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By L. A. Bromley, R. L. McKisson

A high temperature calorimeter designed for use up to 1500°K is described and the theory of its operation presented. This calorimeter was used to measure the heats of formation of Na-Sn alloys ranging in composition from tin to Na2Sn. The values tend to support those reported by Kubaschewski and Seith. ONE method of obtaining the heat of formation of an alloy is to measure the heat of mixing of the elements at high temperature. The principal advantage of this method is that the desired quantity is measured directly, while in conventional room temperature methods the differences of the heats of solution of the elements and the alloy in a suitable solvent are measured. A method of improving the accuracy of the high temperature measurements, when the precision of the measurement is lower than that of the heat capacity values for the elements, is to add one component at room temperature to the other at the high temperature, so that part of the heat of reaction is dissipated in heating the cold component to the high temperature. Thus, only a fraction of the heat of reaction is measured, and a result of higher precision is obtained. The limitations of the high temperature technique are that volatile systems cannot be studied, and that many alloys melt at temperatures higher than those at which the calorimetric apparatus operates readily. Nevertheless, a calorimeter operating at 1500°K would be useful in investigating many of the lower melting alloy systems and the low melting mixed oxide systems. A unit designed for these applications was built and is described here. The Na-Sn system was chosen for investigation because the temperature involved, 880°K, would adequately test the operation of the calorimeter. Further, the data reported in the literature for the various alloys of sodium and tin differ markedly, and it was hoped that this investigation would help to fix the values of the heats of formation in this system. Design of Apparatus A detailed discussion of the considerations involved in the calorimeter design is given by Mc-Kisson and Bromley,' and a brief summary follows. Fig. 1 shows a sectional view of the calorimeter. The inner graphite chamber is maintained at constant temperature by means of the circulating molten tin bath in which it is submerged. The tin is contained in a graphite vat. This unit comprises a thermostat whose heat capacity is about 7000 cal per "C. The main heating element consists of a machined graphite spiral with a room temperature resistance of about 1/2 ohm. These parts are separated from the powdered carbon external insulation by the cage, a cylindrical graphite chamber. The electrical insulators and separators, the auxiliary heater spool, and the loading tube liner are made of sintered alumina. The tin vat stirrers, the sample stir-rer, the melt thermocouple well, and the power leads are made of molybdenum. The auxiliary heater is wound with molybdenum wire and serves to compensate for the heat loss up the loading tube. All of the individual components in the high temperature region of the calorimeter will withstand at least 2000°K, and the various contacting materials should easily withstand 1500°K. The external container for the insulating carbon powder is a copper shell upon which copper tubes are soldered to serve as cooling coils.

Jan 1, 1953

By Edward Roberts

This is a progress report of an investigation by personnel of the Bureau of Mines from June to September 1951 to introduce preservative chemicals into growing timber. It also describes in detail the impregnation process, known as the collar method, developed by the United States Department of Agriculture2/ Twenty-eight trees were treated by this method, and a complete record was kept of each individual tree and of each timber cut from it. These timbers have been placed in a coal mine, and their tendency to decay is compared to that of adjacent untreated sets. Although several years will be required before final conclusions can be drawn, this report explains the appearance and encouraging results of the treated timber to date. Also included are some comparative costs of untreated timber, treated timber by the commercial pressure method, and treated timber by the collar method. INTRODUCTION In the hope of increasing the useful life of cut timber, experiments to impregnate growing trees with wood-preservative chemicals by utilizing the natural flow of sap have been carried on for centuries. None of the various methods used in these experiments has ever gained any widespread use because they have been commercially impractical.

Jan 1, 1953

By W. A. Wissler, B. E. Field

COBALT is a silvery white metal with a slight bluish cast. It strongly resembles nickel in its appearance and properties, notably its resistance to corrosion, although its alloys with other metals differ decidedly in their properties from those of nickel. The name "cobalt" was derived from the German Kobold, meaning goblin, and this came to be applied to the cobalt minerals which, although they resembled ores, did not readily yield metal when smelted by the primitive processes available in the Middle Ages. Cobalt minerals were used as pigments by potters and glass- workers before the Christian era. Cobalt blue glass was found in the tombs of the Egyptians and in the ruins of Troy, and many colors used by the ancient Greeks and Romans contained cobalt. The ancients were entirely unaware that the colors they used were caused by cobalt and the metal itself was not isolated until about the middle of the eighteenth century, by Brandt, although the preparation of cobalt compounds had been carried on in a small way ever since the opening of the silver-cobalt deposits at Schneeberg, Germany, in 1470. By the middle of the nineteenth century, several firms in England were engaged in the refining of cobalt products and the consumption of cobalt oxide in the British ceramic industry in the year 1866 had reached 67,000 lb. COBALT METAL AS A NEW RAW MATERIAL IN ALLOY TECHNOLOGY Nickel and cobalt are usually found together and, although the relative amounts of the two have varied greatly in different ores, those

