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By W. P. Sykes

In an earlier paper1 the composition-temperature limits of the gamma iron phase in the iron-tungsten system were reported as approximated by thermal analyses. At that time no attempt was made to develop metallographic evidence of the coexistence of two phases in the iron-rich solid solution at temperatures between 900" C. and 1400" C.

Jan 1, 1931

By R. B. G. Yeo

Pronounced isothermal martensite formation at room temperature was measured dilatometrically in a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pctAl, 2.58 pct Ti and 0.25 pct Cb. It is shown that martensite will form isothermally if stabilization of the austenite-martensite transformation is eliminated by removal of carbon. The decarburization of two iron-nickel alloys allows isothermal transformation to martensite to occur at temperatures above their athermal Ms temperatures. In an Fe-22.4 pct Ni alloy, at the 0.008 pct C level, the Ms temperature during air cooling is 85°F higher than that during- water quenching-. At the 0.15 pct C level this difference is reduced to only 5°F. The introduction of carbon causes stabilization during air cooling which lowers the Ms temperature virtually to the same level as determined during mate?. quenching. Thus in the 0.15 pct C alloy, the Ms temperature is almost independent of cooling rate. It is suggested that rival theories of martensite formation should be reexamined in alloys of sufficiently low carbon and nitrogen content to eliminate the complication of stabilization. The Ms temperature of a steel containing 0.01 pct C, 24.9 pct Ni, 0.26 pct Al, 1.58 pct Ti and 0.15 pct Cb, solution treated at 1500°F and air cooled as 1/8-in. diam specimens, was found to be 57 °F. 1 However, when held for several hours at room temperature the steel hardened slightly and became appreciably ferromagnetic. Isothermal transformation to martensite was first revealed by Kurdjumov and Maksimova2 in an iron-base alloy containing 0.6 pct C, 6.0 pct Mn and 2 pct Cu. Most of the other studies of isothermal martensite have also been confined to highly alloyed steels which transform at subzero temperatures; for instance, DasGupta and Lement, 3 Cech and Hollomon, 4 Machlin and Cohen,5 Shih, Averbach, and Cohen.6 Averbach and cohen7 noted a rapidly decaying volume increase at room temperature in a steel containing 1 pct C, 1.5 pct Cr and 0.2 pct V. cina8 and Marshall, Perry, and Harpster9 have described the isothermal transformation to martensite at room and subzero temperature in stainless steels. Kurdjumov10 has recently reviewed the subject, noting that the isothermal formation of martensite can be observed only in the temperature range somewhat below Ms or below -50°C. The isothermal formation of martensite may be characterized as follows: 1) It occurs in steels of widely different compositions, the main prerequisite being a low transformation temperature. 2) The transformation occurs by the formation of new plates and not by the growth of old ones. 3) The isothermal transformation is suppresed by stabilization during slow cooling or holding at temperatures near room temperature. However, the factors governing this mode of transformation are still not fully understood. The formation of martensite isothermally suggests an activated process. The early theories of martensite formation did, in fact, utilize classical nucleation concepts. Kurdjumov 11 first proposed the presence of thermally activated nuclei of different sizes and compositions which would grow if they reached critical size during cooling. This treatment was enlarged and developed quantitatively by Fisher, Holloman, and Turnbull12,13 and was later reviewed by the latter two authors.14 Fisher15 associates Ms with a nucleation rate of one per cc per sec. At slightly higher temperatures the nucleation rate is so low that isothermal formation of martensite is not observed in reasonable times. At slightly lower temperatures the nucleation rate is so high that it could not be suppressed by rapid cooling. By judicious use of parameters Fisher 16 was able to obtain good agreement between classical nucleation theory and the incubation times of martensite formation.4 However the application of these principles to martensite formation in iron-nickel alloys15 predicts that an alloy containing about 30 pct (31 at. pet) Ni would not transform. The presence of an Ms temperature at -223° C in an alloy containing 34.1 pct (33 at. pct) Ni led Kaufman and cohen17 to reject the hypothesis of homogeneous nucleation in favor of the reaction path theory originally proposed by Cohen, Machlin and Paranjpe.18 This theory conveniently explains the formation of martensite athermally but becomes labored when dealing with isothermal formation. Kaufman and cohen19 did explain the isothermal activation of embryos by assuming it to be a result of the expansion of their boundary dislocation loops but this treatment predicts an upper temperature limit of isothermal martensite formation.

