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By C. R. Simcoe, T. J. Koppenaal

The effect of direct and alternating currents on the quench aging behavior in an Al-4 pct Cu alloy has been investigated by use of resistivity measurements. The reaction rate increases with direct current density in the investigated range of 1000 to 3000 amps per sq cm. Alternating current of a specific frequency is observed to decrease the reaction rate by a factor of about two. ErDMANN-JESNITZER et al.,1,2 investigated the effect of direct and alternating current on the quench and strain aging behavior of low-carbon iron. In both cases they observed that direct current accelerates the aging reaction and that an alternating current can completely inhibit the aging process. The purpose of the present research was to investigate these phenomena in the quench aging behavior of an Al-4 pct Cu alloy and to determine the correlation, if any, between the increase in the observed reaction rate and possible heating effects accompanying the aging with direct current. EXPERIMENTAL PROCEDURE The aluminum-base alloy used in this investigation contained 3.98 wt pct Cu (1.72 at. pct) with impurities of 0.003 pct Si, 0.002 pct Fe, and 0.001 pct Mg. The alloy was rolled into a ribbon about 0.36 mm thick and 3.7 mm wide. The ribbon was split end from end with the ends being used as electrical contacts and the central unsplit section, about 5.3 cm in length, serving as the specimen. Solution treatment was accomplished by quenching from a salt bath at 520° ± 2°C into water at 25° ±0.5°C; the specimen was immediately transferred to a liquid nitrogen bath. All aging was done at 75° ± 0.2°C in a rapidly stirred ethylene glycol bath. Resistivity measurements were made by the double potentio-metric method employing a standard resistor; for purposes of convenience, the resistance measurements were made at 77°K. The transfer of the specimen from the aging bath to a liquid nitrogen dewar was accomplished in less than 1 sec. The aging kinteics were studied with the specimen being aged under the influence of direct current, alternating current, and without any type of current. The amount of heating caused by direct currents was investigated by soldering a thermocouple on the specimen surface and measuring the temperature change after applying various current densities. The temperature was observed to increase (from 75°C, the aging temperature) about 0.8°, 3.0°, and 8.5°C with direct currents of 1000, 2000, and 3000 amp per sq cm, respectively. When employing alternating current, the circuit was monitored with an oscilloscope and adjustments made to produce a normal sine-wave pattern. RESULTS Prior investigations3'4 in the aging characteristics of A1-4 wt pct Cu have shown that the resistivity initially increases, reaches a maximum, and then decreases to values significantly lower than the as-quenched resistivity. This type of behavior is seen in Fig. 1 which shows the resistivity at 77°K as a function of aging time at 75°C observed in this investigation. At this aging temperature, the resistivity maximum is seen to occur in about 1 to 1-1/2 min and it further decreases to the as-quenched value in about 24 min. The behavior observed with the application of direct currents of 1000, 2000, and 3000 amp per sq cm during aging is shown in Fig. 2. With increasing current densities, (+) ?pmax decreases and the rate of the aging process increases. The time necessary to reach the as-quenched resistivity value decreases from 24 min for aging without current to about 16, 10, and 7 min for aging with 1000, 2000, and 3000 amp per sq cm direct current, respectively. Fig. 3 shows the results obtained when two changes were made during the aging with 2000 amp per sq cm

Jan 1, 1963

By H. W. Gudenau, R. S. Chatty, W. Wenzel, M. Ponthenkandath

During several experimental programs conducted at the Institute of Ferrous Metallurgy, Technical University, Aachen, whisker formation was observed when iron ores were reduced at low as well as at high temperatures. Thus, in an attempt to find the reason for the volume change taking place during reduction, iron whisker growth was observed. Whisker growth appears to be one of the important reasons for the swelling of pellets. One set of experimental observations determined that when iron forms as needles rather than as a crust on the surface of oxide, the pellets became very porous. In related experiments, the beneficiation of finely disseminated iron ores, in which the metallic iron is separated from the gangue in granular or nodular form, was achieved by a reduction-concentration method. In this process, which is conducted at sufficiently high temperatures, oxide whisker growth, resulting from the formation of volatile suboxides and a gas transport mechanism, plays a vital role in the joint deposition of SiO, and iron from the vapor stage.

Jan 1, 1973

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By Phillip O. Tyree, Joseph W. Mussey

Bio-epigenetic sulphur deposits occur in Pecos, Reeves and Culberson Counties of far West Texas. Sulfate reducing bacteria, utilizing hydrocarbons as energy, transformed gypsum into replacement limestone and hydrogen sulfide. Hydrogen sulfide, retained in the pores of the replacement limestone, was subsequently oxidized by highly oxygenated groundwaters, and native sulphur precipitated. West Texas sulphur was first recognized at surface exposures by William P. Blake, a geologist attached to the Captain Pope Military/ Scientific Expedition of 1854. Attempts were made in the early 1900's to mine these sulphur vent exposures by a retort method, but the ventures met with little success. In 1967, Duval discovered a large sulphur deposit near some of the old sulphur works in Culberson County. Duval also expanded reserves in a small sulphur deposit in Pecos County. The Frasch process, developed for producing sulphur from Gulf Coast salt domes, proved successful in West Texas type sulphur deposits also. However, modifications of the process were necessary to provide economical and efficient sulphur recovery from the varied ore occurrences. West Texas conditions and logistics require the ultimate in productivity to be competitive in the domestic and foreign sulphur markets. Several companies, in addition to Duval, are producing or have produced sulphur in West Texas. As of June 1, 1984, a total of 29.87 million mt (29.4 million long tons) of sulphur had been produced west of the Pecos River. Duval Corporation has produced more than 88 percent of that total.

