Search Documents

By Russell W. Dayton

The metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger,"' i in 1909, was the first to apply polarized light to the microscopic study of opaque substances; Endell and Hanemann(2) were the next, in 1913. In 1919 and 1920, Wright(3,4) prepared two papers on the subject. In the first he developed the detailed mathematical theory from the viewpoint of the electromagnetic theory of light, and in the second described the various methods in use, giving improvements of his own. Schwarz(5)

Jan 1, 1935

By Russell W. Dayton

The metallurgical polarization microscope has been utilized in several researches in the last few years, thus attaining a fair degree of prominence, but little has been written in a manner suitable to a metallurgist concerning the theory of this instrument. In this investigation the theory was carefully studied, and the results are presented here in a detailed manner, yet as simply as possible. The theory is discussed with particular reference to the three chief functions of the instrument: (1) determination of anisotropy; (2) effect of strain; and (3) identification of inclusions. Each of these is investigated experimentally, with especial attention to the mechanism of producing any effect. Where possible, the discussion is supplemented by photomicrographs. The instrument used had numerous defects as a polarization microscope; these and their remedies are discussed. In the microscopic study of transparent mineral sections (chalcography) the use of polarized light has aided tremendously in the identification of a mineral. The determination of strain in transparent substances (photoelasticity) by the use of polarized light has lately become a commercial process, used in testing finished glass articles. The success of the use of polarized light with opaque materials has not been so great. The magnitude of the effects obtained is much less than that of the corresponding effects with transparent materials, and the mechanical difficulties are much greater. Königsberger,"' i in 1909, was the first to apply polarized light to the microscopic study of opaque substances; Endell and Hanemann(2) were the next, in 1913. In 1919 and 1920, Wright(3,4) prepared two papers on the subject. In the first he developed the detailed mathematical theory from the viewpoint of the electromagnetic theory of light, and in the second described the various methods in use, giving improvements of his own. Schwarz(5)

Jan 1, 1935

By A. G. Spillette, R. L. Nielsen

The purpose of this paper is to further the understanding of reservoir response to hot-water injection by desuribing a two-dimensional, mathematical model of the process. Key assumptions are that no gas phase is present, and that the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. The resulting system of three partial differential equations is solved simultaneously through the use of a "leap-frog" application of standard alternating direction implicit methods for the solution of the mass-balance equations and the method of characteristics for solution of the energy-balance equation. The utility of the mathematical model is demonstrated by comparing numerical and analytic temperature distributions for hot-water bank injection and by comparing calculated with observed field behavior. Additional calculations show that hot waterfioding can recover significantly more oil than cold waterflooding, and that a hot-water bank recovers, with less energy input, nearly as much oil us continuous injection. Introduction Consistent field success with hot fluid injection processes requires good reservoir description and a thorough understanding of recovery mechanisms. The latter is fostered by a combination of well designed experimental studies and physically sound mathematical modeling. The purpose of this paper is to further the understanding of reservoir response to hot-water injection by describing a two-dimensional mathematical technique, indicating its validity, and demonstrating its utility for studying the effects of reservoir and operating parameters. Published experimental studies of hot fluid injection processes are few." Even if extensive data were available, two considerations discourage exclusive reliance on laboratory or field work. First, because of the severity of scaling requirements," laboratory results must be interpreted with care. Second, because of the one-shot nature of field experiments — injectivity/productivity tests and pilot floods—results seldom are available over the desired range of operating conditions. These factors emphasize the need for devoting attention to mathematical modeling to complement laboratory and field work. Through the use of mathematical models, scaling uncertainties can be bridged and response can be predicted for unique combinations of reservoir and operating conditions. Numerous mathematical models developed during recent years enable us to calculate temperature distributions, thermal efficiency (or conversely, fraction of heat lost), and oil recovery behavior for hot fluid injection. Ramey" and Spillette' recently have provided reviews of these methods. Most models have concentrated on predicting temperature distributions and thermal efficiency; few have been directed at predicting oil recovery.'."1° Although these techniques are useful for estimating effects of reservoir parameters and operating conditions on process performance, results are limited by the assumptions made and by the methods of coupling independently solved fluid-flow and energy-balance equations. A computer-based method is presented for predicting total reservoir response to hot-water injection that obviates most simplifying assumptions. The model simulates fluid flow and heat transfer in two dimensions within a vertical cross-section spanning the oil sand and adjacent unproductive strata. Known numerical procedures are used to solve the governing partial differential equations. The mathematical model handles the effects of reservoir heterogeneity, gravity, capillarity, relative permeability and temperature-dependent fluid properties. In addition, a wide range of operating conditions can be modeled, including hot-water followed by cold-water injection. Mathematical Description of Hot-Water Injection Key assumptions in the mathematical model for hot-water injection are that (1) no gas phase is present and (2) the injected fluid reaches thermal equilibrium instantaneously with the reservoir fluids and sand. Relative permeability and capillary pressure are assumed independent of temperature. Darcy's law for multiphase fluid flow relates the velocities of the oil and water phases to the phase pressure gradients by the following relations:

