Search Documents

By W. A. Tiller

The unidirectional freezing of a semiinfinite liquid from one end has been treated by calculating the solute and temperature distributions in the liquid and solid phases with time, when the solid-liquid interface advances at a rate proportional to (time)lt2. The nucleation probability for new grain formation is calculated as a function of the constitutional and thermal properties of the alloy, the pouring conditions and the catalytic efficiency of the nucleating agents. The transition from columnar crystal formation to equiaxed crystal formation is assumed to occur at a critical nucleation frequency for a particular alloy and the quantitative dependence of the ratio (columnar zone length/equiaxed zone length) upon the freezing conditions has been predicted. The effects of (i) fluid flow in the liquid, (ii) heat transfer through a mold wall, and (iii) a finite ingot length, have been explicitly tveated as departures from ideality. These departures from ideality are found to have very important consequences on the ingot stmcture. In Part I&apos; of this series, a qualitative description of the general ingot structure was developed. The factors that determine i) the ratio of the equiaxed zone length to columnar zone length and ii) the grain sizes in these zones, were discussed. In the present paper, topic (i) will be treated quantitatively, and it is intended that topic (ii) will be treated quantitatively in Part 111. The complete treatment has been split in this manner for ease of development and coherency of presentation. The treatments are quite mathematical in nature and, although some of the conclusions to Part 11 depend upon the treatment presented in Part 111, it was felt that the intended audience would find the material more readable and more useful in its present form. To this same end, it seems worthwhile to reiterate some of the qualitative aspects of grain nucleation during ingot solidification before embarking on the mathematical description. QUALITATIVE ANALYSIS In the conventional method of casting, a liquid alloy with a certain degree of superheat is poured into a mold. The outer rim of liquid metal cools rapidly to the liquidus temperature of the alloy and begins to undercool. As the degree of undercooling increases, nuclei of solid begin to form in this chill layer, this nucleation being catalyzed by certain heterogeneous particles in the liquid. The grains in the chill layer which are generally of random orientation, begin to grow inwards because of heat conduction through the mold. The grains usually develop a columnar shape since the frequency of nucleation of new grains in the liquid ahead of the advancing interface is generally insufficient to seriously impede the growth of the original grains. Due to the slow diffusion rate of solute in the liquid, a solute distribution is formed in the liquid adjacent to the interface which is either an excess or a depletion if the partition coefficient, ko, of the solute is < 1 or > 1, respectively. Thus, the liquidus temperature of the liquid adjacent to the interface is a function of position. The actual temperature in the liquid is also a function of position and the temperature gradient at the interface decreases as the interface moves away from the mold wall. Since the rate of advance of the interface decreases with time, the equilibrium temperature distributions and the actual temperature distributions as a function of interface position, X, can be illustrated as in Fig. 1. Thus, a region of liquid may exist in which the actual temperature is below the liquidus temperature. This liquid is contitutionally supercooled and therefore unstable with respect to the nucleation of new grains. Now, since the supercooling in Fig. 1 increases as the interface moves further away from the mold wall, the nucleation rate of new grains will increase. When the nuclea-

