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By O. Hoover, M. Herman, V. V. Damiano

The Jetter and borie' teclznique of determining textures using a spherical specimen has been applied to tlze study of compression-rolled beryllium sheet. Snzall spheres the order of 1 mm in diam cut from the beryllium sheet were autotnatically rotated about tz41o axes using the G.E. single-crystal goniometer. Quantitative pole figures were obtained without tke need to apply absorption corrections. Compression-rolled beryllium exhibited peak intensities ,for (0002) planes of positions tilted 10 deg to the rolling plane and a near random distribution of (1010) planes about the nornal to the rolling plane. TECHNIQUES for determining textures of rolled sheet material are amply described in the literature. The techniques are found to be variations of two basic methods. One due to Decker, Asp, and arker, referred to as the transmission method, utilizes a thin-sheet specimen in which the X-ray beam enters the specimen from one side and the intensity of the beam which emerges from the opposite side is measured. The second method due to chulz,3 referred to as the reflection method, utilizes a thick specimen and the intensity of the beam emerging from the same side is measured. The two rotations of the specimen in the beam are designated a and 8. In order to completely determine the texture of sheet material, it is generally necessary to use a combination of the two methods. The calculations involved in correcting the raw X-ray data for absorption effects and the combining of the data obtained by the two methods are very laborious and time consuming. To avoid the intensity corrections which arise as a result of the changing diffraction volume and path length within the sample other methods have been proposed. The Norton method utilizes a cylindrically shaped specimen cut from the sheet material. Since the rods have rotational symmetry, the absorption correction is constant for rotations about the sheet texture. Jetter and Borie' employed a spherical specimen to analyze the fiber texture of extruded aluminum rods. The spheres were rotated rapidly about the fiber axis to include a large number of grains in the X-ray beam and changes in intensity with respect to tilts of the fiber axis were measured. The absorption correction was constant for all angles and was neglected. The Jetter and Borie' technique finds excellent ap- plication to very fine-grained low-absorbing metals in which the entire sphere volume can contribute to the diffraction volume. In the case of low-absorbing metals, however, serious limitations on specimen thickness occur as demonstrated by Braggs due to de-focussing effects. Peak shifts may occur which negate the assumption that integrated intensities are proportional to peak intensities. These limitations in sphere size to the order of 0.5 to 1 mm for beryllium require that the grain size be sufficiently small to include a large enough statistical sample. The present paper describes the application of spherical specimens less than 1 mm in diam to the quantitative determination of pole figures for compression-rolled beryllium sheet having a grain size the order of 10 p. EXPERIMENTAL 1) Specimen Preparation. Two techniques for spark-machining beryllium spheres were tried. One involved the use of a hollow cylinder as a cutting tool. The tool was fed into the rotating cylindrical specimen as shown in Fig. l(a). The hollow cylinder was carefully aligned such that the axis of the cylinder and the axis of the specimen lay in the same plane and were 90 deg to each other. As the hollow cylinder was fed into the rotating cylindrical specimen, a spherical shape was formed as shown in Fig. 1. Alignment was very critical. Slight misalignment resulted in the formation of a barrel-shaped specimen instead of a sphere. A second technique involved the use of a cutting wheel shaped as shown in Fig. 2 with a groove of the desired radius. A section of the sheet specimen was first turned into a cylinder on the left part of the cutting wheel. It was then shifted to the right and a spherical specimen was turned as shown in Fig. 2. The axis of the cylinder lay in the plane of the sheet. Flats corresponding to the rolling plane of the sheet were used to grip the specimen during the machining operation and these served to identify the rolling plane of the sphere. 2) Rotation of Spec=. The spherical specimen is shown mounted on the G.E. single-crystal goniometer in Fig. 3. The knob A of the goniometer shown in Fig. 3 rotates the specimen about the pedestal axis. These angles have been designated as @ angles. The knob B rotates the specimen about an axis perpendicular to the pedestal axis. These angles have been designated as p angles. A device was made to automatically drive the single-crystal goniometer by means of two flexible shafts connected to the A and B knobs as shown in Fig. 3. The motor system was designed to rotate the knob A, thus rotating the specimen through angles of $I while the B knob remained stationary. After one complete