Jan 1, 1962

By T. B. Massalski, Horace Pops

The occurrence and the temperature dependence of the athermal martensitic transformation in bcc Cu-Zn ß-phase alloys have been studied by cold-state microscopy, differential thermal analysis, and electrical -resistivity measurements. CinenzatograpJzic studies have shown that in the majority of alloys the transformation occurs in two stages. A thermoelastic phase, having a 'needlelike" uppearance, forms initially at the MS temperature and grows relatively slowly, chiefly in the edge (lengthwise) direction. With further cooling, an additional martensitic phase forms in rapid bursts at a lower temperature, MB, Both martensitic phases appear to have the same cry stallographic habit hut their modes of formation and growth are different. For the composition range studied, between 38.55 and 41.49 wt pct Zn, the habit planes determined are close to the (2.17 ,12) plane of the matrix, in general agreement with the prediction of the phenomenological theory of martensite formation. Thermal cycling through the MB temperature produces permanent plastic deformation in the 0 matrix and gradutally eliminates the typical burst phenomena. Thermal cycling only through the MS temperature produces no noticeable deformation effects. THE bcc Cu-Zn ß-phase alloys tend to become unstable at low temperatures and undergo a martensitic transformation,'-3 but the details of the transformation have not been completely determined. Following earlier metal log raphic and X-ray work1 Tichener and ever' determined by means of electrical-resistivity measurements the temperature range of the martensite transformation during continuous cooling. The transformation temperature was found to decrease with increasing zinc content, becoming about -130°C for an alloy containing 40.04 wt pct Zn. Hull and Garwood3 made a metallo-graphic study of Cu-Zn 0 brasses at temperatures down to -160°C, and determined the habit plane of the transformation product for an alloy containing 38.88 wt pct Zn. No metallographic studies below liquid-nitrogen temperatures have been reported. The martensitic transformation in ß-brass alloys can also be induced by deformation.1,4 The MD temperature corresponding to the appearance of the strain-induced martensite is some 300°C higher than that observed without strain, and hence the transformation can be strain-induced in alloys containing a higher percentage of zinc. Massalski and Barrett4 found that alloys containing as much as 51.89 wt pct Zn could be transformed into a faulted hcp structure by cold working at liquid-helium temperature. Because the details of the MS temperature and morphology reported in the literature are somewhat incomplete, a further study has been made of some of the above features. A design of a cryogenic stage for optical metallography5 has permitted the examination of specimens at temperatures down to 4.2oK, and the use of a cinecamera has permitted a study of the morphology on cooling and heating. The particular aim of the present work was to examine the transformation temperatures, the habit planes, and the growth morphology over a wide composition range in the ß-phase field. The effect of thermal cycling upon the subsequent transformation was also examined.

Jan 1, 1964

By O. R. Foster

The use in the iron blast-furnace of slags high in magnesia has been generally condemned, not only on the ground that magnesia renders the slag less fusible, but also because it is said to have less power to remove sulphur from the iron. Percy? says the use of dolomite as a flux should obviously he avoided, because magnesia " tends to induce infusibility," but says nothing of its relation to sulphur in the charge. Bell suggests the absorption of SO2, by lime and magnesia in the blast-furnace, but leads the reader to suppose that the really active agent is lime. Howes says: " The greater desulphurizing power of lime than of magne-

Jan 1, 1900

By Gerhard Derge

THE introductory paper1 of this series described the potential behavior of tin in sodium carbonate and bicarbonate solutions whose pH ranged from 8.4 to 11.2 and demonstrated that significant and reproducible results could be obtained by proper attention to experimental technique. In examining the corrosion of tin under such conditions, it is desirable to know the effects of anions, aside from carbonate, that are likely to be present in commercial materials packaged in tin. Therefore, in this paper the potential behavior of tin in carbonate solutions to which sodium fluoride, chloride, bromide, iodide, sulphate, nitrate, monobasic phos-phate, dichromate, perborate and acetate have been added will be described. For most of the additions, solutions containing 0.001 and 0.01 .moles of the added material were studied. The experimental procedure was exactly the same as that described in the first paper; the pH of the electrolyte was controlled by adjusting the ratio of carbonate to bicar-bonate as follows: pH 0.1 M NaHCO3 8.4 2 parts 0.1 M NaHCO3, 1 part 0.1 M Na2CO3 9.5 1 part 0.1 M NaHCO3, 2 parts 0.1 M Na2CO3 10.0 0.1 M Na2CO3 11.2 The reagents used were all of C.P. grade. The anions studied may be divided into three groups: (1) anions that had little or no effect upon the potential curves-sulphate, nitrate, and acetate; (2) those that helped to prevent corrosion at low pH only-fluoride, chloride, bromide, and iodide; (3) those that helped to prevent corrosion at high pH also-phosphate, perborate, and chromate.

