Search Documents

By John C. Calhoun, R. C. Newman

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

Jan 1, 1949

By John C. Calhoun, R. C. Newman

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

Jan 1, 1949

By H. M. Howe, E. C. Groesbeck

Fig. 1 shows a volute aging break which developed spontaneously in a hardened and tempered steel helmet between 19 and 38 days after it had been tested ballistically. A similar break, shown in Fig. 2, developed spontaneously in a similar helmet about 40 days after the ballistic testing. In this case the rupture occurred abruptly and with a loud report. The path of rupture in this second case, though much the less regular, is the more interesting of the two, in that it is an approximation to two parallel volutes centered at the point of impact of the projectile, just below D. Several weeks later, after the photograph for Fig. 1 was taken, a similar doubling of the volute crack occurred in this helmet, starting from the end of the eyelash crack near A and spreading thence to the left contra-clockwise for about 1/2 in. The negatives from which these pictures are made have not been touched up in any way, save writing the letters on them. In both cases the trajectory of the bullet was normal to the initial surface at the point of impact, and in both the helmet passed the ballistic test without detectable cracking, under a velocity of impact not far below that which usually causes perforation. The initial surface itself was very nearly spherical throughout the region covered by the break.

Jan 1, 1920

By E. E. Barker

ALTHOUGH flotation was known to be a successful process prior to 1912, Utah Copper Co.'s ores were not entirely treated by this process until 1923. Experiments had been conducted, of course, prior to that time, and in February, 1917, the first unit of the Arthur plant was changed over from gravity concentration to flotation. On May 16, 1918, the entire Arthur plant was on flotation, excepting the coarse concentrate which was tabled prior to fine grinding. The reasons for the delay in adopting flotation at these plants were, first, that it was decided to await the outcome of the litigation with the Butte & Superior Mining Co., which began with an injunction served on Oct. 3, 1911. This litigation continued for years. Then the demands on the plants in the war years 1916, 1917 and 1918, really precluded any further drastic changes during that period, as all efforts were bent on maximum tonnage, and the cry of tonnage, rather than of recovery, was the major issue. The postwar depression followed these years of intensive production, so that it was not until 1922 that the Magna plant was equipped to use this process. Excepting, then, the amount of coarse concentrate that was tabled, 1923 was the first year when the Utah Copper Co.'s ores were on, a full flotation basis. EFFECT OF FLOTATION ON ORE RESERVES The object of this paper is to point out the effect that flotation has had on the operations of the Utah Copper Co. In 1905, when D. C. Sackling began making history in copper, the ore reserves were 34,000,000 tons, with a grade of 2 per cent. copper and a mill capacity of 700 tons daily. The point of cut-off between nonprofitable and profitable grades was 1.2 per cent. A few years later the capacity was increased to 6000 tons, when 1.1 per cent became the point of cut-off. Ore reserves had climbed to 80,000,000 tons, having a grade of 1.9 per cent. In 1911 there was an ore reserve of 300,000,000 tons, with a grade of 1.5 per cent and a cut-off of 1 per cent.; in 1918 the ore reserve was approximately 400,000,000 tons, and a grade of 1.38 per cent., and point of cut-off 0.95 per cent., based on normal costs and prices. Up to this

