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By B. F. Buie

For over 200 years meerschaum has been a significant item of trade between the Near East and countries to the west. Best-known for its use in making smoking pipes and cigar and cigarette holders, it is also used in making a variety of decorative and ornamental items. It is easily carved, and is given an attractive, lustrous finish by rubbing. No published specifications are known, but compact form, purity, uniform whiteness or light color, and uniform, porous texture appear to be requisites. Fig. I a shows the appearance of a piece of crude meerschaum from Turkey; Fig. lb a carved item; and Fig. lc, d, and e show the fibrous and porous texture as revealed by the scanning electron microscope. Neither a major industrial mineral nor a precious stone, meerschaum nevertheless holds a record of long-and continuing-association with art and personal affairs of man. It is also a mineral to which modem methods of exploration and production probably could be profitably applied. An interesting account of the preparation and use of meerschaum in the early part of this century is given by Sterrett (1907). Geology and Mining Mineralogy Meerschaum is recognized now to be the compact variety of sepiolite, the claylike variety of which is one of the minerals included in the chapter on clays. The word meerschaum, from the German meaning "sea foam," was in earlier times used synonymously with sepiolite, a word of Greek origin suggestive of the resemblance of the compact variety-then the only variety known-to cuttlefish bone. At one time meerschaum was used as the commercial name, and sepiolite for the scientific name. However, to think of meerschaum as the name by which sepiolite is known commercially is no longer valid, in view of the recent emergence of the earthy variety as a competitor of bentonite and other clay materials. Present tendency is to restrict the term meerschaum to the compact variety, and to use the term sepiolite as a more general name to include both the compact and earthy varieties. This is the terminology followed in this publication. Meerschaum typically is white to light gray, has a hardness of 2 to 2 ½ , conchoidal to irregular fracture, and specific gravity varying with porosity from about 2 to less than 1. The composition is somewhat variable,- but is near that determined by Schaller (1936) for sepiolite as 2MgO.3SiO2.4H2O. A more modern for mula based on X-ray determination of the crystal structure is given by Caillére and Henin (1961) as (Site) (Mg9)030(OH)6(0H2)46H20. The reason for the firm, compact nature of meerschaum, in contrast with the earthy variety of sepiolite, is not fully understood. It may be due to the presence of a very minor amount of some bonding material such as silica. Scanning electron microscope (SEM) photographs of a specimen from Turkey (Figs. lc-le) indicate that the meerschaum is composed predominantly, if not entirely, of crystalline fibers which merge into sheetlike forms in a complex, intertwined mass. Detailed X-ray and crystal structure data, as well as some data on thermal stability range, are given by Caillère and Hénin (1961) for the sepiolite family of minerals. Mode of Occurrence and Origin Most authors have attributed the origin of meerschaum to alteration of serpentine or other magnesian minerals. The occurrence in alluvium and other surficial deposits does not necessarily indicate that the alteration was supergene. In fact, hydrothermal origin appears more likely for some deposits, though not for all.

Jan 1, 1983

By John B. Myers

Vermiculite is the commercial name used to describe a micaceous mineral that expands appreciably when heated. This process, called exfoliation, results in a light weight material. The light weight material is also called vermiculite, or more exactly, expanded vermiculite. Practically all uses of vermiculite are for the expanded material. Composition and Properties Vermiculite, in its natural state, has the characteristic micaceous habit and a perfect basal cleavage and readily splits into thin laminae, which are soft, pliable, and inelastic. The monoclinic crystal faces are often marked by triangular lines at 60° and 120°. The hardness varies from 1.5 to 2 or more, depending on the composition. The specific gravity varies from 2.2 to 2.7; specific heat 0.2; fusion temperature 2,000° to 2,500°F; luster pearly to greasy; color amber, bronze, brown, dark green, and black. Feel is like talc and sometimes soapy when wet. When heated quickly at elevated temperatures, vermiculite exfoliates by expanding at right angles to the cleavage into long wormlike pieces (the name vermiculite is from the Latin vermiculari, to breed worms). This important characteristic of expansion is believed to be a mechanical separation of the layers when the contained water is converted to steam. The increase in bulk volume of commercially prepared material is 8 to 12 times, but individual flakes may expand as much as 30 times. There is no expansion parallel to the cleavage. Vermiculite may also be expanded by several chemical processes such as soaking in hydrogen peroxide, weak acids and other electrolytes. The color changes during expansion. Heat-treated material changes to a light golden bronze or cream color depending on composition. The conditions of heating affect color. Heating in an oxidizing atmosphere produces reddish colors and heating in a reducing atmosphere produces dull gray colors. The iron is generally not oxidized during chemical expansion. Vermiculite is hydrated magnesium-aluminum silicate. Although there has been much research on the chemical and structural composition, there is not yet complete agreement on the exact formula and composition. This is to be expected since vermiculite is not a mineral of fixed composition and different workers have examined different varieties. It has been proposed that vermiculite is not a single species but a family of related minerals. This has also resulted in many names for the particular vermiculite found in a certain deposit. All of this difficulty arises from the very nature of its crystal chemistry. Unlike most minerals, certain crystal structure properties and the chemical composition can be changed by the ordinary forces of nature or in the laboratory. This would suggest that vermiculite be thought of more as a variable mineral rather than a group of related species. It was stated on page 261 of this volume in the chapter on Clay Minerals by H. H. Murray of the Georgia Clay Co., that vermiculite is an equidimensional, expandable clay mineral. Gruner (ref. 14, Chap. 12) showed that the structure consists of a layer made up of two silica tetrahedral sheets with a central magnesium, iron octahedral sheet separated by two layers of water molecules and adsorbed magnesium and calcium ions. Mathieson and Walker,2a in a recent publication, agree that vermiculite must be regarded as a true clay mineral. The characteristic properties of the mineral, such as high cation ex-

