in homogeneous alloys is still lacking. The relative chemical activity of grain boundaries and adjacent grains, inferred from the boundary structure, has been used to explain intergranular cracking in a brass.' This concept is probably correct as a general hypothesis, but it requires much more extensive development in order to explain satisfactorily the observed phenomena. For example, the specific function of the solute in an alloy must be considered, because intergranular failure does not occur in pure metals,' which are structurally similar to homogeneous alloys. Also, in this connection, an inter crystalline fracture path in binary copper alloys can be changed to a transcrystalline path by relatively small ternary additions.' The fracture path in ß brass is predominantly transcrystalline,' in contrast with an inter crystalline path in a brass. Whether the two different fracture paths are the result of a difference in composition, crystal structure, or the state of long range order is unknown and cannot be determined with ß brass, because only the ordered state can be obtained at room temperature. The study of chemical activity at structural sites in the Cu-Zn system is restricted by the formation of opaque films in an ammonia environment in which stress corrosion cracking is generally observed. Furthermore, both components of the alloy are chemically active and the interpretation of observations is therefore relatively complicated. The Cu-Au system is a better choice for the purpose of studying structural factors. In particular, CuAu is very susceptible to cracking in ferric chloride and opaque films are not formed in this solution; it may be obtained in different states of long and short range order; and, finally, only copper is oxidized in dilute ferric chloride, which considerably simplifies the chemical problem. To provide information necessary for a more general explanation of stress corrosion cracking in homogeneous solid solutions, the following structural factors have been investigated in a Cu-Au alloy having a composition corresponding to Cu,Au: 1) the effect of long and short range order; 2) the structural sites from which copper is removed from the annealed and cold worked polycrystalline alloy; and 3) the effect of annealing time and temperature on structural reactions in the cold worked alloy. Experimental Procedure A Cu-Au alloy of nominal Cu3Au composition was cast from cathode copper and high purity gold and fabricated into sheet and wire. Chemical analysis for copper and gold indicated 48.92 wt pct Cu and 51.01 pct Au. Quantitative spectrographic analysis indicated 0.01 pct Ag, 0.002 pct Pd, 0.001 pct Pb, and 0.002 pct Fe, with traces of magnesium, silicon, and zinc. Presumably most of the remaining 0.055 pct corresponds to the limits of analytical precision. Heat treatments of wire and sheet were conducted in argon or vacuum. Wire specimens, 0.064 in. diam, were heated for 1 hr at 850 °C to establish a definite

Jan 1, 1957

By H. J. de Haan, J. van Lookeren

In view of their size and favorable characteristics, Shell's heavy-oil fields on the eastern coast of Lake Maracaibo, Venezuela — known as the "Bolivar Coast" — are obvious candidates for the application of thermal recovery methods. During the last decade various methods have been tested, such as steam drive,', steam soak and in-situ combustion.3 Steam soak was discovered as a promising production method rather accidentally in 1969, during early steam drive testing in the Mene Grande Tar Sands1 When steam erupted at the surface due to breakdown of the overburden, the injection wells were back-flowed to relieve the reservoir pressure. This resulted in high oil production rates, all the more impressive because the reservoir is unproducible by primary means. It was concluded that injection of limited amounts of steam might be a very effective method for stimulation of heavy-oil wells. To obtain information that would be more widely applicable, testing of the process was continued in the eastern part of the Tia Juana field (Fig. 1). Here even more favorable results were obtained than in Mene Grande. This created sufficient confidence to prompt a large-scale project, which was considered essential for an adequate evaluation of ultimate recovery, steam requirements, mechanical problems and economic prospects. To obtain an early answer on the ultimate recovery a fairly depleted area was selected in the western part of the same field ("A" in Fig. 1). The first steam was injected in March, 1964. This paper describes the performance until the end of 1966. The production mechanism and well inflow performance are discussed in some detail. In view of the favorable results obtained so far, steam soak operations have expanded considerably since the start of this project. Presently, five other projects are under way, of which two are about the same size as the one under discussion, with further extensions being programmed. Description of the Project Reservoir Data Shell's part of the Main Tia Juana reservoir has a proven area of 8,800 acres and an average net oil sand thickness of 130 ft. It contained an initial quantity of 2,750 million bbl of stock tank oil (STOIIP), with an API gravity ranging from 10 to 15 API and a viscosity of 100 to 10,000 cp (at 122F). As a geological unit it is known locally as the Lower Lagun-illas member of the Lagunillas formation, which is early Miocene in age. The sand bodies are believed to be distributary channel sands deposited in a lower coastal plain. Most of the channel sands have lateral and some vertical communication. The field was developed mainly in the period from 1936 to 1950. The ultimate primary recovery is estimated at 18.1 percent of STOIIP, of which 12.5 percent STOIIP had been produced by the end of 1963 from some 540 wells. By then the average pressure had decreased from an initial value of 960 to 550

