Search Documents

By A. L. Holley

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

Jan 1, 1880

By A. L. Holley

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

Jan 1, 1880

By G. A. Parks, C. Kovacs

The xanthate flotation of chrysocolla can be improved by preheating the ore to 500° to 600°C. Addition of water vapor reduces the preheating temperature required. The temperature range of flotation improvement correlates well with the range over which dehydroxylation occurs. This observation is consistent with changes in the structure and properties of the mineral as detected by measurement of solubility, D.T.A., T.G.A., X-ray diffraction, and infrared absorption and with recently proposed explanations of chrysocolla flotation. A brief experiment by one of the authors several years ago showed that exposure of chrysocolla to high temperature water vapor resulted in increased recovery by subsequent xanthate flotation. Recently renewed interest in flotation and thermal properties of chrysocolla1-5 prompted further study of this effect and more detailed reporting.6 This paper explores the response of pure chrysocolla recovery in Hallimond tube flotation tests to the time and temperature of exposure and to changes in the water vapor pressure. Brief attention is paid to the effects of such treatment on accessory minerals. A single experiment with flotation of chrysocolla from an ore is reported. MATERIALS Chysocolla from Inspiration, Gila County, Ariz. was crushed in a porcelain mortar, cleaned of visible and magnetic impurities, and screened to obtain -48 +65 mesh (Tyler) material for flotation test work. The clean material contained 28.5% Cu and was identified as chrysocolla by comparison of X-ray diffraction, D.T.A., and infrared absorption data with that reported for similar materials by others.4,5,7 Samples of malachite and chalcopyrite, prepared in a similar way, were also identified by X-ray diffraction. The sources of these materials are unknown. A sample of chysocolla-bearing oxidized copper ore from Pima, Ariz. was crushed and dry ground for thermal activation and subsequent flotation. PROCEDURES Activation: The apparatus used for exposure of materials to high temperature water vapor is illustrated in Fig. 1. The furnace temperature was controlled to ±5°C Water vapor pressure was controlled by pre-saturating a nitrogen carrier stream with water in an adjustable thermostatted saturator (multiple bubbler). A water manometer and capillary orifice flow meter were used to measure nitrogen flow rates for activation and for subsequent Hallimond tube tests. Gas flow rate and temperature were adjusted prior to introduction of samples. Exposure time was measured from the moment of introduction of the sample to the furnace, hence includes an initial drop below the control temperature. After heating, the samples were removed from the furnace and stored at room temperature in air. Representative samples of activated materials were examined by X-ray diffraction and infrared absorption.

Jan 1, 1967

By George B. Langford

ON THE QUESTION of postwar controls there are today three schools of though ; some advocate state control of everything the socialists ; second are those who advocate the removal of all governmental control over industry - the freedom of enterprise ideal ; and third are those who advocate a middle course - sufficient control to stabilize economic and industrial life, and to prevent violent fluctuations such as we saw in the interwar years. I advocate this third course. I firmly believe un free enterprise, but not in freedom of enterprise, or laissez faire, and there is a great and significant difference between these two.