Jan 1, 1953

By Fred C. Bond

MOST investigators are aware of the present unsatisfactory investigatorsstate of information concerning the fundamentals of crushing and grinding. Considerable scattered empirical data exist, which andare useful for predicting machine performance and give acceptable accuracy when the installations and materials compared are quite similar. However, there is no widely accepted unifying principle or theory that can explain satisfactorily the actual energy input necessary canexplain commercial installations, or can greatly extend the range of empirical comparisons. Two mutually contradictory theories have long existed in the literature, the Rittinger and Kick. They were derived from different viewpoints and logically lead to different results. The Rittinger theory is the older and more widely accepted.'TheRittinger In its first form, as stated by P. R. Ritted.'tinger, it postulates that the useful work done in crushing and grinding is directly proportional to the new surface area produced and hence inversely proportional to the product diameter. In its second form it has been amplified and enlarged to include the concept of surface energy; in this form it was precisely stated by A. M. Gaudin' as follows: "The efficiency of a comminution operation is the ratio of the surface energy produced to the kinetic energy expended." According to the theory in its second form, measurements of the surface areas of the feed and product and determinations of the surface energy per unit of new surface area produced give the useful work accomplished. Computations using the best values of surface energy obtainable indicate that perhaps 99 pct of the work input in crushing and grinding is wasted. However, no method of comminution has yet been devised which results in a reasonably high mechanical efficiency under this definition. Laboratory tests have been reported- hat support the theory in its first form by indicating that the new surface produced in different grinds is proportional to the work input. However, most of these tests employ an unnatural feed consisting either of screened particles of one sieve size or a scalped feed which has had the fines removed. In these cases the proportion of work done on the finer product particles is greatly increased and distorted beyond that to be expected with a normal feed containing the natural fines. Tests on pure crystallized quartz are likely to be misleading, since it does not follow the regular breakage pattern of most materials but is regularrelativelybreakage harder to grind patternat the finer sizes, as will be shown later. This theory appears to be indefensible mathematically, since work is the product of force multiplied by distance, and the distance factor (particle deformation before breakage) is ignored. The Kick theory4 is based primarily upon the stress-strain diagram of cubes under compression, or the deformation factor. It states that the work required is proportional to the reduction in volume of the particles concerned. Where F represents the diameter of the feed particles and P is the diameter of the product particles, the reduction ratio Rr is F/P, and according to Kick the work input required for reduction to different sizes is proportional to log Rr /log 2." The Kick theory is mathematically more tenable than the Rittinger when cubes under compression are considered, but it obviously fails to assign a sufficient proportion of the total work in reduction to the production of fine particles. According to the Rittinger theory as demonstrated by the theoretical breakage of cubes the new surface produced, and consequently the useful work input, is proportional to Rr-l.V f a given reduction takes place in two or more stages, the overall reduction ratio is the product of the Rr values for each stage, and the sum of the work accomplished in all stages is proportional to the sum of each Rr-1 value multiplied by the relative surface area before each reduction stage. It appears that neither the Rittinger theory, which is concerned only with surface, nor the Kick theory, which is concerned only with volume, can be completely correct. Crushing and grinding are concerned both with surface and volume; the absorption of evenly applied stresses is proportional to the volume concerned, but breakage starts with a crack tip, usually on the surface, and the concentration of stresses on the surface motivates the formation of the crack tips. The evaluation of grinding results in terms of surface tons per kw-hr, based upon screen analysis, involves an assumption of the surface area of the subsieve product, which may cause important errors. The evaluation in terms of kw-hr per net ton of —200 mesh produced often leads to erroneous results when grinds of appreciably different fineness are compared, since the amount of —200 mesh material produced varies with the size distribution characteristics of the feed. This paper is concerned primarily with the development, proof, and application of a new Third Theory, which should eliminate the objections to the two old theories and serve as a practical unifying principle for comminution in all size ranges. Both of the old theories have been remarkably barren of practical results when applied to actual crushing and grinding installations. The need for a new satisfactory theory is more acute than those not directly concerned with crushing and grinding calculations can realize. In developing a new theory it is first necessary to re-examine critically the assumptions underlying

Jan 1, 1953

By C. E. Birchenall, W. Batz, H. W. Mean

AT temperatures between 1095' and 1347ºC, 13 runs have been made on the diffusion of silicon in iron. In two of the runs the couple compositions were entirely within the loop of the Fe-Si system; the base alloys contained 0.0 and 1.0 wt pct Si. The other runs in which the couples consisted of a 2.3 wt pct Si alloy welded to a 3.7 pct Si alloy were a phase throughout. The alloys were made by melting electrolytic iron and commercially pure silicon. Trace impurities were not determined. The butt welded couples were diffused in an inert atmosphere of argon or hydrogen. After cooling, cuts of two mils or greater thickness were machined parallel to the weld interface. The chips were analyzed for silicon. When the concentration and distance data were examined on the conventional probability plot,' no marked variation of the diffusion coefficient with concentration was indicated over the narrow composition ranges employed. Therefore, a single diffusion coefficient is recorded for each run in Table I. The temperatures and atmospheres of the diffusion anneal are listed along with the compositions of the base alloys. For a iron the silicon diffusion coefficient is given by the equation: D = 0.44 e-48,000/RT where R is the gas Constant and T, the absolute temperature. However, since the scatter in the data is fairly large, the activation energy may be in error by as much as 6000 cal per g-atom. The two ? iron points do not permit estimation of the activation energy with any reasonable certainty. They do indicate that the coefficients reported by Smithells2 and Jost,3 based on the work of Fry,4 are much too high. Although very dilute solutions in iron of manganese,5 nickel,8 cobalt,7 and molybdenum8 give dif- fusion coefficients quite close to those obtained for self-diffusion in iron, the silicon values are considerably higher, though of the same order of magnitude. This seems to be consistent with the fact that the silicon atom is the only one of those listed here which is appreciably smaller than iron. The authors are grateful to the Office of Naval Research for their support of this work under Contract N6ori-47, Task order IV, Project NR 031-184, to J. K. Stanley and the Westinghouse Research Laboratories for the silicon alloys used, to several steel companies for the silicon analyses, and to C. Wells, of the Metals Research Laboratory, Carnegie Institute of Technology, for numerous suggestions during the course of the work. References 'C. Wells: Atom Movements (1951) Chapter 2. A.S.M. 2C. J. Smithells: Metals Reference Book (1949) p. 405. Interscience. Pub. Co. 3W. Jost: Diffusion (1952) p. 223. Academic Press. 4 A. Fry: Stahl und Eisen (1923) 43, p. 1039. T. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 315. "C. Wells and R. F. Mehl: Trans. AIME (1941) 145, p. 329. 7M. F. Hawkes and R. F. Mehl: Trans. AIME (1947) 172, p. 467; Metals Technology (August 1947). .J. L. Ham: Trans. A.S.M. (1945) 35, p. 331.