Jan 1, 1928

By E. E. Barker

Although flotation was known to be a successful process prior to 1312, Utah Copper Co.'s ores were not entirely treated by this process until 1923. Experiments had been conducted, of course, prior to that time, and in February, 1917, the first unit of the Arthur plant was changed over from gravity concentration to flotation. On May 16, 1918, the entire Arthur plant was on flotation, excepting the coarse concentrate which was tabled prior to fine grinding. The reasons for the delay in adopting flotation at these plants were, first, that it was decided to await the outcome of the litigation with the Butte & Superior Mining Co., which began with an injunction served on Oct. 3, 1911. This litigation continued for years. Then the demands on the plants in the war years 1916, 1917 and 1918, really precluded any further drastic changes during that period, as all efforts were bent on maximum tonnage, and the cry of tonnage, rather than of recovery, was the major issue. The postwar depression followed these years of intensive production, so that it was not until 1922 that the Magna plant was equipped to use this process. Excepting, then, the amount of coarse concentrate that was tabled, 1923 was the first year when the Utah Copper Co.'s ores were on a full flotation basis. Effect of Flotation on Ore Reserves The object of this paper is to point out the effect that flotation has had on the operations of the Utah Copper Co. In 1905, when D. C. Jackling began making history in copper, the ore reserves were 34,000,000 tons, with a grade of 2 per cent. copper and a mill capacity of 700 tons daily. The point of cut-off between nonprofitable and profitable grades was 1.2 per cent. A few years later the capacity was increased to 6000 tons, when 1.1 per cent. became the point of cut-off. Ore reserves had climbed to 80,000,000 tons, having a grade of 1.9 per cent. In 1911 there was an ore reserve of 300,000,000 tons, with a grade of 1.5 per cent. and a cut-off of 1 per cent.; in 1918 the ore reserve was approximately 400,000,000 tons, and a grade of 1.38 per cent., and point of cut-off 0.95 per cent., based on normal costs and prices. Up to this

Jan 1, 1928

By A. E. Dwight, Paul A. Beck

Known CsCl-type phases in transition metal alloys are shown to be formed preferentially at an electron concentration of approximately 6; a tetragonally distorted version of the CsCl structure is stable at -e/a = 6.5. The relationship of the distortion to electron concentration is verified by experimental data for the quasibinary systems Time ,Os) , Ti(Re,Ir), and Ti(Re,Pt) and the ternary system Ti-Ru-Rh. It was noted some years ago1j2 that the occurrence of CsC1-type ordered structures in equiatomic binary alloys, AB, of transition metals correlates with the location of the component elements in the periodic table. One of the components, A, must be to the left and the other component. B, must be to the right of the chromium group. It was pointed out2 that the CsCl structure does not occur in CrFe. is metastable in VFe,3 and is stable in TiFe up to high temperatures, and that this progressively increasing stability may correspond to an increase in electron transfer between the two components and to a correlated decrease of the magnetic moment associated with the iron atoms. Such a decrease was in fact later demonstrated by Nevitt. 4 The binary CsC1-type phases that are formed by a transition metal with either another transition metal or a lanthanide are listed in Table I. Thirty-three of these phases occur at an average electron concentration (average number of electrons outside of closed shells) of e/a = 6. The five phases that are formed at an electron concentration of e/a = 5.5 appear to be borderline cases. This is suggested for instance by the fact that TiRe is bcc. without any long-range order, while TiTc (at the same electron concentration) has a CsCl ordered structure. Six of the undistorted CsCl phases formed by transition metals with one another have an average electron concentration of e/a = 6. 5. Table I. With the exception of Zr4,Rhs4 and Hf48Rh52. the B component in these phases is a first long-period transition metal, i.e.. iron or cobalt. TiNi. with an electron concentration of e/n = 7, appears to undergo transformation at around room temperature to a more complex ordered struct~re.~ The five other CsCl structures known to occur at e/a = 6.5 have either scandium or a lanthanide metal as the A component; the difference in the elec-tronegativity and in the e/a ratio between the component elements is in these phases very large, A(e/a) - 7, and they may be expected to have a rather strong ionic bond component. Presumably the ionic bond stabilizes the CsCl-type structure at the equiatomic composition and it overrides the electron concentration requirement. When the B element is not from the first long period and the A component is not a rare earth metal. equiatomic (AB) alloys of transition metals with an average electron concentration of e/a = 6.5 in most cases have a crystal structure closely related to the CsC1-type, but slightly distorted tetragonally, Table I. This was first found6 for VRu, NbRu. and TaRu. It was noted6 that the undistorted CsCl structure is also stable in the three systems. but at a lower electron concentration, near e/a = 6. In these systems this requires a deviation from equiatomic stoichiometry. which is otherwise ideally suited for the CsC1-type structure. A similar situation was later found in the Ti-Rh7 and the Ti-Ir systems. 8 The Ti-Rh alloys undergo a second distortion and become orthorhombic when the rhodium content becomes somewhat larger than 50 pct. As mentioned previously. TiRe does not have the CsC1-type ordered structure. In order to investigate how close TiRe is to the borderline of stability of the