Jan 1, 1944

By William A. Mitchell

AN X-ray diffraction pattern for "calcined cold precipitated ferric oxide" is reproduced dia-grammatically along with data for other iron oxides by R. C. Mackenzie.1' This pattern, which shows spacings higher than those for any other form of iron oxide, was obtained from material prepared and photographed at several different times over a period of weeks, but later attempts to reproduce the results were unsuccessful, the pattern of hematite being obtained every time.2 In an attempt to solve this problem, the original photographs showing the strange diffraction pattern were examined and a marked similarity to the hematite pattern was noticed, suggesting that the pattern was in fact due to hematite but corresponded to a shorter wavelength of X-rays than the Cu Ka which was assumed to have .been used. The eight strongest lines were provisionally identified with the strongest hematite lines and, by means of the corresponding hematite spacings, the X-ray wavelength was calculated for each line. This gave an almost constant value, with the exception of the innermost line which was somewhat diffuse, and confirmed the presence of hematite. The value obtained, 0.703 ± 0.015Å, corresponds to the molybdenum Ka wavelength. The X-ray tube used was a four-filament demountable tube with a copper target. Other photographs, mostly of soil clays, taken during the same period gave normal patterns of Cu Ka radiation with one exception. This was a calcined soil clay with a high iron content and also showed Mo Ka lines of the hematite structure. The explanation is almost certainly that the copper target was contaminated with molybdenum, but it is not known how this occurred. Specimens of alumino-silicates gave their normal Cu Ka pattern, but as the K absorption edge of iron is a little longer than the Cu Ka wavelength, specimens with a high iron content greatly reduced the intensity of the Cu Ka diffraction lines relative to that of the lines due to the shorter Mo Ka wavelength. The formation of hematite on calcining cold precipitated hydrated ferric oxide3 is thus confirmed. References R. C. Mackenzie: Investigations on Cold-precipi-tated Hydrated Ferric Oxide and its Origin in Clays. Problems of Clay and Laterite Genesis, p. 69, Fig. 4, F. AIME Symposium, St. Louis, Mo. Feb. 19-22, 1951. Published 1952. 'R. C. Mackenzie: Ref. 1. Note added on proof. V. C. Hansen and L. T. Brownmiller: Equilibrium Studies on Alumina and Ferric Oxide and on Combinations of These with Magnesia and Calcium Oxide. American Journal of Science (1928) 5, No. 15, pp. 225-242.

Jan 1, 1954

By P. Breidt, E. S. Greiner

THIS note reports a determination of the melting point of germanium, and the liquidus of the Ge-Ga alloys; lattice constants of the a phase are given. The alloys were prepared by melting germanium (>20 ohm-cm resistivity) and gallium (99.6 pct) in evacuated silica tubes. The materials (50 to 70 g) were heated at 1000°C, held in the liquid state for about ¾ hr, and then cooled rapidly in the tubes. Points on the liquidus were obtained by thermal analysis which consisted of obtaining time-temperature data during heating and cooling the materials in high purity graphite crucibles and a helium at- mosphere. Temperatures were determined with a Pt—Pt-Rh thermocouple protected by a silica sheath. The couple was calibrated against a National Bureau of Standards calibrated couple and also against the freezing points of copper, silver, aluminum, and the 28.1 wt pct Cu, 71.9 wt pct Ag alloy eutectic. The samples for X-ray analysis were prepared by heating small pieces of the ingots in evacuated glass or quartz tubes at temperatures between 600" and 900°C for periods ranging from 2 hr to 22 days, periods deemed sufficient for equilibrium to be attained, followed by quenching in water. The heat-treated samples were ground to powder for X-ray analysis. The lattice constants of the germanium-rich phase (a) were determined with a baok-reflection focusing camera. The X-ray reflections (331 and 422 Cr Ka, 422 and 333 Cr KB) were corrected

Jan 1, 1956

By Charles Will Wright

THOSE that attended the seventeenth International Geological Congress held in Russia last summer had an excellent opportunity to gather data and to form impressions on the progress made in the industrialization of the country, particularly with regard to the mineral industries. Several trips to places of interest were arranged, supplementary to the technical sessions held in Moscow, the one to the Ural region being that which I selected as being most likely to be of interest. The accomplishments of the last decade in opening up new mines and building new metallurgical plants in the Soviet Union have been outstanding. This could only be accomplished by a central government ready to employ the best technical talent, which was

Jan 1, 1937

By Frederick M. Becket

AFTER all the chronology that has been given, what is the present status of chromium steels? For the purpose of this discussion the different types of chromium steels can be divided into three classifications-those containing relatively low , percentages of chromium, say 5 per cent or less; the medium-chromium steels containing up to about 18 or 19 per cent chromium; and the steels containing still higher percentages of chromium, and some of the special alloys. Chromium has some unique effects in steel, so it is well to make a few generalizations. The affinity of chromium for carbon is great and the metal is unique in the manger in which it supplements and enhances the effects of carbon. Chromium retards -considerably the thermal transformations on cooling and exerts an opposing influence both on the absorption and precipitation of the carbides in steel. These statements make it easy to understand the fact that chromium .steels are capable of producing a hardened product at a much slower rate of cooling than is, true of plain carbon steel, and that chromium carbide or -the mixed carbides of iron and chromium do not contribute to brittleness to as great a degree as does iron carbide.

