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By C. Wagner

When an alloy solidifies and the composition of the solid differs from the composition of the liquid, atoms of the alloying elements rejected at the solid-liquid interface have to diffuse toward the bulk liquid. Diffusion may be supported by convection. Theoretical calculations have been made for a liquid without convection, for a liquid involving natural convection, and for solidification of a liquid alloy at the surface of a rotating disk as an example of forced convection. WHEN an alloy solidifies, the equilibrium composition of the originating solid phase differs in general from the composition of the liquid phase. Thus, segregation may take place, i.e., the composition of the solid phase formed at different times differs from the bulk composition. The degree of segregation depends on several factors such as the partition ratio of the alloying elements between the liquid and the solid phase, the rate of solidification, and convection. To clarify, a theoretical analysis has been worked out. The following presuppositions are made: 1—Calculations are confined to the solidification of binary alloys in which the concentration of component A (solvent) is much greater than that of component B (solute). 2—The equilibrium concentration of the alloying element B is assumed to be lower in the solid phase than in the coexisting liquid phase. 3—At the solid-liquid interface, partition equilibrium is assumed. 4—The dependence of the partition ratio of the solute between the liquid and the solid phase on concentration and temperature is disregarded since only small concentrations of the solute are considered. 5—The concentration of the alloying element B in the solid phase is supposed to be lower than the saturation concentration for the formation of a second solid phase. 6—diffusion in the solid phase is disregarded, since diffusion rates in the solid state are comparatively low. When the partition ratio of the solute between the liquid and the solid phase is greater than unity, a part of the solute is rejected at the solid-liquid inter- face and has to diffuse toward the bulk liquid. Thus there is necessarily a concentration difference in the liquid between the solid-liquid interface and the bulk liquid as has been pointed out by Hayes and Chipman,' Rutter and Chalmers,' Tiller, Jackson, Rutter, and Chalmers, and others (see Fig. 1). In view of the concentration gradient in the liquid phase, the ratio of the concentration of the solute in the solid phase to that in the bulk liquid differs from the equilibrium ratio, although at the solid-liquid interface, partition equilibrium is assumed. Under certain limiting conditions, the solid may even have virtually the composition of the bulk liquid as is shown below. General Equations Let u be the linear crystallization velocity in cm per sec, D the diffusion coefficient of component B in the liquid phase in cm2 sec-', c',, and c", the concentrations of component B in the liquid and the solid phase, respectively, in mol per cm", and s the distance from the solid-liquid interface toward the bulk liquid at a given time t. The partition ratio is assumed to be equal to a partition constant K. Thus. The difference in the specific volume between the liquid and the solid phase may be disregarded. In view of the discontinuity of the concentration of the solute at the interface according to Eq. 1, u(c', — c",), , , = tic', (S = 0)(1 — K) gram-atoms B per unit area per unit time are rejected at the interface and have to diffuse toward the bulk liquid. From Fick's first law it follows that uc',,(s = 0) (1 ~K) == - D(dc',,/?>s). _-„. [2] The concentration profile in the liquid near the interface depends on the interplay of diffusion and convection as is discussed in the following sections. A schematic concentration profile is shown in Fig. 1. The "effective thickness of the diffusion boundary

