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By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at subcritical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.1 Westgren, Phragmén and Negresco2 identified the following carbides in chromium steels: [Cementite Fe3C (containing up to about 15 per cent Cr) Trigonal carbide Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide Cr4C (or Cr23C3) (containing up to about 25 per cent Fe) Orthorhombic carbide . Cr3C2 (containing only a few per cent Fe)] The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus.4 By means of dilatometric and microscopic studies, sections of the diagram were established. This diagram showed the presence of the special carbide Cr7Ca in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in r per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7Ca occurs in chromium steels containing more than about 1 per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. EXPERIMENTAL PROCEDURE The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into 1-in. round bars, and all heat-treatments were conducted on specimens of this section .size. Sections of the bar stock 8 in. long were hardened in air, oil or water depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after auenchine. The quenched bars were cut into

Jan 1, 1942

By J. T. Burwell

The crystal orientation in silicon iron that has been given a particular treatment described by Goss,l has been studied by Goss, by Bozorth2 and by Sixtus,3 but their results do not agree and are almost entirely qualitative. The following pages give a description of the orientation of the crystals in the material as determined by means of X-rays and expressed graphically in a pole figure. The treatment consists of hot-rolling the material into strip and then giving it two cycles of cold reduction followed by recrystallization. This produces remarkably good properties in the rolling direction, the product having a maximum permeability in this direction of more than 25,000 and a permeability at 16,000 Gauss of more than 2200. It is now generally agreed that Goss's original conclusion1 that the crystals in the final product are randomly oriented was incorrect, since Bozorth2 and Sixtus,3 using different methods, have shown that there is a decided preference in orientation. Those writers, however, expressed their results only in terms of one or more ideal orientations with deviations therefrom. X-ray Data A strip of the material containing 3.1 per cent Si, prepared by Goss,† 1.2 by 0.0125 in., was etched rapidly in warm dilute hydrochloric acid until it was 0.005 in. thick, in order to eliminate the effect of the two surface layers. The specimen was then mounted in an integrating camera similar to one described in the literature.4 The purpose of this camera is to translate the specimen during exposure, so that a statistically large number of grains contribute to the pattern photographed. The camera also allows the plane of the specimen to make various angles with the X-ray beam. An area 5 by 1.2 in. was scanned by a beam of unfiltered radiation from a molybdenum target tube operating at 37 kv., and the measurements were made principally on the peak of the white radiation. X-ray photographs were taken at intervals of 15" in a plane

Jan 1, 1940

By J. T. Burwell

The crystal orientation in silicon iron that has been given a particular treatment described by Goss,l has been studied by Goss, by Bozorth2 and by Sixtus,3 but their results do not agree and are almost entirely qualitative. The following pages give a description of the orientation of the crystals in the material as determined by means of X-rays and expressed graphically in a pole figure. The treatment consists of hot-rolling the material into strip and then giving it two cycles of cold reduction followed by recrystallization. This produces remarkably good properties in the rolling direction, the product having a maximum permeability in this direction of more than 25,000 and a permeability at 16,000 Gauss of more than 2200. It is now generally agreed that Goss's original conclusion1 that the crystals in the final product are randomly oriented was incorrect, since Bozorth2 and Sixtus,3 using different methods, have shown that there is a decided preference in orientation. Those writers, however, expressed their results only in terms of one or more ideal orientations with deviations therefrom. X-ray Data A strip of the material containing 3.1 per cent Si, prepared by Goss,† 1.2 by 0.0125 in., was etched rapidly in warm dilute hydrochloric acid until it was 0.005 in. thick, in order to eliminate the effect of the two surface layers. The specimen was then mounted in an integrating camera similar to one described in the literature.4 The purpose of this camera is to translate the specimen during exposure, so that a statistically large number of grains contribute to the pattern photographed. The camera also allows the plane of the specimen to make various angles with the X-ray beam. An area 5 by 1.2 in. was scanned by a beam of unfiltered radiation from a molybdenum target tube operating at 37 kv., and the measurements were made principally on the peak of the white radiation. X-ray photographs were taken at intervals of 15" in a plane

Jan 1, 1940

Jan 1, 1952

By A. C. Fieldner

THE older coal chemist had a much simpler conception of coal than we have today. To him coal was a mineral composed essentially of carbon, hydrogen, oxygen, nitrogen, sulfur, ash, and water, in various proportions. His studies on the constitution of coal were directed along the conventional lines of proximate and ultimate chemical analyses and making deductions from these data without any real appreciation of the fact that coal is a conglomerate of various chemical compounds, including many of the most complex structures known to organic chemistry. The view of the modern coal chemist is well expressed by Franz Fischer, I who says that while proximate and ultimate analyses are important both from the scientific and technical point of view, they tell the chemist no more concerning the number and kinds of chemical compounds that constitute coal than the reader would learn of the contents of a book if told that the printed contents consisted of 15 per cent. of the letter "e," 5 per cent. of the letter "n," 1 per cent. of the letter "g," 4 per cent. of the letter "b," etc. As the reader must have the grouping of letters into words and words into sentences, so the chemist must have the grouping of atoms into molecules and the proportion of each molecular compound in the coal aggregate before he acquires an adequate knowledge of the constitution of coal. Modern investigators2 are laying the foundation of a new chemistry of coal based on the biochemistry of plants and the chemical changes involved in processes of fermentation and decay. As