Jan 1, 1969

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.' Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.'s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.' It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

By Chester Fulton

IN Polk County, Florida, the mining of raw phosphates began some 50 years ago with dredging operations on the Peace River, and in other near-by places by removal of shallow overburden with negroes and wheelbarrows, or with mules and scrapers, and the excavation and screen-ing of deposits found close to the surface. There were many individual operations of comparatively short life. Later steam shovels removed the overburden, and still later hydraulic methods were substituted for the steam shovel. Within the last 10 years large electrically operated drag-lines have almost entirely replaced hydraulic mining for overburden removal. The matrix is still mined by hydraulic giants and pumped to the washer or recovery plant. The many small operations have long since disappeared and the most desirable phosphate lands have gradually been acquired through purchase or merger by the seven companies that are operating in the field today. These companies are producing and selling about 2,000,000 long tons of phosphate per annum, or about two-thirds of what the industry likes to think is the normal output, with 1929 and 1930 in mind. To produce these 2,000,000 long tons of raw phosphate, they mine and treat about 1,000,000 tons of tailings from older and less efficient opera-tions, about 11,000,000 tons of matrix, and remove from above this matrix some 22,000,000 tons of overburden. The mining practice that has made possible the excavation and handling of 34 million tons of material to win but 2 million tons of merchantable product, selling for probably an average of only $4 per long ton when dried, should be of interest to the mining profession, though little has been written of it. The Florida Pebble Field, as it has come to be known, comprises an area (Fig. 1) within a radius of about 18 to 20 miles centering around Mulberry in Polk County, a small town 30 miles east of Tampa, Florida's largest port on the gulf coast.

Jan 1, 1936

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 S. Acar, P. Somasundaran

The results obtained for the selective flocculation of natural ores do not usually agree with the corresponding properties of the constituent minerals when present alone. This is mainly due to the presence of dissolved mineral species which can interact in many ways with other components in the system and alter their behavior. In this paper, the effect of dissolved species on the flocculation and electrokinetic properties of sulfide minerals is discussed. Dissolved iron, copper, and nickel (Fe, Cu, and Ni) species are found to affect the properties of natural chalcopyrite and pentlandite in certain pH range. These effects are interpreted in terms of species adsorption leading to activation or depression of reagents, surface precipitation, and complexation of species

Jan 1, 1986

By Chester S. Conrad

SEVERAL years ago Pittsburgh Consolidation Coal Co. intensified efforts to combat the hazard of mine fires. The program consisted of three parts in the order of likely accomplishment: 1) Purchase and installation of newer and more practical fire fighting equipment. 2) Establishment of trained fire fighting teams at every mine plant. 3) A drive to remove the causes of mine fires. Experimentation with alternating current on section equipment is a major development in this part of the program. Use of alternating current to power mining equipment had been recognized as being most practical from the standpoint of safety. A means to re- place the d-c traction motor is all that has delayed complete section mechanization with a-c power.