Jan 1, 1985

By J. Landau, A. Dim, R. Houlihan

Recent developments in the application of solvent extraction in hydrometallurgical processing make it desirable to reassess the present state of availability of suitable equipment for these applications. The range of solvent extraction applications now includes very large scale applications with a modest demand on separation performance (the treatment of some base metals) and applications in which the decisive factor is a very high requirement on separation performance. The extraction column to be described in the present paper is of the type in which mechanical energy is provided for the two- liquid system inside the column. The active elements for this are reciprocating sieve plates designed and mounted so as to uniformly load the driving mechanism, to eliminate vibration of the plant, to have sufficient control over the degree of dispersion of the dispersed phase, and to reduce axial mixing effects, which are highly detrimental to the separation performance of production-scale plant. The operating features of the reciprocating-plate column will be illustrated mainly by experimental results obtained on a 4" diameter column in the extraction of uranyl nitrate with TBP. Some mechanical features of the operation of reciprocating-plate columns will also be discussed.

Jan 1, 1973

By C. H. Samans, G. F. Tisinai

HARDENING and embrittlement of the ferritic chromium stainless steels at temperatures near 885 °F have been known for a long time.' However, no satisfactory explanation has been given. Both ordering and precipitation hardening have been suggested. Fisher, Dulis, and Carroll2 discovered a chromium-rich body-centered-cubic precipitate in embrittled alloys. Subsequently, Williams' and Wright4 also have found evidence of this body-centered-cubic constituent. William's hardness, electrical resistance, and magnetic studies led to his proposal of a new constitutional diagram for the Fe-Cr alloys. The new feature of this diagram is the eutec-toidal decomposition, below about 970°F, of the s phase into two stable body-centered-cubic solid solutions, one rich in iron and the other rich in chromium. An observation of Heger5 that the amount of s phase has increased and the amount of chromium-rich body-centered-cubic phase decreased in the interval 5000 to 32,600 hr at 900°F, even though the alloy increased in hardness, casts some doubt on this diagram. If precipitation hardening causes the embrittlement, the precipitate probably is always coherent with the matrix, since no evidence of overaging has been reported. It cannot be stated positively, however, that Fisher's body-centered-cubic constituent is the embrittling phase. According to Preston's data,6 such a chromium-rich phase should have a parameter less than about 0.5 pct larger than that of the iron-rich matrix lattice. Moreover, the constitutional relationships whereby Fisher's constituent forms, and whether it is stable, metastable, or a transition phase, are not yet completely clear. The recent studies of Wright4 and of Lommel,7 as well as the earlier studies of Becket8 and of Hochmann,9 have shown that 885°F hardening occurs in relatively pure Fe-Cr alloys. No evidence of its occurrence or absence in chromium itself has been reported. The rate of hardening in high purity alloys seems appreciably slower than that in alloys containing larger amounts of impurities (chiefly carbon and nitrogen). This may be due merely to the absence of hardening and straining effects from precipitated carbides and/or nitrides. These observations on high purity alloys make it seem unlikely that 885 °F hardening is caused by a constituent containing other than iron and chromium atoms, e.g., carbides and/or nitrides. Wright,4 Lommel,7 and Lena and Hawkes10 emonstrated the accelerating effects of a finely dispersed precipitate of (probably) chromium nitride on the hardening reaction. This appears to be evidence that lattice straining increases the rate of nucleation of the hardening constituent. Some new observations on 885°F hardening are reported here. They show an effect of preheat treatment that should contribute to a better understanding of the 885°F hardening phenomenon. They also clarify a discrepancy which exists in the literature. Some investigators have reported most rapid hardening at 885", whereas others have reported it at 930°F. The present work also shows that 885°F hardening does not occur in electrolytic chromium, and that any long range ordering type of reaction affecting any sizeable part of the volume is unlikely. Materials Studied Table I shows the currlposition of the alloys used in this investigation. In these alloys carbon and nitrogen are present in roughly similar amounts. Presumably both elements precipitate, as carbides and/or nitrides, during the heat treatments given.