Jan 1, 1970

By J. W. Marx

A method is given for predicting the complete gravity drainage characteristics of arbitrarily long columns from centrifuge drainage measurements on reconstituted core samples. Oil residuals corresponding to hundreds of years of normal gravity depletion can be obtained in a few hours on the centrifuge. The gravity flow rate at any stage of the depletion process may be determined from the time correlation derived, and experimentally checked, in this study. INTRODUCTION Apart from the original observations of Muskat et al1, research publications2,3,4 on the subject of gravity drainage have been largely concerned with establishing in detail the saturation, S as a function of the height, z, in a draining column at any given time, t. Some form of numerical integration must be employed to obtain production rates and cumulative production even when S(z, t) is known. Furthermore, the relevant experimental work has been concentrated on drainage of a single wetting liquid from unconsolidated media. Since oil production usually concerns the drainage of a partially wetting liquid from consolidated media, in the presence of connate water, and since it is unlikely that sufficient information exists to establish S(z, t) in detail for any natural reservoir, the published research work appears to be, at best, only qualitatively applicable to production problems. With this in mind, the present study was undertaken by the writer. Experiments were planned whose results would have two advantages over existing measurements: 1. Observations were to be made on specific reservoir rock, reconstituted with formation water and formation oil. This would reduce their generality, from the research viewpoint, but increase their utility for production purposes. 2. The measurements were to be self-integrating, i.e., the phenomena were to be described and interpreted in terms of cumulative results. THEORETICAL DEVELOPMENT It was commonly known that centrifuging a liquid bearing porous medium increases the drainage rates and minimizes capillary end effects. The specific problem lay in selecting an acceleration, a, such that the mean residual saturation of a model cylinder was equal to the residual saturation of an arbitrarily long prototype column when the latter was drained by earth gravity alone. The physical conditions required to permit a valid scaling of model drainage time, tm with prototype drainage time, t, may be stated as follows: (a) At t = tm = O, So = Smo; (b) At t = tm? 8 Sr. = Smr.; (c) For all intermediate values of t and dS/dt=dsm/dtm whenever S = Sm; (d) S(z) = Sm(z) = a constant when t = tm = 0. 1 Here S = T I S(z)dz, where h is the length of the « Jo cylindrical column being drained and the subscripts S,Sm, and refer to model, initial, and residual systems, respectively. The first three conditions mean, simply, that an 3 vs t plot will be numerically identical with an S, vs t, plot,

Jan 1, 1957

By Rudolf Gahl

SOME time ago the Detroit Copper Mining Co. had to decide the question whether it would pay to re-treat slime-tailings, and several machines were tested in order to ascertain the type of construction which would give the greatest saving. In previous tests on the ore of this company, several tables proved far inferior to the Frue vanner, and for this reason they did not receive any serious consideration. In the late tests, however, one table was found to surpass the vanner in the percentage of saving made. The Frue vanner used in these tests had been adjusted approximately to the slope which the slime-vanuers in the concentrator of the Detroit Copper Co. had at that time, about 2 in. between the inside of the wooden posts, or 0.272 in. per ft. It had not been determined, however, if this slope was the most economical one for treating the slime-feed in the mill, or for re-treating the tailings from the slime-vanners, and I was instructed to ascertain by test-runs, under different conditions, the best adjustments for the work to. be done. In order to determine if a change in the adjustments of the machines would improve the results, it seemed sufficient to continue running the tests between the vanner and the table before mentioned, keeping the feed and all other conditions the same, but. varying the adjustments of the vanner .from run to run. I employed a vanner-man of long experience to operate these machines, who expressed the opinion that a slope between 2 3/8 and 2.5 in. between the posts (0.323 and 0.340 in. per ft.) would give the best results. Some runs made this way gave a considerable improvement. While for a slope of 2 in. (0.272 in. per ft.) the saving had been only 40.5 per cent. of that of the table, it .was 49.2 per cent. for 2.5 in. (0.340 in. per ft.) slope. A decrease of

