Search Documents

By L. Guttman, C. S. Barrett, J. S. Bowles

THE transformation from the face-centered cubic (Al) to the face-centered tetragonal (A6) structure in certain alloys of the indium-thallium system reported in the preceding paper1 exhibits many interesting crystallographic and metallo-graphic features, most of which presumably are similar to those of other cubic to tetragonal transformation such as, for example, the one which occurs in the chromium-manganese system,2 the one which, judging by microstructures and X-ray pat-terns,3 probably occurs in the copper-manganese system, the ones accompanying ordering in FePt,4 Copt,&apos; and AuCu,5 and the transformation near 115°C in barium titanate.6,7,8 If, as mentioned in ref. 1, the transformation is second order, the phases in equilibrium do not differ in composition, and it is both possible and likely that the mechanism is a diffusionless one. The present paper reports the results of a detailed study of the indium-thallium transformation and presents a theory for the atomic movements of the transformation which accounts for the observations. Experimental Crystallography of Transformation Markings The transformation from cubic to tetragonal in the indium-thallium alloys produces microstruc-tures of the type illustrated in fig. 1. These structures are observable either as relief effects produced on a smooth surface by the transformation, or after polishing and etching. These microstruc-tures are markedly similar to those found in copper-manganese alloys: iron-platinum alloys," and barium titanate,7,8 where it has been demonstrated that the lamellae are parallel to the (101) planes of the original cubic crystal. That the observed lamellae in indium-thallium alloys are also parallel to the (101) planes was proved by the following analyses performed on single grains in polycrystal-line samples containing 20.75 atomic pct T1. A study of the microstructures of a number of specimens revealed the fact that in many specimens the transformation markings continued unchanged in direction across the (111) interfaces of annealing twins. This at once demonstrates that the lamellae are parallel to a plane that is common to both parent and twin orientations, i.e., a plane in the zone <112>. This conclusion is compatible with the lamellae being parallel to (101) planes. To make a more complete determination of the habit plane of the lamellae, two grains were selected in which annealing twins ({Ill) twins) had been present in the high-temperature modification (cubic). The traces of the annealing twins, and of the transformation markings in both parent and twin crystals, were plotted together in stereographic projection, and a parent-twin pair of orientations was found that accounted for all lamellae as (101) planes. The projection of one of these twinned grains is reproduced in fig. 2. In view of these results the probability of there being another solution for the habit plane remote from (101) is very small, but to explore the possibility that the habit plane deviates slightly from (101), a more precise analysis was undertaken. In this, the orientation of a grain in the cubic modification was determined from a Laue back-reflection photograph taken with the sample at 90°C. The traces of the lamellae that formed in this grain on cooling were plotted in the stereographic projection

Jan 1, 1951

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.&apos; Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,&apos; and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By Joseph L. Gillson

BRAZIL has had an industry based on ocean beach deposits of heavy minerals containing monazite, zircon, rutile, and ilmenite for well over 40 years, but except at the very earliest period, prior to 1906, and again during World War 11, has this industry been at all comparable in size with similar operations in other countries. Limiting factors have been neither a lack of reserves nor lack of markets (except for zircon). Although poor local transportation and shipping facilities have handicapped the development in Brazil, these conditions were perhaps equally bad (when mining operations started) in the Indian State of Travancore, and in New South Wales and Queensland, Australia, in which states the principal production of beach deposits of heavy minerals has occurred. The outstanding restraints on the Brazilian industry have been the lower quality of the Brazilian minerals, the relative small size of individual deposits that were known until recently, the lack of interest of Brazilian investors in mining ventures, and the unfavorable climate for investment of foreign capital under Brazilian mining law. The lower quality of the minerals is indicated by the fact that the Brazilian monazite carries only 5 to 6 pct Tho2*, and the ilmenite 561/2 pct TiO2, whereas the corresponding Travancore minerals carry 9 pct Tho, and 60 pct TiO, respectively. The Brazilian zircon is a dirty brown color (which can be removed readily) as compared with the gleaming whiteness of the Australian zircon. An inadequate market for the abundant zircon that will be available in any operation in Brazil is certainly a heavy restraint, since otherwise it could be an important byproduct. The oxide of zirconia, baddeleyite, that has come from Brazil is from other sources.&apos; Since the Brazilian beach sands carry only a little rutile, that mineral has not been available as a valuable byproduct to help finance the operations. Substantial tonnages of rutile have been exported from Brazil. The sources of this mineral are stream placers and residual deposits over gneisses in the States of Goyaz, Minas Geraes, Ceara, etc. (Leonardos,&apos; and Chambers". With these handicaps, Brazilian production from beach sands has been marginal, and there has been only one consistent producer. This is a company, originally French, which was called Companie de Franco-BrazilliCne, but, with the downfall of France in 1940, became Brazilian under the name Monazita e Ilmenita do Brasil ("Mibra"). This company has operated several deposits in the vicinity of Guara-pary, in the State of Espirito Santo. Its office and plant has been at Guarapary. Recently a company called, "Fomil" (Fomento Monazita-Ilmenita) started operations. This company was organized by the Foote Mineral Co. of Philadelphia, and such share as a foreign company can hold under Brazilian law has now been acquired by the Lindsay Light and Chemical Co. of Chicago. When the writer went to Brazil in the fall of 1940, he found that no general survey of the beaches had been made except for a thorough study of part of the area by Abreu.4 The paper by Miranda6 had not then been written. The federal Geological Survey and Department of Mines knew only of the existence of the deposits in Espirito Santo south of Vitoria, and had a hazy idea that others might be found north of Vitoria. One deposit in Bala was known in Rio, but the larger one at Guaratiba was not known, although a Frenchman had prospected