Jan 1, 1955

By Ken-ichi Hirano, B. L. Averbach, Morris Cohen, N. Ujiiye

The influence of plastic deformation in compression on the self-diffisivity of a iron has been measured in the temperature range of 742º to 885°C. The diffusivity is enhanced in proportion to the strain rate, but this dependence decreases with increasing temperature. The magnitude of the strain is relatively unimportant in this connection. Strain rates from 0 to -2 x 10-3 sec-1 were investigated, with a corresponding increase in diffusivity up to 3 x 103 times. The results are analyzed in terms of vacancy diffusion and the excess vacancies introduced during dejornzntion. It is concluded that grain boundaries are the main vacancy sinks in polycrystalline iron and that the vacancy lifetime is therefore dependent on the grain size. A typical vacancy lifetime at 800°C with a nzean grain-boundary intercept of 0.3 cm is of the order of 1 sec. LATTICE imperfections are considered to be the dominant mechanism of diffusion in close-packed crystals. Vacant lattice sites are usually the most important defect, but the enhancement of diffusion along grain boundaries and other short-circuiting paths has been well documented. Inasmuch as plastic straining produces a variety of defects, it would be expected that the application of stresses sufficient to cause plastic flow during a diffusion run might result in an increase in the self-diffusivity. Enhanced self-diffusion in a iron under compressive creep has been observed by Buffington and Cohen' and subsequent coworkers.2 Lee and Maddin3,4 have also found an enhancement in the self-diffusivity of silver single crystals undergoing torsional deformation. On the other hand, Darby, Tomizuka, and Balluffi5 have not observed any significant diffusion increase in single crystals of silver deformed either in tension or in compression, although the results in this case may have been affected by the occurrence of recrystallization. With poly crystalline silver, however, Forestieri and Girifalco6 have found en- hanced diffusion during compressive creep. A small decrease in the self-diffusivity of zinc single crystals under compressive loading has been reported,7 but the applied stresses in these experiments were too low to cause appreciable plastic deformation. For the cases in which enhanced diffusion has been found, a number of common effects have been noted. Usually, the ratio of the diffusivity during straining, Ds, to the diffusivity in the unstrained condition, D,, varies linearly with the strain rate, and does not seem to be a function of the plastic strain, at least up to ? = 0.2. Values of Ds/Du of the order of 100 have been reported'-4 but the enhancement decreases with increasing diffusion temperature. The activation energy for diffusion decreases markedly with increasing strain rate and approaches a level of roughly one-half the unstrained value. Most of the current explanations of these observations assume that excess vacancies are generated by the deformation, but rather large concentrations of excess vacancies and/or long lifetimes are required by these theories.',',',' Since the original work on iron, there has been an important improvement in the compressive-loading technique.2 The early data were also analyzed without taking into account the motion of the coordinate system in the specimens undergoing plastic deformation. This problem has now been solved by a number of investigators (see Refs. 11, 12, and the appendix of the present paper). Consequently, the strain-diffusion runs on iron for the Ds measurements were repeated and extended over wider ranges of temperature and strain rate. In addition, the original diffusivity data9 on the unstrained iron have been corrected for the divergence of the beam in the counting system and new data points have been added, resulting in somewhat different values for the self-diffusi-vities in a iron.10 The new values for Du are used in this paper. A comparison of Ds and Du confirms the large enhancement in the self-diffusivity of iron during compressive creep, as previously reported.',2

Jan 1, 1963

Jan 1, 1889

By G. M. Schwartz, G. A. Thiel

THE first record of the quarrying of dimension stone in Minnesota dates back to 1820 when limestone was quarried locally for part of old Fort Snelling. Limestone quarries were operated at Stillwater, Mankato, and Winona as early as 1854. Granite was quarried first at St. Cloud in 1868, and within a few years thousands of tons were shipped to widespread points. Rough dimension stone for large buildings furnished the first important market, but beginning in 1886 paving blocks were in demand. The largest shipment was in 1888, when 1925 cars were shipped from the St. Cloud area. Quartzite was quarried first at New Ulm in 1859 and somewhat later at Pipestone and elsewhere in southwestern Minnesota: The productive dolomite quarries at Kasota were opened first in 1868 and have continued as large producers of a variety of stone to the present time. At present, the industry is controlled by relatively few operators, and for that reason detailed figures on dimension stone are not released for publication. A general idea may be obtained from the data in the Minerals Yearbook for 1948. The figures for total stone produced in Minnesota are 1,804,000 tons valued at $5,090,652. Probably the largest item in the latter figure is received from dimension stone. A better idea of the situation, in relation to the country as a whole may be gained by using the data for 1930 when more companies were operating in Minnesota, and complete figures were published. In that year Minnesota produced granite valued at $2,668,119 and ranked third among the states in value. Minnesota's production of granite was almost exclusively for dimension stone. In the same year Minnesota produced 300,000 tons of limestone (dolomite) valued at $840,860, and this likewise was mainly dimension stone. In finished limestone Minnesota ranked second among the states in 1930. Sandstone and minor amounts of quartzite are the only other dimension stones that have been produced in Minnesota, but the quarries are now inactive. The commercial stones of Minnesota have been described in two reports by Bowled and by Thiel and Dutton.2 The early history of quarrying in Minnesota and extensive notes on the various rocks are given by N. H. Winchell.3 Small limestone and dolomite quarries were numerous throughout the area of Paleozoic rocks in southeastern Minnesota. Early production was largely dimension stone. With the increased use of Portland cement, most of these ceased production, and today only those at Kasota and Winona remain in operation. In recent years many quarries have reopened and new ones started, but these are devoted to the production of crushed rock and agricultural lime. As the application of modern quarrying and finishing methods increased, small companies in the granite business have dropped out, and the remaining companies have modernized their plants, purchased old quarries, and opened up new ones, thus furnishing a wide variety of granites suitable for most of the customary uses. It is the purpose of this review to present notes on' the geology and operations of each of the quarries now operating within the state. Granites and Related Igneous Rocks The term granite as used in this report includes granites, gneisses, diorites, gabbros, and other igneous rocks. The granites of greatest economic importance are found in three widely separated regions, see Fig. 1. 1-Central Minnesota in the region of the city of St. Cloud, 2-the upper Minnesota River valley region, 3-the northeastern portion of the state, commonly referred to as the Arrowhead region. The St. Cloud Region: The rocks of the St. Cloud region are mainly granites and related rock types such as monzonites and quartz diorites. The stones may be grouped into three major types, namely, pink granite, red granite and gray granite. Most of the pink granite occurs in the area to the southwest of St. Cloud. The rock is best described as stone with large pink crystals set in a finer grained black and white background. The minerals of the matrix occur in remarkably uniform sizes, and the pink crystals are sufficiently uniform in. their dis-