Sep 1, 1909

By W. J. Slatosky

W. 0. Philbrook (Cairiegie Institute of Technologyogv—Mr. Slatosky has presented an interesting and constructive paper that represents another step along the way of converting steelmaking from an art to a science. I am confident that his computer will be practical and successful and that with a very few months of experience it will provide a significantly better degree of control than his record of 65 pct of heats within range obtained with the slide-rule calculator . A paper such as this, with a lot of symbols and condensed mathematics, is difficult to comprehend quickly. Since I have had an opportunity to study it carefully, perhaps my evaluation of its validity and accomplishments will save time for others. Mr. Slatosky has correctly used standard principles of stoichiometry and heat balances, which are available to anybody, but he has also brought to them two original contributions: 1) He has developed from operating data some empirical relations for predicting the final FeO content of the slag (at 0.5 pct C end-point) as a function of slag basicity, lance height, and scrap, ore, and scale in the charge. This improves the accuracy of prediction of temperature or scrap requirement compared with assuming an arbitrary, constant FeO content at the end of each heat. There is no assurance yet that exactly the same relations will hold for other furnaces or practices, but similar correlations can be expected. 2) He has combined calculations that are ordinarily carried out laboriously as a number of individual steps into a single, simple linear equation that can readily be fed into a machine. This involved a tremendous amount of painstaking detail work as well as the imagination to see the possibility and work out the steps. While his particular Eqs. [3] and [6] are valid only for the furnace design, charge weight, and blowing time used at Aliquippa Works, only a few numerical values have to be changed to adapt it for other conditions. In order to arrive at a useable solution, Mr. Slatosky had to make some basic assumptions about the process that are similar to those used by others. He neglected variation in some process variables and assumed an arbitrary average value for waste gas analysis and temperature for want of more exact information at the present time. All of these judgments are clearly stated. In addition, some thermody-namic data presently available are not adequate for the job, notably in relation to heats of formation and sensible heat in slag, and some expedient has to be adopted to get around the difficulty. Other people might prefer slightly different judgments about these details and hence obtain somewhat different numerical solutions. This is not of serious importance, however, because the errors accumulate in the "heat loss" term and are largely self-compensating for a constant heat time. Although the extended Eq. l(a) in Appendix I was set up as a rate equation originally, for convenience in using an analogue computer as stated in the paper, the time dependence was removed by later mathematical manipulations and assumptions about the process. The final result is an integration of element and energy balances from initial to final states; this procedure is as legitimate here as in any other form of heat-balance calculation. The formal handling of stoichiometry and thermochemistry appears to be correct, and it is assumed that any arithmetical errors would have come to light in applying the calculations to furnace practice. Mr. Slatosky's approach is not necessarily unique, in that other people might start with apparently different equations or prefer another form of final equation for another type of computer. However, he has presented an accomplished result that appears to be a theoretically sound and practically useful way of applying scientific principles and rapid computation for better control of steelmaking. His success will undoubtedly encourage himself and others to improve on the mathematical model and its use as better informatioq becomes available. John F. Elliott (Massachusetts Institute of Teck-t2ology)-The last comment by Mr. Richards that a calculator is quite unnecessary for an L-D operation ?-equi??es a rebuttal. The L-D furnace is a very high capacity process which places a premium on close control. When one is making steel at rates between 100 and 200 tons per hr, one cannot afford the luxury of an extra 5 or 10 min at the end of a heat correcting for an error that should never have been made in the first place. Mr. Slatosky's paper is a very sound application of the simple principles of stoichiometry and the energy balance. It is a satisfactory and valuable start, but only the start of the development of methods of control for this process. An analysis of the process shows that it should be very suitable to control by a computer. This is especially the case when various grades of steel are to be made. In fact, it would seem that the organizations who are planning new and bigger installations of L-D vessels should consider carefully the advantages that would stem from computer control of a vessel with the operator present to do little more