Jan 5, 1925

By P. P. Gregory

Natural petroleum gas occurring in the oil-bearing reservoirs is found to exist either as free gas associated with the oil and/or in solution in the oil. In some virgin fields practically no free gas is encountered under the reservoir conditions of pressure and temperature, although in other fields a considerable section of the "pay" horizon is occupied by free gas. In other words, a given oil field may or may not have a gas cap before the exploitation takes place. However, when the reservoir pressure is reduced to a point below the critical saturation pressure by withdrawals of fluids from the producing formation, the gas dissolved in the oil inevitably begins to come out of solution and becomes free gas. Under the controlled methods of production and drilling, a portion of this gas is produced with the oil to the surface and a portion of it remains within the reservoir to accumulate at higher structural levels toward which it migrates by virtue of its low specific gravity. The rate of growth of a gas cap in a given structure depends primarily upon the rate of decline in the reservoir pressure. If the rate of pressure decline is rapid, the gas cap likewise will grow rapidly. On the other hand, shrinkage in the gas-cap area was noted in some fields in which reservoir pressures wereincreasing. Determination of Gas-oil Contact and Thickness of Gas Cap The gas-oil contact can be conveniently located in the process of drilling a well and by electrical logging. However, very little can be found in the petroleum literature concerning methods of predetermining gas-oil contacts in producing reservoirs. Therefore, the writer feels justified in describing briefly a simple, workable, and inexpensive method of determining gas-oil contacts and outlining the limits of gas-cap areas in a field where such knowledge may be essential for efficient production and development operations. The method involves the determination of the following data: (I) Structural data, such as the depth or elevation of the top' of "pay" horizon; (2) reservoir pressures; (3) tubing and casing pressures at the well head; (4) static oil-pressure gradient; (5) static gas-pressure gradient. These data can be secured with a minimum of expense, inasmuch as the

Jan 1, 1938

By C. R. Knopp

Gas-oil relative permeability ratio is an important relationship in oil reservoir predictive calculations. A correlation has been developed from 107 gas-flood k/k tests on Venezuelan core samples. The correlating parameter is based on restored-state water saturation tests and' is applicable to both consolidated and poorly consolidated sandstone reservoirs. Data of the correlation show that there are no distinguishah1e differences between the mass-data groupings for the two c1assifications A procedure is recommended for running .sufficient relative. permeability analyses to compute a geometric mean of the sample group. The geometric mean is more representative of the total core, and probably the entire reservoir. For example, while only one in four of the k,,/k,., test curves agreed closely with the resultant correlation of this report, the geometric mean curves of the 16 suites (three samples or more). showed good agreetment ill three cases out of four. INTRODUCTION The gas-oil relative permeability ratio is an important, fundamental relationship in most oil reservoir predictive calculations. Predictive calculations are made to estimate future reservoir production characteristics and ultimate oil recovery. The k1,/k2, relationship is specifically needed to relate the surface gas-oil ratio to the reservoir oil and gas saturation, and to calculate the relative movement of these phases within the reservoir whenever some of the more complex driving mechanisms are present. Laboratory k1/k2, tests are not generally run as a routine analysis. Consequently, k1/k2 data often are not available when needed because the cost of laboratory work could not be justified or the need for such data had not been properly anticipated. When laboratory k1/k2, data are available, they are often very difficult to interpret. For example, wide divergence is sometimes shown in a family of k1,/k1, tests representative of the producing horizon in a single well. With these considerations in mind, a study was made to determine if a relationship might exist between the k1,/k2, curve and some other simple laboratory test criteria. The most probable k1/k2, curve correlation for Venezuela described in this paper is the result of the investigation. The presented correlation defines the most probable gas-flood k,,/k,, curve through the medium of air-water capillary displacement and centrifuge water saturation tests. The laboratory procedures of these tests are. relatively simple, and inexpensive; test data should be. widely available- from routine analysis. DATA AVAILABLE, LABORATORY METHODS The report correlation utilized 107 gas-Hood k1/k2, tests run on sandstone cores of Venezuelan reservoirs. Table 1 is a general tabulation of data pertinent to the tests, while Table 2 summarizes the data. Thetests include 96 from Western Venezuela and 11 from Eastern Venezuela. Eighty-two- of the 107 test samples were sandstones that varied from poorly consolidated to-unconsolidated; 25 were consolidated. The average sample porosity was 26.7 per cent and the average permeability was 1,121 md; these values typify the better sandstone reservoirs of' Venezuela. The Welge gas-flood technique,' based on fundamental Buckley-Leverett frontal displacement theory, was introduced in about 1952 and is widely accepted in the industry. The laboratory procedure is relatively simple, rapid, and can be performed on small core samples. While there have been some minor variations in sample preparation and laboratory procedure in the tests used for the correlation, these tests can be generally summarized as follows. The core sample was first sol vent-extracted and dried. Connate-water saturation was restored by the oil-flushing or evaporation-blow down methods. At the beginning of gas flood the hydrocarbon pore volume was completeiy saturated with the test oil phase. Unsteady-state gas-oil displacement then began with the injection of nitrogen or helium. while the displaced oil and gas phases were incrementally metered at the out-flow face. From the test data, the k,,/k,, curve was calculated by the Welge method.' The individual oil and gas relative permeabilities were also calculated." CORRELATING PROCEDURES In attempting to establish a basis of correlation, we found that broad mid-range sections of 105 of the 107 k,,/k,, test curves could be closely duplicated by a straight line. Only two curves did not show a degree of linearity in this region. Correlation-curve definition parameters were subsequently developed from this observation of consistent mid-range linearity. Possible correlating variables were limited to the physical properties measured on core samples that (1) were widely available as common test data and (2) could be easily and cheaply obtained through future laboratory work. The more obvious possibilities were porosity, permeability and