Jan 1, 1970

By D. S. Eppelsheimer, D. N. Williams

The cold rolled textures of iodide titanium and of three samples of commercial titanium were examined using the Schulz-Decker Geiger counter technique. The iodide titanium and two of the three samples of commercial titanium showed a (0001) [1010] texture rotated 30' toward the transverse direction about an axis in the rolling direction. The third sample of commercial titanium showed a double texture. THE metals of the hexagonal system tend to deform similarly if the c/a ratios are similar. Thus titanium, zirconium, and beryllium, with c/a ratios of 1.601, 1.590, and 1.570, respectively,l should have similar cold rolled textures. The cold rolled texture of high purity iodide titanium has been described as (0001) [1010] rotated 30" toward the transverse direction about an axis in the rolling direction.' The texture of zirconium has also been reported as (0001) [1010] with a transverse rotation from the ideal position of approximately 30" about an axis in the rolling direction." This texture differs from that reported for titanium however since a continuous spread of (0001) poles toward the transverse direction was reported rather than distinct (0001) maxima 30" from the rolling plane normal. Beryllium has a texture similar to that of zirconium although the angle of transverse rotation of the (0001) poles is much less.' These three metals thus show a common type of cold rolled texture, as yet unexplained, which can be described as (0001) [1010] with various degrees of rotation toward the transverse direction about an axis in the rolling direction. Since titanium showed the greatest degree of rotation from the (0001) [1010] position, the cold rolled texture of titanium was re-examined using a semiquantitative Geiger counter X-ray technique to obtain more accurate experimental data from which a theoretical interpretation of this new type of hex- agonal rolling texture could be developed. The cold rolled textures of iodide titanium and of three samples of commercial titanium were determined. Table 1 gives the analyses of the titanium samples. Experimental Procedure Preparation of Samples: Prior to the final rolling operation each of the samples was given an initial reduction of approximately 50 pct and annealed to remove the gross effects of any previous treatments. Samples were annealed in vacuum, high purity helium, and air to determine whether annealing atmosphere had any effect on the cold rolled textures developed. All samples were annealed 1 hr at 800°C. Grain size determinations were made using the formula, 1.075 in which n is the number of grains counted in an area A (in sq mm) and M is the magnification of the area counted.' This formula gives the diameter between opposite flats assuming hexagonal grains. At least three areas containing more than sixty grains each were counted in each grain size determination. Rockwell B hardness readings were made on the annealed samples. The results of the measurements of

