Search Documents

By F. V. Shallcross

Physical properties of thin films of CdS and CdSe formed by vacuum deposition onto glass sibstrates have been studied as a function of deposition and processing conditions. The crystallinity and surface features of CdS films were examined using electron microscopy and electron and X-ray diffraction techniques. The films were poly crystalline; the preferred orientation and crystallite size increased with film thickness, substrate temperature, and deposition time. The CdS films consisted primarily of hexagonal-phase material, in contrast to similarly prepared CdSe films which have previously been observed to contain mixtures of cubic and hexagonal phases. As-deposited CdS films showed no major dependence of Hall mobility on crystallite size or degree of preferred orientation. Hall mobility and carrier concentration in CdS and CdSe .films were measured at various temperatures; both parameters increased with temperature and yielded activation energies which depended on fabrication conditions. Surface-desorption phenomena and overcoating of the semiconductor with SiO affected the observed electrical properties significantly. THIN films of cadmium sulfide1,2 and cadmium sele-nide3,4 have been employed by various workers as semiconductors in the insulated-gate thin-film field-effect transistor, known as the TFT. These devices are most commonly made by vacuum deposition of all materials onto an amorphous substrate such as glass. A knowledge of the microstructure and electrical properties of semiconductor layers used in the thin-film transistor is essential in order to form a realistic model for the device and to improve its performance, reproducibility, and reliability. This paper will describe studies of the physical properties of vacuum-deposited CdS and CdSe films prepared under various conditions. Structural characteristics examined in- cluded phases present, crystallite size, nature of preferred orientation of crystallites, surface roughness, and structural homogeneity throughout the film thickness. Electrical properties measured were Hall mobility and conductivity and their dependence on temperature and ambient. Thin-film properties are affected by many fabrication parameters including purity and physical form of evaporant, deposition rate, film thickness, design and temperature of the evaporation crucible, geometry of the deposition chamber, nature of the residual atmosphere, composition and temperature of the substrate, and details of postdeposition processing. PREPARATION OF FILMS In this work the semiconductor films were deposited in a conventional oil-diffusion-pumped system with pressures in the 10-8 torr range. The CdS evaporant was obtained from the Eagle-Picher Co. as a high-purity coarse-grained crystalline powder; the CdSe was a high-purity sintered powder supplied by the Harshaw Chemical Co. The evaporation crucible was a resistance-heated molybdenum-wire basket coated with aluminum oxide and filled with a quartz wool plug at the top. The source to substrate distance was usually 10 cm. This region was enclosed by a Pyrex inner cylinder. The substrate was heated with an overlying Pyrex plate coated with tin oxide. The substrate temperature was controlled using a thermocouple attached to the lower side of the heater. This thermocouple was calibrated against another thermocouple attached to a dummy substrate and by observation of melting points of various metal films deposited in the system. The substrates were polished borosilicate glass plates and conventional glass microscope slides. Substrate preparation included cleaning with an ultrasonically agitated detergent bath followed by isopropanol-vapor de-greasing. Film thickness was measured interferomet-rically during and after deposition. STRUCTURE OF CdS FILMS Structural studies were performed on CdS films using electron diffraction, electron microscopy, and

Jan 1, 1967

THE first session of this meeting was held Tuesday evening, in the chamber of the Common Council, the President, Mr. David Thomas, in the chair. Mayor Carroll, of Troy, gave a cordial welcome to the Institute, which was responded to, on behalf of the Institute, by the first Vice-President, Mr. R. W. Raymond. The Council reported the names proposed for membership with recommendation for election. The following named gentlemen were duly elected: Anthony, J., . .Williamstown, Pa. Babcock, George, . . .Troy, N. Y. Blake, Theo. A., . . . . . . Sa n Francisco, Cal. Blossom, T. M., . . . . . . New Pork. Boalt, James A., . . .San Francisco, Cal. Bowman, Amos, . . . . San Francisco, Cal. Chester, Prof. A. H., . .Clinton, N. Y. Dewey, C., . Pittsfield, Mass. Dock, Gilliard, . Shamokin, Pa. Emerson, O. D., . .New York. Endres, John J., . .Pittsburgh, Pa. Firmstone, Frank, . Easton, Pa. Fowle, W. B., . Philadelphia, Pa. Frazier, Prof. B. W., . . .Bethlehem, Pa. Gardner, George A., . New Pork. Goodyear, Watson A., . .6an Francisco, C al. Griswold, Chester, . Troy, N. P. Griswold, J. A.,* . . .Troy, N. Y. Hague, J. D., . . .San Francisco, Cal. Hahn, 0. H., . .Eureka, Nev. Harkness, T. C., . . . . . . Wilkes-Barre, Pa Harris, Samuel, . . .Hudson, N . Y. Henry, &. T., . Oxford, N. J. Holley, A. L., . .Brooklyn, N. Y. Howe, H. W., . . .Troy, N. Y. Hunt, Dr. T. Sterry, . Boston, Mass. Jannet, J., . Troy, N. Y. Knapp, John A., . .New Pork. Laughlin, Henry A., . . .Pittsburgh, Pa.