Jan 1, 1929

By B. H. Bergstrom

The Gaudin-Meloy1 size distribution equation requires the evaluation of two constants, xo and r. The common log-log representation of a screen analysis as cumulative weight percentage passing versus size, readily yields the required constants as illustrated for curves A and B in Fig. 1. The 100% passing (y = 1.0) size is simply x,. If the straight portion of the curve be extrapolated to the 100% passing (y=1.0) abscissa, the intercept is the Schuhmann size modulus, k. The ratio of xo to the size modulus, k, is r as shown: The Gaudin-Meloy equation requires that the slope, a, of the size distribution approach unity in the finer sizes, as is the case for curves A and B. Often distributions are better characterized by slopes other than unity. The schuhmann2 equation is able to represent these distributions if the upper portions of the curves are ignored. Empirically, the Gaudin-Meloy equation can be modified to yield slopes other than unity by writing it as Here, a is the familiar Schuhmann slope, and xo is the 100% passing size. The value of r is still given by Eq. 2. Eq. 4 with its easily determined constants is more versatile than either the Schuhmann or the Gaudin-Meloy equations, since a wide variety of size distributions can be closely described. It is easier to fit than the Rosin-Rammler3 equation, and has the advantage that the top size, x,, is finite. REFERENCES A. M. Gaudin and T. P. Meloy: Model and a Comminution Distribution Equation for Single Fracture, AIME Transactions, 1962, Vol. 223, pp. 40 to 43. R. Schumann, Jr.: principles of comminution, I., size Distribution and Surface Calculations, AIME Technical Publication No. 1187, 1940. P. Rosin and E. Rammler: The Laws coverning the Fineness of Powdered Coal, J. Inst. Fuel, 1933. Vol. 7, p. 29.

Jan 1, 1967

By Horace Pops

ThE shape of the primary solid-solubility limits in copper-rich Cu-Si-Zn alloys has been discussed recently1 in terms of the atomic size effects and the electron concentration, e/a. Although these limits are parallel to lines of constant e/a near the Cu-Zn binary system, they deviate and become sharply restricted near the Cu-Si binary system. Hence, it appears that the primary solid solutions with higher silicon contents are restricted by the presence of the intermediate phases, [, X, and p, which follow them in the ternary system. owever, a similar restriction in solid solubility might also result from an interaction in the copper matrix between silicon and zinc. Evidence for such possible interactions has been observed, for example, in the Al-Mg-Si systion.A where a contraction of lattice spacings in the ternary solid solution appears to correspond to an electrochemical interaction between the two solute elements, magnesium and silicon. The observed contraction is associated with restricted solid solubility. It was also shown1 that the extent of the primary solid solubility did not follow the trends predicted by the lattice-distortion oncept." This again suggested that the solubility limits are strongly affected by the stability of the intermediate phases, I, 1, and X . In order to test the above hypotheses, lattice-parameter measurements of the fcc @-phase alloys were determined within the ternary system at a constant electron concentration (e/a = 1.30) and also at a constant zinc content. Alloys of predetermined composition were prepared from high-purity metals and melted and cast under reduced pressures of helium in quartz capsules. Since the weight losses were very slight and did not exceed one part in 2000, the nominal compositions listed in Table I were accepted without chemical analyses. The ingots were homogenized

Jan 1, 1964

By Thomas A. Steven

Most mineralized areas in the central San Juan Mountains, Colorado, are associated with the youngest subsidence structures in a large volcanic cauldron complex that formed concurrently with eruption of the surrounding ash-flow field. Two local types have been recognized: (1) fissure-vein deposits along faults characterized by relatively late movement, and (2) hydrothermally altered and mineralized areas associated with postsubsidence Fisher Quartz Latite centers. The first type has provided most production in the past; the potential of the second type has yet to be adequately tested.