Jan 1, 1962

By J. H. Brophy, J. Wulff, H. W. Hayden

The mickel-activated sintering of tungsten occurs in two stages of densification. A kinetic analysis of the second stage has been based on an appropriate model of the process. As in the first stage, the rate-controlling mechanism for the second stage is also the solution of tungsten in the nickel carrier phase. The transition from the relatively rapid first-stage results from the spherozdization of pores and the initiation of grain growth. Finer grain size due to higher-nickel content leads to more rapid and higher degrees of densification 1 HE sintering of tungsten is accelerated by small additions of nickel, cobalt, and iron.' Experimental evidence in detail has shown that nickel-coated, hydrogen-reduced tungsten powder may be sintered to more than 90 pet of theoretical density at l100o C.2, 3 Simultaneously, a kinetic analysis of the process showed that it took place in two distinct stages. In the first stage, nickel evidently served as a carrier phase through which tungsten atoms could move. This stage was kinetically similar to the "solution-precipitation" step postulated when the carrier phase is a liquid,4 although in the Ni-W case, there is no evidence of the existence of a liquid phase either in equilibrium phase relationships or in microstruc-tures at the temperatures under consideration. It has been shown that this stage corresponds to a process which is rate controlled by a phase boundary reaction.3 More recent evidence has been presented5 showing that after the initial rapid stage of sintering, densification continues in the final stage but at a slower rate, although no mechanism for this stage of densification was defined. An analysis of later stages of densification in solid state sintering has been presented,6 but it is not directly applicable in the present case of activated or carrier phase sintering. It is the purpose of this investigation to study the final stage of nickel activated tungsten sintering in greater detail The effect of varying nickel content has been examined, and a possible kinetic mechanism defined. EXPERIMENTAL PROCEDURE AND RESULTS Commercial hydrogen-reduced tungsten powder from Wah-Chmg Corp., having a nominal particle size of1 µ and a B.E.T. specific surface area of 5500 sq. cm per g was mixed with aqueous solutions of hydrated nickel nitrate in proportions sufficient to produce nominal compositions of 0.25, 1, 3, and 5 wt pet Ni. This solution was then evaporated to dry-ness at approximately 150" C for 15 hr. Following evaporation, the resulting powder cake was broken with a mortar and pestle and reduced in hydrogen at 800oC for 1 hr. Following reduction, the powder

Jan 1, 1962

By G. W. Thomas

Jan 1, 1967

By Lawrence H. Van Vlack, Alfred S. Keh

The distribution of sulfur in iron was found to be dependent upon the time and temperature of the treatment as well as the chemical composition of the sulfide. With higher temperatures, the sulfide phase spreads more extensively between the iron grains. A complete network, however, does not form until approximately 1300°C (2372°F), ot which temperature the dihedral angle approaches zero. Silicon has little effect on this change. Aluminum, oxygen, and manganese all modify the temperature of sulfide network formation to a higher value. The microstructures which result and have significance in relation to hot-shortness are discussed. SULFIDE inclusions in steel were recognized by metallurgists before the turn of the century. Considerable attention has been paid to them, and numerous studies have been made on the working properties of steel as affected by them. It has been suggested that ho t-shortness of steel is due to the presence of an enveloping liquid sulfide film at the grain boundaries of the steel in the range of the hot-working temperatures. However, several facts have been observed in commercial steels which do not seem to be completely consistent with this explanation: 1) the frequent absence of continuous films of sulfide as observed under the microscope, 2) the absence of hot-shortness in some high sulfur and resulfurized steels, and 3) the limitation of hot-shortness to a definite temperature range. The role that manganese plays in steel to eliminate hot-shortness is well known, but the theory behind it is still under question. Moreover, the effect of de-oxidizers such as aluminum and silicon, and the effect of oxygen are still not clearly known. In this study, the effect of heat treatments and of additions of manganese, aluminum, silicon, and oxygen upon the distribution of sulfide inclusions in iron was investigated. Both the as-cast and the heat treated structures were studied, using microscopic and autoradiographic techniques. Part of the results were interpreted in terms of Smith's' concept of microstructure. Review of Literature Metallurgists used to consider sulfide inclusions as suspended particles. It was Wohrman' who first pointed out that sulfide inclusions are soluble in liquid iron. Many observed facts may be understood on the basis of this concept of solubility. Wohrman found that small castings contain small inclusions. and larger castings contain larger ones. Also, inclusion sizes are smaller near the chilled surface. For the same size ingot, the average inclusion size in a given heat of steel depends upon the rate of solidification. That is, with slow solidification, enough time for precipitation and agglomeration of these