Jan 1, 1960

By R. V. Higgins, A. J. Leighton

A fast method is needed for calculating thoroughly the performance of two-phase flobr~ in reservoir rock with complex geotrietry. The authors present such a method and .slzow its accuracy by romparison with laboratory performrrnce of a five-spot pattern. In making the performance c.alculations, the octant of the five-spot pattern was divided into four channels. The computer tinle required for the culculation was one rllinrcte. This is rorighly about minute per channel. INTRODUCTION By using an electronic computer it is now possible to make reservoir performance calculations in which fewer assumptions and more significant variables are included than was possible with a desk calculator. These performance calculations include such variables as the properties of the reservoir rock and its contained fluids, properties of the rock-fluid system and even different well-spacing patterns. Usually, the more variables that are included the higher the computer cost—and time on the computer is expensive. As a result, a short procedure is needed so the many variables will be included and accurate performance calculations will result. If a reservoir is composed of alternate layers of permeable and impervioi~s rock, and if each conducting layer has a different relative permeability, the combined computer cost for calculating each layer by the present long computer programs (which includes different well-spacing patterns and other variables) would be expensive. The performances of complex spacing patterns in a field often are studied by a potentiometric model, but in these model studies the analogy is to the flow of only a single phase. This paper presents a procedure to calculate the performance of a five-spot pattern with two phases flowing using a potentiometric model as a guide for the dimensions of channels and other related data. The time required to calculate the complete performance is about one minute on the IBM 7090 or four minutes on the IBM 704. The procedure can be extended to calculate the performance of more complex well spacings or an entire field with little modification. The procedure has been tested on the performance of the laboratory water floods of a five-spot pattern reported by Douglas, et alThe range of viscosity ratios in the laboratory experiments is from 0.083 to 754, which is extensive. The accuracy of the performance calculations is excellent as shown by the plotted points in Fig. I. The recovery as influenced by the geometry of the five-spot, taking into account the deviation from true radial character, has been predicted by Aronofsky and Ramey." The authors used a potentiometric model to determine the sweep efficiency to breakthrough of the flooding agent. Dyes, Caudle and Erickson,' by means of a laboratory model, show the influence of mobility ratio on recovery after breakthrough of the injected material. Dyes, et ai, used the X-ray shadowgraph technique and miscible phases in their studies. Craig, Geffen and Morse from the analysis of the performance of their laboratory model correlate many variables, including average saturation of a flooding agent determined by permeability relationship. Craig, et al, used X-ray shadowgraphs to determine the sweep efficiencies in sandstone models. In this report the sweep efficiency is not needed, and the important effect of continuously changing saturation gradients before and after breakthrough

By A. E. Dwight, P. A. Beck

A search was made for ordered phases of AB3 composition in various combinations of Ti- and V-group elements with CO-and Ni-group elements. Three new TiNi3-type phases ZrPd3, HfPd3, and HfPt3 were found. In addition, twelve new Cu3Au-type phases TiRh3, Tilr3, ZrRh3, Zrlr3, HfRh3, Hflr3, VRh3, VIr3, CbRh3, Cblr3, TaRh3, and TaIr3 were also found. The lattice contraction for all three structures considered increases with increasing relative size of the A atom, suggesting that it is mostly the A atom that cont~acts. It was noted that, for the same radius ratio the lattice contraction is larger when the A atom is Ti than if it is Cb OY Ta. It is well known that elements or disordered solid solutions, which have structures with spherical close-packing, may be described in terms of various stacking schemes of close-packed layers. Stacking of the type abab corresponds to the hexagonal close-packed structure, and stacking of the type abcabc corresponds to the face-centered-cubic structure. In binary alloys of the first, second, and third long period transition elements various AB3 phases occur with close-packed ordered structures. It was observed that these ordered structures also may be described by suitable stacking of close-packed ordered layers, Fig. 1, as first shown by Laves and Wallbaum for TiNi3.' It is clear that the units of translation in such a close-packed layer consist of four atoms, one of which (black circle) is atom A and the three others (empty circles) are atoms B. Because of the alternation of A and B atoms in every second row of each layer, the unit-cell dimension in the layer is equal to the sum of the diameters of atoms A and B: a0 = 2(rA + rB). Stacking of such layers in the sequence abab results in a hexagonal close-packed structure of the MgCd, type. The unit-cell dimension in the basal plane is approximately double of that for the disordered hexagonal close-packed structure, but in the direction of the hexagonal axis it is about the same, so that 2co/uo = 1.63 in case of spherical close-packing. Ordered hexagonal close-packed structures of this type were found to occur in MoCo3,2 WCo3,, and UPt, .4 When the ordered layers shown in Fig. 1 are stacked according to the scheme abcabc, the resulting ordered structure is of the AuCu, type (cubic). Structures of this type were found to occur in TiPt3,5 CrPt,,' CrIr,,' and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.' In this case, the unit-cell dimension is doubled not only in the basal plane, but also in the direction of the hexagonal axis, so that co/ao = 1.63. Structures of this type were found to occur also in TiPd3,5 ZrPt,," and UPd,.4