Jan 1, 1968

By J. C. Fisher, J. H. Hollomon, David Turnbull

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By David Turnbull, J. H. Hollomon, J. C. Fisher

Understanding of the diffusion problem has recently been furthered by the analysis of Birchenall and Meh1.l They pursued the problem of the variation of the diffusion coefficient with composition for non-ideal solid solutions. Their analysis follows the tradition of Wagner,l Jost, Dehlinger, and Darken & who assumed the net flux of diffusing material to be proportional to the gradient of a quantity related to free energy. The basic assumption in Birchenall and Mehl's formulation of the problem is that the net flux of diffusing material is proportional to a thermodynamic activity gradient. To estimate the applicability of the derived relations, they corrected the diffusion coefficients of carbon in austenite by utilizing Smith's6 activity data for carbon, and the diffusion coefficients for zinc in copper with activity data computed from the vapor pressure measurements of Har-greaves.' The corrected coefficients for carbon were virtually independent of carbon concentration. For the diffusion of zinc in copper a moderate variation of diffusion coefficient with concentration remained after the correction. The problem of diffusion can be formulated in another way than that used by Birchenall and Mehl. The method is that of chemical rate theory and has been used by Eyring and his coworkers8,9 as well as by Eyring and Zwolinskilo in a discussion to Birchenall and Mehl's paper. As yet the method has not been applied to substitu-tional solid solutions. On the basis of their assumptions, Eyring and Zwolinski derived a relation between the diffusion coefficient and activity that is identical with that of Dehlinger and Darken but which does not correct for the variation of the diffusion coefficient with concentration as well as does the relation derived by Birchenall and Mehl. It was thought that the theory of diffusion would be more complete if the inconsistency between the two analyses could be rationalized and if diffusion in substitu-tional alloys were analyzed on the basis of the concepts of the chemical rate theory. Chemical Rate Theory According to the theory of absolute reaction ratess the reaction +..... +X, Eq I is viewed as taking place in two steps. First the reactants A1, A², . . . A; combine to form an activated complex M with which they are in equilibrium: A1 + A1+ . . . + A=M. Eq 2 Second the activated complex decomposes to give the products XI, XZ, . . . Xi: M?X, + X²+ . . . +Xi Eq g It has been showns that the number of activated complexes decomposing per unit volume per unit time is given by the expressiont kT -h CM † The transmission coefficient has been taken as unity.