Jan 1, 1962

By A. S. Nowick, C. Y. Li

It is deMonstrated that quenching from an elevated temperataupe accelerates the grain boundary relaxation in two solid solutions (aAg-Zn and a Cu-Al). This result is consistent with the proposal that, in solid solutions, grain boundary relaxation occurs by a mechanism of&apos; self diffusion. Nevertheless, an alternative possibilitg, that quenching introduces vacancies into the boundary itself, must also be considered. THE phcnomenon of grain boundary relaxation has been well known for many years,1,2 yet the mechanism of this process is very poorly understood. One of the most interesting suggestions which relates to the mechanism of grain boundary relaxation was that of Ke,3 who claimed that the activation energy for grain boundary relaxation and for lattice self diffusion were essentially the same. The implication is therefore that the elementary step in the two processes is the same. This suggestion is particularly startling in view of the fact that activation energy for self diffusion along a grain boundary is very significantly lower than that for volume self-diffusion. Later evidence5-7 showed that there really are two grain boundary peaks, one which appears in high-purity metals, and the other (which develops at a higher temperature than the first) which appears in solid solutions beginning at solute concentrations in the range of 0.1 pct. Data for silver6 show that Kg&apos;s hypothesis is surely incorrect for the grain boundary peak in the high-purity metal, since it has an activation energy of only 22 kcal per mole, but that the hypothesis may still be correct for the grain boundary peak in various silver solid solutions, for which activation energies in the range 40 to 50 kcal per mole are observed. If the elementary step in the grain boundary relaxation process were the same as that for self-diffusion, it would be expected that the relaxation process could be hastened by quenching, 2.c. by introducing a non-equilibrium excess of lattice vacancies. Such a quenching effect has already been demonstrated in the case of another anelastic relaxation process, viz., the Zener relaxation effect. The Zener effect, which occurs in essentially all solid solutions, may be attributed to the reorientation of pairs of solute atoms in the presence of an applied shear stress,&apos; and therefore must take place by means of a volume diffusion mechanism. The hastening of this process through quenching9 has been one way of demonstrating that atom movements in the lattice take place through a defect mechanism, presumably single vacancies. In order to see if the grain boundary relaxation is affected by quenching, it is particularly convenient to compare the grain boundary relaxation with the Zener effect, by choosing a specimen for which both relaxation effects appear. Specifically, a fine-grained sample of a solid solution shows in the curve of internal friction vs temperature, first a peak due to the Zener effect, then a second rise (and eventually a peak at substantially higher temperatures) due to the grain boundary relaxation. The same phenomena are also observable in static anelastic measurements, such as creep at very low stress levels. Thus, for the same fine-grained solid solution, the creepstrain, when plotted against log time, falls on a sigmodial curve with a sharp inflection point, due to the Zener effect, which is followed by a second rise and inflection resulting from the grain boundary relaxation. To look for a quenching effect, static measurements are preferable to the dynamic internal friction measurements, due to the fact that quenching effects tend to anneal out too rapidly at the temperatures at which the internal friction is measured.9 RESULTS AND DISCUSSION Creep experiments in torsion were carried out in an apparatus similar to that described by Ke1, whereby a wire is held under constant torque and its angular displacement is observed as a function of time. The alloy Ag-30 at. pct Znwas selected because of the large Zener relaxation that it displays. The two samples used were a "coarse grained" wire with a mean grain size about twice the diameter of the wire (diam = 0.032 in.), and a "fine-grained" wire which had several grains across the diameter. In Fig. 1 a comparison is made of the creep curves at 160°C of these two samples after they had been cooled slowly from 400°C. Curve A, which represents the coarsegrained sample, shows a unique relaxation process due to the Zener relaxation, with a relaxation time, T , in the vicinity of 100 sec. Curve B, which represents the behavior of the fine-grained sample, on the other hand, shows first the same relaxation process as that in A, followed by a turning up of the curve which corresponds to the onset of a second overlap-

Jan 1, 1962

By R. E. Lund

The design, operation, and performance of an integrated pilot plant for recovering zinc and copper from a complex sulfide ore are described. Metallurgical processing comprised selective sulfate roasting in a fluid bed, leaching in a weak sulfuring acid solution, recovering copper by cementation with scrap iron, air oxidation to remove soluble iron, more-or-less conventional purification for removal of impurities deleterious to zinc electrolysis, recovering zinc by electrolyzing solutions, and recycling spent electrolyte to the sulfating roaster. The effects of several feed preparation and roasting variables on the sulfation response of zinc, copper, and iron are set forth, together with the electrolyzing characteristics of the zinc solutions.