Jan 1, 1966

By F. von Gemmingen, E. J. Fasiska, L. Zwell

EARLIER studies of the dependence of creep on structure1 and of the dependence of creep rupture on creep behavior2 did not include detailed discussion of the phases present in the specimens under examination. It is of interest to determine the nature and amounts of such phases present since it is well known that these are dependent on composition, heat treatment and creep conditions.3 This investigation has therefore been undertaken to identify these constituents and to determine their relative amounts. This report presents the results of this investigation and describes an improved "extraction replica" technique developed in the course of the work. The composition of the Type 316 austenitic stainless steels studied in this investigation is given in Table I. The specimens were solution treated at 2000°F for 1/2 hr and water quenched. Those specimens subjected to prestrain at room temperature Methods for extracting precipitate particles from materials for electron and X-ray diffraction analysis have been described by Fisher,4 Smith and Nutting: and Booker and coworkers.6'7 Electrolytic extraction methods have been described by Andrews and Hughes.8 The first two methods have been used at this Laboratory, but have not proved satisfactory for many problems requiring X-ray diffraction analysis. It has been difficult to remove the replicas or to avoid tearing them during removal. These difficulties are overcome by backing the replica with a water-soluble plastic such as Dupont 51-05 Elvanol (polyvinyl alcohol). The backing increases the thickness of the replica so that it can be mechanically stripped from unloosened particles without folding or tearing. This procedure eliminates the stripping of wet replicas, which usually have a low tear strength. By stripping replicas after drying, it is possible to extract partially loosened particles which otherwise would remain imbedded in the metal. The modified method is as follows: after the specimen is polished, it is etched for 60 min in modified glyceregia consisting of 30 ml glycerol, 7 ml nitric acid, and 4 ml of hydrochloric acid. The sample is then washed, air dried, and coated with a 20 pct Baker and Adamson 1611 collodion (85 pct amyl acetate by volume) film. After the collodion film is dry (about 15 min), the sample is again etched in the modified glyceregia for 50 min, washed with isopropyl alcohol (to prevent dissolving the collodion) and air dried. A very thick coat of polyvinyl alcohol (about 50 pct solution "Elvanol Dupont 51-05" in water) is poured over the sample and is permitted to dry for about 24 hr. The composite film containing the precipitates is then stripped from the specimen and floated, polyvinyl alcohol side down, in water (at about 50°C) until the polyvinyl alcohol dissolves. This usually takes about 15 min. Should any of the polyvinyl alcohol remain on the replica, it does not give a crystalline diffraction pattern and therefore does not hinder identification of the precipitates. The extraction replica, floating in water, is picked up on a glass fiber and mounted in the Debye-Scherrer camera for X-ray diffraction analysis. Concentration of the etchant, and also etching time, had to be increased for several of the samples. Fig. 1 shows two extraction replicas taken from different areas of spec. M74-37; X-ray analysis showed a strong diffraction pattern of M23C6 and a medium one of u phase. A

Jan 1, 1962

By J. W. Cunningham, W. A. Tiller, D. H. Lane

The effect of ultrasonic vibrations on ingot solidification has been considered both theoretically and experimentally. The theoretical section elucidates the mechanisms by which the ultrasonic vibrations might refine the ingot structure. The experimental section describes a very efficient means of introducing the ultrasonic vibrations to the freezing interface. The application of this technique to the consumable-electrode arc melting process shows that the columnar mode of freezing may be effectively suppressed yielding an ingot structure consisting predominantly of equiaxed grains. The results support the contention that the ultrasonic vibrations increase the nucleation frequency in the layer of liquid adjacent to the freezing interface. CERTAIN structural characteristics of as-cast ingots are undesirable since they create considerable difficulty for subsequent processing and often produce defects in the finished product. These structural defects are illustrated in Fig. 1(a), and are: 1) planes of weakness where columnar grains growing from the different mold faces meet, 2) strength anisotropy due to the preferred orientation of the columnar grains and 3) inhomogeneity due to segregation at dendrite boundaries within the columnar grains and at the columnar grain boundaries. The type of ingot structure that eliminates 1) and 2) and diminishes 3) is the fine-grained equiaxed structure illustrated in Fig. 1(c). Many attempts have been made to produce the desirable ingot structure illustrated in Fig. 1(c) by inoculating, casting with varying superheats, vibrating or stirring, or by irradiation with ultrasonic vibrations. These attempts have met with various degrees of success, the ingots generally having the structure illustrated in Fig. 1(b). All four methods have been the subject of numerous investigations,1"4 the latter producing the most erratic behavior and inconsistent success. The method of ultrasonic irradiation during ingot solidification has shown considerable promise on small-scale ingots (diam 2 in.) but has not yet been successfully adapted to large-scale operation. The present paper considers the application of ultrasonic radiation to ingot solidification both theoretically and experimentally. The purpose of the paper is to elucidate the mechanism by which ultrasonic energy refines the ingot structure and to describe a method for producing the desirable ingot structure in both laboratory scale experiments and in ingots of commercial size. THEORY Conventional Casting—Before discussing the possible effects of ultrasonic radiation upon ingot structure let us first briefly review the reasons for the breakdown of columnar crystallization to equiaxed crystallization during ingot solidification. The following is a slightly oversimplified description. In the conventional method of casting, the alloy having a certain degree of superheat, T, is poured to fill a cold mold which is at room temperature, Tc,. Due to conduction of heat through the mold wall the outer rim of liquid metal cools rapidly to the liquidus temperature and begins to supercool. At some degree of supercooling, nuclei of solid form at random in this supercooled layer at the mold surface. The grains in this chill layer begin to grow inwards producing a solute build-up, thus lowering the freezing temperature at the interface as illustrated in Fig. 2. As growth proceeds, the temperature gradient in the solid conducts away not only the latent heat of fusion evolved during growth but it also conducts away some of the superheat of the melt so that the temperature