Jan 1, 1952

By W. H. Kantner

In this paper, no attempt will be made to theorize on subsidence. Only known data and actual facts will be given, with a few exceptions noted where other factors and outside influences tend to change subsidence directly resulting from porphyry caving. The area under observation is known as the Southeast Extension of the East orebody. The orebody is irregular in outline and dips to the south and the east, extending in depth from about 425 ft. below the surface to 1050 ft. below the surface. In the upper horizon, the orebody is about 400 ft. long and 150 ft. wide. At 720 ft. below the surface, the ore outline is approximately 450 by 170 ft.; 70 ft. below this, it is 500 by 110 ft., with an extension at the north end to the east 270 by 120 ft. From this elevation to about 900 ft. below the surface, the ore spreads out to the cast and south, being about 700 by 500 ft. between these vertical limits. Below this it pinches out and at 1060 ft. below the surface is only 100 by 100 ft. The nearest point of the orebody—which is on the northwest side—is 600 ft. 'southeast of the Sacramento shaft. The country rock is all porphyry. Fig. 1 is a vertical east-west section showing orebody and original surface. The surface over the orebody was fairly regular and in this area and adjacent to it were portions of the surface plant, roads, and the main plant railroad to the concentrator. Fig. 2 is a map of the surface over the porphyry area. Caving operations started in April, 1925, at the approximate top of the orebody. The first lift was on the 600-ft. level; the ore was extracted by means of the Morenci timbered slide method and was from 425 to 455 ft. below the surface over an area of about 22,000 sq. ft. This lift was finished in May, 1926. The second lift, on the 650-ft. level, was already in production by May, 1926, so extraction of ore was continuous. This lift was 48 ft. high and covered an area of about 30,000 sq. ft. The ore from this lift was extracted by means of a modified Morenci timbered slide method. This lift was finished in March, 1927. The direction

Jan 1, 1934

By R. L. Stone

None of the currently used methods of testing bentonites as binders for strengthening iron ore pellets is entirely adequate by itself. Since more knowledge was needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced, attention was paid to possible new techniques for rating bentonites. With the structural nature of bentonites — in particular, the montmorillonite component — the possibility of rating bentonites on the basis of zeta potential was investigated. These bentonites were also rated by conventional tests and measurements, including colloid content, barrel yield, pH, chemical analysis and physical tests on green and dry pellets. A mechanism for pellet bonding based on electro-kinetic forces between the bentonite and the iron ore concentrate appears to be feasible. In pelletizing, from 6 to 18 lbs of bentonite is added per ton of concentrate to give strength to the green and dry pellets. In some operations even more bentonite than is required for strengthening purposes must be added for moisture adsorption to pennit balling of the concentrate. Since bentonite is thus a major item in pelletizing, more knowledge about the way in which bentonites act as binders and better ways of rating this ability would help in the difficult job of selecting the right bentonite for a given concentrate. The fact of the matter is that although several methods are in current use for testing bentonites, none of these methods are consistently foolproof. For example, a given bentonite may rate high by several standard tests yet turn out to be a poor binder, and of course the reverse also occurs. Actually, more knowledge is needed about 1) which properties of bentonite most affect pellet strength, and 2) the precise mechanism by which strengthening is produced. In this study attention is therefore paid to possible new techniques for rating bentonites. With the structural nature of bentonites as a starting point, we investigated the possibility of rating bentonites on the basis of the zeta potential, i.e., the electrokinetic ootential on the montmorillonite colloids — the main component of bentonite binders. The zeta potential technique was applied to a range of commercial bentonites from several areas in the U.S. and abroad. These bentonites were also rated by conventional tests and measurements, including:

Jan 1, 1968

By Clarence Thom

This chapter presents, in summarized form, standard procedures for making separations of minerals from their ores by the froth flotation process to produce marketable concentrates. These are typical mineral separations which are being made commercially with the reagents and conditions generally used in the mining industry. Typical separations are presented for 17 metallic and 11 nonmetallic ores. The review of each includes a brief description of the mineral and the particular problem presented, general market specifications for its concentrates, an outline of treatment method, and kinds and quantities of reagents usually employed. This chapter does not include de- tails about ore preparation (crushing, grinding, and classification), elements of ore and pulp transportation (conveying and pumping), or concentrate preparation for market (thickening, filtering, and drying). In each presentation it is assumed, if not detailed further, that the ore is ground to the economical point of liberation of the minerals to be separated. Specific information, such as ratio of concentration and recovery, that depends upon the grade of ore being treated is considered beyond the scope of this chapter. Effective flotation separations that produce marketable concentrates may produce widely varying results in terms of percent recovery and still be economically profitable operations. Details of plant practice on specific ores are presented in Chapters 16 and 17. In this chapter the chemical names of the reagents are given. The extent to which different reagents are used in flotation plants in the U. S. is presented in Chapter 4. A compilation of the various flotation reagents, their trade names, manufacturers, and use has been prepared by H. T. Spedden. ANTIMONY The principal ore mineral of antimony, stibnite (Sb2 S3), is generally found in the U. S. in ore bodies in association with other valuable minerals such as galena (Pbs), sphalerite (ZnS), chalcopyrite (CuFeS2), or tetrahedrite (3Cu2 S – Sb2 S3), The sulfo-salt minerals of antimony, such as tetrahedrite or pyrargyrite, are often associated with high silver values, so that the presence of antimony may indicate economic importance even though the actual antimony content is low. Antimony is also significant to the mineral economy because of its occurrence in some ores where lead, gold, and silver are the

Jan 1, 1962

By J. B. Austin

MEASUREMENTS of the rate of decomposition of austenite at constant temperature are commonly represented by plotting the percentage trans-formed on linear coordinates against time on either a linear or a logarith-mic scale, a method that yields a curve that in shape resembles an integral sign (Fig. 1). A graph of this kind is not always convenient because extrapolation to the beginning or end of the transformation, or even inter-polation, may be uncertain unless there are a large number of observations, which seldom happens; furthermore, the degree of consistency of a set of measurements is difficult to judge from such a curve. It is desirable therefore to find some mode of plotting, or even better to find a standard variety of graph paper, that gives a straight line instead of the integral shape. The straight line has many advantages; the number of readings required to fix the position of the curve is greatly reduced, interpolation is easy and rapid, extrapolation can be carried out with greater confidence and, finally, the consistency of the measurements is readily estimated from the scatter of the points. The last advantage is particularly valu-able when the data are obtained by direct microscopic examination alone, because they are influenced by the skill of the observer in estimating the relative size of areas, possibly also by undetected inhomogeneity of the specimen. A search for ways of representing the observations as a straight line yielded two methods which are described in this paper. The paper also includes an account of some interesting relations brought to light in applying these methods to the available experimental data. Usually the best way to derive such a method of plotting is to base it on established principles of chemistry and physics, as has been done, for example, for the temperature variation of the equilibrium constant of a chemical reaction. But so little is known of the mechanism of the decom-position of austenite, and so little is available in the way of well established background for changes of this kind, that it is simpler to rely upon purely empirical means. The general plan therefore is to study existing data with a view to finding some function of the direct observations that will

Jan 1, 1938

By John Wellington Finch

In August, 1927, the writer examined certain copper deposits in New Mexico1 which occur in beds of sandstones and shale, and in connection therewith reviewed the literature upon deposits of this type. Such deposits are known and have been reported upon at various points in Texas, Oklahoma, Arizona, Colorado, Wyoming and Utah, but in New Mexico they have been given more development than elsewhere and apparently occur there more conspicuously than in the other states. Some 25 years ago the writer examined deposits of similar origin in northern Arizona and more recently other deposits in western and southwestern Colorado, and these examinations have led him to realize how widely scattered are the deposits and how generally noncommercial they are. On superficial development, to one without a comprehension of their geologic nature, they are alluring on account of occasional small amounts of high-grade ore and much misplaced capital has been expended upon them. This paper, therefore, aims to present briefly certain theories of genesis, some details of which may possibly be new, and to lead up to practical conclusions which may be useful to other geologists and engineers. A bibliography of the more important literature upon such deposits is given below.2 Coffin's Bulletin upon the Radium, Uranium and Vanadium Deposits of Colorado, published in 1921, is a particularly clear discussion. The most comprehensive recent statement is Butler's.