Jan 1, 1951

By E. F. Ketterer, D. B. Collyer, A. B. Wilder

The microstructural stability of 59 carbon and low alloy steels after 34,000 hr exposure at 900&apos; and 1050°F, including the weld heat-affected zone, is discussed. The tensile and creep rupture properties of the parent metal of many of the steels before and after 10,000 hr exposure are presented. SEAMLESS pipe has been used for many years at elevated temperatures. When seamless first began to be used, operating temperatures and pressures were relatively low and the steel produced adequately met the existing requirements. The need for knowledge of creep properties and graphitiza-tion was nonexistent. Today the requirements for tubular products have changed considerably. Operating temperatures and pressures are increasing continually and corrosion, particularly at high temperatures, presents a problem. Carbon steels have, under these conditions, certain economic advantages particularly in oil refinery use. However, the use of low alloy steels in the generation of steam power has increased appreciably due to the influence of molybdenum on creep strength and the control of graphitization with chromium. The behavior of carbon and certain low alloy steels after long periods of exposure at 900° and 1050°F (480° and 565°C) has been investigated. The steels were examined before and after 10,000 to 34,000 hr exposure. Results obtained with material exposed at 1200°F (650°C) are not presented due to the severe oxidation and resulting decarburiza-tion after long periods of exposure. The graphitization characteristics of carbon and low alloy steels are of fundamental concern to the users of these materials. This is particularly true where welded joints are employed. In order to evaluate properly the behavior of steels at elevated temperatures, it is desirable to employ not only long periods of exposure under controlled conditions, but to use material with known properties and steelmaking practices. The purpose of this investigation has been to study the microstructure of the weld and the tensile and creep rupture properties of the parent metal after long periods of exposure at elevated temperatures. In the report&apos;.&apos; of a previous investigation data were presented on the microstructure, impact strength, hardness, and oxidation characteristics after 10,000 hr exposure at elevated temperatures. When this investigation was planned, methods for controlling the graphitization characteristics of steel were not established and, therefore, a number of special alloy steels were included in the study. During the exposure of these steels, the influence of aluminum in accelerating the rate of graphitization and the inhibiting power of chromium were established by various investigators. Also, the vanadium-bearing steels, because of their outstanding creep properties, received attention. As a result of these developments, considerable progress has been made in the field of high temperature tubular products, and the necessity for special alloys to prevent graph-itization has been restricted largely to the use of chromium. Material Chemical analysis, deoxidation treatment, and austenitic grain size of the 59 steels discussed in this paper are shown in Table I. The steels were forged to 1x1 in. bars with the exception of steels 12B, 12DX, 12DY, 12DZ, 70, 70A, 72 to 78, 82, and 83 which were machined from heavy wall pipe. All bars were surface ground before exposure. Heat treatment before exposure is shown in Table 11. The majority of the steels included were melted in either a basic open hearth or basic electric furnace; how-

Jan 1, 1955

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.&apos; 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,,&apos; CrIr,,&apos; and URu, .4 Finally, the stacking scheme abacabac of the same ordered layers results in a hexagonal close-packed structure of the TiNi3 type.&apos; 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 R. Fawley, M. A. Quader, R. A. Dodd

Stacking fault energies and annealing twin frequencies have been measured for austenitic stainless steels having a) constant 20 wt pct Cr and varying nickel contents, and b) constant 20 wt pct Ni and varying chromium contents. The effect of nitrogen has also been studied and, to a lesser extent, so has the effect of carbon. All measured stacking fault energies plot linearly against the corresponding annealing twin frequencies, suggesting that, for constant prior deformation and grain size, twinning frequency can be used to estimate stacking fault energy. Compositions low in nickel possess the lowest fault energy, while the maximum fault energy within the investigated composition range occurs mound 20 pct Cr-20 pct Ni. Nitrogen has practically no effect on stacking fault energy when increased from 0.005 to 0.05 wt pct, although Planar dislocation glide is associated with higher nitrogen contents; this may be a short-range order effect. Carbon may raise the stacking fault energy a little, and causes pronounced dislocation tangling in deformed alloys. The basically different dislocation structures promoted by nitrogen and carbon, respectively, are not associated with large variations in stacking fault energy, and the reason for the difference remains unknown. INTEREST in the dislocation configurations developed in plastically deformed alloys arises principally from a desire for an understanding of mechanisms of plastic deformation and fracture. Comparatively little basic work has been concerned with austenitic stainless steels, although considerable interest has developed in the fundamental aspects of deformation of these alloys since the suggestion that those compositions deforming essentially by planar glide are particularly prone to transgranular stress corrosion cracking.&apos; Certain facts are well-established. An 18 Cr-8 Ni steel (type 304) has a low stacking fault energy which is increased by higher nickel contents, and the structure of these steels when moderately plastically deformed changes concomitantly from planar to less planar to distinctly tangled dislocation configurations. These changes are thought to relate to changes in stacking fault energy, and considerable effort has been expended in measuring stacking fault energies of austenitic stainless steels through the determination of node curvatures2"4 even though the method has limitations due to formula approximations,5 an upper limit of measurement of 50 erg cm-2 at the most,5 and the necessity of an extremely meticulous experimental technique. Therefore, it is not surprising that only qualitative agreement between different investigators is generally to be found.&apos;-&apos; At high energies where node radius measurements are inappropriate, some use has been made of annealing twin frequencies to estimate relative stacking fault energies, although a recent critical evaluation of the method suggests that it should be used cautionsly with due regard to effects of grain size and prior deformation.6 Finally, there is a question as to whether the structures of some deformed steels are due to ordering effects. In particular, the role of nitrogen in promoting planar dislocation motion has been suggested to be due to ordering,&apos; but similar suggestions have been made for steels having low interstitial contents.4 EXPERIMENTAL Small ingots of austenitic stainless steels (-50 g) were prepared from components exceeding 99.99 pct purity, the nickel and chromium being Johnson Matthey "Specpure" metals. Carbon was added as pure graphite, and nitrogen as CrN. The components were accurately weighed, and it was assumed that the final composition was the same as the nominal composition

