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By Lawrence H. Van Vlack

The energy of the y-iron grain boundary was determined to be 850 ergs per cm2 at 1105°C. The a/a and the a/y boundaries possess somewhat less energy. The microstructures of several iron alloys are discussed in terms of the interfacial energy relationships. THE dependence of the shape of liquid interfaces upon their energies has been studied for some time.1"3 Recently, Smith' concluded that many of the microstructures observed in metals may be attributed to the energies of the interfaces between the grains and phases. While the energies of liquid surfaces have been measured by numerous different methods: only two attempts have been made to determine experimentally the energy of surfaces involving crystalline solids. Udin, Shaler, and Wulff8 used a procedure introduced by Berggren7 to measure the surface tension of solid copper. It consisted of determining the load required on a thin copper wire so that the surface tension was counteracted, and no net strain resulted. Bailey and Watkins8 sed a different technique and were able to determine both the surface tension of copper and the tension of the copper grain boundary. They measured the contact angle which liquid lead makes against a copper surface. They then calculated the above energies from the surface energy of liquid lead by using the Pb vs. Cu/CuY dihedral angle and the surface groove angle formed during thermal etching. They obtained a value of 1800 dynes per cm for the surface tension of clean copper and approximately 640 dynes per cm for the tension of copper grain boundaries. The former value was somewhat higher than Udin's value of 1500 dynes per cm. This paper includes a determination of the energy of the y-iron grain boundary. In addition, the micro-structural relationships of several other metallic and nonmetallic phases with iron were examined and an attempt was made to interpret the observed structures in terms of interfacial energy relationships. Theoretical Considerations In a three-phase material containing a solid and two liquids, there may be two solid/liquid interfaces, one liquid/liquid interface and one inter- granular interface. Liquid/liquid interfacial energies can be measured directly. Therefore, by determining the energy of such an interface and by measuring the required interfacial angles: the energies of the interfaces involving solids may be obtained.10 They may be shown schematically as in Fig. 1. The above procedure requires the following assumptions: 1—The interfacial energies are, in general, unaffected by boundary orientation, and 2— the shapes of the interfaces are unaltered between annealing and sectioning for microscopic examination. The first assumption is good to a first approximation as shown by Dunn and Lionetti11 except for a few critically orientated boundaries. Two conditions may alter the shape of a boundary upon cooling: 1—Precipitation of dissolved material upon one side of the interface, and 2—a change in volume during the transition from one phase modification to another. The former must be detected by microscopic observation. The latter may become appreciable in systems containing an interface between two liquids which solidify after annealing. However, possible movement of the two-liquid interface may be checked in the system diagrammed in Fig. 1 by measuring 8, for example, and comparing it with its value as calculated from the other interfacial angles by: tan8, C11 05 COS- o- + cos 8, cos- The choice of a suitable pair of liquids is limited by several factors. The relative values of the several

Jan 1, 1952

By A. L. Bailey, B. A. Landry

All who are even generally aware of the tremendous rate of increase in coal washing operations must realize the growing importance of the float-and-sink test. I believe it is conservative to estimate that, in the past decade, the dollar volume of float-and-sink testing has increased tenfold. It is a simple matter of economy, then, to examine the factors that determine the cost of adequate float-and-sink testing. When the Coal Preparation Section of the Bureau of Mines entered upon a greatly expanded program of such work in connection with the synthetic liquid fuels investigations, it seemed advisable to examine these factors experimentally. The principal consideration that differentiates float-and-sink test sampling from general purpose sampling, is that the original particle size must be preserved. Therefore, the total cost of the test will be directly affected by any standard that might be proposed to limit sample bulk reduction at any given particle size. For this reason, the relationship of sample size to variability of results was the first factor to be studied experimentally. Of course, the matter is rendered complex by the circumstance that the float-and-sink test, not a simple analytical measurement but a process test, comprehends a number of more-or-less independent items of fundamental data; and as shown in the report, the' variability of the samples differs with respect to these different items. This condition and the wide variety of situations in which float-and-sink test data are used, in combination with other factors, to study complex process operations, indicate the difficulty of setting up fixed standards for float-and-sink sampling and testing. At this stage at least, it is the intent rather to obtain experimental data on the principal Factors involved so that the reader may arrive more intelligently at a procedure adapted to his problem. The authors of this paper have presented experimental data showing the relationship between size of sample and particle size for different variability tolerances with respect to percentage of sink. In further studies, data are being collected to appraise also the variability of the samples with respect to float-ash content and size consist. The scope of this work will be broadened to cover particle sizes up to 4 in., and a third series of tests has yielded similar data for a much cleaner type of raw coal. Thus, the further studies will make available a fairly comprehensive meas- ure of variability with respect to size consist, percentage of sink, percentage of middlings, and percentage of ash in the float, for three coals ranging from 3.87 to 17.68 pct in refuse content (heavy sink material) and from 4.18 to 17.52 pct in middlings. Introduction At present there are no published standards for float-and-sink test sampling. During the rapid expansion of float-and-sink test work, varying procedures have been based on adaptations of the ASTM standards for sampling coal for analyses. For this reason, a special study of gross sample reduction has been undertaken to determine the limits for this step in the operation where no reduction in particle size is to be made before testing. Float-and-sink tests are made whenever a thorough study of coal characteristics is desired. The tests may be made on samples from coal-cleaning units such as jigs or tables, or coal samples may be tested which are taken from a loading boom, railroad car, or the coal seam itself. The resultant gross sample may be large and pose a problem of sample reduction. The question is, then, how much can the sample be reduced and still fall within preassigned limits of accuracy of the original gross sample of coal? Coal from channel samples may be crushed to liberate impurities and then separated into various gravity fractions from which washability curves are drawn; from these curves, it is possible to determine the cleaning characteristics of the coal. However, coal samples from coal-cleaning units cannot be

