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By John L. Lamont, Walter Crafts

THE principle formulated by Grossmann1 for calculating hardenability of steel by multiplying the ideal diameter of "pure" iron-carbon alloys by factors for grain size and alloying elements has been confirmed on many steels and has proved useful in designing substitute alloy steels. Grossmann found that the typical behavior of the multiplying factors was to increase directly in proportion to the amount of the alloy present in a steel. However, the multiplying factor for the effect of silicon on hardenability was found by Grossmann to increase to a lesser degree as the amount of silicon was increased. In view of the in¬creasing use of silicon in heat-treating steels, the effect of silicon on hardenability is becoming more important. Calculation of the hardenability of high-silicon steels made at the Union Carbide and Carbon Research Laboratories, Inc., indicated that the multiplying factor for silicon increased directly in proportion to the amount of silicon present. A more extended study of high-silicon steels covering fairly wide ranges of grain size, carbon, manganese, and aluminum has confirmed that up to 2 per cent silicon the multiplying factor is directly proportional to the silicon content. Manganese and aluminum factors have also been determined. The results of the study offer strong confirmation of the general validity of Grossmann's multiplying principle. TESTING PROCEDURE Steels on which the study of the effect of silicon on hardenability was based were made in high-frequency induction furnaces using Armco iron and standard alloying materials. The ingots were forged to bars, and sections were normalized prior to machining Jominy hardenability test specimens. The Jominy test was carried out under standard conditions.2 The depth of hardness penetration for determination of ideal diameter at "half hardness" was taken at the hardness level indicated in Fig. 20 in Grossmann's paper by the solid line for 50 per cent martensite in plain carbon steel. The depth of penetration of hardness on the Jominy specimen was converted to ideal diameter by the relation given in Fig. 28 of Grossmann's paper. Chemical analysis was determined on a sample taken adjacent to the Jominy specimen. Aluminum was determined as "acid-soluble aluminum" rather than as total aluminum, as it is probably more representative of the aluminum that is effective as an alloying agent. In addition to the elements nominally present in the steels, analyses were made for residual phosphorus, sulphur, nickel, copper, molybdenum and chromium on one heat of those made with the same materials during the same period. Actual grain size was determined by microscopic examination of small samples quenched in water after receiving the same thermal cycle as the Jominy hardenability specimens. Chemical analyses, heat-treatment, grain size, and hardenability are shown in Table I representing three ranges of composition.

Jan 1, 1943

By Axel Sahlin

The day is long past when linen and cotton rags were the exclusive raw material of the paper-trade. Wood-fiber, chemically or mechanically prepared, straw, hemp and Esparto grass have largely supplied the demand, which the old materials did not suffice to fill. But even these newer fibers have been of late supplanted, to some extent, by mineral pulp. Weighting and filling materials have also been resorted to, partly to give body to the fabric, partly to increase its weight and reduce the cost per pound. China clay, sulphate of lime and soapstone have generally been employed as loading materials. Even though these materials lack fiber, their addition must by no means be viewed, as it too generally is, entirely as an adulteration. No doubt, to a certain extent, they weaken the paper ; but for ordinary grades the addition of these non-fibrous substances is a positive advantage, as they close the pores between the fibers and lend to the paper a great degree of opaqueness and a superior finish. Fibrous talc, as a form of pulp, has the same effect, without appreciably weakening the paper. When, therefore, some fifteen years ago, fibrous talc in large quantities, and of marvellous purity and whiteness, was discovered in the neighborhood of the town of Gouverneur, it was not long before the

Jan 1, 1893

By Erwin S. Sperry

The oxidation of metals melted in contact with air takes place with dissimilar results. Tin, lead or zinc are examples of a class, the oxides of which float on the surface of the melted metal. First a film is produced, which covers the surface; then, if agitation from any cause exposes new metal to the action of the air, additional oxidation takes place, and the film is increased in volume. This change goes on until a considerable quantity of oxide (or " dross," as it is technically called) is formed; depending, of course, upon the duration of the exposure of the metal to the atmosphere. When such metals are poured, the dross may be skimmed off; and clean metal will be left underneath. The removal of such oxides is, therefore, merely a mechanical process. In the case of copper, however, the result is quite different. The sub-oxide of copper (Cu2O) is readily soluble in molten copper; and therefore, instead of the formation of a film of oxide, to be finally removed as dross, the surface of the metal remains bright and clear, because the oxide has been dissolved as soon as it was produced. It is customary in the process of copper-refining to leave a small quantity of oxide in the metal, in order to oxidize any traces of bismuth, arsenic or antimony which have not been entirely removed. As a result, these metals exist in the commercial product as oxides, and not as metals, which would form an