Jan 1, 1928

By W. O. Philbrook, R. H. Spitzer, F. S. Manning

The steady-state operation of an isothermal, counter-current reactor in which a mouing bed of hematite particles is reduced by hydrogen has been modeled mathematically using a generalized single-particle kinetic formulation for topochemical reduction with formation of the intermediate oxides, wustite and magnetite. Reduction prof iles have been generated for various oper- REDUCTION of iron ore, as practiced industrially, approaches counter current, granular-bed operation. The total process is extremely complex. Quite under- ating conditions selected to demonstrate the influence of major variables such as gas and solid flow rates, bed length, and particle size. These profiles illustrate , among other things, that the reducing-gas requirement in a countercurrent bed hinges upon the iron-wüstite equilibrium or 'pinch-point" in much the same way as in a staged reactor. standably, nearly all research has been focused on reduction of single particles of oxide under controlled conditions. While this approach simplifies the problem by eliminating interparticle interactions, the remaining intraparticle transport and kinetic processes still constitute a most formidable challenge. Only within the last few years has knowledge of single-particle reactions been developed sufficiently to make modeling of counter current-bed reduction a realistic and useful study of process behavior. The authors have analyzed1"3 extensive laboratory

Jan 1, 1969

By B. E. Morgan, C. K. Dumbauld

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By C. K. Dumbauld, B. E. Morgan

The need for a low-strength cementing composition for use in well cementing is reviewed and results are presented of laboratory and experimental field tests of a modified cement having a controlled ultimate tensile strength of approximately 200 psi. The modified cementing composition may he prepared from either high early strength or normal portland cements by the addition of bentonite clay and a suitable agent for dispersing and controlling the set of the slurry. Substitution of the modified cement for conventional slow-set cements may give better completion results in many wells because the modified cementing composition has lower set strength, lower slurry density, and greater slurry stability than conventional cement slurrieh. The lower ultimate strength allows greater penetration with less shattering of the set cement when perforating casing and cement. The lower elurry density allows the placement of longer columns of cement slurry, and the greater slurry stability reduces the possibility of having an uncemented section caused by the settling of cement particles before the cement set.. INTRODUCTION High strength lias always been one of the accepted criteria of a good cement. During the early use of portland cement in well cementing. emphasis was placed upon securing cements with higher strengths. In 1931, Barkis' reported that, "Normal oil well cements have been improved to develop greater strengths and uniformity of product, which has aided in producing successful jobs in cementing the deeper strings." As long as most wells were completed by the open-hole method. the use of cements having high strengths seemed desirable, and there was no objection raised against high-strength cementing compositions. For a number of years. how-ever, the industry has been completing a large numher of wells by setting and cementing casing through productive horizons and then obtaining production by gun-perforating the section of casing opposite the desired interval. Although this method has been generally successful, difficulties have been experienced in some cases in completing or recompleting wells because of apparent lack of adequate penetration by the bullets through the casing and surrounding sheath of cement and into producing formation. In addition to the penetration trouble: there have been indications that fracturing and shattering of the set cement by perforating might he a contributing factor in causing the failure of some jobs to exclude water or gas from oil producing zones. The possibility that cements having high set strengths were contributing to til difficully ill obtaining satihfartory perforating results has re. ceived attention during recent years. Gun perforating tests conducted in 1944 showed that the depth of bullet penetration into set cement varied with the hardness of the cement, the greater the strength of the cement the less being the penetration. In 1946, Farris2 pointed out that high strength cements were not needed in well cementing, and in 1947, data published by Oliphant and Farris3 showed that set cement was perforated without shattering at approximately 150 psi tensile strength. whereas at approximately 300 psi tensile strength severe cracking and shattering occurred. Oliphant and Farris suggested that wells be perforated at the proper time interval after placement of the cement so that the set cement would have the desired strength. Several difficulties may he encountered in trying to perforate a cement job at the correct time to catch the tensile strength near 150 psi. The rate of strength development of different cements varies considerably. This fact is illustrated by results of tensile strength measurements presented in Fig. 1. These data show that at 175°F the tensile strengths of three conventional slow-set cements varied from 75 to 235 psi at the end of 12 hours. After 24 hours, the tensile strengths varied from 200 to 455 psi. The rate of strength development is affected. also. by the temperature of the forniation, and this adds to the uncertainty of perforating at the rorrect time, since accurate well cementing temperatures may not he known in many cases. Furthermore, in the recomple-tion of wells it is sometimes necessary to perforate cement which has set for a long period and has developed maximum or final strength. In view of the apparent need for a cementing composition having a controlled ultimate strength, an investigation was