Jan 1, 1969

By George P. Chapman

Mica is a platy mineral occurring in a variety of complex hydrous aluminosilicate forms with differing chemical composition and physical properties. Principal minerals in the mica group include: Muscovite-potassium mica (colorless or pale green/ ruby) Phlogopite-magnesium mica (dark brown or amber) Biotite-magnesium-iron mica (black or dark green) Lepidolite-lithium mica (lilac) Selected properties are given in Table 1. Muscovite is most important commercially with phlogopite of lesser use. The laminated structure of mica enables it to be split into very thin films which are transparent and tough as well as having outstanding dielectric and insulating properties. Commercially, mica is used in a number of forms (Chowdbury, 1941; Rajgarhia, 1951; Skow, 1962). Sheet mica consists of flat sheets mined from naturally occurring books of mica, free from defects and capable of being punched or stamped into required shapes. Sheet mica is separately classified into blocks, films, or splittings according to thickness. Built-up mica, or micanite, is made by arranging overlapping splittings in layers , cemented with a binder and pressed together at high temperature. Reconstituted mica, or mica paper, is made by depositing fine flakes of high-quality scrap mica in a continuous film impregnated with binder. Scrap and flake mica are normally unsuitable in quality or size for making sheet mica. Originally the term scrap mica referred to the waste byproduct of mining and fabricating sheet mica, and distinct uses were developed for this material. Subsequently it became economically feasible to mine lower quality mica for these uses, and the term flake mica was introduced. Although the two terms are still used somewhat synonymously, it is considered better, at least in the United States, to use the term flake mica in referring to mica mined for uses other than as sheet mica; and to restrict the term scrap mica to mica mined for or with sheet mica, but which will not meet the specifications. Synthetic mica, such as fluorophlogopite, is produced by slow crystallization of a melted blend of pure raw materials. Mineralogy In the true sense the term mica does not relate to, a particular mineral, but to a group or family of minerals of similar chemical composition and to some extent similar physical properties. These minerals are predominantly potassium aluminum silicates with varying amounts of magnesium, iron, and lithium. The precise formulas and isomorphic relationships of the various group members have been studied, but general agreement has not been reached (Grimshaw, 1971; Hurlbut, 1952; Skow, 1962). The general formula describing the chemical composition of micas is [X2Y4-6Z8020(OH, F)4, where X is mainly K, Na, or Ca; Y is mainly Al, Mg, or Fe; Z is mainly Si or Al (Deer, et al., 1962).] These minerals have an internal structure of the layered lattice type where the silicon atoms are in the center of a tetrahedral grouping of oxygen atoms. The groups are linked together in a single plane by three oxygen atoms that lie within the common plane. Each of these oxygen atoms is shared by two tetrahedra. These linked tetrahedral groups, when continually extended, produce a hexagonal network within the plane. This internal structure of the mica has been used to explain the ex-

Jan 1, 1983

By S. R. Dunbas, D. C. Jillson, E. A. Anderson

THE present work was undertaken to furnish information, lacking in the literature, on the deformation mechanisms active in pure titanium at room temperature. Since it was started, Rosi, Dube, and Alexander&apos; have indicated that slip can occur in coarse-grained (2 to 6 mm diameter) titanium on the {1010} and {1011} planes and twinning can take place on the {1072}, (1122) and (1151) planes. Liu and Steinberg,&apos; working with titanium flakes produced by fused salt electrolysis, found evidence of twinning on the {1032$, {1121), {1122}, (1123}, and (1154) planes. The crystals used in the present work were substantially longer (up to nearly 2 in. in length) and possibly purer. Production of Large Crystals It was the purpose of this part of the work to provide single crystal or large grain specimens for use in the deformation studies rather than to study the mechanism of crystal growth. Accordingly, all further exploratory studies on methods were abandoned when it was found that cold-rolled bars sealed in vacuo in individual Vycor tubes and given three or more cycles of 4 hr at 1200°C and three to five days at 850°C, gave large grains. Eighteen specimens about 0.2 in. square x 2 in. long yielded 33 useful grains, ranging from Va in. to nearly 2 in. in length, with an agreeably wide range of orientations, Fig. l. The 0.25 in. thick strip from which the starting specimens were cut had been reduced 67 pct on 18 in. diameter rolls from a scalped, hot-forged (959" to 1000°C), arc-melted, iodide titanium ingot. Thc bar was at room temperature, but the rolls were at 200°C. Reductions of about 0.03 in. per pass were used. The bar was cut into four segments, each of which was rolled in a somewhat different manner. No effect on the growth of large grains was noted. The composition of the titanium, determined on turnings from the ingot scalping operations, is given in Table I. The Rockwell A hardness of the ingot was 26. The standard starting specimens, about 1/4x1/4x2 in., were milled on all four sides, hand polished on 280 and 400 mesh emery papers, etched for 3 min in a 50 HF-50 glycerine solution, rinsed, and dried in alcohol and ether just before sealing them in Vycor tubes. The average specimen weight was 7.5 g, and the tube volume was 6.5 cc. A vacuum of less than 1 micron pressure was applied. The specimen tubes were placed in an evacuated Inconel muffle to minimize the danger of collapse of the glass tubes at temperature. In practice the specimens were first heated to 1200 °C for 4 hr and then transferred fairly quickly to an 850°C furnace where they were held for three to five days. This cycle was repeated at least three times before the specimens were cooled, removed from the tubes, lightly polished and etched on one surface for examinstion. Those in which large grains had not developed were resealed in Vycor and returned to the cycling. Satisfactory specimens (about one out of every four cycled) were polished with emery paper on all four side;, then metallographically polished using ctchinz between wheels to remove distorted metal and, finally, given a very light etch to reveal the grain boundaries. This was necessary because the surface was roughened by the sublimation of titanium under high temperature vacuum conditions. Specimens were identified by TiXl numbers using supplementary letters to designate specific grains.