Jan 1, 1901

By E. T. Dumble

The domes of the Texas coastal plain are structural features, consisting of bosses or stocks of salt, gypsum or anhydrite, or of combinations of these, intruding into and occurring in connection with broken and uplifted sedimentary beds of Cretaceous and Tertiary age. Some of these domes show on the surface as mounds of greater or less elevation, while others are only known from drilling records. They may be divided into two classes: interior domes and coastal domes. The interior domes include those which occur in a zone 40 to 50 miles in width lying immediately east of the Cretaceous-Tertiary contact, and extending from the Sabine to the Colorado. With a single exception, these domes, so far as now known, occur in approximate alignment with the contact, but at irregular intervals. East of the Brazos, the domes are entirely surrounded by Eocene sediments. The coastal domes are found nearer the Gulf, lying entirely within Neocene territory and stretching from the Rio Grande to the Sabine. They are much more numerous than the interior domes, and, apparently, are ranged along several lines having a general northeast-southwest direction. No domes are known in the Oligocene belt. INTERIOR DOMES The interior domes so far, identified are Butler's, in Leon county, Palestine and Keechi in Anderson county, Brooks and Steen in Smith county, and Grand Saline in Van Zandt. In connection with these interior domes we must also consider the Sabine Peninsula,. of Harris, which is, without question, genetically connected with them. The Palestine and Keechi domes have been described recently by 0. B. Hopkins,1 who gives a clear idea of their corn position and structure. Others have been described at different times, and an excellent resume of the literature is given by De Golyer.2 _

Jan 10, 1918

By H. H. Richardson, E. H. Dix

Of all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations would have been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 525" C. to about 1 per cent. at 300" C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540" C., and that this amount decreases to about 3 per cent. at 20" C. In the same year Ohtani and Hemmi3 reported a solubility of 4.8 per cent. copper at 520" C., 2.6 per cent. at 460" C. and 1.5 per cent. at 420" C.

Jan 1, 1926

By J. Elmer Thomas

If 1929 witnessed a growing realization on the part of the oil industry that supply must be balanced against demand, 1930 proved conclusively that excessive inventories constitute a price depressant even with balanced conditions. Increased attention was certainly paid to economic considerations last year, and the achievement of holding daily crude production, with a constantly mounting potential, to levels 500,000 bbl. below the output of the summer before, deserves special mention. The ill-advised accumulation, however, of gasoline stocks, at least 10,000,000 bbl. larger than necessary, nullified the restraint exercised by the producers and finally necessitated drastic downward price revisions. An event of special significance was the appointment by the Federal Oil Conservation Board, last March, of a temporary Committee on Petroleum Economics that attempted a forecast of demand, an estimate of supply, and an allocation of the latter between the principal producing states. Thus for the first time was an economic program for an entire basic industry drafted by an independent body under the auspices of the Federal Government. The report was widely discussed and generally approved, but its schedules were not adopted by the refining division nor by oil producers in the State of Texas until too late to contribute to the industry's prosperity during 1930. If the restraint of November had been exercised in May a profitable year might have been the result: The gasoline price war in California during June, however, illustrated the point that even with a fairly sound statistical position insistent pressure to expand normal marketing outlets must result in losses to all concerned. The balanced program so painfully attained by producers must be maintained by refiners and distributors to be completely effective. Again in November the Federal Oil Conservation Board, acting on the request of the directors of the American Petroleum Institute, called its Committee on Petroleum Economics back into existence to prepare a new estimate for the next six months. An economic program adopted in advance of the winter period of accumulating inventories may aid this large and essential industry toward the profits to which it is entitled