Jan 1, 1954

By G. T. Higgins

PREVIOUS workers1,2 have found evidence of exaggerated grain growth or secondary recrystallization on annealing sponge zirconium at temperatures high in the a, phase field, but no details of the orientation relationship between the secondary grains and "as-recrystallized" matrix were reported. In other hexagonal metals, namely dilute Mg-A13 and Cd-zn4 alloys, secondary recrystallization has been observed in which the secondary grains are related to the primary recrystallized structure by rotations about the c axis. These rotations are thus comparable with the rotations about the (111) axis observed in the secondary recrystallization of fcc metals. In the current work secondary recrystallization has been observed on annealing iodide zirconium at 800°C and the associated changes in crystallographic texture have been examined. The material employed was arc-melted iodide zirconium of the following composition: Impurity O H Fe Hf Pb I Ni C1 A1 ppm by wt 130 5 230 98 23 28 200 39 30 This was received as 0.25-in. plate, and, prior to the annealing studies, was cold-rolled to 0.040 in. Specimens 1 in. sq were chemically polished and annealed for various times at 800°C in a vacuum better than 5x 10-6 Torr. For metallographic examination specimens were first chemically polished and then anodized8 to enhance contrast between the grains when examined under polarized light. Changes in crystallographic orientation associated with the development of secondary grains were followed by (1011) and (0002) pole-figure determinations using a conventional Schulz goniometer in reflection. Filtered Cr Ka radiation was employed and great care was taken to avoid spurious re- sults due to the close proximity of the Bragg angles for the (1011) and (0002) reflections. Figs. 1 and 2 illustrate the change in grain structure on annealing at 800°C. After 24 hr the structure has ceased to be equiaxed due to the development of certain grains in preference to others. It is notable that the secondary grains do not grow to the extent observed in sponge zirconium.1,2 This appears to be due in part to the fact that normal grain growth is inhibited in the less pure sponge zirconium, with the result that the driving force for secondary recrystallization remains high, while at the same time the number of grains able to develop in the presence of the impurities is also smaller. As a consequence, in sponge zirconium those grains that do develop preferentially are able to grow into the fine -grained matrix without impingement, while in iodide zirconium the preferential growth of many grains leads to early impingement. The pole figures determined for specimens annealed for 5 min and 24 hr at 800°C are illustrated respectively in Figs. 3 and 4. These indicate that the dominant feature of the initial recrystallized texture consists of basal planes at an angle of 321/2 deg to the sheet surface, with a (1120) axis lying parallel to the

Jan 1, 1967

By Raymond Edmundson

BARITE probably was first mined in the United States in 1845, when a small deposit was operated in Prince William County, Virginia1. The next state to produce barite was Missouri, and according to Weigel2, mining began about 1860. Virginia was the leading producer during the early period of barite mining, but by 1893, Missouri was producing almost an equal amount3. From this date, Virginia, although not the leading producer, furnished large quantities of crude barite until oper-ations gradually declined about 1907. Since 1910, there has been only one producer in Virginia. It is not known when barite was discovered in each of the Virginia areas (Fig. 1), but it is reliably reported that mining on a commercial scale began in Campbell-Pittsylvania counties about 1874; Smyth County in 1877; and in the Russell-Tazewell area about 1890. Barite is widely distributed in Virginia, occurring in nineteen counties. The localities that contain material of some economic value have been grouped into six areas (Fig. 1), each designated by the county or counties in which the barite is found. As many of the smaller areas show a similarity in geologic occurrence, they will be considered in this paper as two major groups; namely, Appalachian Valley and Piedmont Province. The first group, which includes the barite deposits of Russell, Tazewell, Smyth, Botetourt and Roanoke counties, lies northwest of the Blue Ridge and its foothills and southeast of the Appalachian plateaus. The other group includes deposits from the Blue Ridge on the west to the western margin of the Coastal Plain, in Campbell, Pittsylvania, Bedford, Grayson, and Fauquier counties.

Jan 1, 1936

By C. H. Mathewson, H. M. Day

The constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were confirmed and supplemented through X-ray analyses by Preston2 and Stenbeck.3 According to Murphy, at 2760 C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower temperatures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region. Preparation of Alloys The silver used in the present investigation was supplied by the United States Metals Refining Co. through the courtesy of the Committee on Industrial Uses of Silver and, since a complete spectrographic and chemical analysis was furnished, no attempt was made to purify it or to further establish the impurities present. The analyses reported by the company are shown in Table 1. Milligan4 has found that the magnesium content is probably less than 0.0005 per cent.