By R. W. Bartlett

The rates of oxidation of tungsten have been determined at temperatures between 1320" and 3170°C and oxygen pressures to 1 amn using a surface -recession measurement technique. Above approximately 2000°C and 10-6 atm the rate is independent of temperature and can be calculated from gas collision theory assuming a constant reaction probability, e, of 0.06. Oxygen molecules react at surface sites where oxygen atoms have previously chemisorbed. This provides a direct pressure dependence at low pressures but at high pressures tungsten oxide molecule s form an adjacent gas boundary layer which lowers the PO2 at the tungsten surface. A correction for this effect using free-convection theory fits the rate data over the entire oxygen-pressure range from 10-8 to 1 atrn as well as data using O2-A mixtures. Below 10-6 atrn and above 2000°C, e decreases with increasing temperature because of desorption of oxygen atoms. Below 2000°C the rate decreases with decreasing temperature at all oxygen pressures following an apparent activation energy of 42 kcal per mole and depending on (Po2)n with n varying between 0.55 and 0.80. MOST of the previous tungsten oxidation studies have employed gravimetric methods and have been limited to temperatures below 1000°C where the weight loss associated with evaporation of tungsten oxides is negligible compared with the weight gain from oxidation.' At higher temperatures, oxygen-consumption rates have been determined from pressure measurements, usually at constant flow rates, by Langmuir,2 Eisinger,3 Becker, Becker, and Brandes,4 and Anderson.5 The sensitivity of this method decreases with increasing pressure and, with the exception of Langmuir's work, these investigations were confined to pressures below 10-6 atm. Above approximately 1300°C, depending on the oxygen pressure, the rate of oxide evaporation is greater than the oxide-formation rate and the recession of the tungsten surface can be measured optically without interference from an oxide layer. This was first done by Perkins and crooks6 who heated tungsten rods in air pressures from 1 to 40 torr at temperatures between 1300" and 3000°C. The present investigation of the oxidation kinetics of tungsten at high temperatures emphasizes oxygen pressures from 10-6 to 1 atm. This is the range of interest for earth atmosphere re-entry applications of tungsten for which little data were previously available. APPARATUS The apparatus is a modification of the type used by Perkins and crooks.' Ground tungsten seal rods, 6 in. long by 0.125 in. diam, were mounted vertically between two water-cooled electrodes, one fixed and the other having free vertical travel. The movable counter-weighted electrode is prevented from undergoing horizontal displacement by three sets of runners mounted at 120-deg intervals. Electrical contact is made by means of a water-cooled mercury pool. A 24-in. vacuum bell jar having a volume of approximately 267 liters was used as the reaction chamber with the sample holder mounted in the middle of the chamber. Power was supplied from an 800-amp dc variable power supply. Temperature readings were made by means of a Latronics automatic two-color recording pyrometer. With this instrument, corrections for emissivity are not necessary provided the spectral emissivi-ties at two closely spaced wavelengths are equal. Supporting measurements were made with a micro-optical pyrometer corrected for emissivity of bare tungsten and window absorptivity. The micro-optical pyrometer was calibrated against a National Bureau of Standards calibrated tungsten lamp and both pyrometers were periodically checked against the melting points of tungsten and molybdenum using the oxidation apparatus. Above 10-6 atm, pressures were measured with an Alphatron gage calibrated against a McCleod gage. At 10-6 atm, a hot-filament ionization gage was employed. A magnified image of the self-illuminated tungsten rod was formed using a 360-mm objective lens mounted outside the bell jar. When the experiment exceeded 1 hr, the image was focused on a ground-glass plate about 10 ft from the tungsten rod at about X8 and the recession of the thickness of this image was monitored with a Gaertner cathe-tometer. When faster rates were encountered, a 35-mm time-lapse cinecamera with a telephoto lens and bellows extension was substituted for the ground-glass plate and cathetometer. Diameter recession rates were determined from the photograph image projected on the screen of an analytical film reader. EXPERIMENTAL PROCEDURE After installing the rod in the apparatus and cleaning it with acetone, the system was evacuated to 5 1 x 10-5 torr. Before oxygen was introduced,