Jan 1, 1954

By C. W. Phillips, D. N. Frey

A commercial Ti-Fe-Cr alloy, Ti-150, exhibits a martensitic transformation on cooling and two nucleation and growth reactions, one above and one below the Mg-Mf region, on isothermal holding below the single-phase ß temperature range. The reactions were followed by metallographic, X-ray diffraction, and microhardness methods. THE rapidly expanding engineering application of titanium and its alloys makes increasingly urgent an adequate knowledge of the effect of heat treatment on this material. The work herein reported is an attempt to determine certain aspects of the behavior of a commercially available alloy, Ti-150, during heat treatment. The alloy, with a nominal composition of 2.7 pct Cr, 1.3 pct Fe, 0.25 pct 0, 0.02 pct N, and 0.02 pct C, was received in the as-rolled condition as a 3/4 in. round. Slugs 0.11 to 0.12 in. thick were cut under a coolant using a silicon carbide wheel. Preliminary work established that the alloy consists of two phases, a (hexagonal close-packed) and /3 (body-centered cubic), at temperatures below 1750" to 1775"F, and of only /3 phase at higher temperatures. The slugs were heated for 1 hr in air at 1800°F to form a single-phase /3 matrix, then transferred to molten tin (1250° to 1650°F) or lead (1150°F and below) for isothermal holding. Holding temperatures ranged from 700° to 1650°F, times from 0.001 to 23 hr. The treated slugs were then sectioned, one part for metallographic examination and diamond pyramid hardness, the other, after deep etching to remove the high oxygen surface,&apos; for comparative lattice parameter determination and X-ray phase identification. Hardness measurements were taken on the lightly etched surfaces of the metallographic specimens; a 1000 g load on a 136° diamond pyramid was used. Five impressions on each sample were made and the average of the hardness calculated. The use of microhardness measurements to follow the course of an isothermal transformation reaction is undesirable because of the possibility of wide differences in microconstituent hardness.&apos; They were used in this case, however, because of the small amount of material available. At the higher transformation temperatures, where the above-mentioned objection was apparent, the readings were proportioned to correspond to the estimated ratio of transformed and untransformed constituents present. At lower temperatures, resulting in much finer microconstituents, the microhardness measurements were more uniform. The standard deviation of the mean of five impressions calculated from these latter values was 4.2 DPH. Employing 2a limits (probability 0.95) the experimental error of the hardness measurements averages was 8.4 DPH. The etchant used was composed of one part glyc-erol and one part 48 pct hydrofluoric acid." Of a number of etches tried, this one appeared most satisfactory. All micrographs were taken at 500X magnification and with oblique lighting to permit easier identification of the acicular structure resulting from rapid cooling. No advantage was gained by using polarized light for metallographic examination. Phase identification and lattice parameter measurements were made with a North American Philips high angle spectrometer in conjunction with a recording potentiometer. Considerable difficulty was encountered with some of the lattice parameter measurements because of the extreme broadness of the few diffraction lines obtained from samples consisting mainly of strained, untempered, quenched structures.

Jan 1, 1953

By T. E. Leontis

ONLY a limited amount of information has been published on the effect of thorium as an alloying ingredient in magnesium. McDonald13&apos;2 showed that the addition of thorium in amounts up to 3 pct increases significantly both the ductility and the strength of rolled magnesium sheet. A recent publication by Sauerwald" indicates that thorium contributes strength and creep resistance at elevated temperatures to magnesium in both the cast and wrought states. The observations of Sauerwald are confirmed in this paper, which presents the results of a systematic study of the effects of compositional variation on the tensile properties, creep resistance, conductivity, density, and metallography of Mg-Th alloys containing up to 50 pct Th both in the sand-cast and in the extruded states. The effect of the addition of cerium to Mg-Th alloys is also reported. Experimental Methods The alloys studied in this investigation were pre.pared in small laboratory melts according to the melting practice described by Nelson4 as the crucible method. Electrolytic magnesium was used as the starting material to which the thorium* was introduced in metallic form. It was observed that the behavior of thorium in molten magnesium with respect to reaction with protective fluxes is similar to that of rare-earth metals. In order to obtain the highest possible alloying efficiency, it is necessary to use non-MgC1, fluxes and to apply all the precautions described by Marande6 for melting, alloying, and casting magnesium-rare-earth alloys. .Under these conditions it is possible to obtain an alloying efficiency in the range of 85 to 95 pct. The Mg-Th-Ce alloys were made with cerium of the highest purity available, not with the commercial product "misch-metal" which contains approximately 50 pct Ce. The total rare-earth content of this material was 97.1 pct, of which 0.3 pct was rare-earth metals other than cerium; the major impurities comprising the balance were iron and magnesium. The thorium and cerium contents of each alloy were determined chemically. Test bars 6% in. long with a 2% in. long reduced section of % in. diam were cast in sand molds using a four-baf pattern. In most cases, a 3 in. diam extrusion billet 10 in. long was cast in a steel mold from the same melt used for making the sand-cast test bars. For the higher thorium alloys, it was necessary to remelt the foundry scrap from the test bars in order to make the extrusion billets. The billets were scalped to a diameter of 2 15/16 in. and the ends faced to a length of 9% in. as limited by the size of the extrusion container. The alloys were extruded into % in. diam rod on a 500-ton direct-extrusion press. The details of the extrusion process are as follows: Billet preheat 925°F (2 to 16 hr) Container temperature 900 °F Die temperature 900°F Extrusion speed 10 ft per min Reduction ratio 36:1 Percent reduction 97.3 Alloys containing up to 10.2 pct Th were preheated at 925°F for 2 hr; all alloys with higher thorium contents were preheated for 16 hr. In order to establish the effect of extrusion temperature, billets of

Jan 1, 1953

By J. O. Lewis

The operation of gas-condensate fields is comparatively new and involves physical principles with which the industry was not prcviously familiar. It has been necessary to devise methods for testing gas-condensate wells and to correlate laboratory and field data. In this paper new methods are advanced for interpreting well G.P.M.† tests whereby dilution by dry gas can be estimated and information supplied on revaporization of condensates by dry gas. Inaccuracies in well test data are discussed. Changes in flow rates can cause changes in the G.P.M. of the effluent and it may take some time for a well to become stabilized after an important change in flow rate. Retrograde tests as usually conducted cannot be directly compared with field G.P.M. data, because the retrograde tests usually include solution gas in the condensates, which are reported On the cumulative basis whereas field data (G.P.M.) usually report pentaneS PlUS on a rate or instantaneous basis. Introduction Though long known to physicists, the phenomena Of retrograde condensation became known to the oil and gas industry Only in recent years, when deeper drilling disclosed that the behavior of vapors under changing pressures was different in high-pressure reservoirs than under the low-pressure operations with which the industry was familiar. These deep, high-pressure reservoirs in which condensation and vaporization behaved inversely to the accustomed manner became known as "gas-distillate," or preferably "gas-condensate" fields. Partly to prevent precipitation and retention of liquids in the reservoir, but still more to prevent the waste of residue gas, the operation known as "recycling," or preferably "cycling," was instituted, in which the residue gas is reinjected into the reservoir, thus maintaining pressure and driving the wet gas to the producing wells. For lack of field experience to serve as a guide, the industry had to assume that theory and laboratory experiments could accurately forecast retrograde behaviors in operating these gas-condensate fields, but it is obvious that these assumptions should be checked at the first opportunities against actual field experience. To make such checks, it is necessary to accumulate a large quantity of reliable field data, but experience has shown that it is difficult to obtain reliable field data and that the laboratory data as usually presented are not in directly comparable form. The problems of correlation involve the complex phase behavior on the one hand, and a knowledge of field data and a visualization of underground conditions on the other hand. This paper is an approach from field experience, The purposes of this article are to discuss the sources of uncertainty in the data and to present methods of analyzing, interpreting and correlating laboratory and field data. Data mostly from lower Gulf Coast fields are presented, from which some conclusions can be derived, but better data from more sources than those available to the writer will be required before satisfactory answers to many questions can be obtained. This paper is presented to stimulate the analysis and publication of data from other fields, the reexamination of field and laboratory methods, and the taking of more complete and reliable field tests. For these purposes, the writer presents some speculations that otherwise would not be appropriate.