Jan 1, 1950

By E. H. Rennhack, J. F. Libsch

Definite transition behavior was found in unalloyed titanium at 0.13 pct 0 equivalent. The addition of 0.5 Sn, 1.0 Al, 0.5 Al, and 1.0 Sn lowers the tvansition temperature of titanium at oxygen equivalents exceeding 0.22, 0.29, 0.40, and 0.51, respectively. Metallographic evidence indicates that progressive amounts of oxygen restrict deformation at low temperatures resulting eventually in brittle fracture. The presence of tin or aluminum is thought to alter the atomic distribution of oxygen within the titanium lattice in such a manner as to facilitate some degree of slip and twinning. 1 ITANIUM-like iron and zinc experiences a transition from ductile to brittle fracture with decreasing temperature. The presence of sufficient quantities of the interstitial elements, carbon, oxygen, and nitrogen in solid solution, has been shown to progressively lower the room-temperature impact resistance of titanium with increasing interstitial content.1"1 Ogden,et al,2 reported finding no transition from ductile to brittle fracture with decreasing temperature in iodide titanium. However, a definite transition was found to occur at 0.36 pct 0 equivalent in an alloy containing 0.47 pct carbon in solid solution. The oxygen equivalent in this case was obtained by assuming the effects of carbon, oxygen, and nitrogen in combination on the impact properties of titanium to be additive on the same basis as their separate effects on tensile strength, namely: Oe = 2/3 (pct C) + pet 0 + 2 (pet N) They concluded that the tendency toward transition behavior is dependent on the total interstitial content in solid solution and not on any one particular interstitial element. Rennhack,4 however, recently found transition behavior in iodide titanium at an oxygen equivalent of 0.17 pct. Ogden, etal3, reported that the strengthening effects of carbon, oxygen, and nitrogen in titanium decrease with the addition of tin. They showed that tin additions increase the tolerance of titanium for the interstitials, that is, 10 pct Sn permitted individual additions of up to 0.4 wt pct of the interstitial elements without any significant loss in ductility. Aluminum tends to decrease ductility and impact strength of titanium for a given interstitial ~ontent.3 Van Thyne and Kessler5 found that the solid solubility of carbon in titanium doubled in the presence of 10 pct Al. The precise effects of tin and aluminum in the nrespncp of rorvfen nn the impact properties of titanium had previously not been determined. The high oxygen tolerance of titanium containing tin may provide a suitable means for improving the impact properties of titanium containing the interstitial elements, particularly oxygen. Unlike tin, however, aluminum has a high affinity for oxygen and will reduce rutile titanium dioxide (TiO2)by a thermit-type reaction.6 Thus, the atomic distribution of oxygen in titanium might be different in the presence of aluminum. The present work was undertaken to: 1) Determine the effect of oxygen on the transition behavior of unalloyed iodide titanium. 2) Determine the effect of small amounts of tin and aluminum on the transition behavior of iodide titanium in the presence of oxygen and other interstitial~. EXPERIMENTAL Three different lots of iodide titanium were employed to prepare the alloys studied in the present work. Their chemical composition is presented in Table I. The compositions of the tin and aluminum used for alloying are shown in Table 11. Oxygen additions were made using calcined rutile titanium dioxide (TiO2)of 99.7 pct purity. Alloy Preparation—Four titanium-base alloys containing separate additions of 0.5 and 1.0 pct each

Jan 1, 1960

By Sidney G. Parker, Jack E. Pinnell

Cubic ZnSe crystals have been grown with HCl, HBr, and I, as chemical transport reagents. The growth of large, well faceted crystals is in the order HCl < HBr < I, with some produced by I, transport being 1 cm on an edge. ZnSe:I crystals showed no strain in cross polarized light and were homogeneous as determined by electron microprobe. These ZnSe:I crystals had a mobility at 25°C of about 300 sq cm per v-sec and contained 103 dislocations per sq cm; further, these crystals were pure cubic and showed both photolumi-nescence and photo conductance. Doping was attempted during crystal growth. ZnS and Zn (S,Se) crystals were also grown by I, transport. ZnSe crystals have been grown by most of the common techniques.1"6 Of these, chemical vapor transport as developed by Kaldis2 showed promise of producing high perfection, cubic ZnSe. With chemical transport, crystals can be grown far below the transition temperature for conversion of cubic to hexagonal structure. A small temperature gradient between source and growth region tends to allow near equilibrium growth, which should lead to good crystalline perfection. Because it is necessary to form volatile compounds, halogens or their compounds are extensively used as transport agents. HCl, HBr, and I, were compared as transport agents for growth of ZnSe crystals. Doping during crystal growth was attempted. ZnS and ZnSxSe1-x crystals were also grown by chemical transport. Electrical and optical properties of the crystals were examined. EXPERIMENTAL Fig. 1 is a sketch of the growth apparatus, which was a modification of Kaldis&apos;. A quartz rod which butted against the seed crystal served as a heat sink to promote growth only on the seed. Initially, crystal growth was attempted with ZnSe prepared by wet chemical methods. Because such a material contained oxides and selenates, HC1 reacted with these oxygen compounds to form H2O and no ZnSe transport occurred. Further, this ZnSe contained about 10 ppm Cu plus other impurities. High purity ZnSe, containing small amounts or no oxygen compounds, was prepared by reaction of H2Se with zinc vapors at 600° to 800°C in an atmosphere of palladium diffused H2.7 The ZnSe thus produced was usually copper free and contained only 1 ppm by weight of magnesium as determined by emission spectrographic analysis. G.E.&apos;s electronic grade ZnS, which had about 10 ppm metallic impurities, was used without further treatment. ZnS-ZnSe charges were prepared by mixing the two compounds together, then sintering 24 hr at 1100°C in an H2S ambient. The gases, HBr and HC1, were commercial grade, of 99.9 pct purity, while the I2 was 99.999 pct pure. The single crystal seeds with (111) faces for growth were mechanically held in place by sealing the outer quartz tube to the growth tube. After the charge was introduced, the system was outgassed at l0-5 torr while heated to 500°C. The desired quantities of transport reagents were then sealed off in the system, which had been cooled to 25°C. The growth tubes were inserted into a furnace with the desired temperature and thermal gradient. The system was allowed to cool for 1 to 12 hr from growth temperatures of about 850" to 25°C. The tubes remained stationary during crystal growth. HCl CHEMICAL TRANSPORT GROWTH Preliminary runs with HC1 had a temperature gradient of 100° to 200°C and no seed or heat sink. Only small crystals were obtained in these experiments as