Jan 1, 1951

By A. Kenneth Schellinger

THE terms surface tension .and surface energy are well known when applied to liquids and are generally described by referring to the excess energy of the air: liquid interface as a result of unsaturated molecular forces surrounding the surface molecules of the liquid due to the presence of the air phase on one side. Such unbalanced forces produce the familiar water droplet of spherical form and are generally summed up as a surface tension measured in dynes per centimeter which can be shown mathematically to be equal numerically to a corresponding surface energy expressed in ergs per square centimeter. A specific surface energy, however, is best thought of as the energy necessary to produce one unit of new surface on a substance. Hence, in producing a bubble in a flotation cell the impeller must supply surface energy corresponding to the air: liquid interfacial area on the interior of the bubble. Inasmuch as it is relatively easy to extend or contract the surface of a liquid, there are a number of successful methods for liquid surface tension, or energy, measurement based upon surface deformation. This happy state of affairs does not, however, extend to solids, which are considered to possess surface energies for the same reasons as do liquids, i.e. because of unsaturated ionic bonds at the solid gas interface. As in the case of the flotation cell producing surface on liquids as new bubbles, it takes energy to produce new surface on solids as new particles. As every mill man knows, this surface is produced on mineral solids in a grinding mill by the action of a tumbling mass of iron balls. But here so much energy usually is wasted by the inefficient action of these balls that a large amount of heat is generated, and the surface energy production may be easily confused with the energy necessary to produce this ineffective heat. The tumbling balls and fracturing minerals ultimately take their energy from a rather large electric motor. It has been variously estimated that from 10 to 20 pct" only of this energy from the motor does not appear as heat and may be presumed to appear as surface energy on the minerals present.. Such a production of new surface on the mineral phases is accompanied, of course, by a size reduction that is inevitable as more and more mineral interior molecules become surface molecules by the fracture exposure. This size reduction of mineral particles, although the most obvious feature and perhaps the sole object of the milling operation, is from this energy viewpoint the outward manifestation of the production of surface energy only. Measurement of the characteristic surface energies of pure minerals and their various mixtures in ores would be a step towards understanding of the energetics of the commercial grinding operation. In addition, the characteristic surface energy of a mineral is probably a physical property specific for that mineral, and therefore, from a scientific standpoint, should be measured. It is interesting to note that, in contrast to the large body of work on the surface tensions of liquid systems and biological systems, the field of solid surface energies has been neglected. Prior to. 1920 it is difficult to find more than one or two references to work on solid surface energies in Chemical Abstracts. Since 1920 such references number somewhat less than 100, while those on liquid systems are numbered in the thousands. Much of this apparent neglect of the field of solid surface energies (the term is intended to be somewhat inclusive at this point and refers both to the solid: gas, and the solid: liquid interface) is because of the lack of a reliable method of measurement rather than any lack of scientific curiosity. It was, and still is, difficult to produce new surface on a solid without the simultaneous production of interior changes in the same solid which may consume part of the energy used. The extension in the surface area can be measured, but the interior crystal-

Jan 1, 1952

By R. I. Jaffee, J. W. Roberts, D. N. Williams

DISPERSION hardening as an alloying process has aroused increasing interest in the past few years. This alloying procedure, in which an insoluble phase is dispersed randomly through a metal or alloy, is believed to be especially suited for the attainment of creep strength at elevated temperatures since the dispersed phase is metallurgically stable. Another advantage is that the physical properties of the matrix phase, such as electrical conductivity, remain relatively unaffected by alloying. These two characteristics resulted in interest in the applicability of dispersion hardening to copper and copper alloys. A study of copper alloys prepared by powder metallurgy methods has shown some strengthening from oxide dispersions.' However, powder metallurgy processing would not be economical for large scale production of dispersion hardened copper-base alloys. Therefore, the research described in this article was initiated to examine methods of forming dispersion alloys which would not require powder metallurgy processing. If powder metallurgy processing is to be avoided, a method must be found by which the dispersion material can be introduced into and dispersed through the melt before casting. When the dispersed phase is an oxide or similar nonmetallic, it is extremely difficult to form a satisfactory liquid: solid dispersion since successful mixing requires that the melt wet the dispersed phase. It is almost impossible to force a nonwetted particle beneath the melt surface. This difficulty can be avoided, however, if the oxide particles are produced in molten copper by reaction within the melt. The problem would then reduce to maintaining randomness until solidification. Four procedures were considered for producing an oxide particle within molten copper by reaction. In all cases, the intent was to react oxygen (0) with a reactive metal (X) to form an oxide (XO) within the copper melt. These reactions were as follows: 1) (Cu-X), + (O)g (Cu)1 + (XO)S [1] 2) (Cu-X)1 + (Cu2O)s (Cu)x + (XO)S [2] 3) (Cu-OK)1 + (Cu-X)1 (Cu)1+(XO)9 [3] 4) (Cu-OK)1 +(X)s (Cu)1 +(XO)s [4] The reactions were carried out in an 8-lb melt of 99.98 pct Cu maintained in the vicinity of 2200oF by induction heating. Where possible the amount of the reactants was controlled to give 1 to 5 vol pct oxide. Mechanical stirring during the reaction period was used to minimize agglomeration of the reaction product. The presence of a reaction product was determined metallographically by study of an ingot cast from the melt at the end of the reaction period. Reaction [I] was studied by dissolving aluminum in the melt followed by forcing oxygen through the melt. The melts became quite sluggish during the reaction period suggesting that A12O3 was formed. However, the reaction product rose out of the melt rapidly, possibly due to the flushing action of the oxygen stream, and little dispersed phase was formed. Reaction [2] was examined by dissolving aluminum, silicon, or nickel i; the melt and then adding Cu20 (melting point 2250F). This procedure was unsuccessful. Although Cu2O was easily stirred into cop-