Jan 1, 1960

By J. M. McDowell, E. C. Doty, F. Morgan

Improvements in the X-ray method of measuring liquid saturation and saturation distribution are presented. Two identical direct current amplifiers have been added to measure continuously the intensities of the X-ray tube output and the beam which has passed through the core under test. The ratio of these intensities is automatically recorded on a modified Brown Electronik Recorder. Arrangements have been made to drive the core automatically and in synchronism with the recorder chart so as to give a continuous curve showing the variation of liquid saturation along the length of the core. By determining the ratio of the two X-ray beam intensities simultaneously the measurements are made essentially independent of small fluctuation in voltage and current supplied to the tube. This improved technique has been used for investigating the fluid distribution along the length of cores and core assemblies when one fluid is displaced by another. Typical results of these studies are shown. INTRODUCTION In a previous publication' a method was described for measuring the oil saturation in cores which was based on the absorption of X-rays by the fluid content of the core. While that technique is capable of yielding accurate results, the original apparatus was not especially convenient for determining the fluid distribution along the length of a core. This was primarily due to the slow response of the amplifier and galvanometer and the necessity of making a point by point survey of the material under investigation. It was, therefore, not only possible for sections of the core having a variable or unusual saturation distribution to escape observation entirely, but changes in output of the X-ray generator between readings on the unknown and the monitor introduced errors in the measurements that could be avoided only by further stabilization of the source or by taking a large number of readings. This paper describes a method and apparatus for recording continuously and automatically the intensity of the X-ray beam that is transmitted by a core. The variation of saturation with time at a given section of the core may thus be found, or by scanning the core by driving it in synchronism with the recorder the saturation distribution may readily be determined. As indicated in the previous paper, the X-ray method possesses an advantage over the weighing technique in relative permeability experimentation in that the core need not be removed from the holder for the purpose of making a saturation measurement. Furthermore, the actual distribution of fluid and the effects upon that distribution of inflow and outflow heads may be investigated. And errors due to gas bubbles or loss of liquid that are frequently sources of error in volumetric methods of saturation determination are avoided. PRINCIPLE OF THE METHOD The energy in an X-ray beam that has passed through an absorbing material is expressed by the well known formula: E = E0, e-cd (1) where E, is the energy in the incident beam, µ the mass absorption coefficient, c the density or concentration of absorbing material, and d is the length of path of the beam in the absorber. The coefficient µ varies with the wavelength of the radiation as well as with the absorbing material. The output of an X-ray tube varies in an approximately linear manner with the tube current, but to the second or higher power of the anode voltage. Moreover, the quality or wavelength distribution of the radiation varies with the voltage.

Jan 1, 1950

By N. K. Chen, R. Maddin

Single crystals of molybdenum were extended at temperatures from 1300° to 2500°C. It was found that with increasing temperatures, the yield becomes more pronounced and the number of slip bands for equal amounts of elongation decreases. Slip at high temperatures fragments the structure. OTHER than the investigations on sodium and potassium by Andrade and Tsien,&apos; the researches of Steijn and Brick&apos; on a iron single crystals at low temperatures are about the only studies of the influence of temperature on glide of body-centered cubic single crystals. The effect of test temperature on glide has been rather widely investigated with hexagonal crystals" and less widely with face-centered cubic crystals. ~~ a result of these studies it can be said that, in general, the onset of plastic flow as measured by the initial rate of strain hardening becomes more abrupt with increasing temperature, and the value of the yield decreases with increasing temperature. Strain hardening, however, is markedly affected by changes in temperature except at very low and very high temperatures where the strain hardening rate becames constant. In the present investigation it is shown that temperature affects the glide of molybdenum single crystals in much the same manner as crystals of other classes, it., for comparable strains the number of slip bands decreases with increasing temperature; shear along the slip bands increases with increasing temperature; the yield becomes more pronounced with increasing temperature of test; and the strain hardening approaches a constant at very high temperatures. In addition, it is shown that, in agreement with the work of Tsien and Chow, Qlip occurs on (110) planes in <Ill> directions. It is further shown that slip at high temperatures fragments the structure into either irregular sized cells or bent atomic planes which are roughly aligned in crystallographic directions. Experimental Procedure Single crystals 3 mm in diameter by about 25 mm long were prepared using the technique previously described.&apos; The furnace in which the crystals were grown served as the extension apparatus for the tension tests. It consisted of a 4 in. water-cooled brass tube 20 in. long which was continuously evacuated at the bottom. Two water-cooled copper electrodes held the specimen by means of spherical collets secured in place in the electrodes by set screws. These electrodes served also to transmit power and stress to the specimen. The lower electrode was clamped to a stand, while the upper electrode was fastened to one side of a lever arm flexibly supported at the top through a slightly offset pinion. A metal bellows operating elastically was attached to the upper electrode to affect a vacuum seal and allow freedom of motion. The level of the arm was adjusted by rotating a graduated nut. Rotation of the electrode was prevented by a key fitted into a groove. After the specimen was mounted and the vacuum secured, the lever arm was adjusted so that the bellows was at its relaxed position. This insured that the total weight of the specimen, the upper electrode, and the downpull of the vacuum were balanced by the horizontal beam. Since the specimen was heated by its own resistance, expansion of the specimen proceeded freely by this arrangement. During the time of heating the specimen, the beam was maintained in a horizontal position by turning the nut at the top. By graduating the lever arm and using a known dead weight on the lever arm to supply a tensile stress, the graduated nut could be read to 0.0001 in. extension. Since