Jan 1, 1939

By A. Coskun, J. F. Elliott

The activity of aluminum in liquid Al-Fe alloys .has been measured by an improved version of the transportation method in which the metallic vapor has been collected by its solution in a metallic condenser. The results can be represented by the equation: log yAl = -3.0(1 - xAl2) (0.6 < XAl < 1.0) This equation applies at 1315°C. MORRIS and zellarsl adapted the transportation method for measuring the vapor pressure of a com- ponent of an alloy at high temperature. We have modified their technique further2 for use with metals that are strong oxide formers. In the present case the method has been applied to the Al- Fe system to obtain the activity of aluminum in the liquid region at 1315°C. Dried ultrahigh-purity hydrogen (Matheson) is the carrier gas. The operations, Fig. 1, of deoxidizing the gas, equilibrating the gas with the sample at 1315";, and then collecting the aluminum vapor are all accomplished within a single, continuous alumina tube to avoid contamination of the system by leaks. De-oxidation to a very low level of PO2 (<10-25 atm) is Obtained by passing the hydrogen through a tightly packed bed of aluminum powder. The temperature of this bed increases to approximately 550°C in the direction of the gas flow. The boat containing three pellets of the alloy is supported on the end of a

Jan 1, 1969

By Valentine R. Garflas

The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 31/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields form about 75 per cent. of the Mcxican petroleum industry. The production of the Panuco field has followed the general history of the American fields, and its gradual decline, which is at present foreshadowed, may be estimated as well as its ultimate economic life. On the other hand, the behavior of the light-oil fields to the south is unlike any in the world so far discovered, and as a result we have concentrated overproductions followed by sudden droughts, both sometimes equally unexpected. The coming in of two or three gushers within adequate pipe-line facilities will flood the market with 100,000 bbl. or more a day, while the flooding by water of a particular pool will, in a few weeks, remove from the market one-half the total production of the Mexican fields.

Jan 1, 1923

By Valentine R. Garflas

The Mexican oil fields, during 1921, produced in round numbers 203,000,000 bbl. of which 176,000,000 bbl., or 86 per cent., were exported, the bulk of these exports, or about 73.3 per cent., going to the United States. The Mexican exports were divided by grades as follows: Light crude, 47.0 per cent.; heavy crude, 22.0 per cent.; tops, 3.5 per cent.; fuel oil from light crude, 24.0 per cent. The balance, or 31/2 per cent., includes the bunker fuel shipments and the coastwise trade in Mexico, which is not classified as to grades. The figures show that, in importance, the light-oil fields form about 75 per cent. of the Mcxican petroleum industry. The production of the Panuco field has followed the general history of the American fields, and its gradual decline, which is at present foreshadowed, may be estimated as well as its ultimate economic life. On the other hand, the behavior of the light-oil fields to the south is unlike any in the world so far discovered, and as a result we have concentrated overproductions followed by sudden droughts, both sometimes equally unexpected. The coming in of two or three gushers within adequate pipe-line facilities will flood the market with 100,000 bbl. or more a day, while the flooding by water of a particular pool will, in a few weeks, remove from the market one-half the total production of the Mexican fields.

Jan 1, 1923

By Augustus Locke

In 1900, when. the public first heard of "secondary enrichment," the Butte chalcocite seemed clearly supergene. Mining, through successive regions of leached capping, bonanza sulfide, and sulfide less rich, had paused at lean bottom levels which, though chalcocite-bearing, suggested the waning of copper. The deepest chalcocite, at 1500 ft., was yet too shallow to disturb the supergene hypothesis. But, with deeper mining, lean levels yielded to fat ones. Here and there they showed, within the same vein, an inverted distribution, chalcopyrite above and chalcocite below. To the miners&apos; astonishment, they carried chal-cocite, unaffected by cross faults, on an independent course to the depth of 2500 ft. The pattern of ore distribution, hitherto revealed only in fragments, was now appearing in perspective, and, in the depth of the chalcocite, was beginning to make Butte differ from all districts where the chalcocite is indubitably supergene. The idea of hypogene origin at length came into favor; by 1913, when Sales&apos; advocated this origin, the argument had become a powerful one. This argument rested on field evidence; but, already, there was beginning to emerge microscopic evidence not included in this argument. Especially pertinent was the proof that (1) the deep chalcocite lies in-mixed with bornite, often microscopic; (2) the deep chalcocite often replaces bornite; and (3) replacement of bornite by chalcocite is accomplished more easily than that of pyrite, enargite, or chalcopyrite. The microscopic evidence has been accumulating for ten years and it demands