Jan 1, 1931

By G. L. Wilhelm

Prior to the construction of a 450 tpd concentrator at the Mayflower mine, owned by the New Park Mining Co. and operated by the Hecla Mining Co., the common mining methods were cut and fill, with waste or gob filling and square set timbering with waste fill. Stoping operations were beset with the usual problems related to waste filling methods- storage and handling of fill material from development, costly waste excavations necessary to obtain a portion of the needed waste rock, slow mining cycles due to filling and inefficient ground support. After Hecla Mining Co.'s successful utilization of sandfill in its mines in the Coeur d'Alene district, utilization of hydraulic fill in stoping operations at the Mayflower was a logical development of the modernization plan then in progress. The mine, located in the southeasterly part of the Park City mining district, Utah, is a medium size producer of lead and zinc ores, with gold, silver and copper as secondary minerals. The mine has been producing commercial ore since 1939 from a dual vein system which outcrops at an elevation of 7200 ft in the Wasatch Range. Access to the present mining areas is gained by a 7200-ft haulage tunnel and by an interior, three-compartment main shaft. The present mining horizons are about 2400 ft deep. The average horizontal cut and fill stopes, ranging from 3-15 ft wide and up to 120 ft long, can be classed as small.

Jan 5, 1968

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,' petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-'I2 increases (where d is the grain diameter). These results can be understood in terms of Petch's analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

By Russell Gibson, F. S. Turneaure

The tin deposit of Monserrat, Bolivia, consists of one major vein 1600 m in length. The ore is unusual because of the notable quantity of teallite, even though cassiterite is the principal tin mineral. The deposit, formed at shallow depth under a wide range in temperature, may be classed as xenothermal. Polished sections reveal a complex history of replacement, with low-temperature minerals deposited before high-temperature minerals.

Jan 10, 1950

By R. J. Wensley

The use of small substations for the supplying of 275-volt energy to the locomotive and cutting machines in coal mines is a well-established practice. A few years ago, when labor costs were lower, these substations were located as near to the load as possible, and an operator was provided for each station. This practice has now become so expensive that substations are being located with reference to other mining machinery, such as hoists or pumps, so that one operator can look after both. Sometimes the substation is operated by one whose duties make him traverse quite a large area. In such cases the interruption of alternating-current supply may produce a long interruption in the direct current, as the station cannot resume service until this man reaches it. Such interruptions interfere seriously with production and may easily counterbalance the supposed saving gained by such operating methods. The grouping of substations for convenience in operating may also result in excessive copper loss and consequently poor trolley voltage, with its attendant evils of low locomotive speeds and increased locomotive motor maintenance. The speed of the coal-cutting machines will also be reduced. By relieving the substation of its burden of the operating labor cost, the most economical location, from an electrical standpoint, may be chosen. The matter of machine insurance should also be considered. If an attendant is caring for several kinds of equipment, he cannot watch the machine continually for signs of trouble; therefore, continued overload, phase failure, low alternating-current voltage, bearing trouble, etc. may result. Some partly automatic equipments have been installed; these have protection against low voltage, reverse current, and bearing trouble and are provided with automatic reclosing circuit breakers. This is a step in the right direction but it does not go far enough to give first-class machine insurance. The saving in maintenance costs is often the smallest item, when considering the automatic substation as machine insurance. When the coils in a machine are roasted out, due to continued overload or to opera-