Jan 1, 1964

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the frothability of pine oil is governed by: 1-rate of aeration, 2-time of aeration, 3-height of liquid column, 4-chemical composition of pine oil, 5-pH value of solution, 6-temperature of, solution, and 7-concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.1 The results also show that the relative frothabilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of reproducibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1-compressed air and its regulating system, 1-3, are eliminated; and 2-a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be .either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifing and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.2 Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 ± 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1952

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.' The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.' Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By Shiou-Chuan Sun

THIS paper presents the design and operation of a frothmeter capable of measuring the frothing characteristics of pine oils and other frothing reagents. The experimental data show that the froth-ability of pine oil is governed by: 1—rate of aeration, 2—time of aeration, 3—height of liquid column, 4—chemical composition of pine oil, 5—pH value of solution, 6—temperature of solution, and 7—concentration of pine oil in solution. The effect of mineral particles on the behavior of froth also was studied, and the results can be found in a separate paper.' The results also show that the relative froth-abilities of pine oils in the frothmeter generally correlate with those in actual flotation, provided that other factors are kept constant. In addition to pine oils, the other well-established flotation frothers were tested, and the results are included. In this paper, compressed air frothing is the frothing process performed by means of purified compressed air, whereas sucked air frothing is the frothing process accomplished by purified air sucked into the glass cylinder by a vacuum system. The term vacuum frothing denotes that froth was formed by degassing of the air-saturated liquid under a closed vacuum system. Apparatus The frothmeter, shown in Fig. 1, is capable of re-producibly measuring the volume and persistence of froth as well as the volume of air bubbles entrapped in the liquid and is capable of being used for compressed air frothing, sucked air frothing, and vacuum frothing. Fig. la shows that for compressed air frothing, the apparatus consists of an airflow regulating system, 1-3; a purifying and drying system, 4-8; a standardized flowmeter to measure the rate of airflow from zero to 500 cc per sec, 9; and a graduated glass cylinder, 13; equipped with an air regulating stopcock, 10; an air chamber, 11; and a fritted glass disk to produce froth, 12. The fritted glass disk, 5 cm in diam and 0.3 cm thick, has an average pore diameter of 85 to 145 microns. The pyrex glass cylinder has a uniform ID of 5.588 cm and an effective height of 63 cm. The inside cross-sectional area of the glass cylinder was calculated to be 24.53 sq cm, or 3.8 sq in. For sucked air frothing, Fig. lb shows that the apparatus for compressed air frothing is used again, with the following modifications: 1—compressed air and its regulating system, 1-3, are eliminated; and 2—a vacuum system, 16, equipped with a vapor trap, 15, and a vacuum manometer, 17, is added. The vacuum system can be either a water aspirator or a laboratory vacuum pump. Any desired rate of airflow can be drawn into the glass cylinder, 13, by adjusting the opening of the air regulating stopcock, 10. The sucked air stream is cleaned by the purifying and drying system, 4-8, before entering the glass cylinder, 13. When this setup is used for vacuum frothing, the air regulating stopcock is closed. The frothmeter has been used for almost 3 years and has proved to give reproducible results, as illustrated in Table I. With a magnifying glass and suitable illumination, the frothmeter also can be used to study the attachment of air bubbles to coarse mineral particles.' Experimental Procedures Except where otherwise stated, the data presented were established by means of the compressed air method. The volume and persistence of froth were recorded respectively at the end of 4 and 6 min of aeration at a constant rate of airflow of 29.3 cc per sec, which is equivalent to 71.6 cc per sq cm per min, or 462.6 cc per sq in. per min. The aqueous solution for each test, containing 1000 cc of distilled water and 19.2 ± 0.5 mg frothing reagent, was adjusted to a pH of 6.9 0.2. The volume of froth is expressed as cubic centimeter per square centimeter and is equivalent to the height of the froth column (the distance between the bottom and the meniscus of the froth). The volume of froth was obtained by multiplying the height of froth by the cross-sectional area of the glass cylinder, 24.53 sq cm. Before each test, the glass cylinder, 13, was cleaned thoroughly with jets of tap water, ethyl alcohol, tap water, cleaning solution, tap water, and finally distilled water. The cylinder with stopcock,