Jan 1, 1957

By W. G. Oldham

By monitoring the capacitance of abrupt p-n junctions it is possible to follow the motion of substitu-tional impurities. A p-n junction is formed by growth of silicon from an Al-Si alloy on an n-type silicon sutstrate at a temperature in the range 650" to 750°C. The diodes are etched and sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed to various temperatltres for 10 mm and the capacitance remeasnred. For very heavily doped diodes (-1019 per cm3) observable capacitance changes occur at neutron fluences of >1015 per cm 3. The results may be interpreted in seceral ways, the simplest of which is to assume simple vacancy diffiision with small impurity -racancy interaction (at the diffiision, i.e. annealing temperature of 700°C). In this interpretation it is found that a typical vacancy makes about 1024 jumps and travels about 10-5 cm before disappearing. The required effective annihilation center density is about 1016per cm3 . Estimates of the vacancy-impurity interaction can be made and the above numbers correctecl, but for arty reasonable assumptions the number of vacancy sinks connot be much reduced. ThE complete annealing of radiation induced defects requires that the vacancies and interstitials either recombine, travel to the surface of the crystal, or travel to an annihilation center, e.g., a dislocation or a precipitate. If the interstitial is ignored except as a possible vacancy annihilation center at low temperatures,* the motion of vacancies may be followed by monitoring the corresponding motion of substitutional impurities. pfister2 has measured the enhanced diffusion of impurities in an asymmetric shallow diffused silicon structure by optically monitoring the junction movement. In these experiments we monitor instead the capacitance of a heavily-doped deep symmetric p-n junction. The sensitivity for this method is several orders of magnitude higher than in Pfister's technique, mainly for two reasons: 1) the junction capacitance of a heavily-doped junction is sensitive to impurity movements in the Angstrom range* com- and 2) the junction may be far from the surface which is a major annihilation center for vacancies. THE EXPERIMENT A p-n junction is formed by the epitaxial growth of silicon from an A1-Si alloy on a silicon substrate at a temperature in the range 650° to 750°C. The technique used is the transport of an aluminum melt through a temperature gradient.4 A 10-mil thick aluminum disc is sandwiched between two silicon wafers and the assembly raised to about 650° C with a temperature gradient normal to the sandwich. After about 8 hr the upper (hotter) wafer has been entirely transported and deposited epitaxially on the substrate wafer. The substrate and overgrowth resistivity are measured with a 4-point probe. The as-grown structure is lapped until the wafer is about 1/2 mm thick with the junction in the center. Contacts consisting of electroless nickel covered by electroplated rhodium are applied to both the p and n sides. The wafer is diced into square dice 1/2 to 1 mm on a side and the dice are etched sufficiently to remove approximately 1 mil of silicon. The following results are all for aluminum (p-side) and antimony (n-side) doped specimens with NA =3x 1018 per cm3, ND = 2-8 x 101A per cm3. The diodes are sorted for consistent V-I and capacitance behavior and separated into groups. After irradiation, each set with an unirradiated control set is annealed and the capacitance remeasured. A special capacitance measurement method is used to insure a low sensitivity to shunt resistance. The diode is voltage driven and the current monitored by a phase lock amplifier. It is possible to adjust the detector phase to a point where shunt resistances as low as 100 O have no effect on the reading. The diodes in this study have a capacitance in the range 1000 to 5000 picofarads and a shunt resistance in the range 100 to l06 O depending on the stage of the anneal. THEORY The theoretical problem is twofold: 1) The computation of the amount of impurity diffusion and hence the impurity profile resulting from a given amount of vacancy motion, and 2) the computation of the capacitance from the impurity profile. A comparison of the theoretical and experimental capacitance (in particular the changes) yields the amount of vacancy motion. Vacancy Motion. A convenient parameter to measure the total amount of vacancy motion is Jv the total number of vacancy jumps per unit volume. Although this parameter varies with position in the crystal, owing to vacancy annihilation at the surfaces, it is approximately independent of position far from the surfaces, i.e. in the junction region. In terms of the number of vacancies per unit volume Nv and the vacancy diffusivity given by