Jan 1, 1949

By J. C. Swartz

Measurements of the effect of precipitation stresses on the solubility of cementite (Fe3C) precipitates in a iron are reported. Solubilities were determined from measurements of the Snoek relaxation due to interstitial carbon after quenching from various equilibrium treatments. Stress-free precipitates were obtained by a spheroidizing treatment of vacuum-melted Fe 0.06 wt pet C. Subsequent equilibration treatments were designed to suppress nucleation of other precipitates. The results for stress-free cementite give a heat of solution of 14.8 i 0.2 keal per mole and an entropy change of 1.1 i 0.2 eu in the temperature range 400" to 715°C. Comparison with previous data indicates that the heat of solution increases about 6 keal per mole as temperature increases from 700" to 1000°C. Data on self-stressed cementite in quench-aged specimens of Fe 0.013 wt pet C indicate 1) an apparent heat of solution of 12.1 i 0.4 keal per mole in the range 280" to 690°C, 2) a strain energy of- 1.1 keal per mole Fe3C accompanying precipitation at 280°C, and 3') a gradual decrease in the strain energy of precipitation with increasing equilibration temperature. In com-parison with 2 and 3 the strain energy calculated for an isotropic model is 1.7 keal per mole Fe3C. The lower values obtained from the experiment indicated substantial stress velaxation by dislocation motion. WHEN a supersaturated solution of carbon in a iron is aged at temperatures in the range 200o to 700oC, the carbon clusters by interstitial diffusion and forms cementite (Fe3C) precipitate particles. Unstressed cementite has a volume per iron atom 9 pet higher than that of a iron;' hence, cementite precipitate particles are usually under pressure from the iron matrix. The pressure would tend to increase the solubility of cementite in iron.' This report describes anelastic measurements of the solubilities of self-stressed and stress-free cementite in a iron. Previous determinations of the cementite solubility are summarized in Table I. The method of cementite formation for each reference was studied to ascertain the state of stress of the cementite. The results judged to be for stress-free and stressed cementite are distinguished in the table. In the next section an estimate of the stress effect is obtained which is clearly too small to account for the large difference between the previous results in parts A and B of the table. THEORETICAL Let AGO be the standard free-energy change of the reaction Fe3C (eem.) = 3Fe (a) + C (in a) [1] in the absence of stresses. Since cementite precipitates appear to be rather pure10 and the carbon is so dilute in the iron,8 the cementite and iron of Eq. [ I] for the stress-free case have essentially unit activities and the activity of carbon equals its atom fraction xoC Then the stress-free equilibrium is expressed by RT In XoC = -?GO 121 To first approximation the change in the chemical potential of carbon due to the precipitation stresses equals the elastic strain energy W accompanying precipitation of a mole of cementite.2 Hence, in the presence of the precipitation stresses the equilibrium is described by RT In x sq = -?G° + W [3] where xsC is the mole fraction of dissolved carbon in the stressed case. An approximate value of W can be obtained from analysis of the inclusion problem in elasticity theory. The inclusion is a small portion of the matrix phase which has suffered a transformation while still imbedded in the matrix. In the absence of the constraint of the matrix the transformation would be equivalent to a uniform dilational strain eT. Both the matrix (a) phase and inclusion (0) phase are assumed to be homogeneous, isotropic materials. When the a and 0 phases have the same elastic moduli, which is approximately true for iron and cementite,11 the total strain energy per mole ß is12 2µVß(eT)2(3 +4 µx)-I [4]

Jan 1, 1968

By Joseph Hyde Pratt, Douglas B. Sterrett, CHAPEL HILL

I. DESCRIPTION. MONAZITE is one of the minerals which, for a long time, was considered rather rare in its occurrence, but, upon a commercial demand arising for it, prospectors and engineers soon located large deposits of it in the Carolinas and Brazil, and the supply has always been able to meet the demand. During 1908 further sources of supply of monazite have been discovered and developed in Idaho. North and South Carolina, however, are the only States that have thus far put any monazite on the market. Monazite is essentially an anhydrous phosphate of the rare-earth metals, cerium, lanthanum, and didymium (Ce, La, Di)PO;. There is nearly always present a varying but small percentage of thoria, ThO2, and silicic acid, SiO, which are very probably united in the form of a thorium silicate, ThSiO4 Some monazites contain but a fraction of a per cent. of thoria, while others have been recorded that showed the presence of from 18 to 32 per cent. ; but the majority contain from 3 to 9 per cent. of this oxide. It is the presence of the thorium oxide that gives the monazite its commercial value. The analysis occasionally shows also the presence of other constituents, as the yttrium and erbium oxides, zirconia, alumina, magnesia, lime, iron oxides, manganese oxide, and titanium oxide. Monazite is light-yellow, honey-yellow, reddish-, brownish-, or greenish-yellow in color, with a resinous to vitreous luster, and is translucent to subtransparent. It is brittle, with a conchoidal to uneven fracture, and is from 5 to 5.5 in hardness, and from 4.64 to 5.3 in specific gravity. It crystallizes in the monoclinic system, and some crystals have been observed that were 6 in. in length. The more perfect crystals are, however,

Jun 1, 1909

By R. G. Jones, W. L. Kinney, R. E. Schilson, R. S. Wilson, G. A. Clark, H. Suralo