Jan 1, 1953

By D. R. McCord

Data of a known statistical quality has been successfully used in a system of conventional fluid mechanics equations essentially free of empirical "conformance factors to prediet early detailed field 03 in a reservoir where gravity drainage is important and oil and rock properties vary con. siderably. The system is useful where comparative recovery predictions for one or more cases of natural depletion and gas cap pressure maintenance are needed and the reservoir is not too heterogeneous. INTRODUCTION Many authors, have examined various facet* of the gravity drainage-gas cap pressure maintenance problem over the last several years. Two of them. Burtchaell and Elkins, have published practical studies. In the case described in the present paper the best development and operating plan for one of the important reservoirs of the Bolivar Coastal Field in Western Venezuela was urgently needed. It was requested that sound comparative economics be presented along with an engineering evaluation of no additional drilling, maximum drilling. several cases of gas pressure maintenance, of water flooding and combination cases. A rapid analysis of the effect on recovery of the range of crude and rock properties indicated that none of the published methods using average properties would yield adequate comparative predictions. This paper covers the predictive system developed to deal with natural depletion and gas cap pressure maintenance. The large amount of data available for this field permitted statistically reliable correlations to be made of most rock and oil properties, and the evident smooth areal variations of these properties encouraged the construction of a lineal mathematical model of material balance and fluid flow equations, which could be manipulated by a modified iterative procedure. The manipulation is much more adaptable to computing machines than manually operated calculators and subsequent studies have been prepared for the IBM Card Program Calculator. A matrix as opposed to linear model has been tentatively worked out by other members of our group to deal with more heterogeneous reservoirs. It is more adaptable to computers such as IBM-701 or the Remington-Rand Univac. In 1950, when the system reported below was developed, no rapid computing machines were available to the author. Their existence and promise encouraged an initial approach by hand. Some details of oil and rock Property correlation are included because there are a surprisingly large number of medium-sized reservoirs in the world that show systematic property variations which are significant for a rigorous analycon. All large reservoirs (over half a billion barrels recovery) with which the author is familiar contain at minimum a significant temperature variation. Using the rock and oil property correlations, past pressure and production, the gas-oil ratio history of the reservoir was computed and found to be in close agreement with field measurements. The future performance under cases of natural depletion, gas injection of 100 MMcf/day, and of 130 MMcf/day, was then computed; a 70 MMcf/day case was also carried far enough to provide data for comparative economics. The 130 MMcf/day case proved to be the most attractive. A 50,000 horsepower gas turbine driven centrifugal compressor plant to take this quantity of adjacent field gas from 30 to 1,950 psia and inject it into the reservoir is under construction. The total cost of the project will exceed 20 million dollars.

Jan 1, 1953

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By Adam L. Wesner, A. C. Richardson

This paper describes the development of a continuous float-and-sink process to produce coal low enough in ash content to be suitable for production of electrodes. The cleaned coal had a combined iron and silicon content of 0.239 pct. The efficiency of recovery was 84 pct. DURING World War I1 the demand for electrode carbon was greater than could be met by the supply of petroleum coke available for this use. It was believed that coke made from an extremely low-ash coal might be a suitable substitute for petroleum coke. Requirements for electrode carbon to be used for the production of aluminum are that the silicon plus iron content shall be not more than 0.14 pct of the coke. However, during the period when petroleum coke was in short supply, it appeared that relaxations of the specifications might be allowed to permit 0.4 pct iron plus silicon in the coke. For this work, the specifications were that the coal should contain less than 1 pct of ash, and the combined iron and silicon content of the coal should not exceed 0.28 pct. Heavy-liquid separations made on a number of coals showed that if certain size fractions of some coals Were separated at low specific gravities the resulting float products would meet the required specifications. The objective of this work was to develop a continuous, commercially feasible process for producing low-ash coal. After consideration of various processes, the method chosen was a float-and-sink separation using a solution of calcium chloride as the separating medium. Eagle Seam coal was used for the experiments. The —10 +35 mesh fraction was found to be the most promising feed for producing the low-ash content coal. A batch of 30 tons of — --in. coal was screened at 10 and 35 mesh; the yield of —10 +35 mesh was 20 pct of the feed. This fraction comprised the feed for the separation tests. In spite of the fact that this portion was screened a second time at 35 mesh, the coal still contained 16 pct that was finer than 35 mesh. Three-fourths of the undersize was in the —35 +48 mesh range. A representative portion of the —10 +35 mesh fraction was subjected to batch float-and-sink separations to determine the best gravity to be used in the continuous tests to obtain a high recovery of low-ash content coal. The heavy liquid used was a mixture of carbon tetrachloride and benzene which assured complete wetting of all of the particles. As usual in batch separations, adequate time was allowed for each separation so that even the near gravity particles had ample time to separate. The separations were made at increments of 0.01 sp gr from 1.25 to 1.28 and also at 1.32 and 1.59. Each specific-gravity increment was assayed for ash content. From these data it was concluded that 1.27 sp gr was best for the continuous separation of the coal. The products from the batch separation were composited into float 1.27 and sink 1.27 sp-gr fractions; these were assayed for ash, iron, and silicon. Table I shows the results of the batch separations. The composite float 1.27 fraction contained 66.04 pct of the total weight, and had an analysis of 0.79 pct ash, 0.073 pct iron, and 0.112 pct silicon, or 0.185 pct iron and silicon combined. These data are indicative of the results possible if a perfect separation is made at 1.27 sp gr under static conditions. Inasmuch as the method under investigation is a dynamic system these results could not be obtained. It remained to be determined, however, just how close to the theoretical results the actual continuous separation would be.