Jan 1, 1924

By O. M. Schaus

GRATIFYING progress continues towards the elimination of the hazards confronting health and safety in and about mines. Employers and employees are diligently co-operating. One of the outstanding movements towards this end is the National Safety Competition conducted by the U. S. Bureau of Mines. William W. Adams, of the Bureau, has stated that "Through 1936 there has passed by a dozen years of this National Safety Competition, as it started in 1925 with an enrollment of 210 mines and quarries in 28 states and 68 million man-hours of employment. For 1936 it covered 328 mines and quar-

Jan 1, 1938

By G. R. Speich

A cellular precipitation reaction in which cells consisting of an Ni3Ti (DO24) phase and austenite are formed has been studied in an austenitic Fe-30 Ni-6 Ti alloy. The variation of the growth rate and interlamellar spacing of the Ni3Ti cells with temperature has been determined m the range 400" to 975°C; the interlamellar spacing is proportional to the degree of undercooling; the growth rate can be expressed by an equation of the form G = K?T)2 exp(-Q/RT). The habit of the Ni3Ti lamellae is (001)Ni3Ti (111)y;[010]Ni3T2 [010]y. An almost perfectly coherent interface is formed between Ni3Ti lamellae with this orientation rela -tionship and the intervening austenite. This first Ni3Ti cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. CELLULAR precipitation reactions have been studied in copper-base,1,2 Au-Ni,3 pb-sn,4 and iron-base ferritic5,6 solid solutions, and this mode of precipitation has been treated theoretically by smith," Turnbull,8,9 cahn,10 and more recently by bohm.11 In the case of substitutional austenitic iron-base alloys little or no data are available, Cellular precipitation reactions are well known in austenitic nickel-base alloys12,13 but usually these reactions do not proceed to completion because of general precipitation occurring in the matrix, and they have not been studied in detail. Precipitation from an austenitic Fe-30 Ni-6 Ti alloy was studied as part of a larger investigation of the mechanisms of precipitation from substitutional iron-base alloys. This alloy, austenitic at high temperatures, decomposes at lower temperatures by a double cellular precipitation reaction. The first decomposition product consists of alternate lamellae of an Ni3Ti(DO24) phase and austenite. The reaction proceeds to completion, consuming all of the original austenite. This first cellular product is subsequently consumed by a second cellular reaction of much coarser spacing. The first cellular reaction was studied in detail by light and electron microscopy, hardness measurements, and by X-ray and electron diffraction. Interlamellar spacings and growth rates were measured during isothermal aging in the range 400" to 975°C. The orientation relationship between the Ni3Ti and austenite lamellae was determined and indicates that an almost perfectly coherent interface exists between the two phases. This first Ni3Ti cellular reaction is of particular interest because it occurs over such a wide temperature interval. This allows cellular growth rates and interlamellar spacing data to be obtained for much larger degrees of undercooling than reported hitherto. MATERIALS AND EXPERIMENTAL PROCEDURE The Fe-30 Ni-6 Ti alloy was prepared from electrolytic iron, Mond nickel shot, and sponge-purity titanium* by vacuum melting in a zirconia crucible