Jan 1, 1961

By L. W. Sink, B. H. Kear, S. M. Copley, M. F. Hornbecker

IT is well known that under appropriate conditions of chill casting, many metals and alloys develop a columnar grain structure having a high degree of preferred orientation.' In cubic materials, this principle has been employed to produce shaped castings with a unidirectional cube oriented columnar grain structure as well as shaped single crystals with a cube axis parallel to the growth ais.' "he purpose of this note is to describe how this same principle can be enlployed to produce wires, rods, or more complex crystal Shapes with a variety of conlpositions in cube or random orientations by a single casting operation. The procedure for directional solidification of in Fig. 2. Examination under crossed polarizers indicated that the striations were a second phase (presumably the B19 phase) which frequently forms initially at primary grain boundaries and then grows toward the interior as thin ribbons. X-ray studies on filings of this alloy reannealed at 1300°C for 15 min indicated a strong pattern of the fcc phase together with a substantial pattern of the B19 phase. The un-annealed filings, however, showed only the pattern of a cold-worked, fcc structure. In these two-phase alloys it appears, therefore, that the B19 phase is transformed into a disordered fcc structure by cold-working. The mechanical properties of these alloys would be of some interest since a fcc structure might be expected to possess greater ductility than the or-thorhombic B19 structure from which it forms. The author wishes to thank Mr. Harvey Yakowitz and Mr. Richard Manuszewski for obtaining the photomicrograph in Fig. 2. This research was partially supported by Research Grant DE-02455 from the National Institute of Dental Research. columnar grained ingots involves pouring a melt into a preheated mold having a water-cooled copper chill at its base? and controlling the temperature gradient in the mold so as to maintain columnar grain growth from end to end of the ingot.4 This is illustrated schematically in Fig. l(a). It should be noted that the longitudinal temperature gradient promoting unidirectional columnar grain growth is maintained by heat loss primarily through the solidifying ingot to the chill, so that both the temperature gradient and the growth rate diminish with increasing distance from the chill. As the distance from the chill increases? the columnar structure coarsens, and the perfection in preferred orientation tends to increase progressively. Using this same procedure of gradient solidification, Fig. l(b) shows a simple scheme for producing a batch of crystals having the same cube orientation rather than an assemblage of columnar grains. Wires and rods are produced by cementing ceramic tubes to the wall of the mold. The steep temperature gradient produced in the central chamber is controlled by the mold heater to produce favorable conditions for crystal growth. Clearly the success of the operation lies in the selection of individual growing columnar grains by some kind of orifice at the base of each channel in the mold. Using simple constrictions, experience with nickel-base alloys has shown that 4 -in.-diam holes at a distance of -1 in. from the chill yield crystals within 7 deg of (100); closer control of orientation is possible by placing the crystal selector farther away from the chill.

Jan 1, 1970

By A. F. Crawley

The densities of some liquid Pb-Sb alloys up to 11 wt pct Sb and Pb-Sb-& alloys up to 10 pct Sb/10 pct Sh have been determined by a pycnometric technique over a temperature range of about 130°C above their melting points. The data given are accurate within 0.05 pct. Density is shown to vary linearly with temperature , and equations relating these quantities have been formulated. Molar volumes calculated from the density data indicate that volumetric deviations from ideal mixing are undetectable within the limits of experimental error. A continuing research program into some fundamental physical properties of liquid metals is being pursued at the Mines Branch, Department of Energy, Mines and Resources, Ottawa, Canada. This work has received support from the Canadian Zinc and Lead Research Committee in cooperation with the International Lead and Zinc Research Organization. This paper, which reports some density data for Pb-Sb and Pb-Sb-Sn alloys, follows previous work from this laboratory on lead, tin, and Pb-Sn alloys.' Of previous data from others, Greenaway2 and Sato and Munakata3 have reported results on Pb-Sb alloys. No previous work has been published on the ternary Pb-Sb-Sn alloys, reported here. EXPERIMENTAL METHOD Densities were measured by a pycnometric technique which has been described in detail and appraised for accuracy in earlier Mines Branch reports.475 Fig. 1 shows the densitometer with the pycnometer in position for a run. The pycnometer is also shown in some detail. The pycnometer of dense, high-purity graphite, about 14 cu cm in volume, was carefully machined to a uniform, smooth finish. The height was measured by a depth micrometer and the diameter by fitting precision gage blocks between steel balls.' In each case several readings were taken, and the final results were considered accurate within 0.01 pct. The resulting volumetric uncertainty together with small inaccuracies in the coefficients of linear expansion of graphite lead to a maximum systematic uncertainty in the method of ±0.03 pct. As shown in Fig. 1, the pycnometer lid is a threaded cap. Thus, the charge, a cylinder of the alloy, can easily be inserted and the solidified metal can readily be removed after a run. The dimensions of the cylindrical charge are chosen to ensure that, once molten, the metal will not only fill the pycnometer completely but will discharge an excess into the excess-metal float chamber. AS the temperature is increased above the melting point, the volume of metal in the excess chamber increases until the system has equilibrated at the desired temperature. At this point, the excess chamber is moved to one side by twisting the shaft F, leaving a fixed volume of liquid metal in the pycnometer. This volume of fluid is readily calculated using measured coefficients of linear expansion of the graphite which expands anisotropically. The associated weight of fluid is determined as the weight of the solidified metal removed after the furnace has cooled down. Alloys were prepared from 99.997 pct Pb, 99.999 pct Sn, and 99.999 pct Sb, being melted by an electric furnace in a graphite crucible and poured into graphite molds. Several density specimens of the same nominal size were machined from each ingot, and, by comparing specimen weights, relative differences in specimen composition resulting from segregation in the ingots could be detected. In this way, segregation was found to have occurred in Pb-Sb alloys at compositions beyond the eutectic (11.2 pct Sb) and this