Jan 1, 1938

By H. M. Day, C. H. Mathewson

The constitution of the system silver-mercury has attracted the attention of many investigators during the last two decades, but since their results are for the most part in poor agreement, there is little need for a review of their individual contributions. It remained for the very careful thermal and microscopic investigation of Murphy1 in 1931 to give the constitutional diagram in its present and unquestioned form, which is shown in Fig. 1. He devised methods for taking cooling curves on alloys under high pressures and for the microscopic observation of alloys which contained liquid mercury as a structural constituent at ordinary temperatures. The compositions of the intermediate phases were confirmed and supplemented through X-ray analyses by Preston2 and Stenbeck.3 According to Murphy, at 2760 C. silver is able to dissolve 44 to 45 weight per cent of mercury, which may increase at lower temperatures to about 50 per cent. Preston concluded that the saturation boundary occurred at 46 ± 2 per cent at 100° C. From the values reported in the literature, these are the only ones that may be accepted as lying even in the right region. Preparation of Alloys The silver used in the present investigation was supplied by the United States Metals Refining Co. through the courtesy of the Committee on Industrial Uses of Silver and, since a complete spectrographic and chemical analysis was furnished, no attempt was made to purify it or to further establish the impurities present. The analyses reported by the company are shown in Table 1. Milligan4 has found that the magnesium content is probably less than 0.0005 per cent.

Jan 1, 1938

By Walter Kauenhowen

The crude-oil production of Germany without Austria during 1938 amounted to 3,864,518 bbl., representing an increase of 21.7 per cent over the 3,173,373 bbl. produced in 1937. Adding the Austrian production, the crude-oil production of the new German Reich totaled 4,259,717 bbl. during 1938, representing an increase of 25.3 per cent compared with the respective figures of the previous year. According to published official data, and using a conversion factor of 1 metric ton equaling 7 bbl., the oil production of Germany in 1938 was as shown in Table 1. A semiofficial publication1 states that the program of the crude-oil industry for the second year (1938) of the four-year plan was successfully accomplished. According to the same source, new drilling developments at the following localities were promising: Reitbrook near Hamburg, Heide in Holstein, Eicklingen-Sandlingen near Celle, Steimbke near Nienburg, Worms in the Rhine Valley, Gifhorn near Braunschweig, Mölme near Oberg, and at other places. The drilling activity for oil is illustrated by the figures in Table 2.

Jan 1, 1939

By Walter Kauenhowen

The crude-oil production of Germany without Austria during 1938 amounted to 3,864,518 bbl., representing an increase of 21.7 per cent over the 3,173,373 bbl. produced in 1937. Adding the Austrian production, the crude-oil production of the new German Reich totaled 4,259,717 bbl. during 1938, representing an increase of 25.3 per cent compared with the respective figures of the previous year. According to published official data, and using a conversion factor of 1 metric ton equaling 7 bbl., the oil production of Germany in 1938 was as shown in Table 1. A semiofficial publication1 states that the program of the crude-oil industry for the second year (1938) of the four-year plan was successfully accomplished. According to the same source, new drilling developments at the following localities were promising: Reitbrook near Hamburg, Heide in Holstein, Eicklingen-Sandlingen near Celle, Steimbke near Nienburg, Worms in the Rhine Valley, Gifhorn near Braunschweig, Mölme near Oberg, and at other places. The drilling activity for oil is illustrated by the figures in Table 2.

Jan 1, 1939

US 4,185,996 -- Removal of arsenic and sulfur Impurities from arsenic-containing cobalt sulfide ore. The ore is oxidized In air at a temperature of 700 to 800°C for 3 to 8 hr to drive off the bulk of the sulfur The oxidized ore 1s heated with a reducing gas at a temperature of 700 to 800°C for 2 to 6 hr to volatilize arsenic, and the final calcine 1s leached with an acid to eliminate substantially all of the remaining arsenic. A.R. Zambrano, assigned to Hanna Mining Co Jan. 29, 1980. 3 pp. (75-2). Filed. 2-13-78 (877,002).