Jan 1, 1953

By Paul M. Tyler

HISTORICAL concepts of the economics of the glass-sand industry are changing rapidly. The greatly expanded demand for glass containers combined with higher freight rates on raw materials and manufactured products have induced a migration of glass factories toward densely populated centers and the creation of new standards of place value for sub- standard sand deposits. This migration has been facilitated by the construction of pipelines to bring cheaper natural gas and liquid fuel to large cities and may be further speeded by the adoption of modern mineral dressing methods to permit economical utilization of local raw materials. Our national resources of naturally high-grade 1 silica sand are abundant, but most of the best de- posits are situated so far from large centers of population that it now costs $3.00 to $5.00 a ton to carry the sand from the mine to the optimum site for a 1 factory making beverage bottles, scientific and electrical glassware, and miscellaneous blown and pressed ware for local markets. It follows that on the basis of freight savings alone it may be economical to use material from inferior deposits closer to the factory even though the f.o.b. cost of mining and treatment may be much high

Jan 1, 1950

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By M. F. Hawkes, R. F. Mehl

The rate of isothermal transformation of austenite to pearlite depends upon the rate of nucleation, N, and the rate of growth, G, of pearlite in austenite. Values of N are given in terms of the number of nuclei forming in unit time per unit grain boundary area of unreacted austenite; values of C are given in terms of the linear rate of radial growth. Variations in the isothermal rate with temperature result from variation of N and G with temperature. Depth of hardening of a steel depends fundamentally upon values of N and G; changes in carbon and alloy content effect changes in N and G and thus affect depth of hardening. Quantitative studies are available on N and G for the formation of pearlite in plain carbon eutectoid steels.3 Systematic studies in this field are necessary if the phenomena are to be well enough known to furnish a proper basis for full rationalization and for theory. Accordingly, the studies are continuing, both with respect to the effect of alloying elements upon the values of N and G in the formation of pearlite and to the values of N and G for the formation of ferrite in hypoeutectoid steels. The present paper is the first relating to the effect of alloying elements upon the values of N and G for pearlite. It offers special interest since cobalt is known to have an anomalous effect upon the rate of formation of pearlite, accelerating it, whereas all other elements retard it.4 It will be shown that cobalt increases both N and G for pearlite and that this effect is inherent in the Fe-Co-C system and not dependent upon factors relating to austenite heterogeneity nor upon any recognizable adventitious factor. Inasmuch as the rate of diffusion of carbon in austenite and the interlamellar spacing of pearlite are variables related to G and possibly to N (in a manner not yet certain), measurements of the effect of cobalt upon them are also reported here. In the course of the work, measurements were made on the effect of cobalt upon the marten-site temperature and these are given. COBALT AS AN ALLOYING ELEMENT IN STEEL Properties of Cobalt Cobalt resembles iron more closely than does any other chemical element. Its atomic number is 27, hence it is the element immediately following iron in the periodic system. The two differ in atomic structure only in the fact that cobalt contains seven electrons instead of six in the third, or transition, level of .the third shell. The next shell, which is the

Jan 1, 1948

By J. B. Newkirk, R. W. Hendricks, R. Baro

STUDIES of the kinetics of precipitation in binary alkali halide systems are of interest from a theoretical point of view, because of the possibility of controlling diffusion rates by additions of aliovalent impurities. This note reports some preliminary results of a study of the kinetics of precipitation of AgCl from supersaturated solid solutions of AgCl in NaCl containing trace amounts of divalent cation impurities. In their study of the system NaC1- AgC1, Stokes and Li1 derived the phase diagram containing a mis-cibility gap with a broad maximum at approximately 170°C. They found that single crystals quenched from above the miscibility gap and aged at various temperatures within the two-phase region gradually turned light blue, then cloudy white, and finally opaque. The rate of transformation depended markedly on the aging temperature. The light-blue color in the early stages of aging was interpreted to be the result of Rayleigh scattering from precipitated particles less than 0.1 µ in diameter. These qualitative observations have been confirmed by us. However, a more precise tool was needed in order to quantitatively follow the growth kinetics of the precipitate particles. Because of the suspected small size of the precipitate particles and for other reasons, small-angle X-ray scattering was thought to be a suitable technique for this study. Small-angle X-ray intensities scattered from powder specimens were recorded on a General Electric XRD-5 diffractometer using the four-slit geometry described by Neynaber, Brammer, and Beeman.2 The slits were 0.08 mm wide by 10.00 mm high. It was found that, with very careful alignment, meaningful data could be obtained to within 3 min from the middle of the direct beam. Chromium radiation (?Ka = 2.29Å) was used in order to spread the scattered intensity to a relatively high angle, as indicated by Eq. [1]. A specimen containing 21.0 at. pet AgCl was prepared by melting analytic reagent-grade AgCl and NaCl under a chlorine atmosphere in a vycor cap-