Jan 1, 1969

By Carmine D. &apos, Lemuel Tarshis, Joel Hirschhorn, Antonio

Vapor-deposited nickel films in the thickness range 700 to 4360A were tested in uniaxial tension utilizing a microtester designed specifically for this study. Contrary to the findings of some investigators, a definite thickness-strength relationship was observed below 3000 A with a four-to sevenfold increase in strength over that of bulk nickel. The films were characterized by high elastic strains and little plasticity. On the basis of these and other reported data, it is suggested that the high strength level in metal films is related to the manner in which they are produced. Vapor deposition, owing to its severe quenching effect. is believed to promote the formation of point defects which inhibit dislocation movement. IN recent years it has been reported that metals, when in the form of thin films, exhibit extraordinarily high strengths. The data published to date have been primarily concerned with silver and gold because of the ease with which these metals can be vapor-deposited and their high resistance to surface oxidation. Previous investigations into the mechanical strength of thin films has uncovered an apparent dichotomy of view on film behavior. Beams and his co-workers have reported a definite dependence of strength on film thickness. Other workers,"-'6 however, in separate studies on the strength of poly crystalline and single-crystal films have found no such thickness-strength relationship. The study of thin-film strength is extremely difficult because of the many variables associated with film preparation, handling, and testing. Moreover, the manner of test employed by different investigators has varied quite radically, ranging from simple uniaxial-tension to biaxial-bulge testing. The work reported herein was conducted in order to determine the mechanical behavior of a structural metal when in the form of a vacuum-deposited thin film and to gain some insight into the reasons for the high strengths exhibited by metals having such a con- figuration. In this study a method of test was chosen which would yield results which are easily interpreted and lend themselves to comparison with properties of the same material in bulk form. Moreover, specimen-preparation parameters and film-handling techniques are set forth so that other investigators can properly compare their findings with ours. EXPERIMENTAL PROCEDURES A) Film Preparation. Vacuum deposition was performed in an 18 by 30 in. bell jar using a standard New York Air Brake Co. vacuum station with a 6-in. oil-diffusion pump. Before evaporation the system was pumped to a pressure of less than 2 x 10"5 torr. A shield was employed to protect the substrates from the emission of contaminants during the critical melting and outgassing of the evaporant. The source consisted of from one to six filaments (0.020 in. diam). The length of each filament was about 5 in. and was placed 6 to 8 1/2 in. from the substrate in such a manner that the substrate face was at 90 deg incidence with respect to the evaporant beam. The temperature of the source was 2000"~ during evaporation. The films were deposited onto a substrate arrangement which was composed of four basic components, that is: 1) a 3 by 1 in. glass slide; 2) a 22-mm sq micro cover glass on 1); 3) a 22 by 50 mm micro cover glass coated with collodion on 1); and 4) a stainless-steel sheet mask containing twelve rectangular openings of 1-mm and 2-mm widths and lengths of 5 mm laid over 3). Thus, test specimens of 1-mm and 2-mm widths are deposited onto a collodion substrate which precludes epitaxial effects in the specirnens. 17-le The rectangular cover glass and square cover glass were positioned in such a manner that a strip of film would be evaporated along the length and across the width of the large glass slide. This boundary of evaporated film was used to determine the film thickness by multiple-beam interferometry. The square cover glass was used for X-ray and chemical analyses. Thickness of the deposits was varied by changing the number of filaments used (one to six). The duration of evaporation was 30 sec for each filamgnt which resulted in a deposition rate of 8 to 20A per sec. Evaporations were all performed at room temperature; however, radiant heat from the source raised the substrate temperature to 40" to 60°C. All substrates were cleaned by ultrasonic agitation in a solution of spectranalyzed isopropyl alcohol. Collodion was deposited on the micro cover glass by immersion in solution of collodion in amyl acetate. B) Thickness Control and Measurement. Film