Jan 1, 1970

By Takashi Katsura, Avnulf Muan

Equilibrium relations in the system FeO-Fe2O3 Cr2O3 have been determined at 1300°C at oxygen pressures ranging from that of air (0.21 atm) to 1.5 x 10-11 atm. The following oxide phases have stable equilibrium existence under these conditions : a sesquioxide solid solution with corundum-type structure (approximate composition Fe2O3-Cr2O3); a ternary solid solution with spinel-type structure (approximate composition FeO Fe2O3-FeO Cr2O3) and a ternary wüstite solid solution with periclase-type structure and compositions approaching FeO. The metal phase occurring in equilibrium with oxide phase(s) at the lowest oxygen pressures used in the present investigation is almost pure iron. The extent of solid-solution areas and the location of oxygen isobars have been determined. ThE system Fe-Cr-O has attracted a great deal of interest among metallurgists as well as ceramists and geochemists. Metallurgists have studied the system because of its importance in deoxidation equilibria, ceramists because of its importance in basic brick technology, and geochemists because of its importance for an understanding of natural chromite deposits. Chen and chipman1 investigated the Cr-O equilibrium in liquid iron at 1595°C in atmospheres of known oxygen pressures (controlled H2O/H2 ratios). The main purpose of their work was to determine the stability range of the iron-chromite phase. Hilty et al.2 studied oxide phases in equilibrium with liquid Fe-Cr alloys at 1550°, 1600°, and 1650°C. They reported the existence of two previously unknown oxide phases, one a distorted spinel with composition intermediate between FeO Cr203 and Cr3O4, the other Cr3O4 with tetragonal structure. They also sketched diagrams showing the inferred liqui-dus surface and the inferred 1600°C isothermal section for the system Fe-Cr-O. Koch et al3 studied oxide inclusions in Fe-Cr alloys and also observed the distorted spinel phase reported by Hilty et al. Richards and white4 as well as Woodhouse and White5 investigated spinel-sesquioxide equilibria in the system Fe-Cr-O in air in the temperature range of 1420" to 1650°C, and Muan and Somiya6 delineated approximate phase relations in the system in air from 1400" to 2050°C. The present study was carried out at a constant temperature of 1300° C and at oxygen pressures ranging from 0.21 atm (air) to 1.5 x 10-11 atm. The chosen temperature is high enough to permit equilibrium to be attained within a reasonable period of time within most composition areas of the system, and still low enough to permit use of experimental methods which give highly accurate and reliable results. These methods are described in detail in the following. I) EXPERIMENTAL METHODS 1) General Procedures. Two different experimental methods were used in the present investigation: quenching and thermogravimetry. In the quenching method, oxide samples were heated at chosen temperature and chosen oxygen pressure until equilibrium was attained among gas and condensed phases. The samples were then quenched rapidly to room temperature and the phases present determined by X-ray and microscopic examination. Total compositions were determined by chemical analysis after quenching. In the thermogravimetric method, pellets of oxide mixtures were suspended by a thin platinum wire from one beam of an analytical balance, and the weight changes were recorded as a function of oxygen pressure at constant temperature. The data thus obtained were used to locate oxygen isobars. The courses of the latter curves reflect changes in phase assemblages and serve to supplement the observations made by the quenching technique. 2) Materials. Analytical-grade Fe2O3 and Cr2O3 were used as starting materials. Each oxide was first heated separately in air at 1000°C for several hours. Mixtures of desired ratios of the two oxides were then prepared. Each mixture was finely ground and mixed, and heated at 1250" to 1300°C in air for 2 hr, ground and mixed again and heated at the same temperature for 5 to 24 hr, depending on the Cr2O3 content of the mixture. A homogeneous sesquioxide solid solution between the two end members resulted from this treatment. A Part of some of the sesquioxide samples thus prepared was heated for 2 to 3 hr at 1300°C and oxygen pressures of 10-7 or 1.5 x 10-11 atm. Reduced samples (either iron chromite

Jan 1, 1964

By G. F. Jenkins

The word asbestos is a broad term that has been accepted and applied to a number of fibrous mineral silicates found in nature. They are incombustible and can be separated by mechanical means into fibers of various lengths and thicknesses, but differ in chemical composition and other properties. It is generally recognized that there are six varieties of asbestos; the finely fibrous form of serpentine known as chrysotile, and five minerals of the amphibole group, i.e., amosite (not fully recognized as a mineral species name but accepted in asbestos terminology), anthophyllite, crocidolite, tremolite and actinolite. (Figs 1-4.) Physical and Other Properties The structures of asbestos fibers have been studied intensely in recent years. X-ray diffraction patterns 1 to 15 have been used as a means of identification and classification. The amphibole group structures have been fairly well established while the serpentine group has been the subject of many investigations during the past six years. Low-angle X-ray scattering techniques5 have shown that the chrysotile fibrils are "hexagonally close packed" and parallel to each other, having cross-sectional diameters varying from 180Å* units to 300Å units, while the amphibole fibers are many times larger in cross section. The electron micrographs of chrysotile asbestos (Figs 1-4) have also indicated that the fibrils might be in the form of a hollow tube. This point has been the subject of considerable controversy by a number of investigators.7 to 16 Density measurements17 made on a sample of high quality Arizona fiber did not indicate that the fiber had a hollow tube structure; however, the so-called "sheet structure" of the fibril could be distorted in such a way that it gives the appearance of a hollow tube in the electron microscope. It is of interest to quote one investigator, F. L. Pundsack,17 in this connection: Although the empirical composition of chrysotile is 3MgO.2SiO2.2H20, the true unit cell[#] composition is best represented as Mg12(OH)16Si8O20. This cell has dimensions of a= 5.3Å, b = 9.2 Å, and c = 14.6 Å where the "a" direction is the fiber axis. The calculated density of this unit is 2.56 g/cc, a value in close agreement with experimentally determined density values for chrysotile. The exact manner in which the unit cells of asbestos are stacked together to build up a single fiber of chrysotile is not known, but from various