Jan 1, 1962

By Charles Law McCabe, Lyndon H. Everett, Edna A. Dancy

It has been found that the carbide phase present at equilibrium in the system M-H2-CH4, at about 600°C, is MC for the rare-earth metals Ce and Pr. X-ray diffraction analysis showed that the monocarbides have fcc structures with lattice constants of 5.036 + 0.009Å and 5.131 + 0.001Å for CeC and PrC respectively. Gaseous equilibrium measurements were used to calculate the standard free energy of formation of the monocarbides from the elements. for the formation of (+ 1300) for the formation of PrC. THE rare-earthdicarbides, and their crystal structures, have been known for some years,l but only more recently were the carbides CeC,2,3 Ce2C3 2 and CeCS3 reported. In 1958 to 1959, Spedding et al. published work on the lanthanum-carbon system4 and other rare-earth metal-carbon systems,5 proving the existence of M2C3 and MC2, and measuring the lattice constants. They also demonstrated that tri-rare earth carbides, M3C, exist for the rare-earth metals samarium through ytterbium. However, they concluded that the cerium monocarbide reported by Brewer and Krikorian2 and by Warf,3 and given a fcc structure with a lattice constant of 5.130Å bythe former workers, was, in fact, cerium metal with carbon dissolved in it. They were also unable to find any evidence for the existence of Warf&apos;s CeC3, for which no structural details had been given. Even more recently, Palenik22 reported the existence of only M2C3 and MC2, having been unable to find any evidence for the existence of any other rare-earth carbides. There are no published experimentally derived thermodynamic data for the formation of any of these carbides, although Brewer and Krikorian6 have estimated values of for CeC, Ce2C3 and CeC2. The objective of the present investigation was; to determine experimentally the free energy of formation of any of the reported carbides of cerium and praseodymium, through a study of the rare-earth metal-hydrogen equilibrium. EXPERIMENTAL A methane-hydrogen mixture was circulated, in a closed system over previously prepared cerium or praseodymium hydride, and when equilibrium had been attained, the gas mixture was analyzed by selectively oxidizing the hydrogen and condensing out the water formed. The metal hydrides were used as starting material for convenience because, otherwise, the hydrogen in the gas mixture would immediately dissolve in the metals; in addition, the metals would not react with methane alone at the experimental temperature (around 600°C). The circulating system was based on that used by Browning, DeWitt, and Emmett7 for similar studies on iron carbides. It consisted of a quartz reaction vessel, all-glass circulating pump, analysis tube containing copper oxide that could be heated to 300" C by means of a small furnace, a solid CO2-methanol trap, and a double limb absolute manometer, Fig. 1. A cathetometer, capable of reading to 0.005 cm, was used to measure the difference in height between the two columns of mercury. In its final form, the reaction vessel was enclosed in an outer jacket, containing approximately the same pressure of hydrogen as that within, to reduce errors due to diffusion of hydrogen out through the fused silica of the reaction vessel., The circulating system was supplied with

Jan 1, 1962

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes&apos; All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

By Charles B. Kenahan

Vanadium is subject to only light corrosion in phosphoric acid at temperatures up to 60° C. and has a moderate corrosion rate in this acid at 100° C. It is relatively corrosion resistant in sulfuric and hydrochloric acids up to 60° C, but corrodes rapidly at 100° C. It corrodes rapidly in dilute nitric acid at 35° C. Vanadium is almost inert in 10-percent solutions of formic, acetic, lactic, tartaric, and citric acids; in 9-percent oxalic acid it corrodes slowly up to 60° C. and rapidly at 100° C. Vanadium is resistant to corrosion in substitute ocean water, tapwater, and in 3-percent sodium chloride and 10-percent sodium hydroxide solutions. It is readily attacked, however, by 20-percent ferric chloride, 20-percent cupric chloride and 5-percent mercuric chloride solutions. Vanadium is protected by contact with magnesium, aluminum, and steel SAE 4130 in substitute ocean water, by magnesium and aluminum in 3-percent sodium chloride solution, and by magnesium in tapwater. Vanadium protects copper in substitute ocean water. When vanadium and stainless steel are coupled in sulfuric acid solutions, both metals are usually unaffected by contact, whereas the corrosion rate of titanium in sulfuric acid is greatly reduced by contact with vanadium.