Jan 1, 1947

By M. C. Smith, W. V. Green, D. M. Olsen

The creep-rupture behavior of commercial powder-metallurgy molybdenum rod is reported in the temperature range 1600" to 250O°C, at stresses up to 9000 psi and times up to 1 month. The effects of temperature, stress, and grain growth are discussed. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher-stress results reported by pugh.1 BECAUSE of its high melting point, molybdenum should retain useful strength to relatively high temperatures. Combined with its ready availability in the United States, this makes it attractive for many applications in missiles, rockets, and so forth—wherever its susceptibility to oxidation can be tolerated or overcome. The mechanical properties of molybdenum rod in the temperature range —200" to 1540°C have been reported by pugh,&apos; Bechtold,&apos; Parke,3 and Carriker and Guard.4 Madden and chen5 have measured the tensile properties of molybdenum single crystals in vacuum up to about 2500°C. As one further step in evaluating its mechanical usefulness, the constant-load creep-rupture properties of commercial powder-metallurgy molybdenum rod have been investigated in the range 1600" to 2500°C. MATERIAL TESTED Creep specimens were machined from 1/2-in. round commercial molybdenum rod, manufactured from powder by pressing, sintering, and swaging. Spectrochemical analysis of the rod showed "traces" (less than 0.01 pct) of silicon, aluminum, chromium, iron, and zirconium, and "faint traces" (less than 0.001 pct) of manganese, magnesium, cobalt, and nickel. Carbon content was 130 to 200 ppm, nitrogen was 110 to 180 ppm, and oxygen 30 to 35 ppm. A typical microstructure of the as-received rod is shown in Fig. 1. Room temperature tensile properties for five specimens strained at about 0.015 in. per in. per min are shown in Table I. CREEP SPECIMENS USED The specimens used for creep-rupture testing are illustrated in Fig. 2. The 1/4-in.-diam gage section was 3/4 in. long, and terminated at shoulders 5 mils high. These shoulders served as fiducial marks for optical strain measurements. Surface finish on the gage section was 16pin. r.m.s. One specimen, for a "long-time" test described below, was modified by dividing the 3/4-in. gage length into three 1/4-in. long sections with individual diameters of 0.250, 0.230, and 0.210 in., each terminating in a pair of fiducial shoulders. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.6 In it the specimen is held vertically on the axis of a cylindrical tantalum or tungsten heater tube by threaded molybdenum or tungsten grips. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. The bottom specimen grip is held at its lower end by a clevis pin. The testing load is applied to the specimen through the upper grip by means of hanging weights, a constant force-multiplication lever system, and a pull rod sealed to the chamber lid by a bellows. The incandescent specimen is viewed by an external optical system through slots in the heater-tube and radiation shielding, and an enlarged image of it is projected on a ground-glass screen. Gage-length measurements are made on this image with a pair of cathetometers. Thorium oxide coatings were applied to the threaded ends of most specimens, to prevent diffusion-welding of specimens to grips during testing. Without such a coating welding usually occurred, and grips were often broken by subsequent efforts to remove the tested specimens.

Jan 1, 1960

By Oliver Bowles

Dimension stone is a term applied to stone sold in blocks or slabs of specified shapes and usually of specified sizes, contrasted with crushed, broken and pulverized stone covered in another chapter. Dimension stone includes cut stone, rough building stone, ashlar,* rubble, monumental stone, paving blocks, curbing, flagging, and many types of ornaments and novelties carved from stone. Riprap-large, irregular blocks used for shore protection-is classed with crushed and broken stone. Composition, Varieties, and Properties Dimension stones are of many kinds. The principal varieties are granites, trap rock (diabase, basalt, and gabbro), sandstone, limestone, and marble. Slate is covered in a separate chapter. Granite is a visibly granular crystalline rock consisting essentially of feldspar, quartz, and mica or hornblende. The basaltic rocks are darker in color than the granites. They contain little or no quartz and consist largely of plagioclase feldspar, augite, pyroxene, and hornblende. They are classed commercially as black granites. Limestone consists essentially of calcium carbonate. Dolomites and magnesian limestones used as dimension stone are classed with the high-calcium limestones. Marble is a crystalline form of limestone, but in the trade, any carbonate rock which will take a polish is called a marble. Many limestones which are fossiliferous but which will take a polish are sold as a decorative stone for lobbies of hotels and office buildings. Sandstone consists essentially of silica in the form of sand grains cemented into a coherent mass. Although rock occurrences are numerous and widespread, the exacting requirements of use condemn all but a small fraction of them for commercial use as dimension stone. No deposit that has closely spaced joints or planes of weakness can be used because sound blocks of moderate to large size are demanded. Uniform texture and grain size, constant and attractive colors or color pattern, and freedom from impurities that may cause stains or deterioration usually are demanded. Hardness is a variable property. Granites and diabases are as hard as or harder than steel, while limestones and marbles may be scratched with a knife. The hardness of sandstone depends upon the degree of cohesion of the grains. Workability depends to a considerable extent on hardness, but the degree of hardness has little influence on use except where stones are subjected to abrasion as on steps or floors. "Texture" as applied to stone relates to the arrangement, uniformity, and size of the constituent grains. Stones are of many colors and thus can satisfy a variety of tastes. For monumental stone, a marked contrast between polished and tooled surfaces is preferred in order that inscriptions may be read easily. Strength requirements usually may be disregarded because any sound structural stone suitable in other respects is almost invariably many times as strong as would be required for any ordinary use. The pressure on the base course of the Washington Monument, Washington, D. C., is less than 700 psi, and highgrade granites, limestones, sandstones, and marbles will sustain a crushing load of 10,000 to 25,000 psi. A structure made of stone with a crushing strength of 15,000 psi would have to be nearly 21h miles high before crushing of the lower courses would occur. However, stone disintegrates more readily under severe