Jan 1, 1963

By D. Turnbull, J. H. Hollomon

IN the most general sense, solidification refers to the formation of crystalline material from either a gas or a liquid. However, in this symposium, only the formation of crystals from liquids will be considered. Thus, in our present study the problem of solidification becomes that of determining the mechanism of the transition from a liquid to a crystalline solid, and our particular interest is in the transformation of metals from the liquid to the crystalline state. Metal liquids are seldom composed of only one kind of atom. Often solute atoms are added intentionally to make an alloy, or they may be present accidently because of incomplete purification. Furthermore, there may be small solid particles of various other crystals present in the liquid. Such small crystals may persist if their melting points are higher than any temperature to which the liquid is heated. Prior to solidification, the liquid metal usually is poured from one container to another. The second container, called the mold, usually is at a lower temperature than the container, or the crucible, in which the metal is liquified. The first solid that forms upon contact with the mold generally is of a different composition than the liquid, usually containing fewer foreign atoms or dissolved impurities. Heat is evolved upon solidification and is dissipated through the surroundings. Tree-like crystals, or dendrites, grow from the container walls and branch into the melt, enriching the remaining liquid in impurity atoms. In some alloys the remaining, relatively impure liquid continues to solidify until no liquid remains and the branches of the original crystal are cemented together. In other alloys, particles with a second type of crystal structure appear before solidification is complete. First the nature of the liquid and the solid states will be considered and then the mechanism of the initial formation of crystals from pure and alloy liquids. Later the problem of the growth of these crystals and the complexities of solidification in a mold, where the temperatures are not uniform and the composition of the melt changes continuously, will be discussed. LIQUID AND CRYSTALLINE STATES A liquid is an aggregate of atoms arranged with no apparent regularity (over distances of more than a few atom diameters). Nevertheless, any given atom generally has a definite number of nearest neighbors at definite distances, and thus order may be said to exist over a short range. In a crystal, on the other hand, a regular array of atoms continues for many hundreds or thousands of atom diameters, and a long-range order is apparent. Thus, a crystal having long-range order can be reproduced by linear translations for 10-5 cm or more of some fundamental unit possessing short-range order. A crude illustration of the difference between liquid and crystalline structures can be obtained by comparing the possible arrangements of oranges in a crate. If the oranges are simply dumped into the crate haphazardly until it is filled, the oranges will represent a static model of a liquid.

Jan 1, 1951

By C. E. Nelson

The purpose of this discussion is to outline briefly the practices commonly followed in this country for the melting and refining of magnesium and its alloys. The processes used for the various forms of primary magnesium, as far as there are differences in the physical shape or behavior, will be discussed. The refining of general fine scrap or secondary magnesium was presented in an earlier paper.1 Inasmuch as the use of fluxes is an essential part of all the melting and refining processes, the principal aim of this paper will be to deal with these in sufficient detail to point out their unique characteristics, in order to make their use more effective. Types oF Melting Practice All melting and refining processes for magnesium and its alloys require the use of fluxes. These fluxes have a magnesium chloride base and other halide salts or oxides are added to give a density or behavior exactly suited to the particular melting practice. The successful handling of magnesium depends upon the proper use of the correct fluxes. There are four general methods of melting, summarized in the following paragraphs and treated in more detail in the section on Melting and Refining. Open-pot Method The open-pot method makes use of No. 230 flux.2 The flux provides protection during melting and a molten pool of flux into which the solid magnesium melts. It is stirred through the molten metal bath and agglomerates oxide or similar foreign bodies; then on quiet standing separates away, leaving the refined metal ball floating in an encircling layer of molten flux. It forms only a thin fluid film over the surface of the molten metal, which may be ' parted for hand-ladling processes and tends to cover the metal again after the ladle is removed. A very light dusting of the pot surface with fresh flux immediately after the ladle is removed is usually desirable. The open-pot method is used generally in the following processes: (I) alloying and secondary smelting in the production of ingot, (2) in sand foundries for premelting and to a smaller extent for the production of small castings requiring hand ladling, (3) in permanent-mold founding for premelting and also direct ladling to castings, (4) for continuous methods of preparing metal in the production of billets or ingots from which wrought products are fabricated, (5) in general scrap recovery. Crucible Process The crucible process makes use of No. 310 flux, which has the property of being thinly fluid at the start, to provide protection and refining qualities, and then drying out or thickening after a time, leaving a protecting crust on the pot surface until the time of casting. At that time it can be readily skimmed off or held back, thus allowing the contents of the crucible to be poured out directly into castings without fear of flux contamination. This flux is not

Jan 1, 1944

By J. W. Halley, G. L. Plimpton

Because of the two distinct stages in the solidification of rimmed steel, segregation in the rimmed ingot is more complex than that in the killed or semikilled ingot. In the earlier stage, chemical reactions, resulting in evolution of gas and vigorous stirring of the metal, effect a degree of negative segregation unique to rimmed steel. The composition of this zone constitutes the principal quality advantage of this type of steel. In the later stage of solidification, after the evolution of gas has ceased, the segregation follows the general pattern of a more completely deoxidized steel. However, the composition of the liquid remaining after the first solidification stage varies markedly from that of the original melt, some constituents having been partially removed as reaction products while the concentration of others has been intensified by rejection from the metal solidifying in the first zone. The aim, from the standpoint of segregation, in rimmed steel of high quality is to effect a maximum negative segregation in the rim zone without excessive concentration of undesirable elements at the center of the ingot. To achieve this aim, the composition of the melt may be varied and the furnace and pouring practice may be adjusted within certain limits. It is the purpose of this study to discuss segregation in rimmed steel from the standpoint of the mechanisms that produce it and to survey the phases of open-hearth practice that influence those mechanisms. Mechanisms Producing Segregation The mechanisms that determine the degree of segregation in the rimmed ingot are closely interrelated, making it difficult to select the primary factors and to determine a satisfactory order for presenting them. For instance, the question of sulphur segregation is relatively simple, since sulphur is not directly involved in chemical reactions in the ingot; but its concentration in the rim zone is dependent not only on its original analysis in the melt, its segregation coefficient, and the freezing rate, but also on the rate of its removal from the impure film on the solidifying surface. This washing action involves all the factors (such as freezing rate, the carbon-oxygen product, pressure, etc.) that determine the rate of gas evolution and hence the efficiency of film removal. Sulphur distribution between the rim and core is affected by the volumetric ratio between the two zones, and its segregation in the core is a function not only of the freezing rate of the core but also of all the foregoing factors that determine its concentration in the metal when solidification of the core starts. To simplify the presentation, it is proposed to treat the mechanisms affecting segregation independently in this section, reserving a discussion of their over-all effects for the section in which actual segregation data are given. The factors affecting segregation will be treated in the following order: (I) differential solidification, (2) removal of constituents as