Jan 1, 1967

By Sir Robert Hadfield

(New York Meeting, February, 1913.) THE Hadfield method of producing sound steel ingots has been the subject of a paper 1 read before the Iron and Steel Institute, so that it will be unnecessary to describe it fully here. The object of the method is to make possible the production of steel ingots in which the pipe is almost entirely obliterated, and it is applicable particularly to the production of sound ingots, from which good rails could be rolled. The method in brief consists in casting the ingots on cars, usually with the small end down. Each ingot mold is provided with a sand top, rammed up in the well-known manner. After the mold is filled to the desired height with steel, a layer of slag about 0.5 in. thick is placed upon it and the balance of the mold is then filled with charcoal. Then, through suitable piping, an air blast is directed in numerous jets upon the charcoal, which is burned thereby, the combustion supplying additional beat to the top of the ingot, which helps to keep the top fluid and to retard its solidification, while the lower parts are rapidly losing heat by its transfer to the mold. By-one plan the ingots are cast in molds placed upon bogies, movable trucks, or platforms, in the position A, Fig. 1. The ingots are cast vertically on bogies, say four or more ingots on each bogie, as may be found most convenient, and the upper surface of the steel is maintained in a molted condition during the transit of the ingots from the casting pit to the stripper. This is effected by a series of air pipes, for example, three in number, with jets or holes on the under surface of such pipes, placed preferably horizontally, arranged in such a manner as to cause jets of air to impinge on the upper surface of the ingots. These holes or jets are made throughout the entire length of the overhead pipes, the length of such pipes being

Jan 4, 1913

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1944

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1936

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1932

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1932

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1939

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1934

Trans No. Place Date Vol. 1. Wilkes-Barre, Pa. May, '71 1 2. Bethlehem, Pa. Aug., '71 1 3. Troy, N. Nov., '71 1 4. Philadelphia, Pa. Feb., '72.. 1 5. New York, N. Y. May, '72 1 6. Pittsburgh, Pa. Oct., '72 1 7. Boston, Mass. Feb., '73 1 8. Philadelphia, Pa. May, '73 2 9. Easton, Pa. Oct., '73 2 10. New York N. Y. Feb., '74 2 11. St. Louis, Mo. May, '74 3 12. Hazleton, Pa. Oct., '74.. 3 13. New Haven, Conn. Feb., '75 3 14. Dover, N. J. May, '75 4 15. Cleveland, Ohio Oct., '75 4 16. Washington, D. C. Feb., '76 4 17. Philadelphia, Pa. June, '76 5 18. Philadelphia, Pa. Oct., '76 5