This paper discusses the results of the Fry conventional or cocurrent in situ combustion test, which was conduct-ed in a 3.3-acre inverted five-spot. The depth of the formation was between 880 and 936 ft; the oil had a specific gravity of 28.6° APl and a viscosity of about 40 cp at the reservoir temperature of 65°F. Preceding the combustion test, air injection tests were conducted which, in conjunction with geological studies, were used to evaluate the characteristics of the reservoir. Combustion was initiated on Oct. 13, 1961, with ignition being accomplished by a 40 kw electrical heater. The test phase of the project ended on Oct. 1, 1963. During the test, the average air injection rate was 1,520.-000 scf/D. Throughout the test, production of all fluids— gas, oil, and water—was monitored. Cumulative oil production credited to the project was 100,586 bbl. The cumulative air-oil ratio was 11,500 scf/bbl oil, and the oxygen uti1ization efficiency was 87 per cent. INTRODUCTION The Marathon Oil Co. conducted a successful in situ combustion test, beginning Aug. 22, 1961, at the Fry unit, Crawford County, 111. The purpose of the project was to test the feasibility of cocurrent in situ combustion as a means of oil recovery in the Fry type reservoir. Interest in in situ combulstion as an oil recovery tool has been stimulated mostly by the existence of large reserves of heavy viscous crudes with low expected recovery, usually less than 10 per cent. These are the so-called unrecoverable reserves, and most combustion tests to date have been conducted in this type of reservoir.1-4 In contrast, the Fry combustion test was conducted in a reservoir with a relatively high gravity oil having a relatively low viscosity. This paper discusses the performance of the test. The geology of the reservoir and the field operations are discussed in separate papers.5 TEST SITE The Fry combustion test was carried out in a 3.3-acre inverted five-spot portion of a lenticular body of Robinson sandstone. Net sand was 50 ft thick, porosity averaged 19.7 per cent, oil saturation was 68 per cent of pore volume, and water saturation was 20 per cent of pore volume. The oil in place was estimated at 1,040 bbl/acre-foot, or 171,600 bbl within the 3.3-acre pattern. The water in place was 326 bbl/acre-foot, or 53,800 bbl. The oil has a specific gravity of 28.7° API and a viscosity of 40 cp at the reservoir temperature of 65°F. AIR INJECTION PERFORMANCE Air injection took place in two phases, the phases separated by ignition of the reservoir. In the pre-ignition phase, air injection tests were conducted in the summers of 1960 and 1961. These indicated that the Fry reservoir was confined, and a high return rate of injected air could be expected. This proved to be an outstanding characteristic of the project, as cumulative gas production was 95.3 per cent of the air injected. The difference between the cumulative air injected and the total gas produced can be largely accounted for by the quantity of air stored in the reservoir. An estimated 16 X 10 cf of air remained in the burned-out portion of the reservoir and an indeterminate amount of gas was stored in the unburned but pressurized reservoir. Hence, a complete material balance of gases would account for nearly 100 per cent of the air injected. At times during the test, the daily gas production rate was 98 per cent of the daily air injection rate. Fig. 1 presents the air injection history of the Fry com-

Jan 1, 1966

The Library of the above-named Societies is open from 9 A.M. to 10 P.M. on all week-days, except holidays, from September 1 to June 30, and from 9 A.M. to 6 P.M. during July and August. The-Library contains about 55,000 volumes, including sets of technical periodicals and the publications of scientific and technical societies. Members of the Institute, with few exceptions, are forced to spend .a portion of their time in localities isolated from sources of information. To these the Library can render valuable service through correspondence; letters requesting information will receive special attention. The Library is prepared to furnish references and copies of articles on mining and metallurgical subjects; to determine the existence of mining maps, and to furnish general information as to the geology and mineral resources of all countries. All communications should be made as definite as possible so that the information received may be what is desired and not include collateral matter which may not be of interest. The time spent in searching for such collateral matter will be saved, and the information will be sent more promptly and in more usable shape. The members of the Institute can be of service to the Library by forwarding copies of mining reports maps privately issued, and similar material, which will he classified, indexed, and made available to other members. Suggestions for additions to the Library, either by purchase or personal solicitation as gifts, will be welcomed. It is hoped that members while in the city will use the Library freely, and. assurance is given that most careful service will be rendered to them.