Jan 1, 1958

Unlike the bituminous part of the coal industry, the production of anthracite has been fairly well publicized; in fact until about 1845 whenever the coal industry of Pennsylvania was mentioned in papers, magazines or books, anthracite only was meant. Beginning with shipments by river in 1820 fairly complete records of shipments were published each year, and as this variety of coal was the only one used for domestic purposes east of the mountains and north of the Potomac, there was considerable interest in the producing fields on the part of the public. Transportation of anthracite was the cause of the building of the early canals in the state, and later, of some of the earliest railroads. In most publications it has been assumed that commencement of shipments in 1820 was the beginning of the industry; this is far from being so, and it is with the earlier developments this chapter will deal, leaving the later and better known records to existing publications. (See Table No. 53.) The first reference to coal in Pennsylvania by Gabriel Thomas in 1698 has already been mentioned,1 it could only have been anthracite in that section; although of course, he never saw any coal there. Little coal was used excepting by smiths for many years after that. In 1728 the Coventry Forge paid the expenses of a man "to town for Sea Coall and Steell for ye hammer;”2 in 1729 New Castle coal was sold in Philadelphia;3 in 1740 an advertisement mentioned, "very good Pitt and Sea Coal at 18 pence a bushel; at which price 'tis allowed to be cheaper Fewel for Hearth Fireing than Wood at the present Rates,"4 a view not shared by most of the people there for about eighty years; in 1752 Newcastle coal was again mentioned.5 There are no references to coal in the writings of any of the Moravian missionaries, although some who settled near Mauch Chunk in 1746 said that the Indians there made their pipe heads of a soft black stone, which was much more apt to have been slate than anthracite." Several stream

Jan 1, 1942

By William E. Ford, Edward Salisbury Dana

Normal phosphoric acid is H3P04, and consequently normal phosphates have the formulas R3PO4, R3(P04)2 and RPO4, and similarly for the arsenates, etc. Only a comparatively small number of species conform to this simple formula. Most species contain more than one metallic element, and in the prominent Apatite Group the radical (CaF), (CaCI) or (PbCI) enters; in in the Wagnerite Group we have similarly (RF) or (ROH).

Jan 1, 1922

By T. L. Joseph

A study is made of the amount of solution loss necessary to maintain the reducing power of the gas stream in the blast furnace. Curves are presented to show the effect of solution loss, moisture in the blast, and carbon dioxide from the flux on the nitrogen in the THE blast furnace process is based upon the counter flow of gases and solids. As CO, N, and H, flow upward from the combustion zones, oxygen is acquired from the descending charge. In the reduction of iron ore, a portion of CO is converted to CO, and similarly a portion of H, is converted to water vapor. The inert N,, from the air used in combustion, passes through the furnace with little change. Its concentration is, however, decreased by reactions such as direct reduction and solution loss which increase the volume of CO in the gas stream; Similarly the evolution of C02 from the limestone also dilutes the nitrogen. he purpose of this paper is to illustrate an idealized and simplified method of studying furnace processes by following changes in the gas phase between the tuyeres and the stock line. A more specific objective is to evaluate the effect of solution loss upon the CO/CO, ratio in that region of the furnace in which FeO is reduced to metallic iron. This last stage of reduction requires relatively high CO/CO, ratios to exceed the equilibrium requirements. Solution loss or the reaction of COZ with C to produce CO has a pronounced effect upon the ratio of the carbon gases and is necessary to maintain the reducing power of the gas stream if the consumption of coke is low. It will be explained later that indirect reduction followed by solution loss is stoichiometri-cally equivalent to direct reduction. Calculations will be made to show how the composition of the gas in the region of the mantle varies with coke consumption and with different amounts of solution loss. Such calculations show the condi- tions under which gasification of C with oxygen in the charge is needed to maintain the reducing power of the gas. Equilibrium conditions for FeO and the carbon gases will be used to establish a minimum CO/CO, ratio below which reduction will not proceed. The manner in which carbon is gasified in the furnace, at the tuyeres with oxygen in the air or above the tuyeres with oxygen from the charge, will be a basic feature of all calculations. It is hoped that greater interest in the use of top gas as a means of following furnace reactions will be aroused by the calculations and generalized curves which are presented. Bosh Gas Equations Subject to some alteration by the amount of moisture in the blast and by direct reduction, the gas leaving the combustion zones of a blast furnace has a definite composition. Because a relatively small amount of oxygen is acquired from the charge in the bosh and in the crucible, the products of combustion undergo little change until they enter the shaft. Bosh gas is, therefore, essentially the products of combustion of carbon in a deep fuel bed with air. The relative weights and volumes of reacting materials are expressed by the equation: 2~ + 0? + 3.76N, = 2C0 $ 3.76NZ [I] Air Bosh Gas -air = 79% N? = 3.76) 21% 02 Starting with a known mass of C consumed largely by air, Eq 1, but partly by water vapor, Eq 2, the volume and C + H2O = CO $ H? [21 composition of the bosh gas can be calculated and subsequent changes followed as reactions take place at various elevations in the furnace. As shown in