Jan 1, 1953

By C. H. Riggs

This petroleum-engineering study of the Healdton oil field in Carter County, Okla., describes the geology and production history of that field and estimates the oil reserves that could be produced by efficient secondary-recovery methods. The Healdton field, in western Carter County approximately 20 miles west of Ardmore, Okla., was discovered in 1913 and was one of the early important oil-producing areas in the State. Although the volume of oil recovered from the Healdton sands has been comparatively high, studies show that a large reserve remains in the pressure-depleted sand, which can be recovered by efficient water-flood operations. In making this study of the Healdton-sand reservoir, the writers utilized many data already available in company and Government offices. Most of the fluid samples were collected by Bureau of Mines personnel and analyzed in the Bureau's laboratories at Bartlesville, Okla.; but other data, including logs, core analyses, and production records, were obtained from outside sources. These data were examined critically but were not verified, and possible errors in the original data may be reflected in the conclusions. In this study, attempts were made to consider only those aspects of the available information that would contribute to a clear and concise engineering report on the Healdton-sand reservoir. Other phases of the data, as well as those concerning associated reservoirs, were eliminated from consideration as being irrelevant to the particular problem. Cores and drill cuttings of the Healdton sands were analyzed and studied to determine the nature of the reservoir rocks. Analyses of samples of produced oil, water, and gas were studied to fix the different types, the limits of their occurrence, and the suitability of different waters for injection into the Healdton sands. Records of oil, gas, and water produced and of gas and water injected were studied to interpret the production behavior of the field and of certain individual leases. Theoretical calculations were made to predict the probable water-flood behavior and oil recovery, at constant water-injection rates, for individual sands on two leases.

Jan 1, 1953

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.' The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.' Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By R. B. Burt, James A. Barr, I. S. Tillotson

DISCUSSION Howard Howie (Knoxville, Term.)—The authors are to be congratulated on the presentation of a paper containing so much valuable information on the pipeline transportation of phosphate, as there is very little literature on the subject. The writer is especially interested in the paper, as he conceived the arrangement of the Akin and Godwin plants and was in charge of the design work and the engineering incident to their construction. The Akin and other phosphate deposits in the Tennessee phosphate area lie on beds of limestone that are very irregular. The limestone beds, after the phosphate matrix has been removed, are similar in appearance to land severely eroded by the action of water and denuded of top soil. Depressions in the limestone, called cutters, are irregular in depth with vertical or overhanging walls, having the general appearance of cracks in dried clay. They change abruptly in direction, width, and depth, and vary on the Akin tract from 1 to 25 ft in depth and from 1 to 50 ft in width. Pinnacles of limestone commonly occur in the cutters which appear, when exposed, like small clifflike islands in a river. Limestone floats also occur. The phosphate matrix fills the cutters and covers the uncuttered areas, the thickness of the cover varying continually and sometimes rather abruptly. It occurs generally as stratifications of phosphate rock and clay of varying thickness. The phosphate rock in the matrix varies in hardness and in percents of silica, lime, iron oxides, and fluorine, and the clay varies in toughness. In some places the deposit consists of narrow strata of rock almost devoid of clay streaks. In other nearby locations the clay will predominate. When it is excavated, the phosphate rock breaks into thin irregular lumps, locally known as plate rock. Limestone lumps are also excavated with the matrix. Akin plate rock is generally much softer than that occurring in other deposits in the area. Because of the above described physical and chemical variations of the excavated material, the resultant slurry varies in size distribution, specific gravity, and percent of slimes. When the rock is soft or when there is an increase of clay, the slime fraction is greatly increased as it passes through pumps and pipelines, resulting in reduced pipe friction. It is obvious that the longer the pipeline the greater the reduction of coarse fractions into fines, causing a decrease in pipe friction that cannot be accurately evaluated. The matrix is mined with a dragline that drops it into a hopper with a grid composed of 9-in. parallel bar spacings located above the hammer mill. The matrix on, and passing through the grid, is subject to the action of powerful sprays which wash it down to the hammer mill, together with any limestone lumps that are not removed before passing through the grid. The hammer mill reduces the feed to lumps of plate rock and clay, most of which will pass through the 8-in. pump suction. The mixture discharges into a pool containing the pump suction pipe. Water from a hydraulic nozzle moves the mixture to the pump suction intake. The pump, driven by a variable speed motor, is the same size as the pumps mentioned on p. 279. Provision is made to remove any lumps that lodge in a bend in the suction pipe in a manner similar to that used in the Florida phosphate fields. The hammer mill and pump units are mounted on wide steel skids so that they can be moved as the mining operation progresses. The discharge from the pump flows through an abrasion-resistant spiral welded steel pipe 8 1/4 in. actual inside diam, 8 in. nominal diam, for a maximum distance of 2200 ft, which is the limiting pumping distance for one pump. This pipeline, referred to hereafter as pipeline A, discharges into a ball mill without balls, which in turn discharges into a rotary screen attached to it that separates the slurried matrix into 11/4-in. oversize and undersize fractions. The oversize is returned to the mill for further reduction; the undersize is pumped to a Dorrco washer and then flows into a hydroseparator 160 ft in diam. In spite of the size reduction in the hammer mill and the blunging and washing of the slurry in its passage through the pump, pipeline, mill, and washer, the discharge to the hydroseparator frequently contains mud balls almost perfectly spherical. Sometimes the discharge from the 16,000-ft pipeline at Godwin contains mud balls the size of bird shot and smaller. This pipeline will be referred to subsequently as line B. Liquid caustic is added to the slurry at the Akin plant before its passage through the hydro-separator, which decreases the size of particles in the overflow by dispersion. In passing through pumps 1, 2, and 3 and pipeline B, the slime fraction in the underflow is increased by abrasion and blunging and also by continuing dispersive action of the caustic. The matrix for use in the experimental tests referred to on p. 279 was obtained from three small surface openings on the Akin tract that were made previous to the purchase of the tract by the Authority. Matrix used in the 2 and 4-in. experimental pipeline tests was taken from the three openings and proportioned to obtain a sufficient quantity that would be fairly representative of the average in the Akin deposits. Prospecting samples of matrix had been obtained from drill holes which showed no small variation in physical and chemical properties. Some of the physical variation is evident from the size distribution of solids in samples taken during the tests covering line B flows so thoroughly made by the Authority under the direction of Mr. Burt, see Table V, p. 280. Hydraulic gradients for a pipe of 8-in. diam were derived from the 2 and 4-in. pipeline tests using the so-called representative matrix as above described, and plotted on the profile of pipeline B. Gradients of other materials in slurry form passing through pipelines that bore some similiarity to the Akin matrix slurry were also plotted. After a study had been made of the hydraulic gradients plotted on the profile and the varying slurry flow that would probably occur during actual operation, three pumps were ordered, referred to as No. 1, 2, and 3 on p. 279. No. 1 and 2 pumps were installed and the third kept in reserve should the operation of 1 and 2 pumps prove satisfactory, since installation of the third pump would require an attendant, as well as the laying of 5400 ft of pipe to supply it with seal-water from the Akin plant. Subsequently, it was found desirable to install the third pump to maintain capacity when the slime fraction was low and the coarse fractions were large. Reference to Fig. 6 will show that the flow in B line goes upgrade in three locations. At the outlet at Godwin, the slurry flows between two 45" bends for an approximate distance of 18 ft to rise above the ground a sufficient height to discharge into a launder feeding the first classifier. This condition requires extra energy, which is taken care of by keeping the hydraulic gradient a sufficient distance above the high points. Although there are rather heavy upgrades in the line, the choking condition that might occur at the