Jan 1, 1962

By J. E. Castle

The essential foundation upon which to build an effective marketing program in industrial minerals is the ability to produce competitively mineral products meeting precise customer specifications and to ship them promptly and on schedule. Without this prerequisite, all the other factors in a second marketing program-creative sales management, energetic solicitation, advertising, technical service, new products, etc.are without meaning. The primary image to be created in the mind of customers is that of the reliable and prompt supplier of mineral products at competitive prices and of standard, uniform quality. With this favorable image implanted, it becomes possible to integrate the other essential factors into a strong marketing program; and without this image, little can be accomplished. After having .made provision for the basic product ion position outlined, there are then two fundamental considerations in the design of a successful marketing program for industrial minerals. The first of these is that the number of potential customers for the typical industrial mineral product is, relatively small, and indeed compared to the number of customers for consumer products, the number is actually minute. The second consideration is that the customers for industrial minerals are manufacturers and producers rather than consumers. These two factors lead to a necessity that the marketing program be specifically and uniquely tailored to fit the individual mineral product to be sold and to conform to an existing pattern of distribution.

Jan 1, 1962

By T. N. McVay

The Bureau of Mines has developed a field test for detecting the presence of columbium in a variety of minerals containing the clement. The test consists of fusing the mineral or rock powder with potassium pyrosulfate in a porcelain crucible, digesting the melt with hot dilute hydrochloric acid to release the columbium oxide (Cb205), and subsequently reducing the columbium oxide to a lower oxide by adding tin, which gives a blue color to the contents of the crucible. The method will detect 1 percent of contained columbium oxide (Cb205) in a mineral sample provided no tungsten is present. If a mineral containing appreciable titanium is test,-!d in the same manner, the solution in the crucible becomes violet. In the presence of columbium, titanium at first causes a violet coloration of the solution, which after a few minutes is masked by the stronger blue of the reduced columbium oxide. Although tantalum oxide (Ta205) does not interfere with the columbium test, tungsten gives a blue color that is indistinguishable from the color obtained with columbium. A simple method is available to detect the presence of columbium in the absence of tungsten, but when the presence of tungsten is suspected, the sample must be subjected to somewhat more elaborate chemical tests to determine the presence or absence of columbium. Although these latter tests can be made in the field, several steps are involved that arc best performed in the laboratory with simple equipment.

Jan 1, 1962

By E. A. Sigworth

Our interest in metallurgical applications for activated carbon was thoroughly aroused when laboratory studies indicated that each dollars worth of carbon could retain as much as four dollars worth of tin. Since then other data was developed suggesting many Potential uses in the metallurgical field it is hoped that, the information presented in this paper may encourage studies by knowledgeable individuals in metallurgical operations. Activated Carbon accomplishes its results by adsorption which involves selective removal of materials from solution by holding the compounds on the carbon surface at the active areas. An example of adsorption is the dyeing of cloth where the dye is selectively held on the cloth surface and the concentration in the dye solution is thereby reduced. Many theories exist on, adsorption, but the predominant factors involved in metallic ion adsorption probably are that adsorption is indirectly proportional to solubility and is benefited by high concentrations acting to squeeze out molecules in smaller amounts.