Jan 1, 1970

By Edward A. Capillon

The problem of scrap is probably of greater importance in the pro duction of gold, silver and other precious metal alloys than is the case for base metals and alloys. Remelting of gold and silver scrap in the shop is always a costly process because it involves losses by oxidation of thc base metals in the alloy with a consequent increase in the percentage of precious metal. This is most marked in the case of alloys containing the low-boiling and easily oxidized metals zinc and cadmium. Since it is not generally feasible to assay every shop remelt it follows that the possibilities of lost values arc large. So-called rolled gold and silver plate is made by soldering or welding the precious metal alloys onto base metal. Such plate when defective must be sent to the refinery to recover the gold and silver values, thereby involving additional expense in the form of refining charges. It is obvious therefore that gold and silver alloy scrap is an important item in manufacturing cost and must be reduced to a minimum. The amount of scrap resulting from poor metal will depend on a number of factors in the manufacturing operations, not least among which is the melting and casting practice. The notes which follow are a summary of experiments performed at various times to determine what variables in melting and casting are influential in the production of sound alloys. Metals Used in Alloying Pure gold, that is, gold of 24-kt. value is very much too soft for jewelry purposes and it is therefore always alloyed with other metals to increase its hardness and resistance to wear. For the same reason pure silver is seldom used alone but is alloyed with copper, the standard alloy being sterling silver which contains 92.5 per cent. silver and 7.5 per cent. copper. The metals commonly used for alloying gold are silver, coppcr, nickel and zinc. In addition to hardening the gold and producing alloys of different karat values the use of these metals makes possible the production of gold alloys of various colors such as yellow, red, green and white. The gold-silver-copper alloys vary in color from light greenish-white through green, yellow and red depending on the relative amounts of the three metals. Green or yellowish-green colored golds

Jan 1, 1930

By Kendall E. Born

Production of crude oil in Tennessee during 5945 was slightly more than 6000 bbl., the lowest figure since 1916. Approximately 5500 bbl. was produced from the "Mississippi lime" in Scott and Morgan Counties. The remainder was from two wells each in Clay and Fentress Counties. Thirty million cubic feet of gas was marketed off the lease in Morgan County and about 10 million cubic feet was produced in the Jamestown field in Fentress County. The production of oil by counties is shown in Table 1.

Jan 1, 1946

By M. C. Leverett, M. E. True, W. B. Lewis

This paper states the theory underlying the design of two kinds of dimensionally scaled models of parts of idealized oil fields. One of these simulates an oil well and its surrounding sand for a distance of 16 ft. radially from the well. The other model simulates linear flow through layered sands. Construction and operation of the models are described and typical data are given. The unique features in the design of the models are: (I) the treatment of the permeability-viscosity quotient as a single variable and (2) the use of previously reported experimentally developed relations between relative permeability and saturation and capillary pressure, saturation, porosity, permeability and interfacial tension. The models at present simulate flow of oil and water only, through unconsolidated sands. They are superior to unscaled models, which may give rise to erroneous conclusions. The models are designed to study the desirability of various methods of well completion and the effects of various factors on recovery of oil from layered sands. Introduction Recent work on the fundamental behavior of flowing mixtures of fluids in sands has resulted in the development of some new theory in this field, much of which has been presented in previous papers.l-4 However, the application of this theory to the behavior of oil wells or oil fields has proved too complicated for ordinary mathematical techniques, except in very highly simplified cases. A practical solution to this problem appears therefore, to lie in the use of dimensionally scaled models of elements of oil fields. The object of this paper is, first, to present the theoretical and experimental basis of the design of such models, and, second, to describe their construction and operation. Experiments now under way on the models already built will yield material for other reports, which will be devoted to interpretation of the results in terms of oil-field behavior. So far, simple dimensional models of two kinds have been built and are being operated. These models represent different parts of an idealized oil field but obey the same underlying theory. The only fluids represented are oil and water, since certain questionable approximations are necessary for gas-liquid systems. General Theory Dimensional models have been used in other fields for a long time, and their theory is adequately given in the literature. 5 Here, it suffices to state that each physical element entering into a dynamic relation may be given a definite description in terms of three fundamental, but arbitrarily chosen, dimensions. These usually are mass, length, and time, symbolized here by the small letters m, I, and t. Two systems are said to be dimensionally similar or dimensionally scaled if for each element in one system there is a corresponding element in the second system and the ratios of the numerical magnitudes of corresponding elements are constant for all elements of the same dimensional type.

Jan 1, 1942

By H. G. Doll

A new electrical logging method called Laterolog is described which provides for better recording of formation resistivity. In this method a current, preferably of constant intensity, is forced into the formation perpendicularly to the wall of the hole as a sheet of predetermined thickness by means of a special electrode arrangement and of an autonlatic control system. The essential advantages of the Laterolog over the regular resistivity logs are explained. With the Laterolog, the mud column has much less influence than with conventional methods. The Laterolog is, therefore. particularly useful in wells drilled with highly conductive mud. Moreover. when the electrode system is located opposite a bed of moderate or small thickness, the disturbing effect of the adjacent formations becomes practically eliminated, provided the bed is thicker than the sheet of current. which itself is usually a few inches to a few feet thick. The sequences of beds are. therefore, much more sharply differentiated, and, in many cases, it is possible to read directly from the logs values close to the true resistivities of the formations without further corrections. Field examples are shown to illustrate the results of the method in various types of formations. INTRODUCTION As soon as it was introduced into the petroleum industry, electrical logging roved to be a powerful instrument for the delineation of the strata traversed by bore holes and for correlation of such strata." Research and engineering efforts were mostly devoted at this early time to the design of the techniqurs which could provide the best data for these purpoes. Later, attention was directed toward the quantitative analy5i.s of electrical logs, in order to obtain information on. reservoir characteristics, and, in particular, on oil and water saturation.3,4 Efforts have been made, accordingly, with a view to improving the already existing methods, or to finding new methods which could satisfy these new requirements." Quantitative analysis implies a determination as accurate as possible of the true resistivity of the formations. In fact, however; the "apparent resistivity" recorded in front of a given bed by a conventional electrical logging method is frequently quite different from the true resistivity of this bed. This is due to the combined influence of the mud column, of the adjacent formations both above and below the bed, and of the invaded zone, in which the original fluid has been more or less replaced by mud filtrate. When the beds are thick enough, and, as is frequently the case in sand and shale formations, when their resistivity is not much greater than that of the mud, it is generally possible to obtain their true resistivity directly on the electric log, or at least to obtain an approximate value which can be corrected without undue difficulty by means of recently published charts known as "departure curves."" When the beds are thin, and particularly when, in addition. their resistivity is substantially greater than that of the mud column, the apparent resistivities recorded on conventional logs are seriously affected, and it is generally very difficult, if at all possible, to estimate their true resistivity with a good enough accuracy. In the most severe cases, such as are encountered in holes drilled through hard formations with muds of high salinity, the conventional logs are so distorted and rounded that they do not even show clearly the houndaries of the different beds. In order to overcome the effect of the mud column and of the adjacent formations, it is possible to make use of appro. priate systems whereby the measurements involve a comp3ratjvelv thin slice of space at the level of the measuring device. A mention is due, in this respect, to a measuring system. called the "guarded electrode;" invented by C. Schlumberger over 20 years ago. The system, schematically represented in