Jan 1, 1945

By Lloyd Emory

THE region known as. Guyana or Guiana stretches along the north coast of South America from the mouth of the Orinoco River in Venezuela to the mouth of the Amazon River in Brazil. Politically, it is divided into British, Dutch, and French Guiana, extend¬ ing into Venezuela on the north and into Brazil on the south. Because the area is within the sweep of the northeast trade winds and of approximately the same latitude, plant' and animal life are fairly uniform throughout. The geology is very similar as far as the northern coast is concerned. The drainage is taken care of by a number of large rivers that flow northward directly into the sea. The Courantyne River, which roughly divides the area into half, is the eastern boundary of British Guiana.1 The lower reaches of this river are also the center axis of an ancient bay that at one time indented the coast-line at this point. The old shore-line and, in fact, successive shore-lines can be traced from near the present coast-line in, the northwest district of British-Guiana, south-east and inland, crossing the Essequibo River near Dahli, the Demerara near Christianburg, the Berbice at the mouth of the Kuruduni River and the Courantyne at Vaka-Kuyaha Falls. The line then swings around to the northeast and again approaches the coast near St. Lau-rent in French Guiana. This article will be confined to British Guiana and largely to the valley of the Demerara River, but for geographic names .and topographic details it might, however, apply to Dutch Guiana as well. British Guiana, which comprises about 90,000 sq. mi. and is as large as England, Scotland, and Wales combined, may be divided into three belts, the alluvial belt or coastal plain, the foot-hill area (often spoken of as the sand clay belt), and the hinterland.

Jan 1, 1928

By C. M. Nickerson

IT is apparent that repressuring of the oil measures is becoming increasingly important to the oil industry, and is a matter that warrants the best efforts of the petroleum engineer charged with applying this method of operation to a producing property. Considerable attention has. been directed to repressuring in various California oil fields, such as Dominguez and Seal Beach, which have served to sell the more progressive operator on this idea and also to keep him sold. The projects that have received most attention are in comparatively young fields where the fluid levels are high, the wells, perhaps, still flowing, where the wet gas production is of considerable volume, and where there is vital need of immediate conservation of gas, which otherwise would be blown to the air. The new State of California Gas Law, which prohibits the waste of gas, has served to interest the oil industry in -means of conserving the gas that is now being blown to the air because of lack of markets. This vitally affects the operator in the older, well-depleted oil fields of the state, because in many cases he has a limited market for gas, on account of the flush production from the more active oil fields. While the waste of gas is relatively small in these older fields, such as the Midway-Sunset area, it now attains considerable importance, since under the new State Gas Law it must be put to some beneficial use. Repressuring in the older fields of California has not received the attention of the petroleum engineers that is warranted by the present situation. This paper was prepared with the view of presenting the salient features connected with repressuring in the well-depleted oil measures of the older fields, and to show what results have already been obtained in these fields by injecting the unmarketable. gas into the sands, particularly in the Midway-Sunset field in the San Joaquin Valley of California. Other projects in the older fields of the state offer some supporting data in this connection, such as the Shields Canyon and the Brea Canyon fields.

Jan 1, 1929

By Walter W. Bradley

Mining by hydraulic process of the important gold-bearing gravels of the Sacramento Valley in the basins of the Yuba, Bear and American rivers began in 1853, and continued at an ever-increasing rate for 30 years. In its most active days it reached an annual production of $15,000,000, and averaged $10,000,000 per year over the 30 years. During that period no provisions were made to prevent the debris from being discharged into the water courses, and ultimately large quantities of silt, sand and gravel were washed down to the lower valleys; filling channels, causing overflow of agricultural lands and difficulty in maintaining navigable depths in the Sacramento River. Agitation and suits filed because of these damages finally resulted in the injunction decision of Judge L. B. Sawyer,' in the U.S. Circuit Court, Jan. 23, 1884, which closed down practically all hydraulic mining operations not having means to restrain their debris. In 1893 (approved March 1, 1893), Congress passed the act introduced by Representative Anthony Caminetti, of California, creating the California Debris Commission, composed of three officers assigned from the Engineer Corps of the U.S. Army, and since that time it has been legal and possible within the drainage systems of Sacramento and San Joaquin rivers to conduct hydraulic mining of gold-bearing gravels behind dams built under this commission's permit and supervision. In the watersheds of the Trinity and Klamath rivers, which flow directly to the Pacific Ocean and do not affect navigation or agriculture, operating permits from the California Debris Commission are not required. There is a measure of restriction there, however, through what is known as the Trinity and Klamath River Fish and Game District. Chap. 215, Stat. 1931, in order to secure relatively clear water for the fishing season, provides that between July 15 and October 15 each year there must not be discharged into these rivers debris that will cause a turbidity greater than a content of 50 parts per million in the