Jan 1, 1961

By J. H. Frye, J. L. Scott, J. W. Woods

THERE are at least two effects of temperature on the stress required to produce plastic flow. 1) Metals plastically strained for the same amount at different temperatures possess different stress-strain curves and different internal structures (e.g., nature and density of imperfections). 2) There is both experimental and theoretical evidence that the stress necessary to produce plastic flow may vary with temperature even though the internal structure remains constant.1-5 Much of the data in the literature is difficult to interpret because these two effects are simultaneously present. In the work reported here, they are considered separately. Standard 0.505 in. tensile specimens were prepared from high-purity Mond nickel and OFHC copper. Nickel specimens were annealed in hydrogen at 1150°C for 30 min and furnace cooled. This produced an average grain diameter of 1.4 mm. Copper specimens were annealed in vacuum at 525°C for 6 hr and furnace cooled. This produced an average grain diameter of 0.11 mm. Nickel tensile specimens were prestrained in tension at 500°K, whereas copper tensile specimens were prestrained in tension at room temperature. All specimens were cooled to 74°K and heated to room temperature. After these treatments all of the tensile specimens of a given set possessed identical structures. All specimens were returned to the tensile machine and tested at various temperatures and constant cross-head speed. Many of the tensile curves showed well defined yields but, in order to minimize personal judgment, the yield was always chosen as the stress corresponding to 0.2 pct plastic deformation. Results are summarized in the graph of yield vs temperature of test, Fig. 1. All of the specimens corresponding to any one line have had identical treatments and, therefore, have identical internal structures. Thus, each line gives the relation between yield stress and temperature for one constant internal structure. The lowest line, which is for annealed nickel, shows no measurable variation of yield with temperature. This is similar to Blewitt's6 results on copper single crystals, but a variation in yield with temperature was found by Andrade and Henderson' in single crystals of nickel, and by Car-recker and Hibbard8 in annealed polycrystalline copper. The three other lines, which are for prestrained materials, show that there is a linear relation between yield stress and temperature when the internal structure remains constant. Such a relation might be expected from a rate equation such as that of Kauzmannl on the assump- tion that the activation energy is either independent of or linear with temperature. These results would also be expected if the shear moduli of copper and nickel are linear functions of temperature for, as Cottrell and Stokes have pointed out," in all dislocation theories of strength the flow stress appears proportional to the shear modulus of the material. In copper and nickel, since the modulus of elasticity decreases roughly linearly with increase in temperature," it is probable that the modulus of shear also decreases approximately linearly with increasing temperature. A detailed discussion of the effect of these and other factors on the temperature dependence of flow stress in face-centered-cubic metals has recently been given by Seeger.4

Jan 1, 1958

By Paul H. Price, John P. Nolting

The history of the salt industry in West Virginia dates back nearly two hundred years; howTever, the history of salt as an important raw material for the chemical industry is much more recent. The earliest record of West Virginia salt was in 1753, when a raiding party of Shawnee Indians attacked frontier settlements in Virginia taking captive a number of the pioneers. One of these, who later escaped and returned to her friends, described how the Indians camped at a salt spring on the banks of the Kanawha River and evaporated the water to obtain a supply of salt to take back to Ohio with them. Settlement of the Kanawha Valley began in 1774, that same year the Battle of Point Pleasant ended the Indian's power in the Ohio Valley; and settlement of the Kanawha Valley progressed rapidly with a consequent increase in the importance of the Kanawha Licks as a source of salt. In those days the evaporation of the brine was a family matter for which the family wash-kettle was commandeered. In 1797, Elisha Brooks erected the first salt furnace in the Kanawha Valley. It consisted of two dozen small kettles set in a double row, with a flue beneath, a chimney at one end, and a fire bed at the other. He obtained his brine at a depth of 20 to 30 ft by sinking hollow logs, called "gums" into the salt lick and dipping the brine with a bucket. His production was about 150 lb a day and sold for 8 to 10 cents a pound. In 1806, the Ruffner brothers, David and Joseph, prospected for and drilled the first well in America using a spring pole and steel chisel bit. After several failures they succeeded, in 1808, in drilling to a total depth of 59 ft where they secured a good flow of strong brine. Most standard drilling tools, jars, casing, and practically all the basic oil well drilling machinery now in use, were developed in the drilling of salt wells. To evaporate this brine, the brothers built a wood-burning furnace similar to that of Brooks but with a better arrangement and with more and larger kettles. When production was started they reduced the price of salt to 4 cents a pound. By 1817, there were some 30 salt furnaces in the Kanawha area. It was in this year that bituminous coal first was used as an industrial fuel. David Ruffner again pioneered the way by converting his furnace for the consumption of coal. This year also brought about the formation of the first trust which controlled production and set a price of 1 cent a pound for the salt.