Jan 1, 1982

By F. F. Lines

It is not the intention of the writer to enter into a discussion of the relative merits of the duplex process as compared with the straight scrap and pig iron process, working under the same conditions, but rather to present in a general way several modifications of the former process, and then describe the method adopted by the Maryland Steel Co., as best suited to local conditions, and also to meet the metallurgical problem presented in the removal from the iron of an unusual constituent— chromium. The principal factors to be considered in. deciding whether or not duplexing should be employed are: (1) Chemical constituents of pig iron. (2) Variety and quantity of steel to be produced. (3) Relative cost of pig iron and scrap. (4) Regularity of operation. (5) Capital to be invested. (6) An existing Bessemer plant. Having decided to adopt the duplex process, several combinations may be used, viz.: (1) Acid-lined converter with basic open hearth. (2) Acid-lined converter with electric furnace. (3) Basic-lined converter with basic open hearth. (4) Basic-lined converter with electric furnace. (5) Basic open hearth with electric furnace. The combination of an acid-lined converter with a basic open-hearth furnace is the one most commonly employed, and as it is the one best adapted to the conditions encountered at the plant of the Maryland Steel Co., we will briefly outline the advantages and disadvantages of the different methods of working. There are two general methods of blowing, as follows: (1) The charge is desiliconized and partly decarbonized in the converter. On account of the difficulty in regulating the percentage of car-

Jan 1, 1916

By J. L. Rodda

A large amount of time has been devoted to the microscopical study of the copper-zinc alloys, emphasis naturally being placed upon the commercially important alloys of the system. Suitable methods are available for microscopically recognizing the two phases richest in copper, Per cent,by weight FIG. 1.-COPPER-ZINC EQUILIBRIUM DIAGRAM. (Frond National Metals Handbook, 1933.) but none appear to have been developed for the positive identification of the other phases. This is, however, accomplished, for the phases normally encountered, by an electrolytic method described in the following pages. Five phases of the copper-zinc diagram (Fig. 1) are considered for the purpose of this paper: the solid solution of zinc in copper, alpha (a); the intermediate phases, beta (ß), gamma (y), and epsilon (e); and the solid solution of copper in zinc, eta (n). Beta prime is not considered a separate

Jan 1, 1936

By John Henderson

Densities of melts 0f the lime-iron oxide-silica system in contact with solid iron have been measured by the maximum bubble pressure method in the temperature range 1250° to 1440°C and the composition range 0 to 40 mol pct lime, 15 to 100 mol pct iron oxide, and 0 to 55 mol pct silica. Densities range from 4.65 g cm 3 for wustite at 1440°C to 2.75 g cm-&apos; at 1350°C for a melt containing 30 mol pct lime, 20 mol pct iron oxide, and 50 mol pct silica. The results are interpreted in terms of a postulate that the melts can be regarded as a random array of oxygen ions in which regions of local order exist to satisfy the coordination requirements 0.f the cations. An understanding of the nature of metallurgical slags is basic to the development of a sound theoretical description of heavy metallurgical extractive and refining processes. Because these liquids are complex, direct measurements of their properties has not thrown much light on their structure. This has led to the approach of measuring the properties of simpler liquids, and building up their complexity until slag compositions are reached. In this way the density of liquid iron silicates was measured in a previous study1 and the present work represents a further stage in this synthesis. EXPERIMENTAL The technique used in the measurement of density was the maximum bubble pressure method. Details of the apparatus and procedure were similar to those previously reported,&apos; with the exception that a constant voltage transformer was used to supply the power input to the furnace and six silicon carbide resistance elements were used in place of the molybdenum winding. With these modifications melt temperature could be maintained within 1 centigrade degree during the course of a run. The silica used to prepare the melts was washed natural quartz ignited at 1000°C; wustite was prepared by air-melting A.R. grade ferric oxide in an iron crucible and lime was prepared by air ignition, at 1000°C, of weighed quantities of A.R. grade calcium carbonate, previously air-dried at 110°C. The finely ground constituents were intimately mixed in a glass ball mill prior to melting. Temperatures quoted are accurate to * 5°C and the standard deviation of the density values, calculated by the method of least squares, ranged from 0.5 to 1.8 pet. However, replicate determinations of density on different melts of the same nominal composition at the same nominal temperature did not vary by more than 1 pct, Table I, and this figure has been taken as an estimate of the accuracy of the density results. The density of carbon tetra-chloride was also measured as a check on the absolute performance of the experimental method. At 20°C a value of 1.593 * 0.002 g cm"3 was obtained; this compares with the literature value2 of 1.595 g cm"3. Results of experiments designed to measure the dependence of the density of lime-iron oxide-silica melts, in contact with solid iron, on composition and temperature are shown in Table I. Because iron sometimes precipitated in the sample during quenching, the Fe203 chemical analyses were only poorly reproducible and should be taken as a guide rather than as absolute values. Fig. 1 shows the data from various sources for the density of liquid iron silicates and Fig. 2 shows isodensity contours at 1410°C for lime-iron oxide-silica melts, calculated by graphical interpolation of smoothed curves drawn through the experimental results, together with the 1400°C results of Adachi and ogino3 and Pope1 and Esin.4 Fig. 3 shows the isothermal variation with composition of the volume of melt per gram ion of oxygen at 1410°C and Fig. 4 shows regions in which the temperature coefficient of this volume is negative, positive, or negligible (<0.005 cm3 deg-I). DISCUSSION a) Disparity Between Reported Density Results. Consider the system iron oxide-silica, the results for which are summarized in Fig. 1. Although there is some difference in the temperatures at which the various densities apply, this difference is not sufficiently large to account for the observed discrepancies. The reliability of the present results for the low-silica region has been confirmed by measurement of the density of liquid wustite by three different techniques. At 1410°C the density measured by a balanced-column method was 4.55 g cm"3, by a combination balanced-column and gas-densitometer method 4.59 g emd3, and by a pycnometer method 4.53 g cm"3. Schenck, Frohberg, and Hoffermann&apos; have also reported a value of 4.55 g cm"3 for the density of liquid wustite at 1400°C. It must be concluded, therefore, that neither Pope1