Jan 1, 1922

By William Loblowitz

A simplified system of flotation testing has been developed recently at the Bureau of Mineral Research of Rutgers University. The technique involves the known principle of skin flotation and can be used with minute quantities of sample and reagents in a beaker. A vessel containing the conditioned sample with added water and flotation reagents is held inclined and rotated slowly. Water-repellent particles come in contact with air and float on the surface of the liquid, while wettable particles are submerged. The float is poured off and filtered whereas the nonfloat remains in the beaker. The filtrate may be returned to repeat the process. This procedure can be made quantitative. Separations are obtained and are remarkably complete and repeatable. The effect of different reagents, optimum quantities, pH and other variables can be determined in a fraction of the time required for conventional testing. However, the method gives no information on the effect of frothers and the quality of froth to be expected in a cell, and it is not practical for particles finer than 200-mesh. Unlike other preliminary tests, separate float and nonfloat products are obtained, and their contents can be determined quantitatively by chemical analysis or grain counts. After the optimum reagent combination has been determined, the effect of fines and frothing may be verified in the conventional flotation cell. On the other hand, agglomeration-tabling can be directly duplicated from beaker tests. Procedure: Five to ten grams of sample are weighed into a 100-ml beaker. Flotation reagents and a small initial quantity of water are stirred together; additional water is then added to produce the proper water-solids ratio. The beaker is then tilted to 45" and rotated slowly. After three to five rotations, liquid and float are poured off and filtered; the filtrate may be recycled until the separation is completed. One test generally requires less than 10 min. Reagent concentration and pH remain quite constant because of the recycling of the filtrate. Two to four tests may be made simultaneously, and the effect of varied conditions may be observed by comparison. Considerable time is saved in preparation and handling since small quantities of sample suffice for a series of systematic tests. Repeatability One test was repeated four times under constant conditions. The sample used was a quartz sand containing approximately 24 pct feldspar and some clay aggregates. The +28-mesh grains had been screened out, and most of those finer than 100-mesh had been removed by hydraulic classification. The results are presented in Table I. For comparison, 500 g of the sample were separated by agglomeration-tabling using the same reagent combination and quantities as given in Table I. The weight percent float was 18.3 pct, composed almost entirely of feldspar and with only traces of quartz. Most of the remaining feldspar was recovered in a middling product with 2.2 pct by weight.

Jan 1, 1952

By Maurice Ewing

THE purpose of this paper is to present the results of the application of the earth-resistivity method of subsurface investigation to the problem of locating seams of anthracite coal beneath a mantle of soil and subsoil. Details are given of the successful use of this method in locating the outcrops of anthracite seams in actual prospecting. The presence of the outcrop of an anthracite seam is indicated at points where electrical resistivity tests showed relatively low readings. The reason for this is that in some localities the resistivity of anthracite was found to be about 0.0001 megohm-cm. compared to 1 to 200 megohm-cm. for shales and sandstones. For two reasons it is believed that the data sum-marized in this paper should be of particular interest. In the first place, most of the interpretations of the resistivity survey have been checked by subsequent drilling and some by the removal of the overburden and the exposing of the anthracite seams. It is infrequent that the oppor-tunity for checking results so thoroughly is given. In the second place, the fact that recent commentators1,2,3 on the application of geophysical methods to mining have concluded that direct prospecting for anthracite and other types of coal is not promising makes the good results obtained more significant. So far as the authors can learn, the only previous experiment with electrical methods in the Pennsylvania anthracite field was one made by Sherwin F. Kelly in 1922, when he used the self-potential method at Wilkes-Barre4. The profile he made does not show a very marked correlation with the geologic cross section. Kelly points out that stray currents from electric motors in the mines undoubtedly affected his results, but the experience of the present authors with stray currents from mining machinery suggests the possibility that the potentials measured by Kelly were due almost entirely to this effect.

Jan 1, 1936

By Albert J. Phillips

When brasses containing from 61 to 62.5 per cent. copper are very rapidly cooled from temperatures near their melting point to below 0" C., unusual results are obtained. These results are quite unexplainable from a consideration of the old copper-zinc constitutional diagram but they can be satisfactorily explained by means of the diagram revised by Genders and Bailey1 (Fig. 1). Experiments on a 60/40 Brass If an alloy containing 60 per cent. copper is heated to any temperature between approximately 760' C. and its melting point, it will consist entirely of beta. Upon slowly cooling, alpha will start to separate just below 760" C. Since this alpha will contain nearly 65 per cent, copper, the beta will be impoverished by its separation. As the temperature decreases the composition of the separating alpha will approach approximately 61 per cent. and the beta in contact with the alpha will maintain an equilibrium composition approaching 54.5 per cent. copper. If the rate of cooling is extremely slow, especially at the lower temperatures, stable equilibrium will be established by diffusion through the alpha and beta so that eventually 85 per cent. of the alloy will consist of alpha containing 61 per cent. copper, while 15 per cent. will be beta containing 54.5 per cent. copper. With a faster cooling rate diffusion cannot keep apace and the constituents will be cored, the alpha varying from 65 to 61 per cent. copper and the beta from 60 to 54.5 copper. In this case the amount of alpha will be less than 85 per cent. and the beta will be increased correspondingly. The general structure thus obtained is illustrated in Fig. 2. When a more rapid rate of cooling is effected by quenching in water, the alloy is retained largely in the beta form. However, the crystals of beta are usually outlined with dark fringes which at high magnifications are found to be very fine alpha-beta structures almost martensitic in appearance. The separation of this fringe can be greatly suppressed