Jan 1, 1952

By Richard S. McCaffery, Morrison B. Yung

While assaying some copper carbonate ore from the Frazer claims, Similakameen, B. C., I noticed that on parting the gold button a deep orange solution was formed. The button gave off pink bands in the nitric acid, which became deep orange at a short distance from it; and as it traveled over the surface of the porcelain dish, it left a deep orange track behind. As the button brightened in the cupel, it appeared to have a bronze color; but I have since found that when amarillium is in large excess of the gold, the button is a very dark gray. The button parted easily. To the orange solution I added a salt (NaCl) solution, shook in a silver testbottle, and filtered. With H2S I obtained a precipitate, which I supposed due to platinum. However, on further tests, it did

Jan 1, 1903

By Henry E. Colton

NeaR the town of Christiansburg, Va., occurs a singular feature in topographical as well as geological structure, which may be said to have an important bearing on a large area to the southwest. The great water-shed ridge, which divides the waters flowing into the St. Lawrence from those flowing into the Atlantic ocean, coming southwestward, forms all of what was the boundary of Maine as agreed upon by the treaty of 1783, and a part of the present boundary, all of the northern New Hampshire boundary, and entering Vermont, continues south of Lake George. Passing irregularly through New York, it enters Pennsylvania, and there bifurcating, sends one prong to the west as a divide between the waters of the lakes and the Ohio, while the other becomes the steady, regular ridge which gave it the name of Alleghany, and thus passes on southwestward through Virginia. At no point has it ever been the geological divide. Its course, commencing in the Archean rocks, has passed through nearly every series of formation, and comes into Virginia in the Carboniferous strata. The geological divide—the line between the fossiliferous and the non-fossiliferous rocks—lies, in Canada, to the west of it, but from New York south into Virginia is far to the east. Reference to Dr. Hitchcock'k map will show this. But at the locality noted these positions are changed; the water-divide becomes the eastern chain, and the geological divide is the western, returning, it may be said, to the positions occupied in the region where they originated. These relations are shown on the large map accompanying the present paper. For several miles, the track of the Norfolk and Western Railroad

Jan 1, 1888

By E. G. Williams

Manganese-ore has been found upon the Isthmus of Panama throughout' a region of nearly three hundred square miles, over the greater part of which, however, it is known only in small bodies without commercial value. Only six mines, controlled by two companies, have actually shipped ore, although a large area has been taken up in miningelaims. The ore-bearing region extends along the coast of the Carib. bean Sea, beginning on the west near Puerto Bello and extending easterly about 35 miles toward Point San Blas. Ore has been discovered in the interior, at a maximum distance of about 10 m. from the coast. Fig. 1 is a map of a portion of the Isthmus