Jan 1, 1963

By R. A. Generes, H. C. H. Darley

Laboratory tests showed that at elevated temperatures a reaction takes place between all metal hydroxides and clay muds, which results in a thickening or solidifying of the mud, the extent of which depends on the nature of the ingredients. Calcium hydroxide gave the strongest solidification whereas barium hydroxide only caused a mild thickening, indicating that the use of barium hydroxide muds instead of lime muds would be a good way of preventing high-temperature solidification. It was found possible to prepare barium mud in the laboratory with caustic soda and a thinner in the same manner as lime muds, and these barium muds had the same or better toleration of high solids content, resistance to salt contamination, and low gel strengths as the corresponding lime muds. Three field trials have been made with barium mud. The principal difficulty encountered was in determining the correct proportions of the tourly treatments required to maintain low gel strengths. A satisfactory systern was finally developed, and low gels were maintained throughout the third test. The wells on which the trials were made were not carried deep enough to test the resistance to solidification adequately, but oven tests at 350°F were made periodically and no tendency to solidification was noted except immediately after severe cernent contamination had introduced excessive amounts of calcium into the system. Although barium hydroxide costs considerably more than lime, the total mud costs were as low, and on the last well significantly lower, than the average cost of lime mud wells drilled in the vicinity. INTRODUCTION The advantages of repressing dispersion and hydra-tion of clay cuttings carried in the mud, particularly when drilling through thick clay formations, are well recognized. This repression is generally achieved by the use of lime, and lime muds have in consequence the desirable characteristics of high toleration of solids, low thixotropy, and good resistance to contamination. They have, however, the disadvantage of high-temperature solidification. This phenomenon has been described in detail by Gray et al, who have shown that it is the result of a chemical reaction between the hydroxides and the clay minerals. The work described in this paper was undertaken to find a substitute for lime which would not cause this solidification. LABORATORY EXPERlMENTS The principal positive requirement for a substitute for lime is that it should repress the hydration and dispersion of clay. It is well known that monovalent cations promote hydration while polyvalent cations repress it. Therefore, a few representative polyvalent salts and hydroxides were tested to determine whether they could be used as substitutes for lime. Their efficiency at repressing hydration and dispersion was measured by means of the clay-volume test. It has been shown elsewhere&apos; that this test is a good measure of degree of dispersion of clay in suspension and that hydration accompanies and correlates with dispersion, so that measuring one measures the other. The test is made by centrifuging a 1:100 mixture of mud and 1-N NaCl and observing the volume of sediment—the greater the volume, the greater the dispersion. The tendency to caux solidification was measured by heating the muds in pressure vessels for 16 hours at 150°F and 370°F. An approximate quantitative

Jan 1, 1957

By B. S. Lement

No appreciable stabilization of the austenite-martensite reaction occurs in a 15 pct Cr-0.7 pct C steel unless some martensite is initially present. Stabilization is induced by interrupting the subcool below M,; however, disappearance of the stabilization effect as manifest by burst formation of martensite may occur on continued holding at the final subzero reaction temperature. The higher the temperature of intermediate cycling after the initial subcool, the more permanent is the stabilization effect at the final reaction temperature. Appreciable conditioning of retained austenite occurs on reheating to about 500°C. These phenomena are explainable on the basis of the reaction-path theory. A RECENT investigation&apos; carried out by the authors has shown that isothermal transformation of austenite to martensite definitely takes place in a 15 pct Cr-0.7 pct C steel and that appreciable amounts of martensite can form in this fashion. Investigations2-" arried out on other steels and iron alloys make it seem probable that isothermal formation of martensite is a phenomenon of fairly general occurrence. The reaction-path theory of Cohen, Machlin, and Paranjpe5,7 explains isothermal transformation on the basis of thermal activation of strain embryos which generate martensite plates with a velocity approaching that of sound. On the other hand, the nucleation and growth theory of Fisher, Hollo-mon, and Turnbull8 egards isothermal transformation as due to growth of athermally formed martensite nuclei. The experimental evidence obtained thus far favors the reaction-path theory in that the martensite reaction seems to be nu-cleation-controlled rather than growth-controlled. Stabilization is another phenomenon of importance with respect to the austenite-martensite reaction. According to the reaction-path theory, stabilization is a result of relaxation of strain embryos. It is postulated that strain embryos are present at the austenitizing temperature in the form of dislocations or lattice imperfections in the austenite which vary in the extent to which the lattice is displaced along the strain reaction path leading to martensite. On quenching from the austenitizing temperature, athermal martensite starts to form as soon as the M. is reached, because the activation energy of the transformation which decreases with decreasing temperature is lowered to below the level of the highest energy strain embryos. Martensite plates are generated during the cooling below M, from embryos possessing energies above the activation energy corresponding to the temperature at which the cooling is stopped. The distribution of lower energy embryos is changed because of the elastic and plastic strains produced in the remaining austenite as a result of the transformation. This effectively increases the number of strain embryos at all levels of energy below the activation energy and tends to stimulate further martensite formation either iso-thermally or on subsequent cooling. However, if the temperature at which the cooling is stopped is high enough for relaxation of strain embryos to occur, some degree of stabilization against further transformation may be induced. Whether stabilization will be observed on subsequent cooling will depend on the extent of decrease of activation energy with temperature. If the activation energy decreases sharply with temperature, it is possible that transformation will appear to continue with decrease in temperature in spite of the loss of embryos by relaxation. However, with a more gradual decrease in activation energy, stabilization will be manifest by no further transformation on cooling over a measurable temperature range until the