Jan 1, 1943

By A. S. Venkatadri, H. B. Bell

The equilibrium sulfur distribution between molten iron and Ca0-Mg0-Al203 slags containing iron oxide was investigated at 1550°C. The results were used to derive the iron oxide activities at low iron oxide concentrations in the slag by combining the sulfide capacity data obtained from gas-slag work with the free energies of both the sulfur solution in iron and the iron oxide formation in slag. The derived ferrous oxide activities were compared with values based on Tem-kin's kin's and Flood's ionic models. One difficulty in using these models is that the nature of the aluminate ion in slag is uncertain. Nevertheless, such indirect methods, in particular, those described in the present paper, are of value because of the difficulty of measuring small amounts of oxygen in liquid iron in equilibrium with slag. It is shown that these methods confirm the consistency of thermodynamics data on liquid iron and slags. It is well established that decreasing the iron oxide activity in the slag increases the desulfurization of molten iron at constant slag basicity. This effect is most pronounced at the very low iron oxide activities, characteristic of blast furnace slags. Yet a precise quantitative determination of the significance of low iron oxide contents in slag in blast furnace desulfuri-zation is not possible for the following reasons: a) difficulty of separation of iron "shots" from the slag, and b) errors in chemical analysis of small amounts of iron oxide in slags. In view of these obstacles, one must resort to indirect methods of calculating iron oxide activities. EXPERIMENTAL TECHNIQUE The apparatus for providing the sulfur equilibrium data has been described previously1 and was similar to that used by ell' in connection with the study of slag-metal manganese equilibrium. The procedure consisted of: a) melting about 50 g of Armco iron in a magnesia crucible in a platinum furnace, b) adding a mixture of about 15 g of lime-alumina slag and varying amounts of Fe2O3 and CaS, and c) maintaining the temperature at 1550°C for more than an hour in an atmosphere of argon to enable the sulfur equilibrium to be attained. Several melts were made using lime-alumina slags with basic composition 55, 50, and 45 pct lime. During the experiment the temperature was controlled manually using a Pt/10 pet Rh-Pt thermocouple. After the experiment, the Power was shut off and the flow rate of argon was increased to freeze the melt as quickly as possible. The analysis of sulfur in the metal was carried out by the oxygen combustion method3 using uniform drillings from the top and bottom of the metal button. After crushing and grinding and removal of any iron particles with the aid of a hand magnet, the slag was analyzed for sulfur by the CO2 combustion method.4 The E.D.T.A. method was employed for the analysis of lime5,6 and magnesia,= the ceric sulfate method7 for the analysis of slag iron oxide, and the perchloric acid dehydration method5 for the analysis of silica. The remaining amount was taken to be Al2O3 precipitation with ammonium hydroxide in several preliminary melts had confirmed the propriety of using this simple procedure. RESULTS The activity of iron oxide in binary, ternary, and more complex slags has been the object of numerous investigations, and the two experimental methods for its determination are: 1) Equilibrating the metal with the slag in question and measuring the oxygen content of the metal. The ferrous oxide activity is then given by aFeO L%OJSat where [%0]sat is the oxygen content of the metal in equilibrium with pure iron oxide slag. This method was used by Chipman et al.8,9 2) Equilibrating the slag in iron crucibles with known partial pressures of H2/H2O or CO/CO2 mix-tures.10-12 This method is limited to temperatures between 1265" and 1500°C. The very low oxygen content of the melts in this investigation made it impossible to derive the ferrous oxide activity by the first of these methods. Therefore, the iron oxide activities were computed by means of: Sulfide capacity data from the gas-slag work" Temkin's concept14 Flood's approach15 a FeO from Sulfide Capacity. The method of calculating the aFeO involves the sulfide capacity of the slag (c,), the sulfur distribution coefficient (Ls), the free energy of dissolution of sulfur in iron, and the free energy of formation of iron oxide in the slag. Bell and Kalyanram13 have investigated the sulfur absorption characteristics of lime-alumina slags containing magnesia by the Carter-Macfarlane method16 (based on comparing the sulfide capacity of the slag in question with that of a standard slag of unit lime activity) and have derived lime activity values. The relation between sulfide capacity and their lime activity a'CaO is given by: Cs= 3—: Xa'CaO at 1500°C