Jan 1, 1964

By C. B. Foster, S. I. Freedman, E. M. Jamgochian

Coal-oil mixture (COM) combustion technology is regarded by the US Department of Energy (DOE) as near term and Potentially applicable to existing utility and industrial steam generators and for injection into blast furnaces. From work done previously, it has been established that COM can be burned in existing boilers and blast furnaces. Therefore, the issues being addressed by the current DOE program are: (1) determination of best available technology to achieve environmentally acceptable long-term reliable operation and (2) determination of applications for which COM can be utilized economically. Some of the technological options have begun to be determined by projects already under way. However, many projects are still in the early stages of development.

Jan 1, 1980

By John D. Sullivan, Edwin J. Rogers, Chester R. Austin

THE problem of making a building unit combining the necessary physical and mechanical properties and good thermal insulation has been foremost in the minds of architects and ceramic and construction engineers for many years. This paper presents the results of studies on thermally expanding shales or clays to produce light-weight cellular products suitable for making building units. An expanded clay block suitable for building purposes should be large enough so that substantial savings may be effected in labor costs in laying the wall. The permeability should be low and it should have sufficiently good "dry-wall" characteristics to permit exposing the exterior surface to the elements, and to permit plastering directly the inside wall surface. The thermal conductivity should be low and the mechanical properties should be adequate. Obviously, a unit possessing satisfactory qualities for constructing an outside wall would be satisfactory for interior walls and for back-up purposes. The results of studies on bloating various shales or clays† and the properties of the expanded products are reported. In another paper1 basic factors involved in bloating of clays are discussed. Manufacturers of ceramic products, particularly structural clay, may encounter bloating of the ware during burning, and precautions must be followed to avoid this phenomenon. About 1927 the C. F. Burgess Laboratories, Madison, Wis., while carrying on an investigation for the American Face Brick Research Corporation, conceived the idea of intentionally bloating clay while holding it in a restrained condition, with the hope of producing a unitary cellular mass. Work was carried on until about 1931, when studies were terminated because of business conditions. These studies were continued later by The Western Brick Co., Danville, Ill., which developed a process of "inwardly expansive bloating." The major purpose of the latter investigation was to produce back-up tile to compete with concrete blocks made from Haydite or cinder aggregate. Haydite is a light-weight aggregate formed by heating certain clays or shales rapidly in a rotary kiln. While the investigations at the C. F. Burgess Laboratories or at Western Brick Co. were not carried far enough to lead to the commercial production of material for the construction of walls, particularly outside walls, they showed that certain clays could be thermally expanded and that it was possible to produce a material of low permeability with a large percentage of the total voids or cells closed. Commencing in 1939, the Ozark Chemical Co. sponsored a research program at Battelle Memorial Institute for the purpose of determining whether it is technically feasible to make thermally expanded building units, and specifically to get answers to the following questions:

Jan 1, 1942

By L. Bombardieri, H. F. Mills

IRON KING mine, producing gold-silver-lead-zinc ore, is 10 miles east of Prescott, Ariz. At present the 1806 level is being developed. The echelon pattern of ore deposit continues at depth but is less pronounced, and the orebody is now more or less continuous over 2600 ft of strike length. with widths 5 ft to as high as 26 ft where overlapping of lenses occurs in one section of the mine. Better continuity of ore at depth has encouraged systematic mining and improved plant facilities to offset higher operating costs. With favorable persistence of ore at depth. the three-compartment No. 6 hoisting shaft appeared inadequate to handle increased tonnage from greater depths, and in 1952, a four-compartment steel and concrete shaft was started. This is now at a depth of 1906 ft, and shaft pockets and loading cartridges are being installed on the 1806 level. Ore from the new shaft, hoisted in 51/2 -ton Jeto bottom dump skips, is dumped into a 500-ton shaft bin, from which it is fed to a 16x30-in. gyratory crusher and conveyed 415 ft through an undersurface concrete gallery to the secondary crusher and conveying system supplying the 900-ton mill. Lead, zinc, and pyrite concentrates are floated, and the flotation tailings are cyanided after desliming. Waste from the new shaft is dumped into a 250-ton surge bin, fed from this bin to a 24-in. conveyor, and discharged into the glory hole above the block cave. The new shaft is served by a double-drum 400-hp hoist used for ore and waste; the No. 6 shaft conveys men and material To secure a cheap source of waste fill for stoping operations, a block cave area was undercut In the hanging wall near the north end of the mine above the 600 level. Waste from the block cave is drawn from any of three large drawpoints on the 600 level, and a series of hanging wall transfer raises with controls and bypasses on each level provide a fast low-cost material for fill. The block cave is worked vertically through to surface in the form of a steep-sided hole 350x250 ft and several hundred feet deep, the sides of which cave and provide fill material without any blasting. Fill is a mixture of caliche-cemented surface gravel and small particles of hanging wall schist. Level Development: An orebody 300 times as long as it is wide requires a lot of development work. Former practice consisted of driving a haulage drift about 30 ft from the ore in an andesitic footwall, a drift on the ore, and crosscuts from the haulage drift at 100-ft intervals. Crosscuts are about 90 ft long. At present, only the odd numbered levels are so developed, and on the even numbered levels only the haulage drift and crosscuts are driven. Little or no timber is used for this development. This change resulted in 20 pct reduction of development costs and 50 pet reduction of square set stoping required for removal of floor pillars. Elimination of ore drifts on alternate levels leaves