Jan 1, 1954

By R. D. Nelson, F. E. Bowman

Evidence has been found for a (010)a?(111)B[102]a /,11[341]/B crystallographic relationship between the monoclinic a and B phases of plutonium during the a?B transformation. The results of an X-ray diffraction study, where [010] fiber textured a samples were used in the absence of suitable single crystals indicate that the (OIO)a planes become (111)B planes upon transformation under near-equilibrium conditions. The transformation strain along the fiber axis, which was the [010] direction, was measured dila-tomekically; the measured 8.5 pct expansion compares favorably with the 8.44 pct expansion in the in-terplanar spacing represented by the (010)a?(111)B relationship. From plots of the atom positions in each of the related planes, a correspondence was deduced between the [102]a, direction and the [341]B direction. Further analysis of the two lattice structures in the light of this relationship revealed a rotation about the [102] direction of 1 deg 43 min and a slight shearing in this same direction of about 30 min. THIS paper discusses the (B crystal structure of plutonium and the orientation relationship existing between the monoclinic a and B phases during the a?ß transformation. The kinetics of the a?ß and (3 — a transformations have received extensive consideration, and because of the crystallographic complexity of these phases, the question of the mechanisms by which these transformations occur is especially intriguing. Nelson and Shyne1 evaluated the existing experimental evidence and concluded, from the indirect evidence available, that both the ß ? a and a ? ß transformations occur by a martensitic process. Their data reveal the anisotropic nature of these transformations which suggests the existence of specific crystallographic relationships between the parent and product phases. In this paper, we are concerned with the confirmation of the existence of such a relationship resulting from the a ? ß transformation and the derivation of the crystallographic details necessary to specify it. EXPERIMENTAL RESULTS X-ray diffraction and dilatometric data were obtained from samples of a plutonium having a [010] fiber texture. These cylindrical specimens, approximately 1 cm in diam, were prepared by transforming the ß phase to a under the influence of a uniaxially applied compressive load.&apos; The [0l0] direction is parallel to the direction of applied stress; it is also perpendicular to the (010) planes. This correspondence between the plane normal and the direction having the same indices is, in the monoclinic a plutonium structure, restricted solely to this (010)[010] combination. Such a specimen was mounted in an evacuated, elevated temperature specimen holder on an X-ray dif-fractometer so that the diffracting surface was perpendicular to the fiber axis. The a diffraction pattern, Fig. 1, taken at about 115ºC, revealed the predominance of the (020) reflection. This monoclinic, P 21/rn space group yields no (0k0) reflections when k is odd. The temperature was raised slowly to 160°C to effect the complete transformation to the phase; then it was lowered to 120°C so that a diffraction pattern of the ß could be obtained near the a = ß equilibrium temperature for direct comparison with the a at the same temperature. The (3 diffraction pattern, Fig. 2, obtained under these conditions showed a (222) reflection relatively much more intense than in the random pattern. The other reflections appearing with sig-