Jan 1, 1955

By D. W. Loughridge

INTRODUCTION Raising capital in the 1990s is a timely subject. However, many of us thought why should raising capital in the 1990s prove to be unlike it was in the 19805, the 1970s, the 1%0s, or earlier? There are a lot of creative people in banking and in corporate treasury departments. New tools and techniques are continuing to emerge, many of which are discussed in other papers in this book. While we have new financing tools at our disposal, the underlying issue has not changed. Projects and investments must be judged on their own merits. If they cannot be justified by conventional financial analysis, they should not be built. If they can be justified, it is likely that the financing will be available. The challenges faced in raising capital in this decade will persist to the next. The issues of the 1980s -- currency fluctuation, disruptive merger and acquisition activity, commodity price volatility, political risk, and debt crisis -- will all persist in an increasingly international business environment. I will focus on the financing we have just completed for the Escondida Copper Project in Chile. The Escondida financing is structured along the classic project financing model developed in the late 1970s, but it deals with issues of the 1980s and the 1990s. The financing was intriguing, not just because of the technical issues involved, but also the challenge of reaching an agreement in a large and diverse group. Escondida had the one essential feature that made its financing possible. It was commercially very attractive. It would produce at low cost a commodity (copper concentrates) that direct consumers felt would be in tight supply. The project had the direct support not only of its sponsors, but also its customers, and, very importantly, its host government. The non- recourse financing of Escondida would not have been possible without the support of these parties, and without the robust economics that made this effort worthwhile. The issue was more complicated. Operations in all parts of the world entail some political exposure. This project is in Chile, where there was a constitutional requirement that a plebescite be held when the project would be in its early stages. This plebescite would determine the fate of a 15 year old military dictatorship. The project is copper, a commodity generally deemed to be in surplus. Copper has a history of price volatility (whose price has varied from $.58 to $1.53 per pound over the past two years). It is politically sensitive, not only in Chile, but in the United States, Canada and other developed countries. The project is international, with all the problems of dealing with a variety of currencies, a variety of cultures, and a variety of laws and commercial practices. The project is also large and capital intensive, with a total cost of U.S. $1.1 billion. ESCONDIDA PROJECT Escondida, the largest known copper ore body in the world, was discovered in March of 1981, by Utah International in a joint venture with Getty Oil Company. In 1984, both Utah and Getty were involved in ownership changes, Utah being acquired by BHP. A later restructuring of the ownership of Escondida resulted in BHP, as manager, carrying a 60% interest, Rio Tinto-Zinc Corporation (RTZ) 30%, and a consortium of Japanese companies led by Mitsubishi Corporation with 10%. The Japanese consortium is incorporated as JECO (Japan Escondida Corporation). This ownership structure, which spread ownership around the world, was the first tangible step toward managing both the commercial and political risk associated with the project.

Jan 1, 1990

By R. H. Frazier, F. W. Boulger

THE performance of welded structures is closely associated with the ductile-to-brittle transition temperature of the steel from which they are made. A low transition temperature is desirable because it indicates that the steel is less likely to fail suddenly at low ambient temperatures. Structures such as bridges, ships, storage tanks, and pipelines are usually made from hot rolled semikilled steel. Changes in rolling practice or chemical composition appear to be the most practical methods for improving the toughness of such materials. This results from the fact that production is likely to be seriously curtailed if improvements were obtained by recourse to heat treatment or complete deoxidation. This paper discusses the effect of variations in carbon and manganese contents on the properties of semikilled steels. The transition temperature, a property to which considerable importance is attached, varies with specimen configuration, testing method, and criterion of performance. Both the Navy tear test&apos; and the keyhole Charpy test were used in the investigation. According to the terms used by Vanderbeck and Gensamer,V he tear test was used to measure a fracture transition and the Charpy test to measure a ductility transition. In either case the specimens absorb considerably less breaking energy in tests below the transition temperature than in tests above the transition temperature. Decreasing the testing temperature of notched-bar specimens seems to be equivalent in its effect to increasing the severity of loading on fabricated structures. Therefore, structures built from steels exhibiting lower transition temperatures in laboratory tests are expected to be less susceptible to sudden brittle fractures in service. Consequently, changes in composition which lowered the transition temperature of the experimental steels were judged desirable. Materials and Methods The steels for this study were made in a laboratory induction furnace and rolled to 3/4 in. plate, using a finishing temperature of 1850°F. Precautions taken to insure reproducible melting and testing practices are discussed in detail elsewhere.&apos; All tests were made on hot rolled steels. The analyses of the experimental steels are given in Table I. The list includes steels with manganese contents ranging from 0.21 to 1.46 pct, at each of five carbon levels. The phosphorus, silicon, sulphur, and nitrogen contents of the steels are reasonably constant. The tensile and notched-bar properties of the experimental steels are presented in Table 11. Both upper and lower yield points are listed, and all values are averages for duplicate specimens. Transition temperatures based on three criteria are given. The keyhole Charpy transition temperatures are the temperatures at which the energy-temperature curves based on averages of four specimens cross the 20 and 12 ft-lb levels. Both definitions of Charpy transition temperatures have been used by other investigators. Charpy tests were made at intervals of 10°F, using a pendulum with an available striking energy of 220 ft-lb and a velocity of 18.1 ft per sec. The specimens were oriented parallel to the rolling direction and notched normal to the surface of the plates. The tear test transition temperatures are based on the usual&apos; criterion of the highest temperature at which at least one of four specimens exhibits brittle behavior. The dimensions of the tear test specimens are shown in Fig. 1. The specimen is loaded eccentrically in tension, with pin and shackle fixtures, through the large holes while submerged in a liquid bath at the proper temperature. A specimen developing a fracture area with less than 50 pct shear or ductile texture is classed as brittle. Tear tests were made at intervals of 10°F.