Jan 1, 1951

By H. H. Kaveler

A summary of the reservoir engineering and related geologic data on the Schuler field, Union County, Arkansas, is presented here in a manner intended to interest both technical and nontechnical readers. The Cotton Valley formation and the Reynolds oolite are oil-productive formations in the Schuler field, but the Jones sand pool, at a depth of 7500 ft., developed with 146 wells on zo-acre spacing, is the reservoir of principal interest. The Jones sand sandstone reservoir is an anticlinal trap typically gas-drive or depletion type in performance. The core analyses from 88 per cent of the wells drilled, together with drilling time and electric-log data, yield an accurate estimate of the "productive" sand thickness and its areal distribution over the pool. Accurate production statistics, monthly reservoir-pressure surveys, and bottom-hole sample analyses when correlated by the "material-balance equation" show unusually good agreement with that principle. Estimates of oil initially in place made by the material-balance method and the sand-volume method are in good agreement at 116 to rzo million barrels. The reservoir-pressure history of the pool reflects the reaction of a reservoir to production, proration and secondary-recovery practices. The cost of the extensive program of reservoir study in the Jones sand pool has been estimated, in order to emphasize the value derived from such an investment through better understanding of a reservoir&apos;s reaction to production practices. Unit operation of 140 of the 146 Jones sand wells made possible an effective unitized gas-injection pressure-maintenance program. Res-ervoir-pressure decline was arrested, natural flow was maintained, and pumping and lease equipment were conserved. An increased ultimate recovery of zo million barrels beyond the estimated 34 million barrels primary recovery is indicated at present. Extension of the Jones sand unit to include the undeveloped Cotton Valley formation will permit additional recovery of otherwise uneconomic reserves of oil through wells no longer required in the Jones sand operations. Introduction The Schuler field comprises approximately 4000 acres in and about sec. 18, T. 18 S., R. 17 W. in west central Union County, Arkansas. Three reservoirs are procluctive of oil and gas: the Cotton Valley formation, the Jones sand, and the Reynolds oolite section of the Smackover limestone. The Jones sand pool is the most important reservoir from an engineering viewpoint. It possesses the traditional and somewhat classic characteristics usually associated with an anticlinal trap. Development and operations have followed the dictates of advanced engineering practices. The pool has attracted attention because of the unusually detailed reservoir data obtained, its interesting production history, and the success of the unitized gas-injection pres-sure-maintenance operation now being carried out. The purpose of this paper is to present a summary of the engineering data relating to the field, with particular reference to the more interesting general applications of

Jan 1, 1944

By Herbert H. Uhlig

Although the mechanical properties of high-carbon manganese-iron alloys, particularly the Hadfield manganese steels, have been established, the literature discloses discrepancies in the reported properties for the low-carbon alloys. Hadfieldla summarized the existing data up to 1927, including the investigations of Guillet, Arnold, Strauss, Burgess and Aston, and reported his own values for alloys containing for the most part from 0.06 to 0.I5 per cent carbon. He noted: From these comparisons it wil! be seen that while there is a broad and general agreement as to the character of the alloys at the different manganese percentages, there are disparities in individual cases, especially as regards the degree of toughness or brittleness displayed by an alloy with certain percentages and with particular types of treatment. These differences are not always readily explainable.lb His data showed that alloys containing 4 to 10 per cent manganese water-quenched from Iooo°C. were brittle and hard with maximum brittleness at about 7 per cent. Slight improvement in ductility was obtained with compositions from 10 to 17 per cent manganese. Alloys containing up to 17 per cent manganese slowly cooled rather than quenched from 87o°C., he found, were slightly improved in ductility with significant improvement in alloys analyzing 4.1 and 4.8 per cent manganese. Recently Walters, Kramer and Loring2 reported mechanical properties for alloys made up from electrolytic manganese and ingot iron and containing from 0.02 to 0.04 per cent carbon. They showed that a tempering treatment at 54o°C. (Iooo°F.) for one hour significantly improved the ductility of compositions ranging from 6.7 to &apos; 20.7 per cent manganese. The differences of these compared with Hadfield&apos;s results they considered to originate in this tempering treatment plus the fact that Hadfield&apos;s alloys contained higher carbon and phosphorus (0.06 to 0.I5 per cent C; 0.06 to 0.07 per cent P compared with 0.02 to 0.04 per cent C, <o.ooI per cent P). In this paper it is shown that of the low-carbon alloys (0.02 to 0.03 per cent) containing from 3.3 to 21.5 per cent manganese moderately or rapidly quenched from IOOO°C. some are brittle or ductile, depending on presence or absence of hydrogen. Hydrogen is readily absorbed at high temperatures, and much of it is retained when the alloys are cooled to room temperature. The presence of hydrogen in the range of composition from 10 to 18 per cent manganese is a major factor in determining relative ductility. At 22 per cent manganese, and also at compositions below 10 per cent manganese, factors other than or in addition to hydrogen play a role. These are discussed. Also data are presented to show that hydrogen absorbed by the high-carbon alloys of Hadfield composition is without effect on their mechanical properties.