Jan 1, 1958

By M. C. Flemings, A. A. Tzavaras

Analytical and experimental procedures are descrihed for quantitative determination of volume-fraction microporosity in metals by mimorarlio-graphg. The analysis assumes spherical pores but allows for the observed fact that pores or portions of pores smaller than a given thickness do not project an image on the film. Volume-fraction microporosity was measuured in cast low-alloy steel and shown to vary from 0.6 x 10-4 to 10 x 10 depending on mode of solidification and on whether the material was air- or vacuum-cast. The aim of work described herein was to develop a method of quantitative measurement of the volume fraction of microporosity in cast metals. Microporosity, present in nearly all castings and ingots, is always interdendritic in nature and may be large enough to be seen on a polished surface with the naked eye. More generally, it is smaller in size, and its detection more difficult. Three techniques might be considered for measurement of microporosity: 1) lineal analysis of a polished metallographic surface, 2) density measurement, or 3) quantitative microradiography. As will be shown later, volume fractions of porosity in directionally solidified castings may be the order of 10-4 to 10-3; such small amounts of porosity are difficult to identify and measure on a polished surface. Density measurement is also not a suitable technique (for alloys) when the volume fraction of porosity is low. This is because the density of the base metal is often not known within the necessary accuracy, due to microsegregation or partial phase transformations. In general, it is not possible to completely eliminate microsegregation without also altering the porosity. Because of the limitations of the foregoing techniques, quantitative microradiography was employed to determine amount of porosity. In recent work, microradiography has been found to be useful for qualitative measurement of porosity, including determination of size and shape of individual pores;&apos;)&apos; however, quantitative determination of amount of porosity has not been attempted. I) CALCULATION OF VOLUME-FRACTION POROSITY The following analysis employs procedures similar to those of Cahn and Nutting3 and Hilliard.4 Major simplifications are that pores are assumed to be spherical and to be present in sufficiently small quantities that no overlapping occurs. A basic difference from the previous treatments is that the limited "sensitivity" of microradiography is considered. Assume first 1) cavities are spherical and of uniform diameter, 2) cavities are randomly distributed, 3) volume-fraction porosity and specimen thickness to pore radius ratio are sufficiently small that overlapping of the projected images of cavities is negligible, 4) sensitivity is limited (i.e., holes or portions of holes of less than a given thickness do not project an image on the film). The sensitivity, is defined as: where 5 = minimum thickness of void from which an image will be projected on the film and t = specimen thickness. Now, from Fig. 1, it is possible to distinguish between two different types of holes. These are 1) holes whose centers lie within the region t/2 > X > 6/2, where X is distance from one surface of the specimen (positive into the specimen), and 2) holes whose centers lie within the region (6 — r) < X < 6/2, Holes whose centers lie outside X = (6 -r) project no image on the film. These two types of pores are considered separately below. Type 1 Pores. When 6 is greater than 0, the image of a spherical cavity of radius r appears on the film as a circle of radius a which is smaller than r. From geometry, Fig. 1: a2=r2-52/4 [2] where a = radius of image of pore on film and r = radius of pore. Since the pores are randomly distributed and spherical V =4/3pr2Nv [3] where V = volume fraction of voids and Nv = number of pores per unit volume and the number of images of Type 1 pores per unit area of film, N&apos;A, is

Jan 1, 1965

By B. Ehgartner, M. Karmis, C. Haycocks

INTRODUCTION Interaction effects between mining operations developed on different levels of contiguously placed bedded deposits are a major problem in many parts of the United States. Efficient design criteria, derived from careful analysis of field studies as well as theoretical and model analysis, have shown that many problems that may result from seam interaction can be avoided, minimized, or on occasion used with beneficial results. Selection of seam mining sequence is rarely based only on ground control considerations, but rather on factors such as seam ownership, characteristics and accessibility. Therefore all possible mining sequences and methods must be considered in the development of multi-seam design criteria. Increased utilization of the longwall method of mining creates special problems in multi-seam mining due to the inevitability of caving and, therefore, subsidence. Considerable valuable experience has been gained in this direction from British mining operations where interaction problems are extremely common and the longwall method is the primary method used. However, limitations persist in the application of much of this information to U.S. conditions due to variation in layouts between advancing and retreating longwall systems and the inherent difference in the geologic environment. Considerable field data is available for U.S. room and pillar operations, and where successful pillaring operations have been carried out close parallels may be drawn with ground control mechanisms in longwall operations. VARIABLES AFFECTING INTERACTION Analysis of ground control multi-seam problems shows that factors contributing to interaction may be classified into variables that are fixed by the geo- logic environment and those that depend on engineering design. These may be described as follows (Haycocks et al, 1982): Fixed: (i) Depth*, (ii) Innerburden thickness*, (iii) Innerburden physical characteristics*, (iv) Stress field, (v) Seam thickness, (vi) Coal characteristics, (vii) Completed mining operations either above or below the seam to ve mined, and (viii) Age of workings. Mining: (i) Height, (ii) Dimensions and geometry*, (iii) Method*, and (iv) Spatial location of entries* *These variables are regarded as being critical effects. Few attempts have been made to quantify the variables controlling interaction. Dunham&apos;s (1978) linear regression analysis, combined with the National Coal Board&apos;s MRDE Roadway Monogram, is probably the most noteworthy. This study involved eighteen multi- seam longwall mines in the United Kingdom. The following variables were taken into account: seam depth, pillar width, opening shape, floor and roof conditions, rate of face advance, vertical seam interval, and age and geometry of overlying workings. A multi-linear regression analysis of these variables fitted by appropriate field values developed a prediction equation for lower seam stability. Although the study included many variables, it neglected the nature or geology of the innerburden. The prediction equation was found unreliable, but it did show the significance of geometry as a factor controlling lower seam stability. MINING SEQUENCES Irrespective of the type of mining method selected only four possible mining sequences are possible for two seams. Finlay and Winstanley wrote in 1934. .. "Experience has shown that whether the upper or lower seam was worked first, the subsequent working of the other seam in the same area seriously affected the roads in the seam first worked." Those effects depended upon the four basic mining sequences: 1) The upper seam is mined out prior to mining the underlying seam; i.e., the seams are mined sequentially downward and mining of the underlying seam is not commenced until operations above are completed and have ceased.