Jan 1, 1970

By F. W. Jessen, H. Kazemi

A washing technique has been developed to form a spherical cavity in massive salt. The technique is, basically, a process of controlling the fluid motion in the cavity, the concentration distribution of brine, the rate of dissolution at the walls of the cavity, and the particular settings of the wash pipe, or pipes (inlet and outlet pipe) employed. For a particular arrangement of tubing and casing, fresh water enters from the casing annulus at a position above the bottom of the tubing, and the dissolved material leaves the cavity through the tubing near the bottom of the projected hole. The initial configuration of the cavity is cylindrical, representing the drilled hole situated at the axis of the projected cavity. As washing progresses the original hole is enlarged radially (any direction perpendicular to the axis of the hole). An inert fluid (generally a hydrocarbon, natural gas, or air) which serves as a blanket is injected through the annular space between the original hole and the casing. The controlled downward motion of this blanket maintains the upper edge of the brine region that is expanding on the surface of the projected sphere. A large spherical glass container and a radial model were used to investigate the flow patterns and the concentration distribution of brine occurring during the progress of solution of the salt. Aluminum flakes and dye were injected and flow patterns were observed and recorded on motion picture film. Based on the results of these model studies and other work carried out in this laboratory, the controlled washing technique was formulated. INTRODUCTION Underground cavities leached in salt beds and salt domes have been used extensively for storing hydrocarbons. Little attention has been focused on the shape of the cavities as long as large volumes were obtained and the cavities were structurally stable. The general process involves circulating fresh water and removing brine. Two distinctly different circulating systems can be employed, each of which yields characteristically different shapes. By far the most generally accepted method of washing storage caverns in salt domes is the direct circulation system. Water is introduced through the innermost pipe of a concentric pipe system, and brine is withdrawn through the annulus. In the reverse-circulation method, water enters through the annulus and is discharged through the smallesc tubing string. The size of the operation, and hence the size of tubing and casing used, depends on such factors as cavity volume, length of hole, availability of water, disposal of brine and power requirements. Underground caverns are from 100 to 1,000 ft or more in length, and when completed vary from 40 to 100 ft in diameter, providing storage of 100,000 bbl or more. The volumes of water required per volume of salt removed vary from 6 to 7 for the reverse circulation method to 10 to 11 for the direct circulation method. Up to 80,000 BWPD are often circulated. In the direct circulation method, because water enters near the bottom of the projected cavity, solution of salt is greatest at this point, particularly in view of the fact that when the washing is begun turbulent flow undoubtedly exists in the immediate vicinity of the discharge of the inlet water. As the diameter of the hole increases, flow rates also are increased, so perhaps the condition of fluid turbulence is maintained for some time. During the later stages of leaching, when capacity of equipment may be the limiting factor in maintaining flow rates, there may still exist some turbulence adjacent to the point of influx; however, for the most part laminar flow conditions prevail. There appears, therefore, rather good evidence to indicate that the state of fluid motion is responsible for the typically shaped cavity which results from such washing — namely a cylindrical form, generally somewhat larger at the bottom than at the top. Depending on the number of so-called stages which might be employed, the walls or surfaces of the salt diminish rather uniformly from bottom to

Jan 1, 1965

By J. L. Bray, S. T. Ross

The paper provides electrometallurgical data on the problem of germanium removal from zinc sulphate solutions. Germanium traces have caused much concern to the zinc refiner. Confirmatory evidence of interaction between germanium and cadmium is presented. Statistical analysis of data expands its significance and enhances its value. Further research is outlined. THE literature contains many references to the effects of trace amounts of germanium in the production of electrolytic zinc. One of the authors had experience with this troublesome element as early as 1917 at Trail, B. C. In 1929, Tainton and Clayton&apos; reported that concentrations of as little as one part per million of germanium were sufficient to cause serious losses in current efficiency. Liddell2 reported that trace amounts of germanium cause marked lowering of the hydrogen overvoltage of electrolytic zinc cells, so that commercial production was impaired. Bray3 recorded the history of germanium in relation to electrolytic zinc production, noting that concentrations below 10 ppm have been found to yield low current efficiencies and copious hydrogen evolution. Koehler&apos; stated that germanium "when present to the extent of a small fraction of one part per million per liter, causes serious evolution of hydrogen with a corresponding reduction in current efficiency." Recently, however, S. W. Ross" reported, from Risdon, Tasmania, that "in the course of leaching . .. dissolved traces of germanium... if not removed almost completely ... increase the reversion of cadmium during the filtration of the copper-cadmium precipitate and reduce the current efficiency during subsequent analysis." The copper-cadmium precipitate referred to is the residue from the zinc-dusting purification of zinc sulphate leach solutions. In the face of such conflicting testimony and with the increasing industrial importance of pure germanium and zinc it was decided to investigate the relationship between cadmium and germanium. Furthermore, other work by the authors showed certain discrepancies to exist in the theories of Tainton, et al. In the laboratory, without marked efficiency decreases, the authors have deposited zinc successfully from solutions containing as high as 1 g per liter of germanium. This could be done only when there was no cadmium present. Preliminary investigations of the suspected rela- tionships were carried out by means of emission spectrographic analysis using a beryllium internal standard. Several solutions containing 100 g per liter of zinc, as zinc sulphate, and 1 g per liter of cadmium, as cadmium chloride, were prepared. These concentrations were on the order of those obtained during a commercial low-acid leaching process. Varying concentrations of germanium were added to these solutions so that the range of 0.0000 to 0.5000 g per liter of germanium was covered. A 250 ml sample of each solution was agitated with 2.5 g of zinc dust for 30 min, filtered, and the filtrates were examined spectroscopically. Qualitative evidences of cadmium traces were found in those filtrates which originally contained above 10 ppm of germanium. Reliability of the analytical method did not permit quantitative investigations since cad-Table I. Current Efficiencies Obtained at 0.0000 and 1.5000 G per Liter Cadmium Concentrations Ge Concentrastion,* Cd Concentration,* EtBclenoy, G per Liter G per Llter Pot 0.0000 0.0000 84.270 0.0010 0.0000 94.849 0.0050 0.0000 92.649 0.0075 0.0000 94.039 0.0100 0.0000 96.084 0.0000 1.5000 93.460 0.0010 1.5000 95.158 0.0050 1.5000 92.148 0.0075 1.5000 91.260 0.0100 1.5000 84.546 • Cd and Ge concentrations shown are those existing before zinc-dust purification. mium determination in the concentrations present in zinc-dusted solutions lacks sufficient sensitivity for reproducible results. As a consequence of the inability of the investigators to obtain acceptable results through direct quantitative analysis, an indirect approach was devised. This indirect method involved a study of the current efficiency, in a model zinc cell, as a function of the concentrations of cadmium and germanium. Variables such as cell temperature, voltage, current density, anode spacing, relative electrode area, degree of agitation, cathode preparation technique, time, acid concentration, and solution volume were held constant. Fig. 1 shows the cell used. The current was fur-