Jan 1, 1944

By A. C. Fieldner, Lester L. Hirst, Henry H. Storch

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By John C. Calhoun, R. C. Newman

A report is made of experimental work performed on the capillary retention of water within porous solid systems, the displacement being accomplished with air and various organic liquids. A portion of the experiments were designed to measure the lowering of vapor pressure of water within a porous solid with subsequent conversion of such vapor pressure data to capillary pressure values. The form of the capillary pressure curve at high capillary pressures has been elucidated from this data. Certain theoretical approaches are presented to indicate the correlation between work done by previous investigators. The present work is correlated also with theory. Surface area values are calculated for the various core systems studied. INTRODUCTION Leverettl in 1941 presented a paper which gave the essential concepts of capillary behavior in porous solids. His presentation included both theoretical and experimental aspects of the problem. He defined the term "capillary pressure" and applied it to an ideal porous system. His work included the definition of a dimensionless quantity which was a function of fluid saturation and which could be correlated with porosity and permeability for clean, unconsolidated sands. His experimental work was performed by the drainage of water from packed columns of unconsolidated sands. Subsequently, other authors have presented experimental techniques which permit the determination of capillary pressure data on small core samples. Data have been presented on porous systems other than unconsolidated sand and with the use of liquids other than water. Notable among these are the works of Hassler, Brunner and Deahl,2 Bruce and Welge,³ Amyx and Yuster, and Purcell. Others have indicated the applicability of such data to field problems without regard to the theoretical aspects of the capillary pressure saturation function. Within the recent published literature there have also been reported studies of the correlations between capillary pressure data and other fundamental properties of porous solids. It was the intent of the present reported work to investigate the behavior noted by water and various other liquids within porous systems in an attempt to amplify existing correlations between capillary properties, surface properties, and other fundamental characteristics of porous systems. The experimental work described here was performed as two different investigations but due to its nature it is reported as separate phases of the same general topic. CAPILLARY PRESSURE AND VAPOR PRESSURE LOWERING It has long been recognized that the vapor pressure above the curved surface of a liquid is a function of the curvature of the liquid surface." The capillary pressure is also a function of the curvature of the liquid surface. Both capillary pressure values and vapor pressure lowering are, therefore, functions of the liquid saturation of a porous solid. A quantitative relationship between the vapor pressure lowering and the capillary pressure can be simply developed by considering a porous solid system containing water in equilibrium with its vapor. The capillary pressure at any height within the system is defined as Pc= Pv -P1.......(1) where PI is the pressure in the vapor phase and PI is the pressure in the liquid phase. Consider that both the water and its vapor are continuous phases within the system and that at any point the two phases are in equilibrium. The gradients in the liquid and vapor columns within the porous system are: PI = plgdh dPv = pvgdh By integrating these gradients from the point where h = 0 to the height h, values of PI and PI at the point h are found. Let the point where h = 0 be that where Pc = 0. At this point also Pv is equal to Pve, the equilibrium vapor pressure of the liquid above a flat surface. From the first of these integrations since p is independent of height: P = p1gh + P, From the second, by substituting pv = PvM/RT, where M is the molecular RT weight: Pv M Pvo- RT gh By combining the two last equations to eliminate h, one obtains: P1 RT Pv Substituting, values for Pv and Pi in equation (1) gives PyRT RT Pv which is approximately Pc=RT/Mp1 In Pvo/Pv .......(2) This equation relates the vapor pressure above a curved surface with the capillary pressure across the curved surface in terms of measurable quantities. The equivalent of this equation is given by Freundlich."

Jan 1, 1949

By R. A. Morse, W. O. Keller

The properties of limestone reservoir rocks such as the distribution and degree of continuity of the pore systems, and the relative volumes and permeabilities of the systems making up the complex cause large variations between performance of individual limestone reservoirs and their susceptibility to secondary recovery methods. The effects of these factors on the mechanism of fluid flow cannot be adequately evaluated with presently developed concepts, laboratory data, and geological information. The observance and interpretation of the performance of individual limestone reservoirs provides, at present, the most adequate approach for evaluating the integrated effects upon performance of the many. now immeasurable variations in the properties of limestone reservoirs. INTRODUCTION The development and application of techniques for increasing the efficiency of oil recovery from natural reservoirs is a problem of primary importance to the industry. During the past several years, a great deal of effort has been expended by the technical personnel of the industry toward the improvement of present known methods of oil recovery. and evaluating the factors which control the susceptibility of particular reservoir types to economic application of secondary recovery methods. Providing adequate and accurate laboratory data on the properties of the reservoir rock and its contained fluids. together with good production statistics, are available, methods have been evolved for estimating with reasonable accuracy the performance of an oil reservoir under either continued natural depletion or conditions imposed by introducing additional displacing fluid into the reservoir from an extraneous source through the injection of gas and/or water. The susceptibility of limestone reservoirs to secondary recovery by gas injection is very much dependent upon gas-oil relative permeability relationships for the reservoir in question. In a rock formation in which the porosity is of the intergranular type such as is found in sand stones and some non-fractured dolomites, a representative sample of the pore structure can be obtained in a small core plug. In this type of reservoir, it has been shown that relative permeability data obtained from laboratory experiments can be Properly applied to evaluate the flow relationships actually observed during the depletion of a reservoir. In addition, a good idea of the fraction of the reservoir which will be swept by the injected gas may be obtained from the spacing pattern used and the permeability profile of cored wells. From these data, it has been demonstrated that reliable estimates of performance and recoveries under gas injection operations can be made for reservoirs in which the Porosity is of the intergranular type. Limestone reservoirs on the other hand often present much more complex problems. One reason that the performance of limestone reservoirs is so variable is that there may be, in reality. two or more pore systems, the integrated performance of which will depend upon the physical properties of each system and their inter-relationship. For instance, in a limestone reservoir, the main pore structure, as far as void spaces for storage of hydrocarbons is concerned, may be represented by the intergranular openings of the rock. Usually in limes and dolomites, the intergranular pore openings are very small and the matrix permeabilities extremely low. Often, as in the case of Many dolomite and oolitic lime reservoirs, this is the only pore system, and performance is observed to be very similar to that of a sand stone of similar permeability. However, in the great majority of&apos; the limestone reservoirs, there is present, in addition to the intergranular pore system, a complementary system of openings caused by fracturing or solution.&apos;,&apos; The openings in the latter system are usually many times more permeable than the intergranular pore system due to their much larger size, and may contribute almost all the fluid carrying capacity of the formation, even though their volume may be a very small part of the total pore space in the reservoir. Obviously, the performance of such a complex under either primary or secondary control will deend upon the distribution and degree of continuity of both systems, the relative volumes and permeabilities of the