Jan 1, 1955

By D. W. Frommer, M. M. Fine

Mineral dressing research showed that iron concentrates of commercial quality could be produced from the Pea Ridge deposit near Sullivan, Mo. Magnetic separation and flotation, on a laboratory scale, yielded concentrates ranging from 60.0 to 71.4 pet Fe at recoveries of 89.9 to 97.6 pct. Early in 1957 St. Joseph Lead Co. announced discovery of three new centers of iron ore deposition in east central Missouri.&apos; The discovery resulted from exploratory drilling in the vicinity of a magnetic anomaly or high. A deep hole, drilled into the Pre-Cambrian porphyry to determine the cause of anomaly, penetrated a magnetite-rich deposit.&apos; The magnetic surveys that revealed the anomalies were begun by the Missouri Geological Survey in 1929 and were continued into the 1930&apos;s.3 At that time an area in Crawford County known as the Bourbon magnetic high was located. A second anomaly, similar in size and intensity, was discovered about six miles to the northeast in Franklin County in the vicinity of Sullivan. This area was not studied in detail until the early 1940&apos;s. To determine the cause of the anomalies, the USBM drilled four holes at the Bourbon site in 1943-1944.4 The most productive hole penetrated four mineralized zones having a total thickness of 127.5 ft. These zones contained magnetite in rhyo-lite porphyry at depths between 1600 and 2000 ft. Additional iron ore below 2000 ft was considered a possibility at the time. Some years later, the USGS, Missouri Geological Survey, St. Joseph Lead Co., and others cooperated in sponsoring an aeromagnetic survey of the Bourbon-Sullivan area which resulted in discovery of a third high, about eight miles distant at Pea Ridge. This deposit, with an estimated reserve of 50 to 100 million tons of iron ore, is considered the main find, although other orebodies in the same general area are of definite interest.&apos; When this discovery was announced, St. Joseph Lead also revealed plans to exploit the deposit jointly with Bethlehem Steel Co. A new corporation, Meramec Mining Co., was established, and 1962 was set as the target date for completing physical plant.2 Annual production goals of 2 million tons of beneficiated and pelletized iron ore were proposed. Preparation of the site for shaft sinking was begun in June 1957. Orebody and Character of Samples: Drilling to date has established the Pea Ridge orebody as a crescent-shaped pipe about 300 ft wide. Some drillholes were bottomed at 2800 ft in very good iron ore.6 he orebody is predominantly magnetite, although hematite and a mixture of hematite and magnetite occur in the upper areas and peripheral walls. Drillhole cores representing ore from different areas and depths of mineralization were grouped into composites for testing. These composites consisted of: 1) medium grade mixed hematite and magnetite, 2) high grade mixed hematite and magnetite, and 3) high grade magnetite. The medium grade ore came from three holes with depths of i350 to 1900 ft. The high grade mixed hematite and magnetite cores came from the 1790 to 2812-ft interval of one hole. Partial chemical analyses of the three samples, given in Table 1, reveal that all are excessively high in phosphorus and sulfur, and sample 1 is

Jan 1, 1960

By S. C. Sun

With the aid of emulsifiers, intense high-frequency sound waves are capable of emulsifying any collector in water. The data show also that ultrasonically emulsified collectors are more effective in floating minerals than the nonemulsified collectors. THE use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and OstrawskyV escribed the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanaka3 employed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets In the other. The dispersed liquld is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses, 5a, B proposed for the formation of emulsions, the Bancroft&apos;s adsorbed film or double interfacial tension theory is widely accepted. Bancroft 7, 8 deduced that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids. This film has two interfacial tensions, one with the water and the other with the oil, which are not necessarily equal. The difference in interfacial tension between the two surfaces of the film is chiefly responsible for forming different types of emulsions. For example, if the interfacial tension between water and film is less than that between oil and film, the film will become convex on the water side, thereby tending to form an oil-in-water emulsion. On the other hand, if the interfacial tension between water and film is greater than that between oil and film, the film will become concave on the water side, thereby tending to make a water-in-oil emulsion. In line with this theory, emulsifying agents soluble in water have the tendency to form oil-in-water emulsions, while those soluble in oil form emulsions of the reverse type. Apparatus and Experimental Procedure: The ultrasonic apparatus shown in Fig. 1 consisted of a hypersonic generator (A), Brush Development Co. model Bu-204; a hypersonic transducer bowl (B) whose resonant frequency is 400 kc per sec; and a round-bottomed glass tube (C) of 2.2 cm ID and 21 cm in length. The acoustical output power of the hypersonic transducer bowl was standardized with a Hewlett Packard vacuum tube voltmeter, model 41 0B, across the hypersonic generator output. The glass tube, containing the materials to be emulsified, was placed 1 cm above the central surface of the transducer bowl, which was filled with water as shown in Fig. 2. Ultrasonic emulsification was performed in three steps, although a one-step method has been used: 1) emulsifying the predetermined amounts of col-