Jan 1, 1952

E. G. Spilsbury, New York, N. Y.:—Do I understand correctly that the rolls are at first simple cylinders, one longer than the other, and that flanges are subsequently formed on the longer roll as the result of wear only ? Mr. Payne :—The flanges are formed by the wearing of the shorter roll into the other, which is about an inch longer. When the roll-shells are new, the longer one has machined at each end a ridge about 1/8 in. or 0.25 in. higher than the face. These slight projections help to center and steady the rolls, by locating the flanges in advance. Possibly they might be left off at the start; but Mr. Frazee has found it better, in machining the new roll-shells, to turn such small flanges upon the longer one. In his practice the feed-stream is extended a short distance beyond the two ends of the shorter roll-shell. This allows a small amount of crushing to be done between the flange-ftices and the vertical ends of the shorter roll-shell, which prevents any ridges from forming at the ends of the shorter roll-shell.

Jan 1, 1913

By M. ROWE, H. E. Gilliland, L. BARNES

The authors of this paper are to be commended for a clear exposition of a timely subject. However, some important conclusions, in addition to those presented in the paper, can be drawn from the results of their elaborate and rather complete numerical computations. First of all, the major part of the calculations presented in the paper are for semi-infinite slabs of oil shale (the authors designate this as Model I) and a question must be posed — Are these elaborate computations needed to arrive at realistic estimates of the shale oil displaced. Consider the model of Lauwerier* that corresponds to the authors Model I if thermal conduction parallel to the fracture be neglected. If one also neglects the finite (but relatively small) heat capacity of the material in the fracture, it is easily shown from Lauwerier&apos;s solution that the cumulative oil production would be:

Jan 1, 1969

By Myrick N. Bolles

The concentration of gold and silver in mattes low in copper, and the subsequent separation and recovery of either or both of these metals, is a question the satisfactory solution of which has long vexed metallurgists. It covers a broad and important department of metallurgical science and brings in its train a series of attendant problems continuing from the initial operations of concentration to the final recovery of " values."

Jan 1, 1905

By K. Huessener

In presenting the following data on combustion in the open hearth furnace and the advisability of automatic combusion control, the author finds himself much more severely handicapped by the lack of reliable test results than he had anticipated when he first undertook to write this paper. In order thoroughly to investigate how the results of an open-hearth furnace are influenced by combustion, one would have to draw up a large number of heat-balance sheets, as Kinney and McDermottl have given for one heat in their extremely able paper on "Open Hearth Efficiency,&apos; presented before the American Iron and Steel Institute on October 27th,1 1922. Instead of covering only one heat, however, such heat-balance sheets would have to embrace a large number of heats, and not only for one kind of fuel, but for all the various fuels in customary use. Use of Radiation-protected Pyrometer Such tests necessitate extremely careful temperature readings, and here the first serious difficulty presents itself. Nearly all the temperature readings so far published have been taken with thermocouples for the lower ranges and with optical or radiation pyrometers for the higher ranges. This method of measuring reveals the temperature of the surrounding walls, or in the case of optical or radiation measurements, the temperature of that part of the opposing walls which has been focused by the instrument. The error in ascertaining the temperature of the gases entering or the waste gases leaving the checker chambers is probably not very large, as the flowing gases impart their temperature to the walls of the flues. On the other hand, the uptakes, where the preheat temperature of gas and air are usually measured, are under the influence of radiated heat from the port ends, and correct temperature readings can here be taken only by using a radiation-protected pyrometer of the aspirating type.

Jan 1, 1926