Jan 1, 1949

By L. K. Jetter, J. C. Ogle, C. L. McHargue

The preferred orientation developed in extruded aluminum rods has been studied as a function of extrusion temperature, extrusion speed, and position in the rod. Duplex <111> - <001> textures were developed for slow extrusion speeds at temperatures of 75° to 850° F and for fast extrusion speeds at temperatures of 75° to 450°F. The <001> texture component was shown to be primarily due to re crystallization occurring during fabrication. At fast speeds and billet temperatures of 650° to 850°F, complete recrystallization occurred and <115>or<118> textures were found. The nature of the structure has proved to be an important variable in the production and use of extruded products. Data on the flow of aluminum and aluminum alloys summarized by Smith,&apos; Hardy,&apos; and Locke3 show that the extruded product may possess a deformed, a partially recrystallized, or a completely recrystallized structure, and there may be important variations in the structure from surface to center and from front end to back end of an extrusion. This inhomogeneity in grain structure and preferred orientation affects both the mechanical properties of the extruded section and its response to subsequent heat treatment. Among the fabrication variables causing these differences are temperature, extrusion ratio, and extrusion speed. Preferred orientation which develops during the extrusion of rods is of the fiber-type and, in general, has been assumed to be similar to that developed in rods or wires fabricated by drawing through dies, rolling, or swaging.4 Because of the nature of the flow of metal being extruded, this assumption may be valid for material near the center of the rod but probably is not valid for the outer layers. In most face-centered-cubic metals a duplex fiber texture has commonly been reported in which the grains have either <Ill> or <001> directions parallel to the longitudinal axis. Sachs and fichiebold5 reported cold-drawn aluminum (99.6 pct pure) to have a single <Ill> fiber texture, and this observation was confirmed by Schmid and Wassermann.6 Hibbard, on the other hand, observed a minor <001> and a major <111> texture in 99.994 pct A1 cold drawn to 98 pct reduction in diam.7 He concluded that the <001> component resulted from a small amount of room-temperature recrystallization. Dayal8 concluded that the <001> component was an intermediate component which disappeared at high reductions in 99.5 pct pure Al. Kostron and schippers9 found duplex <111> — <001> textures in extruded 99.5 pct Al, as did Gow and cahnl0 and GOW11 for extruded rods of commercial and superpure aluminum. Similar duplex fiber textures have been reported for aluminum alloys by Kostron,= Unckel,13 and Van Horn.14 The present paper is concerned with the variation in texture with fabricating conditions and with the nature of the texture components in extruded aluminum rod (99.99 pct pure). EXPERIMENTAL PROCEDURE Ingots were chill-cast in cast-iron molds and machined to 3-in. diam by 6-in. long extrusion billets. These billets were upset to 3.125 in. diam and extruded through a flat-face 0.690-in. diam die. Quenching of the rods was accomplished by a water spray at the die face. The combinations of fabricat-

Jan 1, 1960

By F. W. Bremmer

The experiments described in this paper constitute the preliminary work of an investigation outlined to determine the combined effects of steam and temperature on the endurance properties of certain steels. Essentially of a fundamental nature, it was found necessary, in order to make the investigation comprehensive, to test materials treated to give a wide range of properties. The work reported deals chiefly with nickel steel with one series of tests including nitriding steel. Such a study involves numerous variables, and requires an endurance-testing machine of rather special design. Testing Machines The testing machines used were designed by C. E. Weaver;l they are a modification of the White-Souther and McAdam types. Each was driven directly by an individual 1/2-hp. 115-volt direct-current motor, running at a speed of 2200 r.p.m. Fig. 1 shows the assembly drawing and Fig. 2, a photograph of one of the machines. Specimen B is held by the rotating specimen holder A inside the steam box F, which is closed at the top by a tight-fitting, elliptical cover G. The load is applied to the specimen through the rod D and bearing C. E is an oil pipe leading fromthe lubrication system to the bearing C. The steam, which comes from the power house, is admitted through an inlet (not shown in Fig. 1) at the side of the box, the drain being at the bottom. Steam packings were placed around the rod D and the rotating shaft at H, from which the water was drained by means of a vacuum, which usually showed a gage reading of about 10 in. The temperature was measured by a mercury thermometer, and the pressure by a steam gage. Method of Applying Load After the motor has been started and the specimen as a consequence put in rotation, the load is applied by placing the foot pedal A (Fig. 2) in contact with electromagnet B, the winding of which is connected electrically in series with the motor. This operation releases the support under the weights that constitute the load. By this means the load