Jan 1, 1982

By William M. Boorstein, Robert D. Pehlke

The rates of solution (of hydrogen in liquid pure iron and in several liquid binary iron alloys were meas-ured using a constant volume technique. The rates of absorption and desorption were found to be equal un-der all experimental conditions. increasing concen-trations of S, Si, or Te decrease the rate of hydrogen uptake but additions of Al, B, Cr, Cu, or Ni have no measurable effect up to concentrations normally en-countered in steelmaking practice. No relation ship was found between the effect of an alloying element on the equilibrium solubility of hydrogen in liquid iron and its effect on the solution rate constant. Mathe-rnatical analysis of the data indicates that under the present experimental conditions the rate of reaction of hydrogen with liquid iron is controlled by transport of gas solute atoms in the metal phase. Comparison of the present resuts with data on nitrogen taken un der similar conditions establishes that the hydrody-nurnic conditions which exist near the surface of a metal bath are best approximated mathematically by a surface renewal model for the case of rapid in-ductive stirring and by a boundary layer model for more quiescent melts. HYDROGEN has long been recognized as being a detrimental constituent in steel. If dissolved in the molten metal in excess of its solid solubility, hydro-gen can be evolved during solidification and cause bleeding or porosity in ingots and castings. In the solid metal, lesser amounts play a definite role in causing other defects such as hairline cracks, blisters, and embrittlement. For significant refinements to be made in metallurgical procedures designed to control or eliminate hydrogen from liquid iron or steel dur-ing processing, available equilibrium solubility data must be supplemented with reliable fundamental in-formation pertaining to the kinetic factors involved in the transfer of hydrogen to or from the metal. The scarcity of such information in the literature prompted the present investigation. PREVIOUS RESEARCH Whereas much of the existing data on the solution kinetics of gases such as nitrogen were obtained during the course of thermodynamic investigations, the solu-tion rate of hydrogen has been found too rapid to be accurately determined by conventional solubility meas-urement techniques. Consequently, little work on hy-drogen solution kinetics has been reported in the lit-erature. Carney, Chipman, and crant1 attempted to study the rate of solution and evolution of hydrogen from liquid iron by employing a newly devised sampling method. Although no significant quantitative data could be obtained, it was observed that the rate of solution was approximately equal to the rate of evolution of hy-drogen from the melt. Karnaukov and Morozov2 stud-ied the rate of absorption and Knuppel and Oeters3 the rate of desorption of hydrogen from molten iron by measuring pressure changes with time in a constant volume system. Karnaukov and Morozov determined the hydrogen pressures over their inductively stirred melts with the aid of a McLeod gage and therefore, were forced to work at pressures not in excess of 40 mm of Hg. Their experimental data conformed to a mathematical correlation based on diffusion control: and the rate coefficients calculated on this basis were shown to be independent of the initial absorption pres-sure. These authors reported the solution rate of hy-drogen to be eight-to-ten times higher than they had found for nitrogen in a previous study. They also re-ported that under identical conditions, hydrogen dis-solves somewhat more slowly in iron-columbium alloys than in pure iron. Knuppel and Oeters found that the desorption of hydrogen from pure iron at 1600°C was controlled in all cases investigated by diffusion in the metal bath as long as bubble formation was sup-pressed. This was substantiated by Levin, Kurochkin, and umrikhin4 who studied the kinetics of hydrogen evolution from liquid (technical) iron while applying a vacuum. Salter5 measured the rate of hydrogen ab-sorbed by iron buttons, arc-melted by direct current, as a function of hydrogen partial pressure in a hy-drogen-argon atmosphere. A carrier gas technique was used for analysis of the hydrogen absorbed. The initial rate of absorption was found to increase di-rectly with the square root of the partial pressure of hydrogen. EXPERIMENTAL METHOD Because of the rapid uptake and evolution of hydro-gen by iron-base melts, a constant volume technique was devised in order to obtain meaningful kinetic data over the entire course of the solution process. Apparatus. A schematic view of the experimental apparatus is given in Fig. 1. The hydrogen-liquid iron reaction system consisted of a gas storage bulb con-nected to a meltcontaining reaction chamber through a normally-closed solenoid valve. The gas storage bulb, an inverted 250 ml round-bottomed Pyrex flask was joined to the inlet port of the solenoid valve by a glass-to-metal seal. A more detailed illustration of the reaction chamber is shown in Fig. 2. The design of the Vycor reaction bulb was essentially that de-scribed by Weinstein and Elliott6 with the exception of a shorter, larger diameter gas inlet for this kinetic study. In position, the reaction bulb was closely by an eight-turn coil of water-cooled copper tubing which, when energized by a 400-kc oscillator, provided the inductive heating source. The walls of the bulb were maintained relatively cool by circulating cold water along their outer surface, thus preventing