Jan 1, 1970

By H. W. Mathews, J. D. Wheeler

AS predicted by Messrs. Fuqua and Thompson, in last year's paper on West Texas1, 1935 saw a marked increase in activity in this area over recent years. Both major and independent operators shared in the increased wildcatting operations, which resulted in the discovery of eight and probably nine new fields in this area. During 1935 there were 700 wells completed as compared with 468 in 1934 and only 236 in 1933. Of these completions 579 were producers with a total 24-hr. potential of over 700,000 bbl. It is estimated that the new fields discovered during 1935 added from 200,000,000 to 400,000,000 bbl. to the known oil reserve in West Texas. In addition to these new fields, many of the older producing areas scored marked extensions during the year. New Fields Goldsmith.—-The Goldsmith field, in west central Ector County, gives promise of being the year's outstanding discovery in this area. The discovery well was completed by the Gulf Production Co. in June at a depth of 4177 ft.; it gaged 275 bbl. of 36° gravity oil in 3 hr. through 85/8-in. casing on its first production test. The field has been extended to the east by wells drilled by Phillips and Pure on their Cowden block. Present indications are that the field may contain 10,000 productive acres, and this, together with the large flush production from only a small penetration into the pay, leads to the belief that Gulf-Goldsmith No. 1 was the outstanding Permian lime discovery of 1935. It is quite probable that production will prove to be continuous to the Landreth-Scarborough No. 1, 33/4 miles to the northwest, which was completed for a small producer late in 1934. Sand Hills (Ordovician).—From the standpoint of creating excitement, the outstanding West Texas test of the year was no doubt Gulf-Waddell No. 1, on the northwest nose of the Sand Hills structure. This test was started late in 1934 as a deep test to the Ordovician. Thc Ordovician was topped above 6000 ft,., considerably higher than expected. Oil shows in the Simpson were passed and the well was drilled down to the

Jan 1, 1936

By J. D. Wheeler, H. W. Mathews

AS predicted by Messrs. Fuqua and Thompson, in last year's paper on West Texas1, 1935 saw a marked increase in activity in this area over recent years. Both major and independent operators shared in the increased wildcatting operations, which resulted in the discovery of eight and probably nine new fields in this area. During 1935 there were 700 wells completed as compared with 468 in 1934 and only 236 in 1933. Of these completions 579 were producers with a total 24-hr. potential of over 700,000 bbl. It is estimated that the new fields discovered during 1935 added from 200,000,000 to 400,000,000 bbl. to the known oil reserve in West Texas. In addition to these new fields, many of the older producing areas scored marked extensions during the year. New Fields Goldsmith.—-The Goldsmith field, in west central Ector County, gives promise of being the year's outstanding discovery in this area. The discovery well was completed by the Gulf Production Co. in June at a depth of 4177 ft.; it gaged 275 bbl. of 36° gravity oil in 3 hr. through 85/8-in. casing on its first production test. The field has been extended to the east by wells drilled by Phillips and Pure on their Cowden block. Present indications are that the field may contain 10,000 productive acres, and this, together with the large flush production from only a small penetration into the pay, leads to the belief that Gulf-Goldsmith No. 1 was the outstanding Permian lime discovery of 1935. It is quite probable that production will prove to be continuous to the Landreth-Scarborough No. 1, 33/4 miles to the northwest, which was completed for a small producer late in 1934. Sand Hills (Ordovician).—From the standpoint of creating excitement, the outstanding West Texas test of the year was no doubt Gulf-Waddell No. 1, on the northwest nose of the Sand Hills structure. This test was started late in 1934 as a deep test to the Ordovician. Thc Ordovician was topped above 6000 ft,., considerably higher than expected. Oil shows in the Simpson were passed and the well was drilled down to the

Jan 1, 1936

By Dwain K. Butler

INTRODUCTION Characterization of a site for the prediction and simulation of dynamic events requires the determination of mechanical properties of the rock at stress/strain levels and rates and at a scale appropriate for the events and critical structures involved. The structures of interest can be on the surface, underground, or designed to impact and penetrate into the site (projectiles). Dynamic events of interest are equally diverse: seismic waves from distance earthquakes or explosions; close-in phenomena associated with earthquakes and explosions; vibrations associated with heavy equipment or machinery; and stress transients associated with impact and penetration. The complexity of site characterization depends on two factors not specifically related to the nature of the site itself: the stress levels generated by the dynamic event and the sophistication of the prediction and simulation techniques. For very high stress levels, such as occur near a nuclear detonation, and for low stress levels, such as occur during seismic wave propagation, site characterization is simplified, and often certain details of the site are not particularly important, such as shear strength variations in the case of very high stress levels. In the intermediate stress range, however, all descriptive relations are non- linear, a complete finite strain constitutive model is required, and all details of the site, such as lithology and fracture distribution, become important. The site characterization must be complete enough to support the most sophisticated prediction and simulation technique that will be applied to the analysis of the dynamic event. The procedures of site characterization are illustrated in this paper by a specific dynamic event, projectile impact and penetration, and a specific site, an outcrop of Dakota Sandstone near San Ysidro, New Mexico. The structure of interest was the projectile itself: nominally, 1.5 m in length, 0.165 m in diameter, 180 kg