Jan 1, 1960

By R. B. Booth, W. F. Linke

The continuous interest of the American Cyanamid Company in producing superior polymeric flocculants and dispersants for the mining industry has resulted in a broad, general study of the physical chemistry of mineral-polymer systems. The aim of this program has been to establish a sound theoretical basis on which practical problems could be analyzed, and which would lead to the development of new and improved flocculating and dispersing agents. This study has required the cooperative effort of physical, analytical, and polymer chemists, as well as engineers familiar with mining problems. This report summarizes the results of some of our investigations over the past two years. Further studies along these and other lines are in progress and will be reported in the near future. MEASURING FLOCCULATION IN THE LABORATORY The foremost problem in studying flocculation in the laboratory has been to establish reproducible methods of comparing and evaluating the effectiveness of various reagents. Previous workers have measured settling -rates 1,8 filtration rates2 , and sediment volumes3 . Direct observations of the floc size, or the clarity of the supernatant liquid, can also be used. AIthough these parameters are all interrelated, they do not always measure the same physical properties of the suspensions, and hence are not equally useful or reliable. Whatever the method of comparison selected. the testing procedure must be carefully defined and standardized. The results must be satisfactorily reproducible, and for practical purposes must accurately reflect the results obtained in mill use. In order to compare the data obtained in these various types of test, the physical nature of the flocculated system must be examined in some detail. In an unflocculated system, only the larger or denser particles (the "sands") settle at a useful rate. The sediment can be observed to build up from the bottom of the cylinder, while the fines remain in suspension for a long period of time. If the system is not disturbed, even the microscopic fines can be seen to classify themselves as they fall over a period of days. When a high molecular weight polymer is added to the system, the colloidal particles are tied together randomly in flocs, and the sands and fines settle together. The line of demarkation between solid and liquid phases moves downward from the top of the cylinder. The settling rate of the flocs depends on their size and on their effective density. For a given mineral sample, the larger the flocs, the faster the settling. Since the large flocs cannot pack as closely as small ones, they produce a sediment with more pore spaces, and hence of larger volume, which is easier to pump and to agitate. Although it is nearly impossible to measure individual floc sizes, it is relatively easy to determine settling rates and sediment volumes. Of these two, the settling rate is simpIer to measure, and hence generally more practical. Reproducible sediment volumes can only be obtained by allowing the solids to pack for a rather long period of time (e.g., hours to days), and although the volumes thus observed are directly related to the degree of flocculation (average floc size), it is often impractical to wait so long for the results.

Jan 1, 1961

By Simon D. Strauss

The world appetite for minerals in the, third quarter of this century grew at a higher rate than had been anticipated. To illustrate, consider the experience of four, commodities. Excluding the Communist bloc, sometimes referred to as the centrally planned economies, demand for aluminum increased at a compound rate of 8.6% between 1950 and 1975,; copper rose by 4.4%; iron ore by 5.5%; and tin, the laggard in the group, by 2%. Except for tin, the figures are substantially greater than growth rates anticipated in 1950 in the Paley Commission report and other studies. The growth rate was not evenly distributed in geographical areas. Professor Wilfred Malenbaum of the University of Pennsylvania did an interesting study breaking these figures down as among three principal sources of demand -- the United States, other industrialized nations (which he referred to as the "rich lands"), and the developing world (which he referred to as the "poor lands").

Jan 1, 1982

By W. P. Sykes

RECENT investigations of the molybdenum-carbon alloys have been reported by Becker and Ebert1,? Westgren and Phragmén2, T. Takei3, and H. Tutiya4. Takei3 studied the Mo-C system by employing metal-lographic and X-ray methods, and the other publications described the determination of the crystal structure of the molybdenum carbides. In exploring this system by a technique previously applied to the tungsten-carbon series5, the results of Takei were confirmed with two definite exceptions; i.e., first the composition of the eutectic, and second the nature of the carbon-rich intermediate phase. Consequently, a more thorough examination of the molybdenum-carbon constitution was initiated in an effort to correlate the data supplied by the microstructures, diffraction patterns and chemical analyses.

Jan 1, 1935

By Lawrence K. Nordell

This paper reviews practices used In the selection and sizing of belt conveyors and stacker systems commonly used in crushing and grinding plant facilities. Historical and modern methods of sizing this equipment are presented. The new methods Include: 1) probability theory applications for establishing component reliability, 2) "Monte Carlo" simulation techniques used in evaluating alternative system designs and in establishing service factors and corresponding availability Indices of each system, 3) quantifying the system and component operating characteristics using computer assisted modeling tools simulating rigid body and elasto-mechanic behavior for starting and stopping large and/or complex belt conveyors.