Jan 1, 1970

By Harry A. Wahl

Precent fracture design procedures are bared on the total fracture area created. A method to distinguish beI,,.ecn total area and [he propped or effective fracture area has not been available. This paper presents a solution to this problem, applicable to horizontal fractures. The difierences between effective fracture area and torn] area are demonstrared in example calculations. This work is hayed on experimentally determined transport efficiencier of solids in sand-liquid slurries. Newtonian and non-Ne~vtoninn systems are considered. INTRODUCTION Fifteen years after commercial introduction, hydraulic fracturing remains the most successful stimulation technique in the oil field. This success is primarily due to ability of induced fractures to penetrate and alter permeabilities deep within formations. Many fields producing today could not have been developed without the hydraulic fracturing process. Because of wide usage, fracture-treatment design has received a great deal of engineering and research effort. This work, resulting in improved equipment and materials, has increased the benefits from fracture treatments as well as the applicability of the process. A major contribution was the development of fluid-loss additives. Necessarily, the number of parameters to be considered in treatment design has steadily increased, resulting in more complicated design techniques. Almost all present design procedures are based on the precepts set forth by Howard and Fast. Relating the fluid volume lost into the formation, the volume required in extending the fracture, and the total slurry volume injected, they developed an expression for the total fracture area created in terms of pertinent treatment parameters. Fluid loss during treatment was expressed as a function of time for three flow mechanisms. Although modifications of fluid loss equations have been made, the total fracture area concept has remained unaltered. A vast amount of field data indicate that induced fractures must be propped and held open to be effective. A notable exception is the Mesa Verde formation in the San Juan basin. However, analysis of these treatments shows that improved well productivities are obtained when propping agents are incorporated in the treating fluid. Although propped fracture area has been recognized as an important design parameter, a method to distinguish between total area and effective fracture area has not been available. The necessary information on slurry-sand transport in fractures has been lacking. Interest in the propped region of induced fractures is not restricted to areal extent alone. The distribution of sand within fractures is important from the standpoint of fracture flow capacities. Flow capacity affects the increase in well productivity after stimulation. The work of Huitt and Darin4 hows that partial monolayers of sand have large flow capacities compared to thick* dense sand packs. It has been postulated that gelled fluids have the ability to transport sand within the fractures at the deired low concentrations. An early contribution in the area of sand placement in fractures was made by Kern et al.&apos; They studied sand movement in a transparent vertical fracture model. It was observed that the sand tended to settle out in the bottom of the model before moving very far. When the fluid velocity exceeded a certain critical value, all of the sand injected began moving through the crack even though it settled to the bottom. This critical velocity was determined under several flow conditions. Some work on sand movement in horizontal fractures has been reported in Russian publications. Sand movement was studied by Izyumova and Shan&apos;gin&apos; using a transparent "pie-shaped" flow model to simulate a horizontal radial flow system. However, the data were limited, especially in a quantitative sense. Dorozhkin, Zheltov and Zheltow studied the behavior of sand-liquid slurries in a horizontal linear flow model. The quantitative data were restricted primarily to the thickness of sand deposits formed at the bottom of the fracture. An earlier paper provided basic data on the flow of sand in horizontal fractures. This study was designed to yield specific quantitative information on rate of advance of sand particles and pressure behavior under various flow conditions. A comprehensive photographic study was undertaken in a 10-ft windowed flow cell to provide the necessary qualitative and quantitative data. Since the number of potential variables far exceeded the capacity of the initial study, emphasis was placed on the effects of sand concentration, oil viscosity and oil flow rate. A detailed description of these experiments and the results are described in Ref. 9. However. the implications of this work on the fracture design calculations were not discussed. An analysis of these data as well as new data is provided in the following sections. EXPERIMENTAL RESULTS The primary objective of the experimental investigation was to provide information on the rate of advance of the solids in sand-liquid sturries. A 10%-ft long transparent

Jan 1, 1966

By G. Willard Quick

FAILURES in railroad rails have been of vital concern to engineers; railroad executives, rail manufacturers and the general public for years. Failures from transverse fissures originating from internal nuclei have received particular attention in the past 20 years. Dr. J. E. Howard first reported this type of failure in 1911, as being responsible for a wreck-on the Lehigh Valley R. R. in which several lives were lost. Since then many transverse fissures have been found. In 1919, Waring and Hofammann1 etched longitudinal sections of rails in hot acid and found cracks extending both longitudinally and transversely in certain used rails as well as in some new rails.. Since then it has been thought by many that these "shatter" cracks are the nuclei from which transverse fissures subsequently develop in service. Methods for reducing the rate of cooling rails on the hot. bed have been devised to decrease the temperature gradient and consequently the stress gradient in the rails. A study of the tensile properties of rails at elevated temperatures was made by Freeman and Quick,2 who investigated the properties at temperatures through which rails pass on the cooling bed after leaving the hot saw. In their investigation a special study was made of the ductility of the steels in the temperature range 400° to 700° C. In this temperature range it was found that certain rail and other steels showed a marked decrease in elongation and reduction of area. The phenomenon was called "secondary brittleness" and the temperature range the "secondary brittle range." A tentative explanation was presented that internal failure such as "shatter cracks" and "hair cracks" in rails are the result of thermal stresses developed in the steel structure while cooling through the secondary brittle range. The investigation showed that the magnitude of the phenomenon varies for different heats, but that it did not differ for specimens from different ingots or for different rails in a particular ingot. It was also shown that annealing rail steel at a temperature either above or below the critical

Jan 1, 1932

By G. S. Cole, G. F. Bolling

ThE exact type of fluid flow which occurs in a solidifying ingot is important in determining subsequent grain structure. This has been shown in studies of natural Convection" and of forced stirring or other disturbances of the melt."16 We shall explicitly argue that a complement to the existing natural flow in an ingot should be more effective than other types of flow in promoting the columnar-to-equiaxed transition. The ultimate effects of fluid flow upon structure is one of the topics of solidification that we have investigated in the alloy system Pb-Sb, under conditions simulating casting. In Fig. 1, the essential features of a bidirectional growth apparatus are shown; horizontal freezing from water-cooled faces within a low-thermal-conductivity lavite boat is a reasonable simulation of an ingot section. Details such as the furnace and thermocouples are omitted in order to show the location of four permanent. magnets, each with a pole separation of 21 in. providing a central field of about 1000 Gauss. When coupled with a dc current imposed through appropriate connections made at the cooled faces, a flow of fluid is produced as shown schematically. This technique described by Pfann and ~orsi" is ideal for our purpose since the flow indicated is the same as that we observe to occur naturally in this system. Components of 99.999 pct purity were used for study and all due precautions were taken in alloy preparation to avoid contaminants. Sections of the specimens were taken to ensure results representative of the interior as well as the surface of specimens. All proportions of equiaxed and columnar regions were measured by tracing the etched grain structures onto graph paper and simply counting squares. Four alloys were examined at superheats of 40" * 5°C and 100" * 9°C. Preliminary tests had shown that no appreciable enhancement of structure was obtained with magnetic field alone, so that this condition is not reported; it should nevertheless be noted that other configurations of magnetic field will reduce convection and thus enhance columnar growth.&apos;8 For the tests reported the magnetic field was applied to a specimen by bringing the four preassembled magnets to a position 2 mm from an outer tube immediately after the ingot was poured. The dc current of 30 amps passed through the sample throughout the entire solidification cycle, resulting in a power dissipation of 9 w per sq cm of interface. This may be compared to the evolution of latent heat of approximately 18 w per sq cm. Table I contains the results of this experiment in terms of the total area ratio, equiaxed/columnar grains, as a function of the field interactions, solute concentrations, and superheats employed. The total structure of the ingot is seen to be most influenced when both the field and current are applied simultaneously; when current acts separately, little effect may be noted in spite of the heat supplied. In addition, the change in structure from the no field-no current case to the field-current condition is more pronounced at the higher superheat, and the higher the concentration of antimony. An example of the grain refinement, as well as the increased equiaxed zone, is shown in Fig. 2. It is now important to prove that there is indeed an increase in fluid flow due to the presence of the field-current interaction; this is done by temperature measurements in the liquid metal. Let us consider a bidirectional casting in which heat is applied to and removed from the system, in such a way that rate of solidification is zero.* When a sensitive thermocouple