Jan 1, 1962

By B. D. Cullity, K. S. Sree Harsha

When a copper or aluminum single crystal is swaged into wire, the resulting deformation texture depends on the original orientation of the crystal. The<100> and <111>orientations me essentially stable, while <110> is unstable. The greater the <100> content of the deformation texture, the stronger the wire is in torsion. the greater the<111>content, the stvonger it is in tenszotz. The preferred orientation (texture) of fcc wires, either after deformation or recrystallization, is usually a double fiber texture in which some grains have <100> parallel to the wire axis and others have <111>. The relative amounts of these two texture components, as reported by different investigators for the same metal, vary considerably. Previous work in this laboratory&apos; has shown that the starting texture of a wire, i.e., the texture which it has before deformation, can have a decided influence on the texture produced by deformation. In particular, it was found that the deformation texture of copper wire is essentially a single <100> texture, if the wire before deformation contains only a <100> component. This is true even when the deformation is carried to more than 98 pct reduction in area. This paper reports on further studies of the role played by the starting texture. Copper and aluminum single crystals of various orientations have been cold swaged into wire, and quantitative measurements of the resulting deformation textures have been made. The tensile and torsional properties of the deformed wires have also been measured, and the relation between these properties has been correlated with the texture of the wire. These measurements were made in order to demonstrate that a cold-worked wire can be made relatively strong in torsion and weak in tension, or vice versa, by proper selection of the texture before deformation. MATERIALS The copper was of the tough-pitch variety, containing, by weight, 99.962 pct Cu, 0.003 pct Fe, 0.025 pct 0, and 0.0021 pct Si. The aluminum contained more than 99.99 pct .&apos;41; the only reported impurities were 0.001 pct Fe, 0.001 pct Si, and 0.003 pct Zn, by weight. Large single crystals of these metals were grown by the Bridgman method in graphite crucibles and a helium atmospliere. Cylindrical specimens of predetermined orientation, about 1.5 in. long and 0.36 in. in diameter, were machined from the as-grown crystals and then etched to 0.25 in. to remove the effects of machining. Their orientations were checked by back-reflection Laue photographs, and they were then swaged to a diameter of 0.050 in. (96 pct reduction in area). 111 order to study the "inside texture" of the deformed wires, they were etched, after swaging, to a diameter of 0.040 in. before the texture measurements were made. TEXTURE MEASUREMENTS The fiber texture which exists in wire or rod can be represented by a curve showing the relation between the pole density I, for some selected crystal-lographic plane, and the angle $ between the pole of that plane and the wire axis (fiber axis). Such a curve will show maxima at particular values of , and these values disclose the texture components which are present. The relative amounts of these components can be determined2&apos;3 from the areas under the maxima on a curve of I sin F vs F. It is seldom necesszlry to measure I over the whole range of F from 0 to 90 deg, since the existence of maxima in the low-F relgion can be inferred from measurements confined to the high-F region. The X-ray measurements were made with a General Electric XRD-5 diffractometer and filtered copper radiation, according to one or the other of the following procedures: 1) A method developed in this laboratory,4 involving diffraction from a single piece of wire. 2) A modification of the Field and Merchant method.5 This method was originally devised for the examination of sheet specimens, but it can easily be adapted to the measurement of fiber texture. Three or four short lengths of wire are held in grooves machined in the flat face of a special lucite specimen holder. The axes of the wires are parallel to the plane defined by the incident and diffracted X-ray beams, and the holder to which the wires are attached can be rotated step-wise about the diffractometer axis for measurements at various angles 9.