Jan 1, 1957

By W. E. Keck

THE potential iron ores of Michigan can be classified from the stand-point of the predominant impurities into siliceous, sulphurous and phos-phorous ores. Research on the flotation of each of these classes of ore was carried out in the following Planner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly, pure state. There are two varieties of the mineral-specular hematite and massive hematite. The latter is the principal variety, but the former is an Impor-tant mineral of iron in some of the potential ores. Because of this condi-tion, flotation research was performed with both varieties. This research consisted essentially of: (1) a survey of the literature on hematite flota-tion, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the; development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a pro-prietary frother and oleic acid or other soluble oils 2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1937

By Jun-Yan Chen

Ground control problems in sublevel caving become evident as the rock pressure increases with depth. Recently, a finite element analysis of the stability problem of the sublevel caving method was completed by the author. This paper summarizes the results of stress analysis in sublevel extraction drifts under different field stress conditions by using linear elastic and nonlinear elastic-plastic finite element modeling techniques. A critical stress concentration will occur in the uppermost sublevel drifts beneath the caved area or blasted ore area. During the blasting and drawing cycle, a tensile and shear failure condition could develop in the center extraction drift when it would be mined last. Under a high horizontal stress field condition, almost all tensile stress in the back of the extraction drifts will be eliminated and only slight yield can be seen in the floor of the extraction drifts. Compared to the cases under the stress field where vertical stress is the dominant factor, the total yielding zone will be greatly reduced because of an in- creasing horizontal stress field with depth. However, it is predicted that the center of each ore column side will experience excessive shear stress that probably will result in ore failure. The two major conclusions drawn from this study to improve the overall stability of sublevel caving are: (1) the drift width must be carefully controlled and an appropriate stoping sequence selected; and (2) the sublevel caving method can be used in deep min

Jan 1, 1983

By T. B. Counselman

An iron blast furnace of 1000 tons daily capacity will produce a 100,000 cu. ft. per minute of blast-furnace gas. This contains a 25 per cent of carbon monoxide, and has a B.t.u. value of about 95. gas is used primarily for heating the stoves of the blast furnace, secondarily, under boilers, for steam production. Occasionally it is used in gas engines. The raw gas coming out of the furnace carries about 10 grains of dust per cubic foot of gas, under best operating conditions. With furnace "rolling" or slipping, this quantity may temporarily be gre increased. This dust would, of course, deposit on the checkers o: stoves, or plug the burners under the boilers; therefore the gas : be cleaned. Flow Sheet The first step in the cleaning operation, as shown by the flow s Fig. 1, is a dry dust catcher, of which there are several forms, partially cleaned gas next goes to a primary wet washer, where v sprays knock down most of the solid particles. If further cleani desired, the gas may then go to electrical precipitation. Again, the removed is collected in water. Dry dust catchers reduce the dust col from 10 grains to between 4 and 6 grains per cubic foot, and rec roughly half of the total flue dust in the gas. The wet washers rea most of the remaining dust, reducing the dust content to about 1/4 per cubic foot. Electrical precipitators, if used, further reduce the content to about 0.01 grain per cubic foot of gas. The flow sheet s the dust content of the gas at various steps in the treatment and als content of solids in the water. It should be noted that some plant less water on the primary wet washer than indicated, and that ofte solids content of the scrubber water will be 300 grains per gallon, or much higher. Reasons for Recovering Flue Dust.—There are two main incentive recovering flue dust from the scrubber water: (1) the value of the (2) stream or lake pollution, where such a reason applies.