Jan 1, 1903

By R. D. Reiswig, J. M. Dickinson

The 0s-Ir equilibrium diagram was determined. The diagram is of the simple peritectic type, with a peritectic temperature of about 2660°C. The solid miscibility gap is narrower than previously reported, the nearly vertical solvus lines occurring at about 42 and 63 wt pct 0s. Widmanstaetten figures resembling martensite in some of the two-phase alloys account for a previously suspected transformation. In view of the long history of use of such alloys, it is surprising that the 0s-Ir equilibrium diagram has not yet been completely determined. The boundaries of the miscibility gap in this system have been estimated to be between 24 and 39 wt pct 0s and 79 and 100 wt pct OS. It has been predicted3 that alloys of ruthenium, osmium, and rhenium with the fcc platinum metals should solidify peritectically in their two-phase regions. The metallographic examination of natural osmiridium alloys has been said4 to indicate, by the presence of a martensitic structure, the existence of a transformation or a phase separation. On the basis of superconducting transition temperature measurements, a 70 at. pct 0s alloy was found5 to be two-phase prior to annealing. EXPERIMENTAL The elemental components used in this work were obtained from several suppliers as sponge. The purities, stated by each supplier to be in excess of 99.8 pct, were confirmed in each case by a semiquantitative spectrographic analysis. The pure components were premelted in an inert-gas tungsten arc furnace with the evolution of some fume, crushed, and pickled for use as alloy melting stock. Upon arc melting to the final compositions, no fume evolution was observed. Because weight losses of the order of 15 mg or less were observed in preparing alloy buttons weighing 15 g, "synthetic analyses" were used in determining the compositions of the alloys. Alloys used in this investigation contained 15, 20, 33, 40, 42, 43, 45, 50, 55, 60, 63, 64, 66, 70, 79, and 80 wt pct 0s. Heat treatments of the alloy buttons and pieces thereof were performed in a previously described6 tungsten tube furnace under pressures of 105 torr or less. It was found that homogenization treatments on the specimens were essential to remove the severe coring which was present, a 3-hr treatment above 2300°C removing all the metallographi-cally visible evidence of coring. Following the various heat treatments, the specimens were "vacuum-quenched" by melting a tungsten fuse wire and allowing them to drop onto a water-cooled copper plate. In a few instances, specimens were quenched into molten tin for comparison, but no difference was apparent. Vacuum-quenched specimens cooled from 2400°C to below a red heat in less than 60 sec. Typical equilibration times varied from 3 hr above 2300°C to 88 hr near 1100°C. The utilization of successively longer equilibration times and the approach to equilibrium from both directions indicated that the times used were sufficient to give a close approach to true equilibrium. Heat-treatment temperatures were measured with a calibrated Leeds and Northrup optical pyrometer through a 0.120-in. lateral sight hole in the tungsten heater tube. It was known that the assumption of black-body conditions inside the 1-in.-diam by 10-in.-long tube was unwarranted. The empirical results of work with thermocouples and melting