Jan 1, 1930

By O. G. Kiel, G. W. Swift

The concept of "a continuous succession of steady-states", which has been applied successfully by Aromfsky and Jenkins to obtain a solution for the nonlinear partial differential equation describing the transient Darcy flow of gas through porous media, is demonstrated to be equally valid for transient non-Darcy flow. A mathematical model, which numerically solves the partial differential equation, is used to check the validity of the succession of steady-states solution. Comparison of sand-face pressure histories compelted by the two methods shows excellent agreement. The utility of the succession of steady-states solution in predicting performance of gas wells rests in the fact that no special computation equipment is required. The development of the succession of steady-states solution leads also to a practical method for determining and analyzing field test data. A method for taking gas-well test data under constant-rate conditions is presented. Experimental data obtained in the field by employing the constant-rate method are presented and analyzed in accordance with the succession of steady-states solution. Analysis of data in this fashion is demonstrated to give direct "in situ" information for reservoir permeability, porosity and turbulence or non-Darcy coefficient. INTRODUCTION The economics of gas production are dependent upon the transient behavior of flow within the reservoir. For production from a finite reservoir, the transient flow behavior can be subdivided into two parts. At first, the transient caused by the movement of the pressure "wave" into the reservoir is of importance. Later in the production history, the pressure-wave movement ceases and the second transient stage of material depletion becomes controlling. For reservoirs of relatively high permeability, it can be shown that the pressure wave moves into the reservoir and stabilizes quite rapidly. In the case of relatively impermeable reservoirs, quite the opposite is true. Although it is theoretically possible to compute the production capability of a well from the properties of the reservoir as determined by static tests and core analyses, more reliable information is obtained by conducting flow tests on the well and thereby obtaining some measure of "in situ" formation properties. For gas wells, there are two basic types of tests in existence: the flow-after-flow method,&apos; and the isochronal method.&apos; Both of these techniques are tailored to obtain data that can be analyzed in accordance with the empirical performance equation: In addition, the isochronal method makes provision for the sluggish nature of pressure-wave movement in "tight" formations by requiring pressure build-up between flows and by stipulating that data obtained on successive flows be analyzed at equal elapsed flow times. It can be demonstrated that either test is valid for reservoirs of high permeability. Further, since it has been pointed out that the pressure wave stabilizes rapidly for reservoirs of this type, tests of relatively short duration will give stabilized information on the performance of a well. Further decline of sand-face pressure and/or production rate may be determined by employing material-balance techniques. Cullender&apos; points out that for relatively impermeable reservoirs the flow-after-flow method gives invalid results. (See Appendix C.) If the isochronal method of testing is used, there are two alternatives: (1) the tests must be conducted for a sufficient length of time to obtain stabilized information (which may require months to accomplish); or (2) some method for extrapolating the results of short-term isochronal tests must be employed. The first alternative is impracticable because of manpower, conservation and economic considerations. Recourse to the second alternative requires some assurance regarding the reliability of the extrapolation technique. Poettmann and SchilsonJ present an empirical method for predicting stabilized performance. The present investigation was originally initiated to determine the reliability of this technique. To do this, a mathematical model was developed to simulate the Darcy and non-Darcy flow of gas through porous media. The model consisted of a finite-difference approximation of the nonlinear partial differential equation which was solved on an IBM 7090 computer. Long-term production histories were simulated by the model and compared against predictions obtained from the Poettmann-Schilson method. As the work progressed, it became apparent that a straightforward predictive equation could be developed by utilizing the concept of a succession of steady-states. As a result, the emphasis of the work was redirected to exploit the advantages of the new method.

By Lester L. Hirst, Henry H. Storch, A. C. Fieldner

Experimental work on liquefaction of coal was taken up by the Bureau of Mines in 1936 when it became evident that a prudent policy from the national point of view should include preparation for the time when gradual exhaustion of petroleum resources would require supplementing the growing demand for motor fuel with gasoline and diesel oil from coal. At that time (1936) certain foreign nations that had no home sources of petroleum, especially Germany, England, and Japan, were conducting active research and at least two of them were producing liquid fuel from coal on a commercial scale. Germany was reported to have an annual producing capacity of 800,000 metric tons of gasoline per year, and England had just put into operation the Billingham plant of Imperial Chemical Industries for the hydrogehation of bituminous coal and tar by the Bergius-I.G. process. The annual capacity of this plant was about 150,000 long tons of gasoline per annum (3500 bbl. per day). With these developments taking place in foreign countries, it seemed important to undertake a long-range program of fundamental research in this country to establish a sound groundwork for the evaluation of foreign work on synthetic liquid fuels and at the same time to obtain data on the oil yields and operating difficulties using various kinds of American coals and lignite to the hydrogenation process. The results of such research would be useful in determining the yields and quality of liquid products obtainable from various coals so that American industry would be in position to select the most suitable coals and make rapid progress in establishing this new industry when the commercial need should arise. It was hoped, also, that progress in a better understanding of the chemistry of coal hydrogenation would reduce the cost of the process materially. To carry out this program, a small continuous unit capable of hydrogenating 100 Ib. of coal in 24 hr. was installed at the Central Experiment Station of the Bureau of Mines at Pittsburgh, Pa. Small steel autoclaves or bombs of 0.3 gal. (1.2 liters) capacity also were used for batch-hydro-genation experiments in the study of the chemical fundamentals of the process. Much valuable assistance was obtained in planning the experimental program and designing the equipment from the Fuel Research Station of Great Britain and the Fuel Laboratories of the Mines Department of Canada, where such investigations had been in progress for several years. Equipment and General Procedure of Research The industrial liquefaction of coal by the Bergius-I.G. hydrogenation process as practiced at Billingham, England, from

Jan 1, 1944

By H. J. Morel-Seytoux

The influence of patten, geometry on assisted oil recovery for a particular dispIacement mechanism is the object of investigation in this paper. The displacement is assumed to be of unit mobility ratio and piston-like. Fluids are assumed incompressible and gravity and capillary effects are neglected. With these assumptions it is possible to calculate by analytical methods the quantities of interest to the reservoir engineer for a great variety of patterns. Specifically, this paper presents (1) very brieily, the methods and mathematical derivations required to obtain the results of engineering concern, and (2) typical results in the dorm of graphs or formulae that can be used readily without prior study of the methods. Results of this work provide checks for solutions obtained from programmed numerical techniques. They also reveal the effect of pattern geometry and, even though the assumptions of piston- like displacement and of unit mobility ratio are restrictive, they can nevertheless be used for rather crude but quick, cheap estimates. ,These estimates can be refined to account for non-unit mobility ratio and two-phase flow by correlating analytical results in the case M = 1 and the numerical results for non-piston, non-unit mobility ratio displacements. In an earlier paper1 it was also shown that from the knowledge of closed form solutions for unit mobility ratio, quantities called "scale factors" could be readily calculated, increasing considerably the flexibility of the numerical techniques. Many new closed farm solutions are given in this paper. INTRODUCTION BACKGROUND Pattern geometry is a major factor in making water-fIood recovery predictions. For this reason many numerical schemes have been devised to predict oil recovery in either regular patterns or arbitrary configurations. The numerical solutions, based on the method of finite difference approximation, are subject to errors often difficult to evaluate. An estimate of the error is possible by comparison with exact solutions. To provide a variety of checks on numerical solutions, a thorough study of the unit mobility ratio displacement process was undertaken. To calculate quantities of interest to the reservoir engineer (oil recovery, sweep efficiency, etc.), it is necessary to first know the pressure distribution in the pattern. Then analytical procedures are used to calculate, in order of increasing difficulty: injectivity, breakthrough areal sweep efficiency, normalized oil recovery and water-oil ratio as a function of normalized PV injected.