Jan 1, 1937

By G. W. Preckshot, J. W. Gorman

MOLTEN metals offer an excellent medium for the study of molecular diffusion and interphase transfer. In the absence of intermetallic compound formation, solutions of molten metals are solutions of elements. Therefore, complicating factors such as molecular structure, dissociation, association, polarization, and so on, are generally absent. Further, metals remain in the liquid state over a wide range of temperature. Thus, the effect of temperature on transport processes can be studied in more detail. Although some data are available for the diffusion of metals in the molten state at high temperatures,"""".'!' the most useful and accurate data are those for the diffusion of various elements in mercury at room temperature. The effective radius of diffusion for the various elements in mercury may be calculated from the Stokes-Einstein relation.'-These calculated radii are compared with the atomic and ionic radii calculated from X-ray data on crystals." The effective radii of diffusion of the alkali and alkali-earth metals correspond to those of the neutral atom; those of cadmium, silver, lead, zinc, thallium, bismuth, and tin correspond to ionic radii; and those of copper and gold indicate larger radii due to association with mercury or more likely, faulty diffusion data. Independent evidence"' supports the notion that alkali metals are uncharged in amalgams. The concept of metals moving free of their conductance electrons in the liquid state has been discussed by Eyring, et al,'" in connection with studies on the viscosity of pure molten metals. Considering the approximate nature of the tabulated atomic and ionic radii and the variance in the diffusion measurements, the application of the Stokes-Einstein equation to the diffusion of metals in mercury gives gratifying results. It is noted that a number of these metals have article radii eaual to or less than those of the solvent mercury.".'*,"' Soba1,'" sing the inaccurate Roberts-Austin20 data, indicated that the effective radius of diffusion might well be a function of temperature. Additionally in studies of mass transfer between phases, many conflicting opinions have been expressed concerning the assumption of equilibrium at the interface." ,","," The results of the present work on the diffusion of solid copper in molten lead throws light on the tempera- ture variation of the diffusion radius as well as the extent of the interfacial resistance. The theoretical background and experimental procedure are presented here in detail. Results on other systems will be presented in subsequent papers. Nomenclature The following nomenclature is used in the paper: A—cross-sectional area of diffusion column, sq cm C, C,—concentration of solution and saturated solution respectively, g per cc D,D'—-diffusivity, sq cm per sec e—Naperian base h—ratio, k/D k—mass-transfer coefficient, cm per sec L—diffusion column length, cm n—series index q—flux, g per sq cm-sec r—radius, cm or A R—-gas constant t—time, sec T—temperature, K V—volume, cc w—weight of copper-lead alloy on copper cylinder WT—-total copper transferred to lead diffusion, column, g Z—distance from top of diffusion column, cm 2'—distance from copper-lead interface, cm (2' = L-2) u,,—roots of diffusion equation Mathematical Apparatus The model shown in Fig. 1 applies to the diffusion of solid copper into molten lead. Here Fick's first law may be written where all terms are defined in the nomenclature. It is assumed that the volume of the lead column is constant. This is justified since experimental densities compared favorably with calculated densities based on perfect interstitial mixing. Thus there is no counter diffusion of lead. It is clear that 2 in Equation [I] should be measured relative to the interface which moves relative to the diffusion cell but not to the liquid phase. Hence, the frame of reference is the plane of the copper-lead interface. The diffusivity calculated at constant volume, D", is that defined by Hartly and Crank" and is designated herein as D. No Interfacial Resistance—The two situations of the presence and absence of interfacial resistance will be treated. The simplest is the latter which re-