Jan 1, 1953

By Reginald S., Dean

The commercial availability of electrolytic manganese has greatly changed the position of manganese as a nonferrous alloying metal. Manganese metal commercially available up to about ten years ago was reduced with either silicon or aluminum and contained substantial amounts of the oxides of these metals and other impurities. Manganese was accordingly not available as an alloy base and its addition to copper-base and nickel-base alloys was generally limited to a manganese content of a few per cent. Several special alloys like manganin contained up to 12 pct of manganese.

Jan 1, 1953

By C. B. Sawyer

ALTHOUGH the element beryllium was discovered as the oxide by L. N. Vauquelin in 1797, this metallic element was not produced until about 1828, and then only as an impure powder. Thereafter the greatest single contributor to our early knowledge of beryllium was Lebeau who, in about 1899, made pure beryllium crystals by electrolysis of the fluoride and then beryllium copper by the arc-furnace reduction of beryllium oxide with carbon and copper. About twenty-five years later, under the impetus of the work done by Siemens-Halske, beryllium commenced to make relatively rapid gains in industrial importance, principally when alloyed with copper. At the present half century mark, its use is firmly established in beryllium copper and in X-ray disks of pure beryllium. Its use as a moderator in nuclear processes in piles is engaging experimental attention and might become important. Other minor uses, but increasing in interest, are in nickel-base or iron-base alloys as a strengthening agent; as a protective agent against oxidation in aluminum and magnesium-base alloys; and as a ceramic in the form of the pure fused oxide. A false start was made in the wide use of beryllium oxide as a fired fluorescent powder known as beryllium-zinc silicate, a component of the inside coating of fluorescent lamps. This application, wherein general use by the public attained some importance, was abandoned a few years ago. This action was a consequence of the uneasiness which had been generated during the past decade by the sometimes fatal health hazard to the pulmonary tract now generally attributed to beryllium and some of its compounds. Numerous law-

Jan 1, 1953

By C. A. Herbert

This paper sets forth the hazards of accumulations of explosive mixtures of methane and air due to inadequate ventilation, the causes of which are discussed as follows: 1. Lack of well-maintained air courses. 2. Air losses due to leaky stoppings, trap doors, and overcasts. 3. Faulty mining methods. 4. Poor supervision. A modified plan of room-and-pillar panel mine development is suggested, which, it is believed, will eliminate many off the hazards of gas accumulations inherent in the present method of mine development. It is also suggested that some water-proofing agent be used on the roof of permanent air-course entries in conjunction with roof bolting to eliminate the detrimental effect of the moisture-laden atmosphere during summer and thus prevent serious roof falls.