Jan 6, 1915

By F. B. Plummer

THE physical properties of oil-producing sands, such as grain size, porosity, and permeability, are becoming more and more important in petroleum production engineering as oil fields are being repressured and rejuvenated. A number of excellent papers have been published recently on all three of these properties. Faucher, Lewis and Barnes1 give a com-plete survey of the work done through 1932 and contribute also much information on sands that they themselves have examined. Muskat and Botset,2 Wykoff, Botset, Muskat and Reed,3 Hurst,4 and Muskat5 have contributed a great deal to the theory and actual measurement of flow of liquids and gases through porous media. Muskat and Botset have measured the permeabilities of different sands with gases and liquids. They find that the radial is always slightly under the linear permeability. However, in most of the previous experiments small samples of the sand were used, and the method of production of fluid or gas through the sands has not been very close to actual oil-field conditions. In addition, so far as the authors are aware, no measurements of linear and radial permeabilities have been made simultaneously under exactly the same conditions. The multiple permeability apparatus described here is a part of the equipment being acquired by this laboratory for thorough investigation of the physical properties of producing sands. It possesses certain advantages for comparative studies of liquid flow. Additional data and descriptions of other instruments will follow in papers to be written later on. The essential features of the permeability apparatus are as follows:

Jan 1, 1934

By M. S. Seltzer

High temperature steady-state creep rates have been determined jor lead sulfide single crystals whose defect concentrations were fixed by equilibration under controlled sulfur pressure. The activation energy of creep, Qc , for undoped lead sulfide, is a function 01 composilion, decreasing from 2.9 to 2.2 ev as the carrier concentration increases from 9 x 1016 to 8 1018 electrons cm-3 for lead excess crystals, and increasing from 1.7 to 2.3 ev as the concentration of holes increases from 4 x 1017 to 1 x 1018 cm-3 in sulfur excess material. For five different composilions, Qc for undoped and bismuth-doped crystals has been found to be equal to Qpb + Qs, the self-diffusion activation energies for lead and sulfur in PbS. It is well-established1 that high-temperature steady-state creep of pure metals is a diffusion-controlled process, where the activation energy of creep is equal, within experimental error, to the activation energy of self-diffusion. The relationship between the activation energy for steady-state creep and those for self-diffusion in binary compounds is more complicated, however, because two different diffusing species must be considered, and becayse the activation energies may be influenced by compositional variations and by foreign atom additions.2-4 In some cases experimentally determined creep activation energies are correlated with those for self-diffusion of the slower-moving species, but such agreement is by no means universal. Interpretation of experimental results is difficult because few investigations include measurements of creep rates and self-diffusion coefficients of both diffusing species on single crystals of similar composition and foreign atom concentration. The objective of this investigation, therefore, is to determine the influence of stoichiometric defects and foreign atoms on steady-state creep and self-diffusion for a well-characterized binary compound. Lead sulfide, a compound semiconductor which crystallizes in the NaC1-type structure, and whose homogeneity range includes compositions on either side of the 1:l atom ratio, was chosen for study in this investigation. The pressure-temperature-composition relations for PbS are available,5,3 and deviations from stoichiometry may be monitored by electrical measurements.7 Single-crystal specimens are available to allow observation of effects due to bulk phenomena without interference from grain-boundary effects. These crystals have been employed to determine steady-state creep rates under compressive stress for "pure" and bismuth-doped PbS as a function of sulfur pressure and temperature as well as crystal orientation and applied stress in order to establish the relationships between defect concentrations and creep rates. EXPERIMENTAL PROCEDURES Crystal Growth. Lead sulfide crystals, prepared by the Bridgman method, are grown in evacuated quartz crucibles, filled with almost equal atomic proportions of high-purity (99.999 pct) lead and sulfur, and heated to a temperature above the melting point of PbS (about 1127°C) so that the lead and sulfur react to form molten PbS. The crucible and melt are dropped through the hot zone of the crystal-growing furnace at the rate of 1 cm per hr. The maximum melting point of PbS is slightly on the lead-rich side of the 50:50 composition; hence crystals grown from a near stoichiometric melt are usually n-type semiconductors containing excess lead atoms. Typically the lead excess concentration in solid solution with the PbS is 3 x 1018 atoms cm-3. Crystals containing either 1/20 or 1/2 mole pct Bi2S3 were prepared by addition of the foreign atoms prior to crystal synthesis. Preparation of Specimens of Controlled Stoichiom-etry. Since it is difficult to grow crystals of desired composition, the process of crystal growth and control of stoichiometry are separated into two distinct operations. Equilibration of as-grown PbS to a desired composition is most easily accomplished by first annealing the n-type crystals under high sulfur pressure (about 1 atm) at temperatures above 700°C. This process serves to put excess lead precipitates into solution, yielding 0 -type crystals upon quenching to room temperature. Inter diffusion occurs readily in crystals so treated, and the methods described by Bloem may then be employed to obtain crystals of controlled stoi-chiometry. For the creep measurements made in this study, this involves heating crystals in mixtures of H2 and H2S The equilibrium constant for H2S is given by: Thus the sulfur partial pressure is obtained from knowledge of the H2/H2S ratio and Kh2S for the temperature in question. Fig. 1 shows the p-T-x diagram for PbS. It can be seen that, within the stability limits for single-phase lead sulfide, desired compositions may be obtained by equilibrating under a specified sulfur pressure and temperature. Characterization of Crystals. The principal methods for evaluating PbS crystals include measurement of electrical properties and mass-spectrographic analysis. The measured electrical parameters include Hall coefficient, conductivity type, and electrical resistivity Bloem7 has shown that there is a 1:l relation between the defect concentration and carrier concentration obtained. Hence, if the contribution to the carrier con-