Jan 1, 1964

By Emmanuel P. Papadakis

Ultrasonic velocity measurements have been made to study the preferred orientation in cube-textured copper. Methods applicable to thin specimens were employed since the specimens were necessarily of sheet material. The measured velocities in various directions in the sheet differed from the corresponding values in single-crystal copper by 1 to 6 pet. The distribution of the deviations indicated that the align-ment of the (001) planes with the rolling plane was better than the alignment of the [100]and [010] directions with the rolling and transverse directions. Ultrasonic pole figures (velocity us orientation) are shown to be useful in the study of preferred orientation. THIS paper describes one set of experiments in a continuing study of preferred orientation in worked metals. This study has been undertaken to investigate the fundamental properties of metals when used as propagation media for ultrasonic waves. Many such materials are of current or potential use in ultrasonic delay lines. Fundamental studies on ultrasonic propagation parameters such as velocity, attenuation, and diffraction (beam spreading) are of importance in the design of delay lines, in the development of nondestructive testing methods, and in the study of materials themselves. Preferred orientation in worked poly-crystalline metals influences all three above-mentioned parameters, and hence is of particular importance. When polycrystalline metals are subjected to mechanical working, they develop textures dependent upon their crystal structure and the symmetry of the working operation.' The texture consists in the alignment of the crystallographic axes of the grains in preferred directions with respect to the symmetry axes of the working operation. Since the grains are elastically anisotropic, the elastic moduli of worked metals are anisotropic. Hence the velocities of elastic waves in worked metals depend on the directions of propagation and polarization. The worked metal may be thought of as taking on the elastic symmetry of a single crystal: so it possesses the same number of independent elastic moduli as the crystal class it simulates. In general, a worked metal does not adopt the crystalline symmetry of its own grains. For instance, most rolled sheet becomes effectively orthorhombic while all bar stock and wire develop hexagonal symmetry. However, certain metals with cubic crystal structure develop a cube texture upon rolling and annealing.= Nearly perfect alignment of [100]-type directions with the rolling direction, transverse direction, and rolling-plane norma1 can be achieved in certain fcc metals and alloys. These cube-textured rolled metals provide an excellent opportunity to test preferred orientation by means of elastic waves, since a worked metal with 100 pct cube texture would have elastic moduli identical to the moduli of its constituent metal. It is the purpose of this paper to present the results of an investigation upon cube-textured copper. Ultrasonic waves were used. The methods of measurement and the experimental results on the effective moduli will be given. The ultrasonic measurements will be shown to complement X-ray pole figures for the determination of preferred orientation in worked metals. EXPERIMENT To study cube - textured material, it was necessary to use thin-sheet material since a severe reduction in gage (95 to 99 pct) is necessary to produce cube texture. Special ultrasonic methods were needed to investigate the thin material at megacycle frequencies. A) Materials. The cube-textured material tested was a copper alloy containing 1 pct Zn. Specimens already measured for Young's modulus4 by Alers were kindly supplied by him. The specimens were slabs 3.00 by 0.25 in. cut from sheet 0.047 in. thick. The orientations of the long axes of the specimens with respect to the rolling direction were taken in 15-deg steps from 0 to 90 deg. B) Measurements. Two distinct experiments were performed to measure the phase velocity in these specimens. One measured the shear wave velocity for propagation in the 0.25-in. direction and polarization in the 3.00-in. direction. The other measured the velocity of both shear and longitudinal waves propagating in the thickness direction in the sheet. 1) Plate-Mode Measurements. The velocity of the zeroth-order shear mode5 was measured in the 0.25-in. direction in each strip. The specimens were ground thinner over half their length to assure that the first-order shear mode would be cut off below 6 Mc per sec, leaving the zeroth-order nondispersive shear mode as the only propagating mode. Piezoelectric ceramic transducers of 5 Mc per sec resonant frequency poled in their long direction were solder-bonded to the edges of the thin part of the slabs as in Fig. 1 after these edges had been made flat and parallel by fine grinding. These transducers produced waves polarized in the 3.00-in. direction and propa-

Jan 1, 1967

By Charles T. Holland

IN connection with the problems of bumps in coal mines, much has been written concerning the manner in which roof action and methods of mining enter [ ] into the pressure effects observed but little has been written upon the relationship between the physical properties of coal and associated rocks and the cause of bumps. The question of the strength of bituminous coal, of its elasticity, and the energy it can absorb and store has been neglected to a considerable extent in connection with this problem. STRENGTH OF COAL It is generally agreed that one of the necessary conditions for bumps is a strong [ ] coal.1 Therefore, since the strength of coal is an important factor, a study of this property should be made. Several investigators have conducted laboratory experiments upon the strength of coal, using small cubical or rectangular test pieces. An attempt will not be made to go into all of these investigations, but they are briefly summarized in Table I. Experiments of the U. S. Bureau of Mines8 and of Lawall and Holland (pp. 27 and 34 of ref. 9), however, indicate that regardless of whether the coal is a soft and weak semibituminous (Pocahontas No. 3) or a hard and strong bituminous (Stockton) coal, the maximum ultimate unit stress developed in laboratory tests is higher in small cubes than in larger cubes of the same coal.