Jan 1, 1959

By G. Sachs, G. Espey

IT is well known that high residual stresses are created in tubing by the sinking process, in which no internal tool or mandrel is used.1-4 In this process, the wall thickness is usually slightly increased.4,5 In tube drawing with a plug, the residual stresses are gradually reduced with increasing reduction of wall, and, by the conventional approximation methods of stress measurement, no stress is detected in tubing in which the wall reduction is over 50 per cent of the total reduction in cross-sectional area.1-6, It has also been observed that higher stresses are set up by the use of wide-angle dies than by the use of acute dies.2 The actual stress distribution in drawn .tubing has been investigated by a few workers,7-9 but has not been related to the conditions of the drawing process: Some attempts have been made to correlate accelerated cracking tests for stresses in brass products with the magnitude of the circumferential stresses and the condition of the metal.1-10 MATERIALS AND PREPARATION The material used in this experiment was commercial cartridge-brass (70 per cent Cu, 30 per cent Zn) tubing in the straightened and annealed condition.‡ This tubing was of various outside diameters and had a wall thickness of 0.032 in. It was sunk to 1/2-in. outside diameter by means of an experimental 10,000-lb. hydraulic draw-bench, with a maximum drawing speed of 8 ft. per minute. All dies were of 1/2 -in. diameter. Various die materials and contours were used in order to study the effect of die design on residual stresses in the tubing; the specifications for the dies are given in Fig. I. Castor oil was used throughout as lubricant. Chattering occurred in sinking some of the tubing, particularly when dies having the more acute angles were used, but the tubes showing chatter marks did not differ markedly from those with a smooth surface regarding the magnitude of residual stress. The source of the chattering has not yet been revealed. The wall of the tubing becomes thicker during sinking, as previously observed 4,5 The increases in wall thickness were 3, 7 and 9.5 per cent on the average for 6, 20 and 33 per cent reductions in diameter, no effect of the contour being noticeable. The reductions mentioned throughout this investigation do not consider this fact, but are reductions of the outside diameter. For the evaluation of the residual stress two fundamentally different methods were used. The approximation method1,11 of splitting a certain length of tubing was employed to obtain a bird's-eye view of the effect of various drawing conditions on the circumferential stress measured by the diameter change occurring on splitting. For the determination of the complete stress

Jan 1, 1941

By L. R. van Wert

CAREFUL research into the nature of the metallic state has yet to discover, with any certainty, its essential quality. We do riot yet know, for sure, what it is that makes the metallic elements different from, if not actually unique among, all created things. We do know, of course, that metals have certain more or less characteristic properties-they are hard, strong, and tough, and good conductors of heat and electricity, and these so-called metallic properties provide a definition of a sort. How- ever, it is the structure rather than the behavior of the metals which gives the really fundamental information necessary to the understanding of metallicity. But this information is not easily obtained. Nature has a way of keeping secrets. But happily we do possess some knowledge of how a metal is built up, and it is this matter, rather than the presentation of a formal definition, that will be discussed here.

Jan 1, 1937

By O. Schaaber

THE existence of isothermal martensite without the presence of the athermal form thus far has been established only in a 6 pct Mn, 0.6 pct C steel' and a 23 pct Ni, 3.5 pct Mn-Fe alloy.' " Theoretical calculations, moreover, predict this phenomenon to be observable only within narrow composition limits.' In all other steels, it is generally considered that martensite inevitably forms upon cooling below the M, temperature. Even the possibility of isothermal martensite transformation has been questioned for the common steels, although Averbach and Cohen" showed that martensite formation does not stop when the cooling is arrested and that as much as 5 pct retained austenite may transform isothermally to martensite at room temperature. This note presents some observations made on a number of low alloy steels by dilatometric and inductive measurement of isothermal austenite transformation at various temperatures close to the Ms. In the dilatometer studies reported previously, austenitized specimens were immersed in a salt bath maintained at proper temperature and immediately inserted into the dilatometera8' already at thermal equilibrium with the bath. The dilation was read on a dial gage divided into 0.001 mm intervals. Induction measurements were made with a separate excitation source and a test coil, sealed together in a salt-tight case. The increase in the induced voltage caused by the transformation products was recorded at a paper speed of 4 mm per sec. The steels studied are listed in Table I. Specimens prepared from steels 1 and 2 were in the form of hollow cylinders 60 mm long, 10 mm ID, 14 to 16 mm OD, while specimens of steels 3 and 4 were in the form of notched-bar impact test specimens, DVM type. Specimens of steel 5 were in the form of strip, 7x0.3 mm. In the bainitic range, curves representing the amount of transformation vs log time have a single step appearance, as is shown by the curve of isothermal transformation at 320°C in Fig. 1.Y ransformation proceeds in accordance with the Austin-Rickett equationo P -----------= k t" 100-P where P is the percentage of transformed austenite, t is time, and k and n are constants. Near the M, temperature, however, complex curves having two steps are observed. As shown in a previous papera for steel 3 isothermally transformed at 245"C, such complex curves can be separated into two separate transformations or reactions each following the Austin-Rickett equation. The values of n in the equation for a number of such two-step transformations are listed in Table 11 for steel 1. At transformation temperatures of 250" and 235"C, evidence of a second transformation is very

Jan 1, 1956