Jan 1, 1950

By Blandford C. Burgess

Mica is an orchid among minerals. It is formed in pegmatites, one of the most bizarre of igneous formations, and is exceeded by few other minerals in the perfection it may attain as to size, color, and cleavage. First used for window glazing, as an ornament and article of trade, it has become one of the most essential insulators of electricity, heat, and shock. Most internal combustion engines use mica condensers or capacitors and such machines of war as planes, tanks, and submarines are immobile without it. The original manuscript of this guide was written in April 1943 at the peak of war emergency. It was not used be- cause shortly thereafter a decision was made to buy on a one price basis eliminating differentials for both quality and size. This is now presented with the thought that from the standpoint of preparedness we can only consider an- other war imminent and every effort should he made to set up in usable form the experience gained during the Second World War. Colonial Mica Corp. was set up by Metals Reserve Co. as a wholly owned government agency to encourage production of domestic mica and to purchase it. It soon became the exclusive buying agency for such mica. The writer as Southern Manager called on all the private agencies buying mica to assist in formulating buying policies, methods, and prices.

Jan 1, 1949

THE term mountain bump describes the sudden rupture of one or more coal pillars under excessive stress. These bursts occur with varying degrees of violence and sometimes include adjacent strata, especially the bottom rock. Many failures do not develop enough violence to be dangerous and are regarded as an aid to coal production, but severe occurrences are accompanied by tons of flying coal, dense clouds of dust, and excessive gas emission. Such bursts sometimes throw heavy machinery several feet. Major factors to be considered in the problem are the nature of the strata above and below the seam and the depth of cover. Bumps are classified as to their nature, extent of damage, and point of occurrence, e. g., face bump, coal bump, high side bump, low side pavement bump, and district bump.

Jan 8, 1958

By P. H. G. Durville

ANY metal which contains even a small percentage of aluminum possesses certain peculiarities of appearance and properties which are exhibited both when the metal is melted and after it solidifies. Pure aluminum, or an alloy containing a small proportion of aluminum, can be melted without flux-except for a layer of charcoal-because a film of aluminum oxide and metal forms at the surface of melted aluminum. Although very thin, this film is air-proof, and it prevents the metal underneath from oxidizing. This oxidized film does not move easily on account of its toughness and high surface tension. One very important point in connection with this process of still casting has not been strongly enough stressed, namely, that the same kind of surface film with the same peculiarities forms over the surface of all melted alloys that contain even a small proportion of aluminum. Experienced foundrymen know how desirable it is to cast aluminum under its "skin" or under the surface of the film which tends to remain still. In the case of red copper, when in fusion, the surface shows pure copper only. This is due to the fact that liquid copper constantly absorbs the copper oxide which forms on the surface. By closely examining melting copper the oxide can be seen dissolving in the bath, and going into solution just as pulverized sugar dissolves in water. When copper is cast in the open, either in wire bars or cakes, the surface of metal exposed to the air is covered by a film of black, oxide that cannot be absorbed by the metal.

Jan 1, 1927

By Andres M. Liebenthal, Jan M. Mutmansky

This paper is concerned with the layout of a conveyor and beneficiation plant system involving several mines and a single point of delivery. The objective of the procedure is to locate the conveyor lines and beneficiation plants in an optimal manner considering the economics of scale inherent in both the transportation and beneficiation processes. Upon completion of the mining plan, the layout of the conveyor network is achieved through the principle of Steiner minimal trees. The optimal number and location of beneficiation plants for this layout are then determined using a sequential economic analysis based upon the flow of material from the individual sources to the ultimate destination. The practical aspects of the method and the advantages and disadvantages of its use are discussed to link the model to a practical problem.

Jan 1, 1976