Jan 1, 1953

By Bunting S. Crocker

EBBLE grinding at Lake Shore is not a temporary BlE wartime substitute. The tube milling plant, with a 1000 ton per day capacity, grinds a hard siliceous ore to 90 pct — 325 mesh. The plant, prior to using pebbles, was consuming 4.3 lb of 11/4-in. grinding balls per ton of ore, which amounted to 785 tons of balls per year. At September 1951 prices, $132.60 per ton, this steel cost amounted to $104,400 per year, or $0.285 per ton milled. By the Lake Shore method of substituting screened rock for this steel, all of this cost is saved. This is one of the major economies in Lake Shore mill practice. Regardless of the ultimate price of grinding balls, a change back to steel balls is not considered. The present pebble plant is more flexible than a steel ball plant and equally efficient. For example, if it is desired to change the size of grinding media, the pebble charge in any mill can be changed completely in 4 to 5 days, as against 76 days to change completely a 1-in. steel ball charge. To change pebble size it is necessary only to change two sets of screens and clean out the rock feed storage bin. This will take 8 to 10 days as against 3 to 4 months to clean out the customary supply of grinding balls kept on hand. Also it has not always been possible to purchase all desired sizes of balls at any price. In an analysis of savings effected by the use of the pebble mills, the flexibility of the Lake Shore grinding plant should be discussed, as it has a direct bearing on these savings. The plant has always used several units to handle tonnage rather than sending all the tonnage through a single unit. This principle may result in using small diameter mills, but no objection to that is seen. At no time has any advantage been found in cost per ton ground in large diameter mills. Both the capacity and the power of any mill varies as the diameter raised to the 2.6th power. Consequently large or small mills are equally efficient, and a plant, should be designed to use as many units or combination of units as is consistent with reasonable operating practice. Mills under 5 ft diam are harder to reline, etc. To define the case at Lake Shore, 2600 tons per day formerly were milled in seven 7x6-ft ball mills and twelve 5x16-ft (and two 6x16-ft) tube mills.* This gave an excellent test plant and an extremely efficient one. In this plant the ratio of ball mills to tube mills was 1:2. When the much cheaper pebble mills were substituted for the tube mills, this ratio was changed to one ball mill to four pebble mills to take the greatest possible advantage of the cheaper operating mill, i.e., the pebble mill. This flexibility without loss in efficiency has been an important item in the cost savings. It is interesting to note that the use of pebbles for fine grinding was proved first in the laboratory in a 12-in. ball mill. In fact, since 1934 all testing on — 8 mesh material has been done in this 12-in. mill. Scope of the Tests A paper on fine grinding at Lake Shore Mines was published in July 1940.' This paper covered 7 years of intensive research on fine grinding as well as sizing methods and equipment, plant scale grinding tests on 5x16-ft tube mills with and without grate discharges both with 1-in. and -in. balls, the use of laboratory mills to evaluate plant changes, and several reports on classifiers and classification. In the following July the addendum report2 was added in which the idea of series-circuit grinding was introduced, and the results of running five stages of tube mills and bowl classifiers were shown. Since 1940, the ball milling end of the plant has been altered extensively as a result of tests on the use of 3-in. rods in 7x6-ft mills and the use of the Tyler repulping screen with from 7 to 14 mesh screens. These tests are lengthy and may be covered in a separate report later. The scope of this report is confined to ore ground by rod milling and ball milling until it passed through an 8 mesh Tyler Ty-rod screen. The —8 mesh screen undersize then was pumped to a primary bowl classifier in open circuit and the sands from the bowl sent to the primary pebble mills, see Fig. 1. In the pebble mill circuit the ore is ground to 90 pct —325 mesh (24 pct + 28 microns). In studying the flowsheet, attention should be paid to the efficiency of the classification equipment used. The Tyler repulping screen is an efficient machine on the 8 to 10 mesh separation, and the bowl classifier is equally efficient at the 325 mesh separation. Efficient classification is a necessity for series-circuit stage grinding. The ore is hard siliceous porphyry, 60 pct SiO,, 80 pct insoluble. Its grindability at different meshes has been shown near the top of the list in F. C. Bond's grindability tests.' Lake Shore is not shown, but an adjacent mine with identical ore, Wright-Hargreaves, is. Reasons for the Changeover Since 1936 grinding balls have been rising steadily in price with no sign of stopping. For a mill that used 4.5 to 5.2 lb of grinding balls for every ton of ore ground this rise represented an alarming increase in grinding costs. In many cases the quality of the grinding balls fell off as the scrap steel became more difficult to obtain. The ratio of tube mills to ball mills increased with the use of the Tyler repulping screen in the ball mill circuit. Originally only 3.0 lb of balls per ton were used in the tube mills, and this

Jan 1, 1953

By E. S. Machlin, Morris Cohen

The isothermal formation of martensite in a 71 pct Fe, 29 pct Ni alloy is found to take place mainly by the nucleation of new plates rather than by the growth of existing ones, and is dependent on the temperature and time of the isothermal hold, the amount of atherrnal martensite present, the state of internal strain, and the application of tensile stress. The conclusion is reached that the isothermal nucleation is activated by thermal fluctuations superimposed on localized regions of very high strain. The reaction-path concept, involving martensite nucleation at strain embryos by athermal activation on cooling, or by thermal fluctuations on holding, reconciles the athermal and isothermal modes of transformation, and offers a unified picture of the kinetics of martensite formation. THE phenomenon of isothermal martensite formation has been the subject of considerable study lately,'-' and its reality has been thoroughly established. The existence of such isothermal transformation has been claimed to confirm the nucleation and growth hypothesis as applied to the martensitic reaction.1 " However, the isothermal formation of a martensitic phase is also compatible with the reaction-pathw escription of the transformation. The purpose of this investigation is to examine the isothermal mode of the martensitic reaction, both theoretically and experimentally, in order to test the likelihood of the above two mechanisms. Material and Methods The alloy used in this study contained about 71 pct Fe and 29 pct Ni. The complete analysis was 29.5 ± 0.2 pct Ni, 0.036 pct C, 0.02 pct N, 0.19 pct Mn, 0.09 pct Si, 0.008 pct P, and 0.006 pct S. The amount of isothermal transformation was determined by electrical resistance measurements using a Kelvin double bridge. The specimens were in the form of rods 1/16 in. diam x 4 in. long. Aus-tenitizing was performed at 1095°C for % hr either in a pre-purified nitrogen atmosphere or in an evacuated Vycor tube, followed by oil quenching to room temperature. After this treatment, the samples were completely austenitic, and the transformation studies were conducted at subatmospheric tempera- tures. Lineal analysis and X-ray determinations of retained austenite were used to calibrate the electrical resistance changes in terms of the percentage of martensite. The martensite range curve for this alloy is given in Fig. 9 of ref. 6. The M, temperature occurs at about -18°C (255°K). Reaction-Path Theory The nucleation and growth description of the martensitic transformation that occurs isothermally has already been given by Kurdjumow.','2 However, no comparable treatment exists using the reaction-path concept." Consequently this section presents the reaction-path description of the isothermal mode of the martensitic transformation. According to the latter theory, there is a reaction path (a strain) which describes the relative motion of the atoms during their transference from the austenitic to the martensitic state. The possibility exists, therefore, that the nucleation of a martensitic plate is accomplished by an embryo that comprises a state intermediate between that of austenite and martensite. This state may be attained within a finite volume by means of a homogeneous strain of the austenitic matrix. There is a free-energy barrier (F.) along the reaction path, corresponding to a critical strain in a critical volume. When activation is achieved, a spontaneous increase in strain and volume of the embryo takes place to generate the full-size martensitic plate. This mode of nucleation is to be distinguished from the more conventional mode involving embryos of the martensitic phase that merely grow in size by an interface motion. There are two ways whereby embryos in the austenitic phase can achieve the critical state of strain for isothermal nucleation: 1—through the formation of internal strains by plastic deformation or by stress; and 2—through thermal fluctuations, preferably superimposed upon existing internal strains. The activation free energy F,, must be supplied either mechanically by internal strains or thermally by energy fluctuations, or by a combination of both.