Jan 1, 1930

By James Bowron

Considering the importance of the steel trade and the strategic position occupied in it by the Birmingham district, it may be surprising to many to learn that the first pig iron smelted with coke was made in Alabama on Feb. 28, 1876, although merchant pig iron had been produced in Rockwood, Tenn., in 1867 -a plant that is still in operation The heavy deposit of Clinton ore, extending from Pennsylvania into Alabama, varies greatly in accessibility, on account of geological changes such as erosion or anticlinal upthrow; it varies equally as much in thickness and in quality. The brown ores extensively scattered through the South also vary materially in quality—some are relatively low in phosphorus and high in manganese, and vice versa. The red ore varies materially in phosphorus, but the iron produced from this ore was always considered too high in phosphorus for treatment by the acid bessemer or open-hearth process and did not contain sufficient phosphorus for the basic bessemer process. Under these conditions there remained only the basic open hearth as a possible process; and for many years it appeared impossible to use this, because, with coke smelted iron, the silicon was too high to permit its use in basic lined furnaces. Various attempts were made, from time to time, to produce a low-silicon iron, by carrying high lime burdens together with harder blowing, but the blast furnaces of the South were not equipped with the blowing power of today and from 31/2to 5-lb. pressure was the normal working condition. The result of these experiments, therefore, was that a furnace would get a lime set or be hastily changed to avoid scaffolding, and engineers and superintendents were careful not to renew the experiments. After the development of the beds of dolomitic stone in East Birmingham, the carrying of sufficient lime to bring down the silicon in the blast furnace to the permissible open-hearth limit was successfully done at the Alice furnace in Birmingham, commencing July 22, 1895. In a very short time the entire output of that furnace was being sold to different Northern steel manufacturers, with a guarantee that silicon and phosphorus should run below 1 per cent.

Jan 1, 1925

By Charles Barrett

THE copper-silver system presents several points of special interest in the study of segregate structures. The system is simple eutectic, with limited solid solutions terminal with the pure component metals. The extent of solid solubility decreases with decreasing temperature for both the copper-rich and the silver-rich alloys, thus offering a possi-bility for the formation of Widmanstätten figures and also a possibility for aging after quenching. In contrast to the structures studied previ-ously the structures in this system are unique in their; origin, for one terminal solid solution will precipitate the other, and ice versa. In most of the other systems for which crystallographic data on the precipi-tation (or transformation) process are available, either intermetallic compounds or intermediate phases partake in the decomposition process; the absence of such phases thus distinguishes this system. The lattice structures of the two solid solutions are identical in type, differing in lattice spacing by approximately 10 per cent; because of this it seems difficult if not impossible to predict on the basis of present theory either the outward form of the precipitate or the lattice orientation relationships between matrix and precipitate. The eutectic temperature in the copper-silver system1 is 779°C. At this temperature copper -dissolves 4.3 atomic per cent (7.0 weight per