Jan 1, 1984

By Walter Wood

The specifications for cast-iron pipe that have been submitted at this meeting are practically the outgrowth of those which were originally adopted, about 1860, by Mr. Kirkwood of Brooklyn, N. Y. They have been changed but little since that time, the mode of testing pipe in the hydraulic press, as well as the method of coating, not having departed from the original practice. The chief addition to the specifications has been in the adoption of a test-bar 2 in. by 1 in. in crosa-section, broken between 24-in. supports by a transverse strain applied on the flat side. Test-bars were first introduced into pipe-specifications about 1870. At that time a satisfactory test-piece had to stand a tensile strain of 16,000 lb. per square inch. The present test-bar was adopted in order to give some idea of the deflection of the iron that was being used. These deflection-tests have been so satisfactory to both engineers and manufacturers, and have met the requirements of the pipe-trade so accurately, that it is considered best to hold to the . 2-in. by 1-in. bar instead of adopting the short " Arbitration Bar," which yields but little information from the stand-point of deflection. The new feature in these specifications is the effort to reach standards to which pipe shall be cast in the future, thus permitting the manufacturer to make up stock and the purchaser to find material on hand when he asks for deliveries. Heretofore there has never been ally standard weight for pipes? although in some sizes certain weights are more frequently asked for than others. The fixing of standards for pipes permits the adoption of definite standards for fittings. It has been aimed to secure such uniformity for fittings as will permit the same class of fittings to cover two or more classes of pipe. In order to accomplish

Jan 1, 1905

By G. A. Parks, C. Kovacs

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

Jan 1, 1967

By N. Marusov, D. K. Lowe, J. C. Karp

This paper considers, from an engineering viewpoint, several factors involved in creating, designing and locating horizontal barriers for controlling water coning. This is an effort to consolidate new concepts with previous information so that a reasonable selection of barrier materials, dimensions and vertical position can be made. Coning theories previously developed are briefly reviewed and an effort i,s made to reduce the results of coning-theory calculations to a point where routine calculations can be made with a desk calculator. It is expected that these simplified calculations will give usable predictions of the amounts of improvement attainable with barriers of various dimensions. Apparatus and procedures used for testing the suitability of commercial cements are described and test results are presented. INTRODUCTION Just about as soon as the phenomenon of water coning was recognized as an oilfield problem, there were suggestions that the production of water coning could be controlled or completely suppressed by means of horizontal barriers. It was also suggested that natural barriers such as shale streaks were helpful in restricting bottom-water production. The implication was that wells not having the benefit of continuous shale streaks to suppress bottom waters should, in some way, be supplied with an artificial barrier. With regard to the selection of barrier materials, there are many references which give the merits of liquid barriers.',' These liquids include surface-active agents," recipitates' and emu1sions. There is no real need to review the merits of these materials again. This paper deals with the use of solid barriers which could be made from various cements. The two major restrictions placed on these barrier cements are that (1) they must be commercially available in large quantities, and (2) they must be applicable by means of standard tools and equipment with techniques that have been fully developed and are in general use at the present time. A schematic drawing of a horizontal barrier in a reservoir is shown in Fig. 1. Two maximum stable water cones are illustrated-—-one for the wellbore diameter and the other for a barrier. A maximum stable cone is one that has attained its maximum volume at the critical production rate and is on the threshold of producing water. The volume displaced by each water cone and the rise in water table are indications of the amount of water-free oil produced. Corrections for porosity, connate water and residual oil, of course, must be applied. The water-oil interface which defines a maximum stable cone is called a free surface. It is a surface over which the pressure is constant. This free surface has the shape of a limiting streamline at and below which there is no movement or transport. The shape of the water cone describes the pressure drop in the reservoir. The effect of a completely impermeable barrier on the cone shape is essentially the same as extending the wellbore out to the barrier radius. The placement of a horizontal barrier requires that a horizontal fracture be created using a single-point entry technique. Two methods may be employed for filling this fracture. One method consists of propping the fracture before filling with cement. The other consists of fracturing with fracture fluid, then immediately following with cement