Jan 1, 1956

By E. R. Morgan, J. C. Shyne, V. F. Zackay

NITROGEN used as an alloying element in steel has received increased attention in recent years. Its merit as an austenite stabilizer and hot strengthener has long been recojinized, particularly by European investigators.&apos; Recent work&apos; indicates that nitrogen contents of 1/2 pet or more allow the addition of several percent of ferrite-forming hot strengtheners, such as molybdenum, without subsequent austenite decomposition at elevated temperatures. The room temperature properties of such alloys are characterized by high yield and tensile strengths with excellent ductility, even after cold working, as shown in Tables I and 11. The 1350°F creep-rupture properties of Cr-Mn-Mo-N steels are comparable to those of commercial alloys such as Timken&apos;s 16-25-6, containing 16 pct Cr, 25 pct Ni, and 6 pct Mo, as shown in Table 111. Cr-Mn steel containing 1/2 pet N must be made under pressure if ingot gassing is to be avoided. However, there are difficulties attendant to this practice. Pressure melting restricts the ingot size, and the equipment required is costlier and more complicated than comparable air melting facilities. An effort was made, therefore, to determine more economical methods of adding nitrogen. The pressures generated in centrifugal casting usually range from 5 to 10 atm and are sufficient to prevent the gassing of high nitrogen Cr-Mn steels. A centrifugal casting was made of an alloy containing 16 pct Cr, 18 pct Mn, 2 pct Mo, and 0.73 pct N. A risk, 8 in. diam and 11/2 in. thick, was cast at 1000 rpm. It has been calculated that a pressure of 9 atm was developed at the periphery of the disk at this speed. Metallographic inspection of specimens taken from the disk revealed no gas holes or other defects. The elevated temperature properties of radial and circumferential specimens taken from this casting are given in Table IV. The creep-rupture life of this cast nickel-free austenitic steel was equivalent to that of the wrought Cr-Mn-Mo-N steels. Although centrifugal casting appears to lend itself to the manufacture of high nitrogen austenitic steels, its applicability is limited to relatively small sizes. A process applicable to the production of large ingots of high nitrogen steels is suggested by low carbon rimming steel practice. Gas holes formed during ingot solidification are not detrimental so long as they weld shut during hot rolling. An economic advantage of gassing ingots is the increased ingot-to-slab yield, especially if the ingots are mechanically capped. Also, it is probable that higher nitrogen levels can be achieved with mechanically capped ingots than with hot-topped ingots. A series of gassy heats was made under both atmospheric and higher pressures, as indicated in Table V. Several of the air melted ingots were mechanically capped by chilling the molten ingot tops with a steel plate. The ingots were allowed to freeze in steel molds without hot-tops unless otherwise indicated. A comparison of Table 111 with Table V shows no significant difference in the creep-rupture properties of the gassy and the nongassy ingots after hot work- ing nor between the gassy ingots produced under different conditions. References 1 F. Rapatz: Application of Stainless and Heat Resisting Steels Alloyed with Nitrogen. Sinhl and Eisen ( 1941) 61, pp. 1073-1078. &apos;V. I?. Zackay, J. F. Carlson, and P. L. Jackson: High Nitrogen Austenltlc Cr-Mn Steels. Trans. ASM 119551 48, PP. 509-523.

Jan 1, 1957

By W. A. Stickney, J. W. Town

Tests demonstrated that aqueous solutions of sodiu~n sulfide would dissolve over 95 pct of the cinnabal- in 5 pct Hg flrotation concentrates and 60 to 90 pct of the cinnabav in low-grade ol-es. Double-leach tests showed that potassiutn sulfide would dissolve 90 pct of the avsenic sulfide in Hg-As satnples and only 1 to 10 pct of the Hg; the sodium sulfide would then dissolve 80 to 90 pct of the rernaining Hg and 30 to 70 pct of the vemaining As. 1 HIS paper describes the extraction, by alkaline sulfide solutions, of mercury from cinnabar-bear ing ores and flotation concentrates. Leaching time and solution temperature had minor effects on mercury extraction when compared to the effects of reagent quantity and ore type and grade. Cinnabar, although readily soluble in sodium sulfide, was only partially soluble in potassium sulfide and essentially insoluble in ammonium sulfide. A double leach process was developed to extract selectively the arsenic from Hg-As products with K2S and to treat the residue with sodium sulfide-hydroxide solutions to extract the mercury.&apos; Mercury was then recovered from the pregnant solutions either by precipitation with metallic aluminum or by electrodeposition. The solubility of HgS in alkaline sulfide solutions was first reported by Volhard in 1878.&apos; The first reported commercial application was made in 1915 when Thornhill applied the method to the treatment of an amalgamation tailing.3 Mullhollen, in 1911. described the chemical reaction of HgS with Na,S and alkaline hydrate to be:4 Most investigators have reported using a 4-pct sodium sulfide and a 1-pct sodium hydroxide soluti~n.3-4 An increase in temperature or excessive dilution of the solution causes the reaction to be reversed. Church Holmes described a similar process used for the extraction of antimony from silver concentrates at the Sunshine Mining Company&apos;s mill at Kellogg. Idaho.5 More recently. Erspamer and Wells reported the results of leaching studies on a Hg-Sb ore from Alaska.6 EXPERIMENTAL PROCEDURE Leaching tests were made on samples of mercury ore from eight deposits in Oregon, Washington, and Idaho. In addition. tests were made on flotation concentrates from seven of the samples as well as a flotation concentrate from an operating mill. Since previous investigators reported reagent requirements greatly in excess of that required by the equation HgS + Na2S = HgS . Na2S, initial studies were made on chemically pure HgS. Results showed that the reaction actually required about 1 g of Na,S per g of HgS in an aqueous solution rather than 0.338 g of Na,S as indicated by the equation. To check further the matter of reagent requirements, Na2S and HgS were mixed together in equal mole ratios. Water was then added, a drop at a time, until the components reacted; X-ray diffraction analyses showed no HgS nor Na,S present. The yellow hydrate compound which formed would not redissolve until about three additional mole equivalents of Na,S were added to the solution. This indicated that a stable solution would require at least 4 moles of Na2S for each mole of HgS. While these implications may be valid for pure HgS, the possibility of entirely different results caused by the existence of other elements present in ores and concentrates was recognized. Consequently, experiments of the same order were made on samples of a flotation concentrate from a producing mill. The concentrate, containing about 18 pct