Jan 1, 1935

By G. D. Hobson, I. Mrosovsky

Material balance relationships for expansion-type reservoirs above the bubble point have been discussed in recent years by H. N. Hall and M. F. Hawkins, Jr. The former drew attention to the effects of rock compressibility, and the latter to the effects of the compressibility of any interstitial water. Hawkins derived a general relationship which took note of oil, water and rock compressibilities, and then by assuming first, the absence of interstitial water and secondly, no effects due to interstitial water or rock compressibility, obtained relationships symbolically of the same form as those previously derived directly by Hall. Hawkins defined his terms clearly, and noted an approximation, due to the omission of a term involving the product of two compressibilities, made in reaching his final equation. There is, however, possible ambiguity with regard to Hall's written definition of the oil production term. One interpretation would mean that the produced oil and initial oil-in-place, if both required as stock tank barrels, would be obtained by using different formation volume factors in the conversion in order to satisfy the conditions implicit in Hall's formulae. The other would involve an approximation which, if used, was not stated. In both Hall's and Hawkins' studies the effect of the approximation or inconsistency is very slight. Nevertheless, it may be justifiable to give a somewhat more consistent derivation, since the complexity of the final relationships is not thereby greatly increased. Let the initial pore volume be Vi and the volume after a pressure drop of Ap, V. Then V = V, (1 - ?p . cr), where c, is the rock compressibility expressed as change in pore volume/unit pore volume/unit pressure change, and is defined with the initial pressure as base. Suppose that the interstitial water saturation under the initial conditions is Sw. The total volume of interstitial water under those conditions will be ViSw. If the volume of the water after dropping the pressure by ?p is V., this will be given by Vw = ViSw (1 + ?p.c,w), the compressibility of the water being c, which is ex- pressed using the volume at the initial pressure as base. If Boi is the reservoir volume factor of the crude oil for the initial reservoir conditions, and B. the equivalent factor when the pressure has dropped by ?p, with N the initial amount of oil expressed as stock tank barrels. N.Boi = Vi - V,Sw If n is the amount of oil produced (in terms of stock tank barrels) as a result of the pressure drop ?p, the remaining subsurface volume of oil at the lower pressure will be Bw, and Bc can be related to the compressibi:ity of oil and the pressure drop, and if c, is the compressibility factor based on the initial conditions, The relationship derived by Hawkins was case to a standard at the lower pressure, while a term (Ap) had been dropped, because of its smallness arising from its dependence on the products of two compressibility factors. When there is no interstitial water and rock compressibility can be ignored, Eq. 1 reduces to:

Jan 1, 1957

By A. M. Sarem, J. M. Campbell

Molecular refraction is introduced as a new and improved third parameter for prediction of the PVT behavior of hydrocarbon systems. This parameter, characterizing the complex as well as the pure hydrocarbon systems (1) is a direct measure of London dispersion forces which affect the PVT behavior; (2) can be measured directly, accurately and easily for complex as well as pure hydrocarbon systems; (3) varies significantly between the reference substances thus allowing accurate interpolation of PVT properties; and (4) has a fundamentally sound basis. Molal average molecular refraction was used with the pseudocritical mixing rule proposed by Leland and Mueller to predict the molal volume of liquid and vapor for 84 published data points on nC4-nCI0, Cl-nC5, Cl-nC4-nC10 systems in the region of coexisting vapor-liquid and at the critical point. The same technique was applied to predict the densities of liquid hydrocarbon mixtures in the two-phase and single-phase regions near the critical point for seven different systems each having different properties of the heptanes-plus fraction, but all simulating the fluids of either gas-condensate or volatile oil reservoirs. A modification of the Leland-Mueller mixing rule for the determination of pseudocritical properties is also presented which yields more accurate liquid density predictions than the original form when used with the proposed third parameter. INTRODUCTION The PVT behavior of multicomponent systems has received widespread attention in the literature in recent years. A large portion of the reported work has stemmed from attempts to overcome the inherent difficulties encountered when using the standard compressibility-factor chart which shows 2 as a function of reduced temperature T, and and reduced pressure p,. This chart assumes that z, is constant for all systems. The error in this assumption is not pronounced for pipeline-type gases high in methane and low in heavy ends, particularly when contained at moderate pressures. For such gases the error in the calculated z is usually less than 2 to 3 per cent. However, the reliability of this approach becomes somewhat nebulous for gas condensate and volatile oil systems at high pressure. One logical approach has been to recognize the variation of 2,. This idea was first suggested by Meissner and Seferianl and used by Lyderson, Greenkorn and Hougen2 to prepare extensive tables of thermodynamic properties. Other third parameters have been proposed by Stockmeyer, Kihara, Riedel, Lightfoot, Bloomer and Pitzer. These were tested by Satter and Campbel13 for many gas mixtures and it was shown that they were inter-related. All of these third parameters have a common fault — they cannot be directly evaluated for the heptanes-plus fraction. Consequently, one necessary requisite of an improved method for predicting the density of multicomponent hydrocarbon systems, was development of a third parameter that could be evaluated for that fraction. PREVIOUS MULTICOMPONENT DENSITY PREDICTION METHODS Sage and Lacey4 suggested a method of using partial molal volumes for computing the density of hydrocarbon gas mixture for pressures to 3,000 psi. In this technique, they approximate the complex multicomponent gaseous mixtures by a quarternary system of methane, ethane, propane and butane. Sage, Hicks and Lacey5 suggest a method of using partial molal volumes for computing the density of hydrocarbon liquids. The results agree within 3 per cent of the experimental values. However, the composition range is limited to about 10 per cent by weight of methane. Consequently, this correlation does not cover the low-molecular-weight liquid similar to natural gasoline and high-pressure gas condensates.