Jan 1, 1942

By Joseph B. Story, John T. Clarke

A modification, of the Kelvin bridge using an inductor was used to measure the conductivities of molten sodium chloride, calcium chloride, and mixtures thereof. A capillary-type four-lead fused quartz dipping cell was constructed. The effect of a small amount of potassium chloride on the conductivity of the melt was determined. IN the electrowinning of sodium and chlorine from sodium chloride in Downs cells, calcium chloride is added to the sodium chloride in an approximately equimolar amount to permit cell operation at a lower temperature. This lower temperature improves current efficiency and ease of operation, but decreases voltage efficiency by decreasing the electrical conductivity of the melt. A knowledge of the electrical conductivity of the Downs cell melt is necessary to the understanding of Downs cell operation, for the IR voltage drop across the melt is responsible for a significant part of the electrical power consumed by the cell. The work of previous investigators on fused sodium chloride-calcium chloride mixtures was reviewed from the standpoint of consistency with the results of others on the conductivities of the pure constituents. The electrical conductivity of pure fused sodium chloride has been established with accuracy by Van Artsdalen and Yaffe,1 by Edwards, Taylor, Russell, and Maranville,2 and by Lee and Pearson.3 It has also been studied by a number of other investigators.4-13 The best values for calcium chloride are believed to be those of Lee and Pearson,3 since the sodium chloride and potassium chloride conductivity values given by them check the best literature values. A number of other investigators have also reported values for calcium chloride.'-"."' Electrical conductivity data for fused sodium chloride-calcium chloride mixtures have been reported by Sandonnini,12 Vereshchetina and Luz-hnaya,18 Ryschkewitsch,11 Barzakovskii,5 and Alaby-shev and Kulakovskaya.15 Sandonnini reports no data at temperatures lower than 850°C. The conductivity values reported by Vereshchetina and Luz-hnaya, by Ryschkewitsch, and by Barzakovskii for pure sodium chloride and for pure calcium chlor- ide vary somewhat from the literature values believed to be best and the sodium chloride-calcium mixture data of these authors and of Alabyshev and Kulakovskaya (who give no data for the pure compounds) show significant variations. In view of these facts, it seemed that an investigation of the electrical conductivities of fused sodium chloride-calcium mixtures would be worthwhile. Apparatus Bridge System—The bridge used,in this investigation is diagrammed in Fig. 1. In general, the elaborations of this bridge over the simple Wheatstone bridge were for the purposes of a) eliminating lead resistances or making them accurately measurable, and b) eliminating major capacitative and inductive effects or balancing them against each other. Lead resistances in the lower arms of the bridge were kept as low as possible by making the leads short and of low resistance wire. This could not be done in the cell arm of the bridge because of the remoteness of the cell from the other bridge components and because of the high-resistance nickel or chrome1 wires used in the cell. Since maximum sensitivity is attained when the resistances of the four arms of the bridge are equal, 50-O resistors were used in the lower arms of the bridge when fused salt conductivities were being measured, and 1000-O resistors were used when the cell was being calibrated with normal aqueous KCl solution. The cell resistance was of the order of 50 ohms with fused salts and of the order of 1000 ohms with normal aqueous KC1 solution. The resistors used were non-inductive and accurate to 50.05 pct (General Radio Co. Types 500-C and 500-H). The lead resistance between point A in the cell and point E at the measuring resistor was eliminated by using the kelvin bridge principle; that is, the voltape drop across the lead from point A to point E was divided between the cell arm of the bridge and the measuring arm of the bridge in proporation to the resistaxes in the lower arms of the bridge.