Jan 1, 1937

By L. Guttman

THE equilibrium diagram of the indium-thallium system was of interest to us in connection with a study of the superconducting properties of metallic solid solutions in progress at this Institute. For this purpose, a series of alloys was prepared covering the range from pure indium to 75 atomic pet TI, and X-ray diffraction patterns were obtained. Roughly speaking, the results indicated a region of continuous decrease in the axial ratio of the face-centered tetragonal structure from the value ca. 1.08 in pure indium to unity at about 23 atomic pct TI. From this concentration to the solubility limit, the structure was face-centered cubic, a form not reported by Hansen.1 At this point we became aware of the work of Valentiner,2 who had found the same structures at room temperature but had not investigated further the relationship between them. To study the transformation f.c.c.??f.c.t., and to clarify the phase diagram, we undertook the work reported in this paper and that which follows." Preparation of Alloys Pure indium and thallium* (both about 99.9 pct, as estimated from spectroscopic analyses) were weighed out in quantities sufficient to prepare 10 to 25 g of alloy of the desired concentration. (Occasionally indium was mixed with a previously pre- pared solution.) The metals were melted over a flame, in an open graphite crucible, stirred with a graphite rod, and poured into a graphite trough. The rough slug was hammered and swaged into a rod of 2 to 3 mm diam, and annealed in a drying oven at about 125°C for 1 to 2 days. Samples were taken from the rod for analysis, as well as for diffraction and other measurements. The thallium was determined by electrometric titration, using a modification of the method of Beale and co-workers.' The precision of analysis was generally about 2 0.2 pct of the thallium content. The rods were sometimes found to vary in thallium content as much as 1.5 pct from end to end, but since analyses were also made close to the segments used in the various studies, the composition was usually known as accurately as the analyses could be made. Where one less significant figure is given, the error is estimated to be ±0.4 pct of the thallium content. X-Ray Diffraction Measurements Three different cameras were used: (1) A 7 cm Debye camera, with oscillating specimen (manufactured by the Picker X-ray Corp., Cleveland, Ohio); (2) a 9 cm diam Debye camera of the type designed by Bradley;" (3) a 10 cm diam symmetrical focusing back-reflection camera (manufactured by Geo. C. Wyland, Ramsay, N. J.). Samples were prepared from the homogenized rods, either by filing under liquid nitrogen, or more often, in the form of wires or foils made by working at room temperature or liquid nitrogen temperature. Sharp patterns were obtained from specimens annealed at room temperature, although higher annealing temperatures were also used (cf. below). Generally, copper radiation was used; a few patterns were obtained with

Jan 1, 1951

By L. Adler

Any design of a mine roof in bedded deposits which ignores differential deflections at the supports can quickly lead to dangerous overstressing. As illustrated by the typical case presented on page 1029, if one support deflects only 0.1 in. more than its neighbor, stresses 50 pct higher than anticipated will result. Previous studies1-3 have assumed that the mine roof acts like a beam clamped at both ends, with no deflection or slope' at the supports (Fig. 1). Essentially this assumes:5* ?A = ?, = ?b and dA = dB = 0. However, a host of conditions can cause differential sag or deflection at one support, and even an apparently trivial deviation can have major consequences in the beam: variations in spacing, size, and material of supports; local settlement due to floor heaving or lower mine openings; non-uniformity in wedging or bolt tensioning.8 In one particular instance concrete pillars, poured in place, shrank away from the roof upon setting.' When understood and controlled, differential sag becomes a definite advantage, permitting the transfer of loads from one support to another. Where one support is a bolt or prop and the other a pillar or rib, the load on the former can be reduced while the load on the pillar or rib is increased. This means two things: 1) savings can be effected by using smaller artificial supports such as props and bolts and 2) loads can be increased in the rib to induce eventual failure for longwall caving. In this last respect, another factor underlying coal bumps becomes understandable. The design of a mine roof by beam theory assumes that when a bedded formation is homogeneous, iso-tropic, and elastic, it will act like a uniformly loaded beam, fixed or clamped at both ends,6 s in Fig. 1.'" These are important assumptions. The uniform load is the weight of the beam itself or its body load. For a beam of unit width, this load becomes per foot: w = yhb. w = uniform load y = specific weight, lb per ft3 h = depth or thickness of beam, ft b = width of beam, ft Since b = 1, w - yh [ 1 ] A beam fixed at both supports is statically indeterminate to the second degree, that is, two equations in addition to those for static equilibrium are required to determine the reactions at the supports. These equations result from the geometry. From statistics: ^F,= 0;RA + RB — wL = 0 [2] wU S,M0 = 0 ; MB H------------MA — RBL = 0 [3] it Using superposition in which the left support is kept intact and the right one resolved into an active force and moment, we obtain from Fig. 2:" ?b = ?m + ? b2 + ?B3 = 0 dB = dB1 + dB2 + dB3 / wU Ma RBL \ V d°=(-r+-2—r)-zr [5] Where: Subscripts refer to position on axis of beam R = force, lb M = moment, ft-lb w = uniformly distributed load, lb per ft L = span, ft 0 = slope, radians d = deflection, ft E = Young's Modulus, lb per ft" 1 = Moment of inertia about the neutral axis, ft4 Solving Eqs. 2 through 5 for the four unknown reactions, we obtain: 2 L3 Fig. 3 is obtained by plotting MA and M, vs d, and then plotting RA and R, vs d, and adjusting their scales to coincide with MA and M, vs d,. It should be noted in Eqs. 6 and 7 that as dB increases, MA increases the same amount that Mn decreases. Eqs. 8 and 9 show a similar relationship between RA and R,. Proof that MA is the maximum absolute moment occurring in the beam is as follows: where M, = moment at x wx-When where M,., = maximum positive moment Eqs. 6 and 8 into above: For small dn: MA> M,,,

Jan 1, 1960