Jan 1, 1966

By A. Lubinski, J. L. Logan, W. S. Althouse

A4ost gas twells and flowing oil wells are completed and treated through a string of tubing and a packer. Changes in temperature and in pressure inside or outside the tubing will: (I) if free motion of the tubing inside the packer is permitted, increase or decrease the length of the rubing; or (2) if free motion is prevented, induce forces in the tubing and on the packer. If pressure inside the tubing is greater than outside, the tubing may buckle helically even in the presence of a packer-to-tubing tension. The tubing will always buckle, and much more severely, if free motion is permitted. The buckling may be prevented by pulling the tubing in sufficient tension. The prediction of these forces and tubing movement has here to fore been based upon calculations that did not inciude helical buckling. This paper preseitts means with which these length or force changes can be calculated while taking into account the effect of helical buckling. To avoid damaging formations, failure of remedial operations, or damage to the tubing or packer, application is made to practical problems involving calculations of the required length of seals, amount of sluckoff or tension, and prevention of permanent corkscrewing. INTRODUCTION Leakage of a packer may result in costly failures of such operations as squeeze cementing, hydraulic fracturing, etc. To avoid such failures, the authors are often asked questions pertaining to the length of necessary seals, the amount of necessary slackoff, etc. Published work' does not take into account helical buckling of tubing. Investigation of helical buckling was prompted by the fact that allowance must be made for this phenomenon in order to provide relevant answers. In the past, theoretical work on helical buckling was confined to conditions for which such buckling does not The mathematical treatment of behavior in a buckled condition, given in the Appendix, is novel. Assumptions upon which this investigation is based are listed and discussed in a special section. The following are a few of the many kinds of problems which may be solved with this paper. 1. Consider a packer in which tubing may move. Such movement will occur after pressures and temperature are changed. The paper provides means for: (a) calculating the amount of such movement and, therefore. the required length of seals; and (b) calculating the necessary amount of initial slackoff, for which there is no danger of unsealing the packer, if the length of seals is given. Such calculations, as well as those which follow, tully take into account the fact that part of the movement ib due to elastic helical buckling of the lower part of the string. This buckling may occur even in tubing under tension. Insufficient initial slackoff for a given length of seals, or insufficient length of seals for a given slackoff, may result in costly failures. A field case of such a failure will be given further in this paper. 2. In the case in which tubing cannot move in the packer, changes of pressure and temperature result in tubing-to-packer forces and forces in the tubing above the packer, both of which may be calculated. This knowledge is important because, if these forces are too large, the) could damage the packer or the tubing. 3. For wells in which wireline tools are to be run through the tubing, the paper provides means to keep the tubing from buckling, thereby permitting free passage of tools. 4. In deep wells, mainly in the presence of large casing, tubing may become "corkscrewed", i.e., take a permanent helical set. A field case is described further in the text. Using this paper, one may calculate in advance conditions under which permanent corkscrewing would occur, and then take preventive steps. HELICAL BUCKLING Consider a string of tubing, freely suspended in the absence of any fluid inside casing, as shown in Fig. I(a). Now consider an upward force F applied at the lower end of this tubing. This force compresses the string; and if the compression is large enough (which is always the case in actual problems), the lower portion of the string will buckle into a helix, as shown in Fig. 1 (b). The lower end of the tubing is subjected to a compression F. This compression decreases with the distance from the bottom and becomes nil (neither compression nor ten-