Jan 1, 1953

The Mungana group of mines, in the Chillagoe district, yielded 334,000 tons of ore giving 31,831 tons of lead, 7,907 tons of copper and 3,228,600 ounces of silver. The Girofla mine produced approximately 220,000 tons of ore, and with the Lady J ane mine supplied most of the ore from this centre. The deposit was discovered in 1888, but active development did not commence from the main shaft until 1898. A subsidiary of the New Chillagoe Railway and Mining Co. Ltd., the Mungana (Chillagoe) Mining Co. Ltd., worked the mine from 1902 until 1914, selling copper, copper-lead, lead ores and fluxes to the smelters at Chillagoe. The smelters stopped operations in 1914 when the richer ores of the Girofla had been worked out and production from the Lady Jane had ceased due to heavyground and fire. The Girofla shaft was 823ft. deep with a cross-cut at 810ft. At the 710ft. level contour drives had delineated the orebody, which had been stoped about 10ft. above the level. Except for flux ores which had been stoped only for favourable smelter tariffs, the orebody was practically exhausted above the 610ft. leveL Under company ownership the mine yielded 139,265 tons of an average grade of 4.QlYr copper, 16.2% lead and 12.5 oz. per ton silver.In 1921 the Queensland Government re-opened the mine and worked it until 1927. The North Lode (Fig. 2) was discovered almost immediately at the 100ft. level and was worked down to the 410ft. leveL The ore from this branch and the completion of the stope at the 710ft. level yielded about 80,000 tons of ore averaging 0.4 copper, 9.8 lead and 7.8 oz. per ton silver during this period.

Jan 1, 1953

By Dubois Eastman

BEHIND the contrasting liquid-fuel technologies of Germany and the United States lie the basic differences of scarcity and abundance. The chemists and engineers of each nation have developed processes that accommodate available raw materials. In the United States, processing is based on an abundant supply of petroleum, which is refined into a variety of fuels and lubricants. Germany has little indigenous petroleum but has a readily available supply of coal that can be converted into liquid fuels and lubricants. As a result, in Germany several basic processes have been developed for the conversion of coal into synthesis gas (carbon monoxide and hydrogen). In turn, this gas is processed into products. As a normal function of its researches into petroleum processing, the petroleum industry in the United States has made careful studies of various conversion and synthesis techniques. A number of oil companies are carrying out independent development programs with the aim of synthesizing hydro- carbon products that can be marketed at a price that will compete with the price of refined petroleum products. American oil companies hope to perfect synthesis processes that will directly benefit the consumer. A good example of progress in these terms is the synthesis plant at Brownsville, Texas, which is based on the conversion of natural gas to synthetic fuels and other valuable products. When this plant is operated at near capacity, it is expected that the products will be able to compete favorably for the consumer dollar. The complete gasification of coal is a technique well rooted in history. As a controlled process on a small scale, it goes back centuries. As a practical technique on a commercial scale, it dates back to 1839, when "producer gas" appeared in Germany for limited industrial use. By 1873, "water gas," or "city gas" as it is sometimes called, was being manufactured commercially in the United States for use in heaters and stoves. The water-gas process was the cornerstone for modern synthesis. To older methods that were concerned only with carbon and oxygen reactions, it added hydrogen by means of steam. Thus far the goal of conversion was to produce gas for heating, lighting, industrial use, and cooking. The long step forward to synthesis was made in 1927, when Germany started to make gasoline from coal by means of the revolutionary Bergius hydrogenation process. A year earIier, Franz Fischer and Hans Tropsch had announced their process, which finally reached the