Jan 1, 1968

By Arnulf Muan, R. E. Johnson

Equilibrium CO2 /CO ratios of a gas phase coexisting with selected oxide phase assemblages of the system CaO-"Fe0"-SiOz and vnetallic iron have been determined at 1080°C. The data obtained are used to calculate activity-conzposition relations for metasili-cute, orthosilicate, and CaO- "FeO" solid solutions, and to determine a new value for the free energy of formation of C&S&0,. The metasilicate solution is practically ideal, whereas large deviations from ideality exist in the othe,r two solid solutions. BECAUSE of the geochemical and metallurgical importance of the oxides CaO, "FeO", and SiOz, the system CaO-"FeO"-SiO2 has been the subject of several experimental studies during the past 30 years. Following the delineation of phase relations at liquidus temperatures by a group of investigators at the Geophysical Laboratory of the Carnegie Institution of Washington in 1933,1 Chipman and associates in the early forties2,3 determined activities of FeO in liquids of this system. Since that time, many attempts have been made to interpret the data of Chipman et al. in terms of the constitution of the silicate liquids and the interaction parameters among the various constituents of the system (see for instance papers by Richardson4 and by Flood and coworkers5). One of the assumptions made in some of these interpretations4 is that the binary silicate systems CaSiO3-FeSiO3 and CazSi04-Fe2SiO4 mix ideally in the solid state. The objective of the present study is to provide experimental data on activity-com position relations in solid solutions of the system CaO-"FeO"-SiO2. Such data will contribute toward an understanding of the thermodynamics of silicate solid-solution phases in general, and will serve specifically to confirm or refute some of the assumptions made in interpreting liquid slag behavior. PREVIOUS WORK Phase relations in the system CaO-"FeO"-SiO2 in contact with metallic iron were determined by Bowen, Schairer, and Posnjak,1 and additional phase-equilibrium data for this system have been presented by Allen and snow.' A reproduction of the most up-to-date phase diagram for this system is shown in Fig. 1.7'8 Of particular interest in the present investigation are the relations among the various crystalline phases slightly below the lowest solidus temperature in the system, as shown in Fig. 2. The present work will be concerned primarily with some of the composition

Jan 1, 1968