Jan 1, 1982

By J. C. Martin

Equations for three-phase, three-dimensional, compressible flow (including capillarity) are reduced to two-dimensional relations by a partial integration. This reduction allows three-dimensional flow problems to be treated with mathematics for only two spatial dimensions. The results can be used to formulate flow equations for two-dimensional reservoir simulators in which the effects of capillarity and fluid segregation in the third dimension are represented. Such reservoir simulators would retain many of the aduantages of two-dimensional simulators while simulating three-dimensional effects. The principal restriction of the method is that the thickness of the reservoir should be small, compared to the distance across the reservoir. INTRODUCTION In recent years, computers have been used to calculate the performances of many reservoirs. Most of the detailed calculations, however, are based on finite difference solutions of the flow equations, and present day computers are seldom able to handle a sufficient number of cells to produce entirely satisfactory solutions, even for reservoirs represented by two-dimensional arrays of cells. The situation becomes much worse when one wishes to approximate the reservoir by a three-dimensional array. A great saving in computation or a more detailed solution can be obtained for many reservoirs by using the partial integration of the equations of flow presented in this paper. The integration reduces the three-dimensional equations to two-dimensional relations; and, for studies of two-dimensional flows in vertical cross-sections, the equations are reduced to one-dimensional relations. Most reservoir performance calculations currently are based on one- or two-dimensional flow re1ations.l-3 In some cases flow in the third dimension is approximated by assuming a particular type of vertical saturation distribution, such as gravity segregation.l.2. The relations developed in this paper approach those for segregated flow as the capillary pressures approach zero, and they approach those for uniformly distributed saturations as the capillary pressures are increased. For this analysis, the ratio of the reservoir's thickness to the maximum distance across it must be small. The capillary pressures between the oil and water should also be small compared to the maximum pressure difference in the reservoir. This requirement is met by most reservoirs. It is assumed that the capillary-pressure curves are well defined, whether or not hysteresis effects are included. Also, the reservoir must have sufficient vertical permeability to allow the fluids to segregate. The results presented here provide a firm theoretical foundation to Coats' et aL5 assumption of vertical equilibrium and extend the relations to three-phase flow. Coats' assumption of vertical equilibrium, which he verified by calculations and experiment, is developed here mathematically from basic flow equations. DISCUSSION SATURATION AND PRESSURE DISTRIBUTIONS Appendix A presents a mathematical analysis of fluid flow in reservoirs where the ratio of thickness to maximum distance across the reservoir is small. The results indicate: (1) that the fluids along any line perpendicular to such a reservoir's upper surface are in static capillary equilibrium (vertical equilibrium); (2) that, to a first approximation, the fluid pressures and properties are functions of only areal position in the reservoir and time; and (3) that hydrostatic pressure gradients exist along any line perpendicular to the reservoir's upper surface. The results might be expected after studying several physical considerations. First, no flow is allowed normal to the upper and lower reservoir boundaries, which are relatively close together.

Jan 1, 1969

By Frank Rieber

THE study of earthquakes long ago developed the fact that by studying the travel times of the various groups of waves from the same earthquake, as received on seismographs at varying distances, major discontinuities in the earth's crust could be reasonably well defined. Using this original discovery, and adapting the mathematical methods originally devised in seismology for determining the depth below the surface at which such discontinuities occur, other investigators were able to develop a new branch of seismology which promises to be extremely useful in extending the boundaries of our information on local conditions below the earth's surface. As an outstanding example of the applications of this work, we have the so-called "seismograph" exploration of the Gulf Coastal region, which has resulted in the discovery of a large number of salt domes, from many of which oil fields may be developed. The original seismological investigations, from which different major discontinuities in the earth's crust were deduced, as well as these later successful experiments in locating salt-dome structures, involve relatively simple problems. In each case we are dealing with surface materials in which elastic waves will be propagated with a fairly definite velocity. Under this material we have something quite different, in which the elastic waves will be propagated with a much higher velocity. The transition from one medium to the other is likewise relatively abrupt. For example, in the Gulf Coastal region the sedimentary formations have a velocity of 6000 or 7000 ft. per sec., while the velocity of elastic waves in the cap rock of a salt dome may exceed 15,000 ft. per sec. Under such conditions, delineation of the formation is a relatively simple matter, and, furthermore, there is very little opportunity for ambiguous results.

Jan 1, 1928