Jan 1, 1953

By A. F. van Everdingen

The pressure drop in a well per unit rate of flow is conrolled by the resistance of the formation, the viscosity of the fluid. and the additional resistance concentrated around the well bore resulting from the drilling and completion technique employed and, perhaps, from the production practices used. The pressure drop caused by this additional resistance is defined in this paper as the skin effect. denoted by the symbol S. This skin effect considerably detracts from a well's capacity to produce. Methods are given to determine quantitatively (a) the value of S, (b) the final build-up pressure, and (c) the product of average permeability times the thickness of the producing formation. INTRODUCTION Equations which relate the pressure in a well producing from a homogeneous formation with pressures existing at various distances around the well are generally used within the industry. The relation ii quite simple when the fluid flowing is assumed to be incompressible. It becomes somewhat more complicated when the flowing fluid is considered compressible so that the duration of the flow can he considered. In each case the major portion of the pressure drop occurs close to the well bore. However analyses of pressure build-up curves indicate that the pressure drop in the vicinity of the well bore is greater than that computed from these equations using the known, physical characteristics of the formation and the fluids. In order to explain there excessive drops it is necessary to assume that permeability of the formation at and near the well bore is substantially reduced as a result of drilling. completion and, perhaps. production practice. This possibility has been recognized in the literature. A method to compute the pressure drop due to a reduction of the permeability of the formation near the well bore. which is designated as the skin effect. S, is given in the following paragraphs. To start, equations normally used to describe flow in the vicinity of a well are given without considering this effect. These equations then are modified to include the effect of a skin on the pressure behavior. Finally a method is given to estimate the effect of the skin on the pressure and production behavior of a well. PRESSURE EQUATIONS Incompressible Fluid Flow If p is defined as the flowing pressure in a well of radius the pressure at distance r from the well has been shown to be:" The total pressure drop between the drainage boundary, and the well bore is given by These equations are valid only if the flow towards the well occurs in a horizontal homogeneous medium and the fluids are incompressible. The assumptions imply that all fluid taken from the well enters the system at r a condition rarely encountered in practice. Compressible Fluid Flow, Steady State A more realistic equation is obtained if it is assumed that the compressibility, c, of the flowing fluids is small and has a constant value over the pressure range encountered. After the well has been producing for some time so that its rate has become constant and steady state is reached, the pressures throughout the drainage area are falling by the same amount per unit of time, and the pressure differences between a point in the drainage area and the well are constant. When these conditions are met. the rate of production, q, from a well is equal to where dp/dt is the pressure drop per unit time. The fluid flowing at a distance from the center of the well is equal to From the last equation and from Darcy's law it can be shown that The equation holds for a depletion-type reservoir of radius drained by a well located in its center, provided the compressibility of the fluid per unit pressure drop is small and constant, and no fluid moves across the boundary Compressible Fluid Flow — Nonsteady State Table 111 of reference (5) shows the relationship between the pressure at the well bore and the reduced time, The pressure-drop function, p represents the drop below the original reservoir pressure, p caused by unit rate of production for several values of R, the ratio of drainage boundary radius to well radius, r In most reservoirs the values of approach infinity. and under these conditions the values of p shown in Table I of reference (5) can be used where p then signifies the difference between the pressure in the well and the prevailing reservoir pressure per unit rate of flow. The total pressure drop below prevailing reservoir pressure amounts to where the factor converts the cumulative pressure drop per unit rate of production to cumulative pressure drop for actual rate. q. For values of T > 100 the P function may be written (equation VI-15 of reference 5) as Using the time conversion the difference in pressure between reservoir and well becomes If values for the physical constants of the formation and the fluids are inserted, it is found that T exceeds 100 after a few seconds of production (or closed-in time), so that the approximation becomes valid almost at once. A simple relation between the pressure in the well and in the reservoir can also be derived by considering the well as a point source"" '" instead of a unit circle source, that is, by using Lord Kelvin's solution instead of the unit circle source

Jan 1, 1953

By Frank C. Kelton

It is perhaps not widely realized that extraction and saturation processes carried out on oil well core samples alter the properties of these samples to varying degrees. On the other hand it is felt by some that quick-freezing of core samples increases their permeability and porosity significantly. Accordingly, laboratory tests were carried out on 49 pairs of horizontally adjacent samples in order to differentiate between the effect of quick-freezing per se on permeability and porosity of the samples, as distinguished from the effect of the identical saturation treatment on permeability and porosity of the companion samples. Also, additional field data were obtained on comparison of frozen vs unfrozen companion samples. LABORATORY INVESTIGATION OF FREEZING us SATURATION EFFECTS Procedure The samples used in these tests were two-cm cubes cut in horizontally adjacent pairs from cores from eight Gulf Coast and Mid-Continent wells, which cores had not previously been frozen. These samples were extracted with carbon tetrachloride, dried, and air permeabilities run in the conventional manner. They were then evacuated and saturated with brine of 25,000 ppm sodium chloride content, and porosities determined by gain in weight. The samples were partially desaturated by evaporation down to an average brine saturation of 68 per cent. One sample from each pair was quick-frozen by covering with dry ice after wrapping in a single layer of paper, and allowed to remain frozen for about two hours; the companion sample from each pair was not frozen. After thawing the frozen sample, all samples were immersed in tap water overnight in order to leach out most of the brine. Air permeabilities were re-run, and the samples were again saturated with brine to determine a second porosity value. For purposes of averaging of data, the samples were grouped according to four permeability ranges, from 0 to 10, 10 to 100, 100 to 1,000, and 1,000 to 3,840 md. Average permeability and porosity changes for the frozen vs the unfrozen adjacent samples are shown in Table 1. Discussion As may be seen from Table 1, the averages of the per cent permeability increases for the quick-frozen samples ranged from 3.8 to 12.9 per cent among the four permeability groups. The average changes among the four groups of unfrozen companion samples ranged from a decrease of 0.2 per cent to an increase of 9.3 per cent. There was no particular correlation of these changes with magnitude of permeability; however, the increase for each group of frozen samples paralleled the increase for the corresponding unfrozen samples. The differences between the two sets of values are believed to be a valid indication of the effect of the quick-freezing in itself, since the treatment of the two samples in each pair was identical except for freezing. The permeability changes which are strictly the result of the quick-freezing are shown in the sixth column of Table 1. These range from a decrease of 0.9 per cent to an increase of 4.0 per cent; the overall weighted average is 1.2 per cent, as compared to an average increase of 6.8 per cent caused by the saturation treatment of the samples not frozen. The average porosity changes are in general smaller than the changes in permeability, and range from a decrease of 2.3 per cent to an increase of 3.3 per cent. The overall weighted average change ascribed to the quick-freezing is 1.0 per cent of porosity. Many factors can contribute to the changes in permeability and porosity observed when subjecting cores to the simple processes used in these tests. Such are: hydration and swelling of clay, adsorption of ions, changes in surface structure and wettability, expansion and compression effects due to ice formation, shrinking and cracking, leaching of salts and colloids, displacement of particles resulting in either blocking or enlarging of pore openings. Whatever particular mechanisms are involved. however, it is apparent not only from this study but also from other investigations in the literature' not directly concerned with quick-freezing, that the effects produced by commonly used extraction, saturation and drying techniques may be of considerable magnitude The results of this study indicate that for the particular samples and techniques used, such effects are of the order of five to six times the effect of quick-freezing. insofar as changes in permeability are concerned. It may be argued that these samples might not include extremely shaly material where the effect of freezing upon permeability may be much greater. However, had such material been available for these tests, it would undoubtedly have been very susceptible also to alteration by the extraction and saturation treatment used. To investigate this point further, the individual sample data were re-grouped according to the magnitude of the average per cent permeability increases for the pairs of samples, irrespective of permeability. The results

Jan 1, 1953