Jan 1, 1960

By C. S. Matthews, M. J. Fischer

Distortions caused by dip on five-spot sweep pattern were determined by visual experiments on a model composed of parallel plates of glass with holes drilled at the well positions. This model war designed to simulate a reservoir depleted of its primary oil and containing a gas phase. Prior to interference, it was found that the injected fluid took a nearly circular shape about the injection well for the cases studied. However, these circles moved down-dip considerably under the influence of gravity. It was concluded that pattern flooding should be practical for many dipping reservoirs. A quantitative measure is given of how much the well position should be altered to allow for dip. Experimental deternzinarions of injectivity showed this to be about the same in a dipping reservoir as in a horizontal one. INTRODUCTION This investigation was undertaken at the suggestion of the Pacific Coast area, Shell Oil Co., where a pilot water flood in a dipping reservoir was being carried out at the time this paper was in preparation. Prior to the undertaking of this flood there had been considerable speculation as to how gravity would distort a flood pattern in a dipping reservoir. The thought was expressed in some quarters that a five-spot flood would not be applicable to a dipping reservoir because the flood pattern would elongate in the direction of dip and would never form a "seal" around each five-spot. If the flood pattern elongated sufficiently, both the oil and the water might flow largely downdip rather than into the pattern producers. In view of the importance of the California water floods, it was deemed important to determine the effects of gravity on a five-spot pattern in a dipping reservoir. Previous work had also been carried out in this laboratory,1 but only for the single-fluid case. The present investigation extends these results to multifluid cases. Several sets of pictures of flood fronts are presented so that the process can be visualized. From these pictures, curves are obtained which show the correct drilling position for achieving equal times of oil-bank breakthrough. Several injectivity curves are also presented which may aid in prediction of injection rate. ASSUMPTIONS The present results were obtained with a model composed of two parallel plates of glass spaced about 1 mm apart. When the inertial forces are small, as in these experiments, the flow between the plates follows Darcy&apos;s law and is analogous to flow through porous media. In using these plates, it is not possible to scale effects of capillarity correctly as regards a transition zone between injected and displaced fluid. Calculations show, however, that effects of such capillarity should not be important in determining the gross flooding pattern in the field. In fact, in this model the capillary forces tend to circularize the pattern to a greater degree than in the field. To preserve a large ratio between the viscous forces and the circularizing capillary forces in the laboratory model, viswus glycerine was used as the flooding liquid and the rate of flooding was very high. The circularizing force is believed negligible in these experiments. In addition to the effect of the surface tension y, which tends to circularize the pattern, another capillary force must be considered. This is the adhesion tension y cos, which acts at right angles to the circularizing term y. If the plates in the model are "wetted" the same all around the periphery, then the adhesion tension,

Jan 1, 1957

By J. A. Hren, G. Thomas

A high-temperature stage has been used to study precipitation and dissolution in thin foils of Al-20pct Ag alloy directly in the electron microscope. The results show that the aging characteristics are similar to those observed for bulk materials, and in addition, direct evidence is presented for clustering at the solid solution temperature. The limit of solubility of G. P. zones is-350°C. The heterogeneous precipitation, the growth and dissolution of ?&apos;have been studied in detail. Growth of ?&apos; parallel to the basal planes, occurs by continuous motion of inter -facial partial dislocations. Growth stops at intersecting particles due to formation of sessile a/6 <110> interfacial dislocations. Growth normal to the habit plane occurs by the spontaneous nucleation of partial dislocations on alternate (111) planes and the thickening rate is --10-3= times the lengthening rate. The precipitates dissolve in layers and the final product is a whole a/2 <110> dislocation . The nucleation -growth -dissolution processes are thus completely reversible. Kinetic data obtained from the dissolution rates of ?&apos;particles enable the diffusion coefficient to be determined and the activation energy is found to be 37.5(±4) kcal mol-1, which is that expected for dzffusion of silver in aluminum. The velocity of the interfacial dislocations is thus dependent solely on the rate of diffusion of silver atoms. RECENTLY it was demonstrated that a high-temperature stage could be effectively used in the electron microscope to follow directly the processes of precipitation and dissolution in thin foils of A1-4 pct Cu alloy.&apos; These experiments also provided kinetic data which enabled the diffusion coefficient to be estimated. This new development of electron metallography opens up many fruitful areas of research and it was decided to investigate the aging behavior in thin foils of A1-20 pct Ag alloy, particularly the mechanism of heterogeneous precipitation (i.e., precipitation on lattice defects). This system was chosen because the aging characteristics of bulk specimens are now well known,2"7 and because we wished to obtain more details of the role played by partial dislocations and stacking faults in the nucleation growth and dissolution of the hcp ?&apos; phase. This is of interest for the general case of fcc-- hcp transformations. Part of the A1-Ag phase diagram is shown in Fig. 1. The use of a high-temperature stage also enables a study to be made of the clustering process (formation of G. P. zones) and to determine the structure of the solid solution prior to the usual quenching and aging procedures. It is also possible to obtain kinetic data from measurements of the rates of dissolution of precipitate particles. Unlike the results of previous experiments on A1-4 pct CU 1 where much of the initial precipitation occurred on the foil surfaces, the results on the A1-20 pct A1 alloy were identical to those reported for bulk specimens6,7 and no surface precipitation was ever observed. Thus, it was possible to follow the aging sequence: G.P. zones — ?&apos; — ? directly in the thin foils. This paper is concerned with the formation and dissolution of zones and the ?&apos; phase, and no attempt has been made so far to follow the mode of discontinuous precipitation of ?. I) EXPERIMENTAL DETAILS The high-purity A1-20 pct Ag alloy was prepared by the Aluminum Co. of America in the form of 0.001-in.-thick sheets. These were cold rolled with intermediate anneals to a thickness of 0.0004 in.,