Jan 1, 1962

By Robin O. Williams

The increase in internal energy as the result of deformation has been measured for lead, aluminum, silver, nickel, iron, and zirconium by using rapid, adiabatic compression. The stored energy increase is roughly Proportional to the strain; the propor-tionality constant increases rapidly with increasing melting point. The fraction of the mechanical energy which is stored increases more slowly, since the strength of the metals also increases with melting point. The values of the stored energy are considered accurate to about 10 pet. The present values appear about 50 pet larger than the more reliable published results where comparisons are possible. It is possible that this difference is due to the high strain rate used in this investigation. Immediately after deformation all these metals release energy at a rate roughly proportional to (time)-&apos;. This release is considered to be associated with dislocation motion but in aluminum (and copper) some additional process seems to be present. This release can represent 20 pet or more of the stored energy. WHEN pure metals are plastically deformed, most of the mechanical energy is converted into heat. The energy remaining within the metal is significant in that it is the energy of the disorder produced and thus detailed knowledge of this energy is a powerful tool in understanding the nature of deformational disorder. While much effort has been expended on this problem, the amount of information available is limited. The situation as of 1958 has been carefully reviewed by Titchener and ever.&apos; The present results have been obtained by a new experimental approach to this problem. The method necessitates high-strain rates which make comparisons with published results less certain, but a high-strain rate is an advantage in that the energy release immediately after deformation can be followed. EXPERIMENTAL PROCEDURE In the experimental method used, the internal (stored) energy is given as the difference between the mechanical work used in deforming the sample and the heat which is released (the first law of thermodynamics). The work is supplied by two identical hammers swinging freely from a fixed height, the available energy being the product of the mass, the gravitational constant, and the distance through which the center of gravity moves. The initial temperature rise of the sample represents the heat produced by the deformation. The sample temperature is determined by a small thermocouple embedded in and supporting the sample. This process can be repeated over and over to produce increased strains. Most samples are run through about five cycles to a total strain of around 0.7. Further details are covered elsewhere. The determination of the heat is dependent upon the sample weight, its specific heat, the rise in temperature, and any gains or losses to the surroundings. One is dependent on published results for specific heals (the values were taken from a collection).3 The values must be accurate to about 0.1 pet in order that they not affect the results. The best values thus do not contribute to the uncertainty, but this is probably not always the case. The accuracy of the temperature rise is limited primarily by knowledge of the thermocouple characteristics over short temperature intervals, but careful calibration eliminates this as an important factor. One can calculate readily the heat flow between the sample and hammers if the time of contact and the sample temperature are known and if there were no oil at the interface. Assuming the maximum temperature difference, upper values for this interchange have been calculated (the time of contact is determined from the decrease in sample length) and it may or may not be significant. However, no correction is colnsidered necessary because of the presence of a thin oil film which has a thermal conductivity much less than the metals. Except for the possible uncertainty in specific heat, the heat is considered to be adequately known. The mechitnical losses which are recognized as important are: 1) friction between the sample and the hammer:;, 2) the kinetic energy in the hammer suspension system which may not be entirely usable, 3) the rebound energy of the hammers, and 4) the vibration of the hammer heads. All these have been covered in detail elsewhere2 and only the more significant points are made here. The friction turns out to be small except for soft materials (lead)

Jan 1, 1962

By Thomas P. Meloy

Floating "fines" differs from floating "sands" because the fines have a much larger surface area compared to their mass. The forces that arise from this large specific surface the key to understanding the behavior and treatment of fine particles. Though the nature of these forces is not thoroughly understood, enough work has been done to give a qualitative picture of what is happening in a flotation cell. It is the purpose of this chapter to re-examine some of the more, recent theoretical work and-to indicate its importance.

Jan 1, 1962

By L. A. Roe

The year 1867 marks the first year of commercial production of phosphate rock in the United States. South Carolina produced almost all of the domestic output of mineral phosphate until phosphate mining began in Florida in 1888. During the period 1868 to 1949 the total marketed production of domestic phosphate rock was about 186 million long tons of which 71.5 percent was produced in Florida, 18 percent in Tennessee and 7 percent in South Carolina (1). From 1949 through 1960, Florida phosphate rock production has ranged Prom 71 to 77 percent of the total domestic production. Since three-fourths of the domestic phosphate production is from the Florida field, and since most of the phosphate from the Tennessee and Western fields is not processed, but used directly as electric furnace burden, this paper will concern itself almost entirely with water requirements for mining and processing ore from Florida. Figure 1 summarizes phosphate rock production for Florida vs. total United States production over the period 1947-1960.

Jan 1, 1962

By D. W. Bridges

Solvent extraction has become important in recent years as a unit process in extractive metallurgy. The flexibility and simplicity of the technique have attracted widespread attention, and numerous papers describing actual and projected metallurgical applications have been published. However, differences in terminology, procedure, objectives, and standards, as reflected in reports by different operators and investigators, have sometimes made appraisals and comparisons difficult. Consequently, a need appeared for n series of basic reports on the subject. This Bureau of Mines Information Circular is the first of such a series. It deals with the status of solvent extraction in metallurgy, as well as with the rudiments and terminology of the unit operation. In analytical chemistry, extraction of molecular species from aqueous media by immiscible organic solvents has been used for many years to separate and determine chemical elements (61).4 Complex chlorides of iron and other metals are readily soluble in ethers and ketones, as are the nitrates of uranium and thorium. Most metals are extractable as complex salts of some organic reagent, such as dithizone, 8-hydroxyquinoline, or cupferron.