By R. L. Slobod, H. A. Blum

A semiquantitative method for measuring the wettability of reservoir rocks has been developed. These data are needed for reservoir analysis and for interpretation of laboratory displacement studies. The wettability of a core sample is measured by the contact angle for the system oil-water-solid. These contact angles are calculated from the displacement pressure (threshold pressure) obtained by use of the centrifuge, using first oil-water and second air-oil in the same core sample. This method is based on the assumption that the air-oil and oil-water interfaces occupy similar positions in the porous medium when desaturation of the wetting phase is initiated. The assumption is also made that the Contact angle for the air-oil-solid system which is close to zero in value does not change appreciably even when the contact angle for the oil-water-solid system experiences marked changes. "Apparent contact angles'' for five different solids ranging from 31" to 82" have been determined, and changes irr the "apparent contact angle" of a given sample with laboratory use from 33" to 53' {lave been observed. INTRODUCTION Reservoir rocks vary in their wettability, 1,2,3,4 some being preferentially water wet while other are apparently preferentially oil wet. The degree of wettability, in theory, is measured quantitatively by the contact angle for the system solid-oil-water, hut in 1)practice this quantity is extremely difficult to determine." The need for obtaining some measure of this quantity has become obvious in recent years as a result of both laboratory. and field observations. Several reservoir.: such as the Bradford Sand in Pennsylvania and the Wilcox' at Oklahoma City are reported to be oil wet. If these report:: correctly reflect the true nature of the surface of the rock in the ground, then these reservoirs probably will not perform as predicted on the basis of a water wet rock. In the laboratory many core samples have been Observed to be oil wet. These samples, while perhaps not correctly representing the reservoir, have markedly different properties from water wet rock. The location of the phases is different (oil is in contact with rock instead of water), and other quantities such as the connate water, the capillary pressure curve; residual oil. relative permeabilities. and the recovery of oil by water flooding are markedly affected by the value of the contact -4 A further complication observed in the laboratory is the chang-ing of the wettability of a rock specimen with use. such changes mean that repeat runs on the same core are not the duplicate tests desired, but represent new experiments on a more oil wet material. The changes in surface characteristics are sometimes so rapid that by the time an experiment requiring several days is completed, the results may not be representative of the core as originally described, The, rock material itself (Silica. carbonates. etc.), whell Clean and uncontaminated, is water wet. There seems b( : little evidence of the presence of oil wet minerals such as heavy metal sulfides. The oil wetness of reservoir samples, therefore, is believed to be caused by the accumulation of an adsorbed film in which the polar group of a large organic. molecule is adsorbed on the surface leaving the organic or hydrocarbon part of the molecule projecting out from the solid. Such a surface is much more readily wet 17" oil than by water. These considerations indicate the need for a method which will provide some measure of tile wettalbility (Contact(angle if possible) for reservoir rock ..samples) The method should be capable of (1.1 distinguishing between tile wettalility of dif. ferent formation,.. (2) detecting (change. ill wettalbility of a core with use. and (3) measuring the changes in Wettability which may be accomplished with cleaning operations. such as the use of sodium silicate for increasing water wrettalbility." A preliminary report on such a method is preseted below. not with the idea that this procedure alone will Solve the wettabil-ity problem. but rather that it may provide encouragement to