Jan 1, 1963

By H. W. Weart, S. Sarian

The effect of temperature, impurities, and capillarity on the morphology of solid particles in a liquid matrix is investigated. For the NbC-liquid iron system, at least, it is found that those particles which are dissolving will assume a spherical shape; all others will take the equilibrium shape. An aniso-tropic-isotropic transition in the interfacial tension is observed at about 1725°C and is believed to be due to cooperative roughening of the interface on an atomic scale. The presence of boron as an impurity lowers the transition temperature. It is the purpose of this paper to present some observations on the shape of particles in a system consisting of solid particles of nonuniform size in a liquid matrix and to propose an explanation for these observations. Although qualitative only, these observations, which were made largely in the course of a study of particle-growth kinetics,&apos; are presented separately to draw attention to them. They reveal the effect of particle size, temperature, and surface-active impurities on particle shape in the solid NbC-liquid iron system, and are unique in demonstrating for the first time the reversible effect of temperature and impurity concentration on the anisotropy of the energy of the solid-liquid interfaces involved. Some of the changes are readily demonstrated with the few particles whose shapes can be clearly shown in a single photomicrograph, but others are more subtle, and their recognition depends upon some experience and the study of a much larger sample. For this reason, a certain amount of judgment must be acknowledged to underlie their detection, but every effort was made to maintain proper scientific objectivity in evaluating the observations. The observations will be presented first, and then an explanation rationalizing them will be offered. Brief reminders of the relevant theories will be inserted into the discussion at the appropriate points. EXPERIMENTAL The observations were made of the shape of NbC particles dispersed in liquid iron. All specimens were prepared by pressing NbC powder and car- bony1 iron powder treated according to standard powder-metallurgical procedures. Except as noted, all specimens were heated to 1900°C for 1/2 hr. In investigating the effect of temperature, specimens were quenched from 1900°C to various lower temperatures, and held long enough (48 hr) to allow shape changes to be completed. Boron, in the form of amorphous powder, and oxygen, in the form of niobium oxide powder, were added as impurities to some specimens. Nitrogen was introduced into some specimens as an impurity by heat treating the samples under a partial pressure of nitrogen gas. Effect of Temperature. It was first observed that increasing temperature had a marked effect in rounding the corners and edges of the particles. At 1900°C the particles are all very nearly spherical and remain so even when the holding time is extended to 48 hr. As can be seen from Fig. 1, there is virtually no evidence of the presence of low-index planes. At 1300°C, however, most of the particles are prismatic with very slightly rounded edges and corners, Fig. 2. (In making these shape comparisons, attention should be focused on the larger particles, even though the smaller ones would be expected to be the first to change shape, owing to the shorter diffusion distances involved. The cause of the mixed particle shape will be explored later.) It was established that these structures are re-

Jan 1, 1965

By L. R. Page, J. J. Norton

EFFECTIVE methods for determining grade and reserves of pegmatites in advance of mining have been developed in recent years. When intensive work began on the economic geology of pegmatites during the early years of World War 11, it was widely believed that grade and reserves could be estimated only in a most general way. The literature indicated that not all pegmatite deposits are unpredictable, but statements emphasizing unpredictability and irregularity seem to have been more widely accepted. Many standard references reflect the prevailing opinion that minerals: are unsystematic in their occurrence in pegmatites. Pegmatites have been described as "notorious for their irregular structure," and minerals within pegmatites as "irregularly distributed." "irregularly disseminated," of "erratic occurrence," "proverbially erratic in distribution," "characterized by extreme irregularity in ... size and distribution of the essential minerals, and variety and proportion of the accessory minerals," and "spotty.&apos;"" Over many years, however, geologic techniques have been applied with increasing success to economic analysis of pegmatites. Investigations, chiefly since 1939, have shown that mineral distribution and structure of pegmatites are largely systematic and that detailed geologic study can be used to predict the size and shape of mineral deposits in pegmatites. Because the writers are most familiar with the pegmatites of the Black Hills, S. D., examples cited are from that area." Pegmatites mined in other dis- * All examples are described more cornpletely elsewhere.: tricts are similar to those in the Black Hills," and the techniques described here have been applied by geologists and engineers working in other districts. In actual practice few pegmatite mine operators attempt to make accurate estimates of grade and reserves in advance of mining. Many deposits are too small for mining except on a very small scale; few pegmatite mines have more than ten employes. Hence there is little systematic preparation for mining, and the capital outlay may be so small that only a general knowledge of reserves is necessary. Technical personnel are rarely employed by pegmatite mine operators to make such estimates. In the future, however, as capital outlay becomes larger, estimates of grade and reserves will have to be more accurate. Geologic Aspects of Determining Grade and Reserves Estimating grade and reserves requires that the type of pegmatite, the size and shape, and the internal structure be determined by detailed geologic mapping and careful mineralogic study. The wide variations in the texture and distribution of minerals within many pegmatite deposits make a thorough geologic study of this kind necessary before it is possible to decide what sampling methods should be used to determine mineral content or grade. Types of Pegmatites: The first step in economic appraisal of a pegmatite is to determine the min-eralogical and structural type. In general, pegmatites may be classified into two groups: 1) those in which component minerals are more or less evenly distributed throughout the entire body and show relatively minor variations in texture, and 2) those in which component minerals have been segregated into units with recognizable differences in texture, mineralogy. or both. Johnston" has classified these types of pegmatites as homogeneous and heterogeneous, respectively. Cameron et al.10 have used the terms ~inzoned and zoned for similar types. The difference between the homogeneous and heterogeneous types is of great commercial importance. Homogeneous pegmatites can seldom be mined where the products are concentrated by the hand methods now commonly used, but they have been mined in a few places where a milling process has

Jan 1, 1957

J. M. Wadsworth,&apos; Okmulgee, Okla. (written discussion).—It seems to me that thc young man must first be absolutely sure that the work he has taken up is to his liking and then I would advise that he get into the practical end of it and learn as much about it as he can as fast as he can. For instance, in the refinery business the college man, graduated in chemical engineering, should ground himself by going through the various departments in a refinery and working in them until he is thoroughly familiar with the operating problems. In a short time he would be able to apply many things which appear in the abstract form in his college work and this would opcn up an opportunity for him to capitalize on them, promoting his own interest. I do not criticize the present-day college men as a class, but I have found that many of them come into your plant with the idea that mere possession of a diploma should insure rapid promotion; in a short time they are impatient and usually leave. We have found in employing men that the single attribute most difficult to find in them is a lot of energy and whole-hearted interest in the work at hand, and it seems to me that if a man combines these with a careful technical training he should be fairly well equipped to gamble on his future. They must learn that the biggest satisfaction to be gained in life is in their work. Procedure for Attaining Objective of Young Petroleum Engineer H. B. Fell,+ Ardmore, Okla. (written discussion).—Of course, the first thing to be ronsidered in any proposition is the ultimate objective that is desired to be attained. 1 presume that the desired objective of most of the young men graduating in petroleum engineering will be that of chief executive of one of the companies in the petroleum industry, or one of the allied industries, or to become an independent oil producer, or oil refiner, or possibly an oil distributor. The next phase then to be considered is the procedure which should most logically be followed to attain the objeckive of the indivitlual, since in these cases these young men will have been trained in a course in petroleum engineering and it would logically be presumed that the attainment of their objective should be through the operating end of the branch of the business with which they are connected. The operating end is, of course, the department of each branch of the business that develops the resources, or refines the products, or distributes the products, from which the profits are derived, and is a part of any business which is filled with enough interesting work to appease the desires of the most ambitious young men. In order to get the best possible training it would appear to me that the place for a young man to start after graduation would be at the bottom of that branch of the industry which he expects to follow. For example, if he is going in the producing end he can gct no better training than is secured by starting as a roustabout in the ficltl, where he romes in constant rontact with the character of work that is necessary