Jan 1, 1967

By Arthur B. Cummins

Diatomite is a siliceous rock of sedimentary origin, which may vary in degree of consolidation, but which consists mainly of the fossilized remains of diatoms. These are microscopic algae of the order Bacillaria. Diatomite is a unique form of silica, there being nothing else found in nature or produced by the manufacturing arts, that has its characteristic physical structure. There are numerous sediments which contain some diatom residues, admixed with a substantial amount of other materials-clay, carbonates or silica. While these are classified as diatomaceous silts, shales, or mudstones, they are not properly diatomite, a designation which is restricted to material of such qualities that it is suitable for commercial uses. The terms diatomaceous earth and kieselgur are synonymous with diatomite. The expressions infusorial earth and tripolite are obsolete. Diatomaceous silica is a definition best used to distinguish the basic component of diatomite, that is, the substance of the silica shell itself and is the major constituent of beneficiated diatomite or processed diatomaceous products. Some highly indurated materials, such as cherty shale, porcelanite, and opaline cherts which have resulted from diagenetic changes cannot be considered as diatomite although they may have been derived therefrom. On the other hand, diatomaceous oozes or loose sediments consisting mainly of diatom residues with or without much organic matter are source materials in process of becoming diatomite. Composition and Properties Pure diatomite is composed of opaline or hydrous silica, with small amounts of associated inorganic components-alumina, iron, alkaline earths, alkali metals, and minor constituents, all of which may occur in solid solution or as an essential part of the opal complex. Crude diatomite on the other hand may contain variable amounts of organic matter and soluble salts, and the usual contaminants of sedimentary formations-particles of rockforming minerals, sand, clay, or carbonates. As occurring in nature, diatomite contains an unusual amount of free water, which may vary from 10 to 60 pct or more. Diatomite, in the dry deposits which are characteristic of most of the important world deposits, occurs as a lightweight, comparatively light colored, "chalklike" material. The apparent density (dry basis) in situ varies from 20 to 40 lb per cu ft. The structure may be either massive or finely stratified. The earth is highly porous, usually soft and easily friable. It is nonreactive with acids and may be tentatively identified by the above characterizations. Confirmation is by microscopic examination which readily reveals the nature of the material. In deposits which contain organic matter the appearance of the material is totally different. The color may vary from light tan or gray to brown, greenish or nearly black. There is frequently difficulty in distinguishing it in the field from peatlike materials, but the difference is readily apparent after calcination. Powdered diatomite or diatomite products have an apparent density (loose weight) of 5 to 16 lb per cu ft, wet densities of 10 to 30 lb per cu ft, specific gravities 1.9 to 2.35, index of refraction 1.42 to 1.48. Diatomite is essentially micro-amorphous, but does show some tendency toward orientation in structure after a cristobalite pattern. Amorphous silica has been considered as a random association of cristobalite crystallites, the size of which are only slightly larger than a unit cell.20 The prop-

Jan 1, 1960

By G. L. Simard, D. J. Salley, J. Chupak

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,&apos;, &apos; were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.&apos; Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By J. Chupak, D. J. Salley, G. L. Simard