Jan 1, 1952

By C. M. Fellman

AVAILABLE data for the first nine months of the Year indicate that accident occurrence in metal mining was well on its way to an all-time low for 1939. However, the relatively rapid pickup in mining production in the fall will be likely to boost both accident occurrence and also accident rates. Results of the National Safety Competition for 1938, the fourteenth of its kind conducted by the U. S. Bureau of Mines, were published in August, 1939. W. W. Adams, statistician of the bureau, states that "with 345 mines and quarries competing, more than in any previous year except 1931, the contest revealed low accident rates at many of the enrolled plants and, which is even more remarkable, it revealed 113 mines and quarries at which no lost- time accidents occurred during the con- test year." The National Safety Competition provides a means whereby mines and quarries may engage in active competition to stimulate their safety programs. Companies in the contest can compare their records with those of similar plants operating elsewhere and thereby determine to what extent their safety programs are successful. The Joseph A. Holmes Safety Association gave over 150 awards for safety performance in the mineral industries in 1939 and a remarkable phase of these awards was the considerable number given to individual miners who had worked fifty or more years without sustaining a lost-time accident.

Jan 1, 1940

By E. S. Tankins, G. R. Belton

A simple solution model, based upon the formation of molecular species, is developed for strongly electronegative dilute solutes in liquid binary-metallic solvents. Two approximations are considered for the relative concentrations of the species: the random and the quasi-chemical. Equations are presented for the partial molar free energy, enthalpy, and entropy of mixing of the solute. An experimental study has been made of equilibrium in the reaction H2 6) +0 (dissolved) = H2O(g))for the liquid Cu-Co alloys. The standard free energy of solution of oxygen is presented as a function of composition for the alloys at 1550°C and as a function of temperature for five of the alloys. The experimental results for these alloys and also for Cu-Ni alloys are shown to be in reasonable agreernent with the theory in the random approximation. A knowledge of the thermodynamic behavior of dilute solutes in liquid metals and alloys is of importance in understanding and designing refining and alloy-making processes. Accordingly, several attempts have been made to derive suitable solution models to forecast the effect of a third component on the activity coefficient of such a solute in a metal. Alcock and Richardson' reviewed the literature prior to 1958 and also showed that a regular solution model gave a reasonable description in the case of metallic solutes but failed to account for the behavior of the more electronegative solutes sulfur and oxygen. These same authors2 later modified their model by using the quasi-chemical approximation3 to calculate the average composition of the first coordination shell surrounding each solute atom. This modified model was shown to lead to a better qualitative description of the behavior of the electronegative solutes; however, quantitative agreement with experimental data for oxygen in alloys could only be achieved by assuming a very small coordination number. The authors concluded that the major source of error in the model was the assumption that pairwise interaction energies were independent of composition. Substitutional and interstitial random solution models by Wada and saito4 are essentially similar to the first model except that the required interchange energies were derived from the modified solubility parameter equation of Mott, instead of from experimental binary data. Most recently Hoch5 has presented a statistical model for interstitial solutions and has applied the model to the Fe-C-O system. However, as the various interaction energies needed in the model had to be derived from the ternary data, the model does not promise well as a means of forecasting ternary behavior. Each of the above models carries the assumption that the strongly electronegative solutes have the same configurational environment as metallic solutes; i.e., the solute can be treated as a substitutional or interstitial atom in a quasi-crystalline lattice and is surrounded by a normal coordination shell of solvent atoms. There are, however, a number of facts which suggest that this is unlikely. First, the heats of solution are large, being more typical of molecule formation rather than alloying. For example, the heats of solution of monatomic oxygen and sulfur in liquid iron are -90 kea16,8 and -74 kea1,7, 8 respectively. These are to be compared with maximum heats of solution of metallic solutes in liquid iron of about -13 keal (silicon is an exception with -28.5 kea17). The large depression of the surface tension of liquid iron by trace amounts of the electronegative solutes oxygen, sulfur, and selenium9 suggests, by analogy with aqueous systems, the possible existence of polar molecules in the liquid. The effect of these solutes is at least three orders of magnitude greater than normal metal solutes.10 As has been pointed out by Richardson,11 the electron affinities and ionization potentials of oxygen and sulfur are such that it is likely that they exist in metallic solution as negatively charged ions. If this is so, and it is assumed that electrostatic forces play an important role in determining the configuration, it is unlikely that the stable configuration will be that of an isolated ion surrounded by a symmetrical coordination shell of solvent ions. It is more likely that the energy of the system would be lowered by the formation of solute-solvent screened dipoles. The above arguments suggest the formation of "molecular species" between solute and solvent atoms. The idea of the existence of molecular species in such solutions is not new, however', for Marshall and chipman12 have explained in a semi-quantitative manner the C-O equilibrium in liquid iron by postulating the species CO. Chen and Chip-man13 interpreted their measurements on the Cr-O equilibrium in iron in terms of the species CrO. Zapffe and sims14 have also postulated the existence of such species in liquid-iron alloys.