Jan 1, 1964

By J. E. Drury, W. M. Byers, E. J. Lynch

Measurements made with starch ~~~~s indicate that the Presence of starch serves to depress the streaming potential of a clay mud system. Measurements with pure starch slurries show that the addition of NaCl or CaO reduces the streaming potential significantly. The addition of NaOH, however, causes only a minor reduction in potential even when there are large changes in mud resistivity. INTRODUCTION In their excellent study of the streaming potential, Hill and Anderson&apos; proposed that the presence of conductive solids within the filter medium will reduce the generated potential. This theory was demonstrated with measurements on shaly sandstone cores having various "b" factors; the cores with the higher negative b factors showed markedly lower potentials. (The factor b was originally defined by Hill and Milburn2 in an expression relating the resistivity of a shaly sandstone to the resistivity of the interstitial water: log F, = log F,, + b (log 100R,)&apos;. &apos;he factor b, therefore, is a measure of the contribution of the conductive solids to the total conductivity of the sample. It has been found experimentally to be directly related to the amount of chemically exchangeable ion per unit pore volume.) In the logical extension of this hypothesis to the streaming potential created by filtration through mud cakes, they suggested that the presence of nonconductive starch in a drilling mud would have the opposite effect; i.e., it would cause the streaming POtential to be increased. The high streaming potentials that they observed with lime muds were attributed to this cause. A cross-plot of some of their results which are relevant to this discussion is given in Fig. 1. The lime-mud curves and untreated-mud curve are taken from curves given in their paper. The gyp-mud line was estimated from their statement that the measured streaming potential for gyp muds in the range of 1.5 to 2.0 ohm-m was approximately 18 mv/1,000 psi. These gyp-mud potentials were the lowest that they reported for any of the bentonitic-clay muds, and were the only ones which were less than the untreated-mud potentials. This very low streaming potential of gyp muds has also been observed in field studies.&apos; By way of comparison, a U. of Texas publication4 gives the approxi-ate compositions for lime and gyp muds shown in Table 1. These materials are added to a bentonitic-clay mud base. It can be seen that both of these muds contain significant amounts of calcium salts and that the gyp mud has the higher concentration of starch. It would appear from this and from the data shown in Fig. 1 that starch may well be the cause of a streaming-potential reduction, rather than a potential increase. EXPERIMENTAL A series of streaming-potential experiments has been performed using a cell of a design similar to that reported by Wyllie.5 Calomel electrodes were used in both the mud slurry and the filtrate. Pressure in the cell was generated with high-pressure nitrogen. The primary objective of the investigation was to determine the effect of starch on the potential. Five different slurries were made which ranged in composition from untreated ben-tonitic mud (Baroid Aquagel) to a pure starch suspension (Baroid Im-permex). The intermediate slurries were prepared by mixing together a 9-lb/bbl clay mud with a 12-lb/bbl starch suspension in the ratios 1:3, 1:1 and 3:1. When starch was used alone, it was necessary to use an 18-Ib/bbl mixture, since leaner mixtures would not form a suitable filter cake. The clay mud used in the experiments was aged for three months before use. In addition to this series of measurements on the starch-clay mud mixtures, other experiments were performed to determine the effect on the potential of the absolute starch and Aquagel concentration, and the effect of adding various chemicals. RESULTS The effect of starch on the streaming potential is shown clcarly in Fig 2. Increasing percentages of starch resulted in n continually decreasing