By Richard S. McCaffery

This paper considers certain aspects of the acid bessemer process, particularly in its relations to the duplex process—that combination in which the pig iron is first desiliconized and decarburized in acid bessemer converters and then dephosphorized in basic open-hearth furnaces. The acid bessemer process employs an acid-lined converter and produces an acid slag. The blow is usually thought to eliminate the silicon and manganese as oxides and then to burn off the carbon as carbon monoxide On account, however, of the relatively large amount of metallic iron present in the converter, compared with the relatively small amount of the impurities it is desired to oxidize, the first reaction in the converter probably is the formation of iron oxide, which dissolves in the bath and acts as an oxygen carrier for the silicon and carbon. As soon as iron oxide is dissolved throughout the bath, the oxidation of silicon commences; but in the early stages of the blow the mass law would indicate that iron oxide must form first, and this oxide probably increases up to some saturation point. The molten metal in the converter from the early stages of the blow right through to its completion remains basic, while the slag produced is siliceous. This fact is shown by the corrosion of the acid bottom and the tuyeres, which is greatest at the tuyere orifice where oxidation is most active and where there is the most iron oxide. Why does this acid bottom corrode? Because it is attacked by a base. The thought, therefore, suggests itself, why not. make the bottoms of basic or neutral material?' As the converter slag is acid, those parts of the converter coming in contact with the slag should be acid; but those parts of the converter that are in contact with the molten metal saturated with metallic oxides should be basic. or neutral. Bessemer operators have for some time tacitly admitted this condition, for the blast pressures have steadily increased with the object of keeping the metal in suspension, and so preventing bottom corrosion; if the molten metal were not basic, it would not attack an acid bottom. In addition, the tuyeres are bunched together at the middle of the bottom and a clear space is left around the outside of the bottom; if tuyeres are placed too near the side walls the

Jan 1, 1922

By Richard S. McCaffery

This paper considers certain aspects of the acid bessemer process, particularly in its relations to the duplex process—that combination in which the pig iron is first desiliconized and decarburized in acid bessemer converters and then dephosphorized in basic open-hearth furnaces. The acid bessemer process employs an acid-lined converter and produces an acid slag. The blow is usually thought to eliminate the silicon and manganese as oxides and then to burn off the carbon as carbon monoxide On account, however, of the relatively large amount of metallic iron present in the converter, compared with the relatively small amount of the impurities it is desired to oxidize, the first reaction in the converter probably is the formation of iron oxide, which dissolves in the bath and acts as an oxygen carrier for the silicon and carbon. As soon as iron oxide is dissolved throughout the bath, the oxidation of silicon commences; but in the early stages of the blow the mass law would indicate that iron oxide must form first, and this oxide probably increases up to some saturation point. The molten metal in the converter from the early stages of the blow right through to its completion remains basic, while the slag produced is siliceous. This fact is shown by the corrosion of the acid bottom and the tuyeres, which is greatest at the tuyere orifice where oxidation is most active and where there is the most iron oxide. Why does this acid bottom corrode? Because it is attacked by a base. The thought, therefore, suggests itself, why not. make the bottoms of basic or neutral material?' As the converter slag is acid, those parts of the converter coming in contact with the slag should be acid; but those parts of the converter that are in contact with the molten metal saturated with metallic oxides should be basic. or neutral. Bessemer operators have for some time tacitly admitted this condition, for the blast pressures have steadily increased with the object of keeping the metal in suspension, and so preventing bottom corrosion; if the molten metal were not basic, it would not attack an acid bottom. In addition, the tuyeres are bunched together at the middle of the bottom and a clear space is left around the outside of the bottom; if tuyeres are placed too near the side walls the

Jan 1, 1922