Jan 1, 1928

By J. O. Lewis

The operation of gas-condensate fields is comparatively new and involves physical principles with which the industry was not prcviously familiar. It has been necessary to devise methods for testing gas-condensate wells and to correlate laboratory and field data. In this paper new methods are advanced for interpreting well G.P.M.† tests whereby dilution by dry gas can be estimated and information supplied on revaporization of condensates by dry gas. Inaccuracies in well test data are discussed. Changes in flow rates can cause changes in the G.P.M. of the effluent and it may take some time for a well to become stabilized after an important change in flow rate. Retrograde tests as usually conducted cannot be directly compared with field G.P.M. data, because the retrograde tests usually include solution gas in the condensates, which are reported On the cumulative basis whereas field data (G.P.M.) usually report pentaneS PlUS on a rate or instantaneous basis. Introduction Though long known to physicists, the phenomena Of retrograde condensation became known to the oil and gas industry Only in recent years, when deeper drilling disclosed that the behavior of vapors under changing pressures was different in high-pressure reservoirs than under the low-pressure operations with which the industry was familiar. These deep, high-pressure reservoirs in which condensation and vaporization behaved inversely to the accustomed manner became known as "gas-distillate," or preferably "gas-condensate" fields. Partly to prevent precipitation and retention of liquids in the reservoir, but still more to prevent the waste of residue gas, the operation known as "recycling," or preferably "cycling," was instituted, in which the residue gas is reinjected into the reservoir, thus maintaining pressure and driving the wet gas to the producing wells. For lack of field experience to serve as a guide, the industry had to assume that theory and laboratory experiments could accurately forecast retrograde behaviors in operating these gas-condensate fields, but it is obvious that these assumptions should be checked at the first opportunities against actual field experience. To make such checks, it is necessary to accumulate a large quantity of reliable field data, but experience has shown that it is difficult to obtain reliable field data and that the laboratory data as usually presented are not in directly comparable form. The problems of correlation involve the complex phase behavior on the one hand, and a knowledge of field data and a visualization of underground conditions on the other hand. This paper is an approach from field experience, The purposes of this article are to discuss the sources of uncertainty in the data and to present methods of analyzing, interpreting and correlating laboratory and field data. Data mostly from lower Gulf Coast fields are presented, from which some conclusions can be derived, but better data from more sources than those available to the writer will be required before satisfactory answers to many questions can be obtained. This paper is presented to stimulate the analysis and publication of data from other fields, the reexamination of field and laboratory methods, and the taking of more complete and reliable field tests. For these purposes, the writer presents some speculations that otherwise would not be appropriate.

Jan 1, 1947

By Robert M. Grogan

Fluorspar is the commercial name for fluorite, which is the mineral having the composition CaF2, calcium fluoride. Its valuable properties are due to its content of fluorine, and it is the only important commercial source of that element. The name is derived from the Latin fluere, to flow, because the mineral melts easily and is a good flux. History The mineral has been known since Greek and Roman times, when it was used for drinking cups and ornamental slabs. Various peoples including the Chinese and the American Indians have carved ornaments from large crystals. Its usefulness as a flux was known to Agricola, who wrote about it in 1546.1 Mining began in England about 1775 15 and at various places in the United States during the period 1820 to 1840.28 Substantial production was achieved first in the period 1888 to 1900 in consequence of the development and widespread adoption of the basic open hearth method of making steel, in which fluorspar is used as a flux. After that, production and usage was stimulated by growth in the steel, aluminum, chemical, and ceramic industries and accelerated by World Wars I and II. The organic fluorides called "Freons" entered the picture in 1931, and the use of anhydrous HF as a catalyst in the manufacture of alkylate for high octane fuel blends began in 1942. The development of the froth flotation process in the late 1920&apos;s, a differential flotation scheme for separating fluorspar from galena, sphalerite, and other minerals in the 1930&apos;s, and the application of heavy-media concentrating methods to the treatment of low-grade ores in the 1940&apos;s were outstanding technological contributions that enabled increased production of fluorspar concentrates. Composition and Properties Fluorite in its purest form contains 51.1 pct calcium and 48.9 pct fluorine. Substitution of small percentages of cerium and yttrium for calcium have been noted.4 Mechanical inclusions of gases and fluids such as petroleum and water, and of other solid minerals such as pyrite, marcasite, and chalcopyrite are common. The fluorspar of commerce contains attached and admixed mineral impurities, chiefly calcite, quartz, barite, celestite, and various sulfides. It is interesting that the purest commercial form in which the mineral is sold, acid grade concentrate, contains a minimum of 97 pct CaF2, and as such is of comparable purity to many reagents used in chemical laboratories. Fluorite has a marked tendency to occur in large, well-formed crystals sometimes six to ten inches on a side. It crystallizes in the isometric system, frequently forming cubic and octahedral crystals or combinations thereof. The mineral also occurs in massive and in earthy forms, and in crusts or globular aggregates with radial fibrous texture. Crystalline fluorspar exhibits a great array of colors, from colorless and water clear to yellow, blue, purple, green, rose, red, bluish and purplish black, and brown. The colors are often arranged in alternating bands parallel to cube faces. They may be altered by exposure to X-rays, heat, ultraviolet light, and pressure, and are caused by a variety of factors including the presence of trace impurities and displaced ions in the lattice. Sometimes the changes induced by X-rays can be reversed by ultraviolet radiation. The mineral has a hardness of 4, and is the model of that hardness on the Mobs scale.

Jan 1, 1960