Jan 1, 1958

By Y. H. Liu, G. W. Powell

Thin foils made from the gold-rich region of- short (0.15 mm)Au-Ag diffusion couples annealed at 880°C for 1 hr were examined in ax electron microscope and the structures were compared with that of pure gold subjected to identical heat treatments. The couples underwent Plastic deformation (bending) during the diffusional anneal. The foils prepared from the diffusion zone have a higher dislocation density and incidence of subboundaries than pure gold. The plastic bending of the couple can be interpreted in terms of the climb of edge dislocations, which are pavallel to the bend axis, along the direction of diffusion. THE interaction of lattice defects during interdiffu-sion between two metals has been considered by several investigators. In particular, da Silva and Mehl,1 Barnes,' and Bardeen and Herring3 have proposed models based on interactions between point and line defects to account for the Kirkendall effect (marker movement). Each of these models is based on dislocation climb, which can either add or remove lattice planes, induced by an under- or supersaturation of vacancies. A theoretical treatment of the nucleation and growth of voids by the condensation of vacancies has been presented by Seitz.4 Stresses can arise in a binary diffusion couple as a result of the vacancy flux and the gradient in the lattice parameter. rinkmman' has investigated the effects of diffusion-induced stresses on void formation; the results of his analysis suggest that voids can form and grow under the influence of these stresses in the absence of an excess vacancy concentration. The relationships between vacancy supersaturation and diffusion-induced stresses and void formation have been elucidated also by Balluffi and seigle6 who concluded that the stress generated by a vacancy supersaturation aids the growth of voids. Experimental evidence which indirectly shows that stresses are produced by chemical diffusion has been obtained by several researchers.2,7-9 This evidence consists in part of the observation by light microscopy of the formation of subgrains, a process characteristic of the high-temperature deformation of some metals during creep.'0 More striking, however, is the plastic bending of short (0.2 mm) Cu-Ni couples observed by Barnes2 and of boron-doped silicon crystals reported by Queisser.9 Diffusion-induced dislocations in iron and silicon have been investigated by Ainslie et a1.11and Schwutte and Queisser,12 respectively, the former using transmission electron microscopy and the latter an X-ray transmission technique. Matthews and Crawford13 observed the formation of boundaries by the climb of interfacial misfit dislocations in thin, vapor-deposited Au-Pd couples diffused in situ in an electron microscope. In order to obtain additional information on the phenomena associated with defect interaction and diffusion-induced stresses in binary couples, an electron transmission study of foils prepared from the diffusion zone of short Au-Ag couples was undertaken. The initial objective was to investigate the processes occurring at various points of the diffusion zone. Subsequent research demonstrated that foils could be prepared only from the gold-rich region of the diffusion zone using the technique described herein. EXPERIMENTAL PROCEDURE Preparation and Annealing of the Diffusion Couples. The couples were made from annealed, high-purity (99.999 pct). polycrvstalline gold and silver sheets (0.075 mm thick). Shall (0.075 by 5 by 17 mm) elec-tropolished coupons of gold and silver were pressure-bonded by heating the two metals in a graphite device to 770°C and holding at this temperature for approximately 30 min. The quality of the bond was ascertained by metallographic examination at 150 times. Each couple subsequently was annealed at 880°C for 1hr; under these conditions, the extreme portions of the

Jan 1, 1968

By J. L. Ratliff, R. I. Jaffee, H. R. Ogden, D. J. Maykuth

An experimental program was carried out to improve the low-temperature ductjlity of tungsten through the combined use of dispersed oxides for grain-size control and Groups VII and VIII metal additions for matrix softening. Separate binary -alloy studies showed that increasing amounts of finely dispersed thoria or zirconia and critical amounts of rhenium, osmium, and iridium were effective in significantly reducing the ductile-to -brittle bend transition temperature of tungsten as well as in increasing its re crystallization temper - LIKE most of the high-melting point bcc metals, tungsten undergoes a marked transition from ductile to brittle behavior with decreasing temperatures. The material factors which influence the transition temperature include grain size, metal purity, and the presence of dispersed phases. ature and decreasing its recrystallized grain size. The beneficial effects shown by each of these additions on transition temperature and grain size in binary combinations appeared to be additive in tevnary combinations. Thus, combined additions of 2 to 8 vol pct thoria with 5 pct Re, 0.87 pct Os, or 0.30 pct Ir were effective in lowering the transition temperature of tungsten pom 2000 to 75"C, increasing its re crystallization temperature from 1600 to 1800°C, and decreasing its recrystallized gain size from 1175 to 6800 grains per sq mm. The mechanism by which these factors are operable in tungsten is not yet clearly understood. Nevertheless, it has become increasingly apparent that the interrelationship of grain size and matrix composition governs to a large extent the degree of low-temperature ductility which can be achieved. Though it is not possible to accurately assess the relative importance of these variables, the available evidence suggests that, at low temperatures, grain-size effects predominate over purity effects. This was indicated in recent studies by Allen, Maykuth, and Jaffee,' involving single crystals containing 20 to 40 ppm 0 and 1 to 30 ppm C. Thus, while each

Jan 1, 1964