DITHIOPHOSPHATES and xanthates are the principal collectors for sulphide minerals, and consequently any knowledge of mineral-collector systems of this type is of value. In the present investigation an attempt was made to obtain information on the interaction of a typical dithiophosphate with galena. In carrying out this study, radioiso-topes, so much discussed in the past few years,&apos;, &apos; were extensively employed. By using radioactive dithiophosphate synthesized from radioactive phosphorus, a rapid and sensitive analytical procedure G. L. SIMARD is in the Research Division, Stamford Research Labs., American Cyanamid Co., Stamford, Conn.; J. CHUPAK, formerly in the Research Division, Stamford Research Labs., is now at Camp Detrick, Frederick, Md.; and D. J. SALLEY is in the Research Division, Stamford Research Labs. AlME New York Meeting, Feb. 1950. TP 2815 B. Discussion (2 copies) may be sent to Transactions AlME before April 30, 1950. Manuscript received Oct. 17, 1949. was at hand. This permitted determination of such important quantities as the rate of uptake of dithiophosphate by the mineral, the amount existing at equilibrium on the mineral surface and in the solution, and the desorption of the agent from the surface. Such measurements were possible even on single crystals of galena. In addition the exchange of dithiophosphate between the solution and the sorbed phase was examined, a matter which could be accomplished only by the use of isotopes. It is desired to point out at this time that throughout this paper the term "sorption" has been employed to designate the uptake of agent by mineral, without implication as to the nature of the process by which the uptake was accomplished. Experimental Materials: Galena: The galena was from the Tri-State district. For studies on ground mineral four preparations were used during the course of the investigation. These were prepared from selected large crystals by wet grinding in order to reduce surface oxidation. Alcohol was chosen as a convenient medium for this purpose. The ground mineral was then fractionated by sedimentation in alcohol, dried by evacuation, and stored in a nitrogen-filled desiccator. Data on the preparations are tabulated in table I. The size analysis indicated that the areas of the preparations were of comparable magnitude, even though the absolute values may be somewhat incorrect. Dithiophosphates: Nonradioactive dithiophbsphate (di-isopropyl or di-secondary butyl) was obtained by purification of a commercial product. An aqueous acid solution of the agent was extracted with petroleum ether, the ether layer dried, and the dithiophosphate precipitated as ammonium salt with anhydrous ammonia. Several repetitions of this process resulted in a nearly colorless, flaky product of good purity. (General formula (RO,)PSSNH,). Radioactive dithiophosphate was synthesized by heating radioactive elementary red phosphorus* • For early experiments (1943 to 1944), the elementary red phosphorus was obtained from the cyclotron group at the Crocker Radiation Laboratory of the University of California. Berkeley, through the courtesy of Dr. Joseph W. Hamilton. For more recent work (1946 to 1949). the elementary radioactive Phosphorus has been supplied by the Oak Ridge National Labarotories on allocation from the U. S. Atomic Energy Commission. with sulphur at 270" to 300°C to produce radioactive P,S,. The latter was then treated with the desired purified alcohol (isopropyl or secondary butyl) at 60" to 80°C to form the dithiophosphoric acid derivative. Purification was effected in the same manner as for the nonradioactive material. The effectiveness of the purification method was established by the isotopic dilution method." The same technique was used to show that only negligible decomposition of neutral or of carbonate solutions of the dithiophosphate took place over a period of a day; this was true whether or not galena was suspended in the solutions. Procedures: Radioactivity: The activity of a solution was obtained by counting with a small glass-jacketed, silvered Geiger counter, using a conventional scaling circuit.&apos; Crystals and other solids were counted under a bell-shaped, mica-window counter tube. Sufficient counts were made so that the probable error of counting was of the order of +I-3 pct. The specific activity in terms of counts per minute

Jan 1, 1951

By Charles Hart

THE art of electric smelting came with the turn of the present century and owes its existence to the introduction of alter-nating current, which found its first wide use in the establishment of the great power plants at Niagara Falls, N, Y. Prior to that time current was largely direct. The fur-naces were electrolytic in nature and found their first metallurgical use in the produc-tion of aluminum, and this process still prevails. The normal production of pig iron up to that time was carried on in blast furnaces in which charcoal, coke and anthracite were used as the fuel. This new electric process called for sufficient carbonaceous material to reduce the oxides and impregnate the pig iron with sufficient carbon, but the remainder of the energy was to be supplied by electric power. The chemical reactions are essentially the same in electric smelting as obtains in the older blast furnace. All of these data are so well known in both methods as to need no discussion at this time, for they can be found in scientific publications and books written during the first two decades of this century.

Jan 1, 1940

By G. F. Comstock

THE subject of transverse fissures in steel rails has been discussed very thoroughly in recent years from various points of view and the final opinions expressed may be roughly classified into two groups: (1) That these fissures are the result merely of fatigue of the steel and are independent of the quality of the metal. (2) That the quality of the metal and the mill practice must have something to do with them. The first point of view was most-ably and logically presented by J. E. Howard,1 and in the discussion of this paper, as well as in several other preceding publications, Dr. P. H. Dudley, Consulting Engineer of the New York Central Lines, has strongly defended the other opinion.2 The steel makers of the country have naturally rallied under Mr. Howard&apos;s banner, hoping to place the entire blame for these. failures upon the railroads with their high wheel-loads, hard steel, heavy traffic, and sometimes inferior roach-bed; while the railroad men,, on the other hand, have been busy accumulating statistics and records in the effort to find an actual reason in the rails themselves that would account for the seemingly haphazard occurrence of transverse fissures under varying conditions and at widely separated points. The view that these fissures were due merely to normal fatigue under alternating stresses seemed most reasonable to the writer until quite recently, because from work clone in this laboratory, as well as the work of other investigators of the problem, no structural differences, in the vast majority of cases, were found between metal at the nuclei of transverse fissures and metal at similar positions in the same rails or in other rails that had not developed fissures. . Within the last year or two, however, since the method of etching polished sections for the microscope with a cupric chloride solution has been tried systematically. on lengthwise sections, passing through the nuclei of transverse fissures, evidence

Jan 11, 1918

By E. Ackerman, L. Y. Tu, S. C. Sun

The use of ultrasonics in forming emulsions is not new. As early as 1927 Wood and Loomis&apos; reported preparation of emulsions with ultrasonics. In 1935 Rschevkin and Ostrawskyz described the use of great ultrasonic power in producing fine emulsions of various oils and paraffin in water. Recently Oyama and Tanakahmployed ultra-emulsification to increase the effectiveness of sodium ethyl xanthate in flotation of chalcopyrite and galena. An emulsion is a two-phase system consisting of two incompletely miscible liquids, the one being dispersed as finite droplets in the other. The dispersed liquid is known as the internal or discontinuous phase, and the surrounding liquid is termed the external or continuous phase. There are two types of emulsions; one is oil-in-water (O/W) and the other water-in-oil (W/O). The word oil refers to the liquid other than water. Circumstances exist in which the emulsion type is not clearly defined, and the internal and external phases both contain portions of the opposite phase. This is said to be a dual emulsion. Among the many hypotheses&apos;, 6v proposed for the formation of emulsions, the Bancroft&apos;s adsorbed film or double interfacial tension theory is widely accepted. Bancroft ""educed that in the process of emulsification the interfacial tension between oil and water is lowered by the formation of an emulsifying film, which contains the adsorbed molecules and/or ions from the emulsifying agent and the two liquids.