Jan 1, 1962

By J. A. Coll, R. W. Cahn, A. Lawley

WHILE the creep properties of pure face-centered-cubic and close-packed-hexagonal metals have been thoroughly investigated and are well established, body-centered-cubic metals have been studied less extensively. Moreover, very few fundamental studies on the creep of solid solutions, irrespective of crystal structure, have been reported. The present study is concerned with the creep of a series of body-centered-cubic solid solutions. The present position concerning creep of pure metals is, briefly, as follows.1"3 Creep at first takes place at a steadily decreasing rate; this is the stage termed primary or transient creep. Except at the lowest temperatures this is succeeded by a stage of secondary or steady-state creep. At high temperatures and stresses, this may be succeeded by an accelerating stage, termed tertiary creep, with which we shall not here be concerned. There is no well-defined physical model at present for the transient stage; in general terms, transient creep is best regarded simply as a manifestation of work-harden ing. Steady-stage creep can certainly take place by several different mechanisms: the choice of dominant mechanism depends primarily on temperature. We shall here be concerned only with high-temperature steady-state creep, a term usually reserved for creep at absolute temperatures higher than 0.5 Tm, where T, is the melting point. In this range, the activation energy for creep is, for many metals, equal to the activation energy for self-diffusion, and this is generally interpreted in terms of a "climb mechanism.1-4 The creep rate is determined by the speed at which dislocations, impeded by obstacles the nature of which is disputed but which are probably established during transient creep, can climb by means of a diffusion process, until they are able to by-pass the obstacle. In solid solutions, the intrinsic resistance to the slip motion of dislocations may be much larger than in the solvent, to the extent that the motion of dislocations in the glide plane, rather than their escape by climb out of this plane, may become the rate-controlling factor. weertman5 has considered this possibility from a theoretical point of view, and concluded that some form of "viscous slip" is likely to be rate-controlling at comparatively low stresses. The resistance to slip may arise from "atmospheres" of impurities forming around dislocations; a high Peierls force in materials of high cohesion; or some structural peculiarity such as clustering or ordering of solute atoms.= We shall be concerned here with the case of ordering. The only published investigations concerned explicitly with the effect of order on creep refer to creep in ß-brass by Herman and Brown,7 and in Ni-Fe alloys, by Kornilov and panasyuk8 and by Suzuki and Yamamoto.9 Recently, Herman and Brown&apos;s paper has been supplemented by a determination of the tensile yield point of ß-brass as a function of temperature.10 Both studies showed a sharp drop in resistance to deformation of ß-brass over a range of a few degrees just above the critical temperature Tc at which order finally disappears. These observations are especially noteworthy, because in ß brass the degree of order diminishes steadzly to zero as the temperature approaches Tc. It is, therefore, the disappearance of the last traces of long-range order which has the largest effect on the resistance of the alloy to plastic deformation. In the Ni/Fe alloys of various compositions, resistance to creep at a given temperature and stress is maximum at the stoichiometric composition, both below Tc, (long-range order), and above T,. (short-range order).&apos; Near Tc, the creep resistance of an ordered alloy is much higher than that of the same alloy in the disordered condition.9 The aim of the present investigation was to study the creep behavior in the neighborhood of Tc, of another system of ordering alloys. The iron-aluminum alloys were considered the most suitable. because: i) The order again diminishes steadily to zero as the temperature approaches Tc; there is no sudden drop in order at Tc, and it therefore is

Jan 1, 1961

By H. B. Huntington

Some of the basic problems in understanding elec-tromigration in metals are discussed, along with the attempts that are being made to handle them. One such problem is the effect of the electrostatic forces. It is now acknowledged that the momentum exchange with charge carriers plays generally a dominant role in the driving force but the question remains to what extent the electrostatic force may still be effective. The electromigration of interstitial impurities is also an area which presents some intriguing questions. For the substitutional impurity, moving by the vacancy mechanism under the influence of an electric field, the correlation considerations are somewhat more complex than have been previously recognized. Another problem of basic importance in the calculution from first principles is the strength of the "electron friction" force, say for a simple one-band metal. A related problem growing out of the preceding is the prediction of the direction of the "electron wind" force for metals with band structure involving both holes and electrons. THE term electromigration has come to be used to describe the flow of matter in condensed phases carrying high electronic currents such as metals and alloys, whereas one usually reserves the term electrolysis for situations where the current is largely ionic, particularly in the liquid state such as molten salts. It follows that the mass transport number in electromigration is always very small, of the order of 10-7. Studies of electromigration date back some 30 years but the modern period would appear to date from the work of Seith and Wever1 who in the mid 1950&apos;s first incorporated markers to display mass motion relative to the lattice and first suggested that the direction of the mass flow was primarily determined by the sign of the charge carriers. Since that time interest in the field has grown steadily and more rapidly recently as certain technological applications became apparent. Chief of these is certainly the deleterious effects that electromigration can cause, even at relatively low temperature, to current-carrying elements in integrated circuitry.2 These phenomena have been the subject of intense study and considerable ingenuity. On the constructive side electromigration has proved a useful tool in the purification of certain metals.3 The interest of this paper is, however, centered more on the basic aspects of the subject than on its technological applications. That high electric currents should give rise to mass flow in metals and that the driving force should be more directly associated with momentum exchange with the charge carriers than with the electrostatic field are ideas that no longer cause surprise or particular interest. The field has matured to the point where the general concepts are widely accepted and continued progress in basic understanding rests on more detailed and quantitative exploration. It is the purpose of this paper to point out what are some of the current problems. As a result, we expect to raise more questions than we answer. The first of these will be the role of electrostatic forces, if any, in electromigration. A second section will deal with the electromigration of interstitials. A third and final section treats with electromigration of substitutional impurities or of the matrix atoms themselves. ELECTROSTATIC DRIVING FORCE In the conceptual treatments of electromigration it has been customary to write the driving force in terms of an effective charge number Z* and to divide it into two terms F = e£Z* = e£[Zel- z(pd/Nd)(N/p)(m*\m*\)] [1] The first of these represents the electrostatic force under immediate consideration in this section and the second and usually dominating term for metals arises from momentum exchange with charge carriers, commonly called the "electron drag" term. As can be seen it is set proportional to the electrons per atom, z, and the ratio of the specific resistivity of the moving entity to the corresponding resistivity per matrix atom. The (m*/Im*I) factor takes into account the fact that the sign of the charge carrier determines the sign of the driving force. The specific resistivity of the moving entity is averaged over its path. In the case of motion of the matrix atoms by vacancies this gives rise to approximately one-half the resistivity at the saddle point since the scattering power of the atom at its equilibrium position bordering the vacancy differs only slightly from that of a normal matrix atom. Although the formulation of the "electron drag" term in Eq. [I] is based on a highly simplified model for electron defect scattering, the essential features implicit in the expression are common to all the theoretical approaches that have so far appeared in the literature.4-6 As for Zel, most treatments of electromigration have included the quantity as the parameter which measures the direct interaction of the electrostatic field with the ion and equated it to the nominal valence of the latter. However, there has been considerable discussion whether this interaction may not be 0 in many cases.6 If the moving ion is always enveloped by the same distribution of shielding charge, then clearly its motion will not involve any work done by the electric field and one can expect there will be no electrostatic force exerted on such a neutral composite. From this point of view the shielding charge around the ion would be said to be complete and hence the entity within the Debye shielding sphere would be unaffected by the electrostatic field per se. There is, however, the prospect that, as the moving ion progresses, new charge comes in to participate in the shielding action