Jan 1, 1965

By Blake M. Caldwell, Harrold D. Owen

The continued use of permanent-type, we11 completion Iras pointed LIP the need for more powerful through-tubing perforating equipment. A new expendable shaped charge perforator has been developed in which the charges are run through the tubing in a vertical position and then opened out to a horizontal position when at the desired shooting zone. The performance of this new tool is comparable to that of conventional casing type perforators. This paper describes the new tool and its applications. Performance data in targets rind under various actual well conditions are presented. INTRODUCTION The general acceptance and increasing use of pernianent-type well completion by the oil industry has indicated the need for through-tubing perforating equipment with performance comparable to that of conventional casing type perforators.'.' To achieve the performance desired, a new, expendable, shaped charge perforator has been developed with adequate power for effectively perforating both 51/2-in. and 7-in. casing below tubing. This has been accomplished without resulting severe damage to the casing and can he obtained under extremes of pressure and temperature. The design of this new tool is a radical departure from previous concepts of tubing guns since it was felt that the two major limitations imposed by previous designs severely handicapped performance. The first of these limitations was the restriction imposed upon the length of the charges by the necessary small inside diameter of the carrier. This resulted from the necessity for compromises in designing a hermetically sealed gun small enough to allow free passage through 2-in. tubing, yet with sufficient wall thickness to withstand some minimum pressure. In an effort to overcome this limitation, the charges were in some cases placed at an angle with the axis of the well with resulting loss in effective depth of penetration. The second limitation concerned the extreme distance of the charges from the casing when the gun was fired. An example of the latter situation is demonstrated by the fact that a conventional 13/4-in. tubing gun centralized in 51/2-in., 17-lb casing has a clearance of more than 1-9/16-in. on all sides. This means that a considerable portion of the force from each charge must be expended in penetrating this 1-9/16-in. of well fluid before it even reaches the casing. With the gun centered in 7-in., 23-lb casing, the amount of fluid penetration required of each jet is in excess of 21/4-in. In a situation where the 13/4-in. gun is touching one side of the 51/2-in., 17-lb casing, the jets from the charges on the opposite side have more than 3%-in. of fluid to penetrate. A similar situation in 7-in., 23-lb casing necessitates the penetration of more than 4-9/16-in. of fluid. The penetrating effect of the charges is severely impaired in passing through so much fluid. Under such conditions, there is usually insufficient force left to penetrate the casing. Previous studies have shown the decided disadvantage of having to shoot through such an excessive quantity of well fluid.'.' The problem. then, was how to position large powerful charges close to the casing prior to firing and still manage free passage through 2-in, tubing. The solution appeared to be in some method of folding sealed charge units in an open type, expendable. 13/4-in. carrier for travel through the tubing, and unfolding them upon their arrival at the shooting zone in the casing. It was desired to control the mechanism electrically from the surface through the regular shooting cable, making the release of the charges independent of the physical characteristics of the well, yet with a provision to prevent the gun from firing until the

Jan 1, 1955