Jul 1, 1955

By T&apos Ke, ing-sui

NUMEROUS investigators have observed that internal friction accompanies cold-working of metals and the effect of annealing is to reduce this internal friction.1,2 However, - most of the experiments were made at high stress amplitudes and the principal purpose was to study the increase of internal friction as a result of the applied cyclic stress during measurement. In order to study the internal friction introduced by cold-working applied prior to the measurement, the stress level applied during the measurement of internal friction must be sufficiently small. The results of measurement are significant and can be used for a base of comparison only when the applied cyclic stress is so small that the internal friction is independent of stress amplitude. Internal friction of cold-worked metals under small stress level has been studied by a number of workers8 -" he internal friction was measured around room temperature with a frequency of vibration of the order of kilocycles per second. The purpose of this paper is to report a study of the change of internal friction when severely cold-worked aluminum was annealed at successively higher temperatures until it was completely recrys-tallized. The measurements of internal friction were made over a range of temperature extending from room temperature up to the temperature of prior anneal. The frequency of vibrations used was about one cycle per second. The apparatus used for the internal friction measurements to be reported in this paper was a torsion pendulum with the specimen in wire form as the suspension fiber. The description of this apparatus and the method of measurement have been previously given.7,8 The applied stress was sufficiently small SO that the magnitude of internal friction is independent of stress level at each temperature range concerned. Corresponding to this stress the maximum shearing strain on the surface of the specimen is of the order of l0-5 and lower. The in- ternal friction (Q-1) is reported as 1/p times the logarithmic decrement. Internal Friction Versus Temperature of Anneal: Fig. 1 shows the internal friction measurements performed upon 99.991 pct aluminum subjected to 95 pct reduction in area. The final diameter of the wire is 0.033 in. This figure gives a general survey of the effect of temperature of anneal and of temperature of measurement. The internal friction of the cold-worked specimen was first measured at room temperature. It was then annealed at 50°C for one hour and the internal friction measured at 50°C and at room temperature. The same wire was successively annealed at higher temperatures for one hour and measurements were taken at the annealing temperatures and lower temperatures as before. Such a procedure was followed in order to stabilize the internal friction at the temperature of measurement so that during the measurement which generally takes about half a minute, there is no detectable change in internal friction. This series of measurements .was made up to 450°C. After each annealing a short test piece of the specimen, which had received the same past thermal and mechanical treatments, was taken out for metallographic examination. It is seen from fig. 1 that up to the annealing temperature of 250°C we have the following observations: for any given temperature of measurement, the internal friction is lower the higher the temperature of prior anneal. When the annealing temperature is 290°C or higher, the internal friction at the annealing temperature drops abruptly to a value which is much smaller than that for the previous curve. Metallographic examinations showed that the recrystallization of the specimen was completed after the annealing at 290°C. Fig. 1 shows that, as far as internal friction is concerned, there is no abrupt transition between the processes of recovery and recrystallization. Averbach has also reached the conclusion that recovery may be a process analogous to recrystallization on the basis of X ray extinction measurements in brass." The effect of annealing temperature upon the internal friction at room temperature is shown by curve I of fig. 2. In this figure the internal friction at room temperature was plotted as a function of annealing temperature. It is seen that the internal friction decreases rapidly at first with an increase

Jan 1, 1951

By Lewis Delano

IT HAS been generally recognized that, owing to the extreme friability of, galena, fine grinding has a tendency to cause excessive sliming of the mineral, so operators of lead mills have attempted to avoid this condition by commencing concentration at as coarse sizes as any mineral is freed. Jigging has been the basis of the milling process, making a clean coarse concentrate and a large amount of tailing, which was considered sufficiently low-grade to be rejected. However, developments and improvements in concentration processes are everywhere changing the low-grade tailing of yesterday into material worth retreating today. Investigations of the work of the Hancock jig on the Bonne Terre ore- have shown that the best results to be expected will give a tailing assaying 0.75 per cent. lead; the average over all conditions and grades of ore will be between .0.80 and 0.90 per cent. By crushing the jig tailings in ball-mills and retreating by tables and flotation, a tailing of considerably lower grade can be made; the problem then becomes an economic one of increased crushing costs versus higher recovery. In considering the entire elimination of jigging, the increased smelting charges; due to a greater amount of slime galena will be counterbalanced by the lower operating cost, in-creased recovery, and the many advantages of a simpler flow sheet. In developing these problems in the Bonne Terre mill of the&apos; St. Joseph Lead Co., a long series of tests has been carried out covering every stage of crushing and concentration, and a large number of possible flow sheets were considered and tried. Only the final results and a few comparisons will be given here. At the same time, a careful and detailed cost-keeping system has enabled us to compare milling costs with the various flow sheets, and to calculate the economics of the problem&apos; with great accuracy. .

Jan 8, 1920