Jan 1, 1970

By R. G. Grieves, G. Thodos

A method is presented for the accurate calculation of the cricondentherm and cricondenbar pressures of multicomponent hydrocarbon mixtures of known composition. The mixtures may contain six and quite possibly any number of components including paraffins, isoparaffins, olefins, acetylenes, naphthenes and aromatics. The approach is similur to that used for calculating critical pressures and cricondentherm and cricondenbar temperatures. The critical pressure, the normal boiling point and the approximate vapor pressure behavior of each component are all that art required. A stepwise culculation procedure is necessary for mixtures containing more than two components. From an analysis of 22 binary systems and 118 mixtures, the average deviation of calculated cricondentherm pressures from reported values is 2.4 per cent. For nine multicomponent mixtures the average deviation is 1 per cent. Considering 19 binary systems and 108 mixtures, the average deviation of calculated cricondenbar pressures from reported values is 1.7 per cent. For 15 multi-component mixtures, the average deviation is 2.2 per cent. INTRODUCTION A knowledge of the phase behavior in the critical region of multicomponent hydrocarbon mixtures is of value both in industrial processing operations and for the optimum operation of gas condensate reservoirs. Accurate methods of calculating the critical temperatures and critical pressures4,6,7,8,9,23 and cricondentherm and cricondenbar temperatures6p10 of multicomponent hydrocarbon mixtures are available in the literature. If the cricondentherm and cricondenbar pressures could be calculated with equal accuracy, the entire phase diagram of a multicomponent hydrocarbon mixture could be well approximated. The work of Etter and Kay6 is limited to systems containing the normal paraffins and has not been tested on systems containing a heavier component than heptane. In addition, the development of their multicomponent equations is based upon a limited number of mixtures containing from three to six components. Silverman and Thodos have considered systems containing both paraffinic and non-paraffinic hydrocarbons, but their correlation is limited to binary systems and is highly inaccurate for methane systems. Eilerts has done extensive work on the cricondenbar pressure; he has produced an excellent correlation for binary systems. However, his procedure for multicomponent mixtures is chiefly useful for highly complex mixtures requiring a knowledge of the vapor-liquid equilibrium behavior of the mixtures; he has not considered the cricondentherm pressure. The objective of this study was the development of an accurate and rapid method for the calculation of the cricondentherm and cricondenbar pressures of multicomponent mixtures containing all types of hydrocarbons and having a wide volatility range. The approach that was adopted is similar to that used by Grieves and Thodos for cricondentherm and cricondenbar temperaturesl0 and for critical pressures.9 However, methane systems had to be considered separately and a modified stepwise calculation procedure was utilized for the cricondertherm pressure. The correlations were developed in a manner similar to those for critical pressures and cricondentherm and cricondenbar temperatures. Based upon binary data reported in the literature it was observed that the ratios of cricondentherm and cricondenbar pressure to the pseudocritical pressure (molar average), pt/ppc and pp/ppc, respectively, in two-component systems depended upon the mole fraction of the low-boiling component and upon the diversity in properties of the two components. A dimensionless boiling-point parameter Tb,/Tb was chosen to represent the diversity in properties of the components. For a binary system, Ti,&apos;is the molar average of the normal boiling points of the two components involved. For a multicomponent system it is either the molar average of the normal boiling points of all of the components involved or the molar average of the normal boiling point of the pure low-boiling component and of the atmospheric boiling point of the low-boiling-free mixture of

Jan 1, 1965

Jan 1, 1944

Jan 1, 1944

By H. B. C. Nitze

Monazite is a phosphate of the rare earths, cerium, lantha num, and didymium (Ce, La, Di)PO,. It also contains thoria (Tho,) and silica, which are present in varying percentages, probably as impurities.

Jan 1, 1896

Jan 1, 1936

By D. K. Grubbs, A. B. Moose

A brief overview of domestic sources of anorthosite in Oklahoma and Wyoming is presented, including drilling data on anorthosite and limestone exploration.

Jan 1, 1982