Jan 1, 1967

By E. C. W. Perryman

IN spite of the large amount of work which has been carried out on the recrystallization of aluminum and its alloys, there has been no complete investigation of the recrystallization characteristics of A1-Mg alloys. The most complete investigation is that reported by Bungardt and Osswald&apos; who, working with commercial-purity materials, found that the temperature both of beginning and of complete recrystallization increased with magnesium content up to about 2 pct Mg, then decreased with a further increase in magnesium up to 5.0 pct, and thereafter increased again. Michaud and Segolz working with 99.93 pct A1 also found the temperature of beginning of recrystallization to decrease as the magnesium content increased from 2.13 pct to about 4.5 pct. Chossat3 using aluminum of 99.99 pct purity found that 0.12 pct Mg had no effect but that 0.4 pct Mg increased the recrystallization temperature by about 30°C. That no effect was found for 0.12 pct Mg does not agree with the later results reported by Demer and Beck4 who found that 0.025 pct Mg in 99.99 pct A1 increased the time for complete recrystallization and furthermore increased the activation energy for the recrystallization process. Kratz" using 99.997 pct A1 found that 0.5 pct Mg increased both the temperature of beginning and of complete recrystallization by 100°C. Chadwick and Hooper" working with commercial-purity material found that 1 pct Mg increased the temperature of complete recrystallization by about 40 °C for cold reductions in the range 17 to 72 pct. With smaller amounts of cold work produced by stretching (10 pct strain), they found no significant effect of magnesium. The latter result agrees with that obtained by Williams and Eborall&apos; who found no effect of 2 pct Mg on the recrystallization temperature of commercial-purity aluminum strained 10 pct or less by stretching. Experimental Procedure Material Used: The chemical analyses of the materials used throughout this investigation are given in Table I. Fabrication: The alloys were cast in iron molds which had been washed thoroughly with alumina. After scalping, the ingots were annealed for 16 hr at 450°C, pressed, annealed at 450°C for 16 hr and hot rolled to 0.25 in. After hot rolling, the slabs were alternately annealed and cold rolled to 0.036 in. Cold-rolling reductions between intermediate anneals were kept at about 30 pct and a high intermediate annealing temperature of 450°C was used so as to obtain, as nearly as possible, similar starting grain sizes for the different materials. All intermediate anneals were done in a salt bath and were followed by cold-water quenching so as to retain all the magnesium in solid solution. The final cold reductions investigated were 20, 30, 40, 50, 60, and 80 pct. The initial grain sizes, that is, the grain size before the final cold reduction, were all very similar. Annealing Procedure: Specimens, 1 in. sq, were cut from the 0.036 in. sheet and annealed in a salt bath, the temperature of which was controlled to k2"C. Separate specimens were annealed for different times at 350°, 375", 400°, and in one or two cases at 415°C and after annealing were quenched in cold water. The time taken for a specimen to reach temperature was approximately 5 sec. Metal-lographic examination after annealing showed that no precipitation of Mg+413 occurred during cooling. Procedures Used for Determining Recrystallization Characteristics: All specimens were electrolyti-cally polished and etched by the method described previously1° and polishing was continued until about 0.002 in. had been removed from each side of the specimen. Using this technique, the smallest recrys-tallized grain which could be observed with cer-

Jan 1, 1956

By Jeffrey L. Thompson, Kenneth A. Gutschick, Robert C. Freas, Robert S. Boynton

Lime, the "versatile chemical," is, generally speaking, a calcined or burned form of limestone commonly known as quicklime, calcium oxide or calcia, or, when water is added, calcium hydroxide or slaked lime. Almost 40 different lime products are available, a fact which has contributed to the rather loose use of the term lime as well as to much confusion and misunderstanding. The term is frequently, albeit erroneously, used to denote almost any kind of calcareous material or finely ground form of limestone or dolomite. Lime is usually made from high-calcium or high-magnesium limestone, generally having a minimum of 97% combined carbonate content. Normally, high-calcium limes contain less than 5% MgO. When the lime is produced from a high-magnesium limestone, the product is referred to as dolomitic lime. Calcination, or the production of lime, has its origins in the earliest days of alchemy, with the general reaction class having been identified in an Arabic text printed in 1000 A.D. It was much later, however, in the mid-1700s to the mid-1800s before this basic reaction became understood from a scientific perspective. The production of lime has been so basic and simple that its underlying scientific principles have over the years received only intermittent investigation. Rather, much of the thought and inquiry has been directed toward the development of kilns. Thus, it has only been in the last 15 to 20 years that lime has received any concentrated scientific investigation relative to the thermodynamics and kinetics of the calcination and hydration reactions. Calcination refers to a broad class of reactions, of which the lime/limestone reaction is just one, wherein a substance is heated to less than its melting point, resulting in a weight gain or weight loss. In the calcination of limestone to produce lime, the basic chemical reaction is as follows: [CaCO3 (limestone) + heat (1000° to 1300°C)= 100 CaO (quicklime) + CO2 T 5644 or CaCO3 • MgCO3 (limestone) 10084 + heat (900°C to 1200°C) CaO • MgO (quicklime) + 2CO2 T 56 4088] While there is nearly universal agreement about the equilibrium conditions related to the limestone/lime reaction above, there have been numerous and varied calcination models developed for the reaction. Recent investigations have resulted in the development of the model shown in Fig. 1. From this model it can be seen that calcination is a function of both temperature and CO2 pressure. It does not, however, provide any indication of the rate at which the reaction takes place. Calcination is strongly time variant with different limestones. In a very broad sense this relates to the fact that the calcination reaction starts on the exterior surface of the limestone and then proceeds toward the center. As the calcination reaction takes place, the CO2 released at the reaction interface must make its way through the lime to the exterior surface. Therefore, because calcination is limited by gas diffusion to the surface of the partially calcined limestone, natural impurities in the stone, differences in crystallinity, grain boundary chemistry, density variations, and imperfections in the atomic lattice all play a significant role in

Jan 1, 1983