By J. P. Neumann, Y. A. Chang

Lattice parameter measurements of the hcp phase in the system Ag-A1 near the stoichiometric composition Ag2Al were carried out for specimens quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K. The three heat treatments resulted in the same lattice parameters at room temperature. None of the specimens showed any superlattice lines. The lattice parameters of this alloy were also measured at temperature from 77° to 750°K. An anomaly in the temperature variation of the lattice paramete.rs occurs in the region near 400°k, which may be associated with local ordering. FROM measurements of the diffuse scattering of X-rays, it is known that the [ phase in the system Ag-A1 near the stoichiometric composition Ag2A1 ex- hibits a considerable degree of short-range order at room temperature.&apos; Moreover, based on the position of the short-range order peaks a superlattice model had been proposed in the same study and it was suggested that lowering the annealing temperature to 420°K might result in long-range order. In the present study, the diffraction patterns and the lattice parameters of three differently heat-treated specimens, i.e., quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K, were determined from 77" to 750°K. The purpose of these measurements was to investigate 1) whether long-range order could be established by prolonged annealing and 2) whether the lattice parameters at room temperature depended on the heat treatment, since it had been proposed earlier2 that the lattice parameters in this phase are related to the atomic arrangement. 1) EXPERIMENTAL TECHNIQUES Silver and aluminum, both 99.99 pct purity, were melted in a zirconium oxide crucible under helium in

Jan 1, 1969

By G. U. Greene

The various lead producers have given the subject of lead drosses much attention in recent years but the problem of their economical treatment is yet to be solved. Formerly the copper in the furnace feed was removed from the furnace in the form of matte. The speiss at that time consisted principally of the iron arsenide. The practice today is to roast off most of the sulphur and the copper in the feed forms a dross in the furnace, which is removed from the furnace with the lead. This material is poured into the drossing kettles and allowed to cool down to but slightly above the freezing point of lead. The copper dross, containing almost all of the arsenic and part of the antimony, is skimmed off and treated in a small reverberatory furnace at most plants. This is essentially a liquation process. The skimmed dross contains from 70 to 80 per cent lead, and much of this lead is liquated out. The products from this treatment are: (1) impure lead, (2) speiss and (3) matte. The speiss from the reverberatory furnace was studied in this research. The literature on the subject is of very little assistance, as almost no work has been done on the problem of establishing the exact identity of the various phases present. One author(1)† states that speiss consists of a series of isomorphous compounds of the general formula FexAsy in which the Fe may be replaced by Ni, Co, Cu, Pb, Ag, Au, Pt, Zn, Cd and the As replaced by Sb, S and Bi. Hofman(2) states that the iron arsenide present is Fe5As. Experimental Work In the present research, the author used for methods in an attempt to determine the composition of the various phases: (1) chemical, (2) microscopic, (3) roentgenographic and (4) thermal. Previous to this research, considerable time had been spent making analyses of different speisses, but unfortunately no very definite conclusions could be made as a result of these analyses.

Jan 1, 1937