Jan 1, 1962

By David J. Mack, T. V. Philip

The effects on the Cu-A1 eutectoid transformation of the addition of a third element from the second long period and from Group IIB of the periodic table, were studied by isothermal transfomation techniques. The valency of the third element shows the most pronounced effect on the eutectoid decomposition. With some exceptions, the atomic size factor of the third element shows some consistent effects on pearlite nucleation and growth. The atomic concentration or the electronegative valency of the third element shows wo consistent effect on the eutectoid decomposition. Addition of the third element helps spheroidization of pearlite. SINCE the pioneering work of Davenport and Bainl on the eutectoid decomposition in steel by the isothermal transformation technique, an enormous amount of data has been accumulated on the eutectoid transformation characteristics of commercial steels. While the eutectoid reaction in steel is of tremendous industrial importance, it appears to be quite unique among the eutectoid reactions. Though the metal-lographic structures developed in the Fe-C and Cu-A1 eutectoids are similar, it is now evident that the two eutectoid reactions are quite dissimilar. The eutectoid decomposition in the Cu-A1 system is more complicated partly due to the appearance of transitional phases in addition to the equilibrium phases. * The first isothermal studies of aluminum bronzes were made by Smith and Lindlief2 and later by Mack,3 Klier, and Grymko,4 and recently Hayne 5,6 A few other systems, structurally analogous to the above, have been studied by the same technique.7-10 Kasberg and Mack1&apos; studied the effects of iron on the transformation of commercial aluminum bronze. The effects of manganese and nickel on this aluminum bronze and those of iron, manganese, and nickel on the binary Cu-A1 eutectoid have been recently studied.12 The object of the present investigation was to study, by isothermal transformation techniques, the effects (with respect to the fundamental factors of alloy formation) of the addition of a third element on the transformation of a Cu-Al eutectoid alloy, 11.8 pct Al. The third elements chosen for the purpose were silver, cadmium, indium, tin, and antimony from the second long period, and beryllium, zinc, and cadmium from group 11B of the periodic table. They were added in nominal amounts of 0.5, 1.0, and 2.5 pct by weight to a eutectoid Cu-A1 alloy. These third elements were expected to show the effects of electron valency, atomic size factor, and electronegative valency effects on the binary eutectoid transformation. PFLEPARATION OF ALLOYS AND PROCEDURE All alloys were made as 400-g heats by induction melting in a graphite crucible with a graphite lid. The molten alloy with a layer of graphite powder on top was stirred at regular intervals by a graphite rod. When the melt was judged to have acquired sufficient superheat, a pinch of common salt was sprinkled on top and any crust scraped off to one side. It was then chill cast into a 5/8 in. rod. The alloys with silver were prepared by remelt-ing the high-purity Cu-A1 eutectoid alloy used by Mack3 with high-purity silver (99.99 pct pure from Hardy and Harmon, Inc.). In the preparation of all the other alloys, polished electrolytic copper shot (from Belmont Smelting and Refining Co.) and high-purity aluminum (99.99 pct pure from Aluminum Co. of America) were used.

Jan 1, 1962

By F. X. Tartaron

The comparison of actual energy of comminution with theoretical surface energy presents a wide gap. On the other hand, Solid State Theory presents a viewpoint that places actual energy of breakage in understandable relationship with the theoretical strength of materials. Therefore the physical background of comminution theory favors Kick&apos;s Law. A11 discussions of comminution theory appear farfetched when comparison is made of the actual energy of crushing with the energy input called for by thermodynamic theory. Quoting Taggart:&apos; "The work required to crush halite was of the general order of 0.10 kg cm per sq cm of new surface produced (based on air percolation) whereas the theoretical energy of this new surface, based on thermodynamic calculation by a number of investigators is 1 x 10&apos;4 kg cm per sq cm or the work expended was 1000 times the new surface energy — an indicated crushing efficiency of 0.10 pct." It is frustrating to probe into comminution theory with the prospect that the energy one is measuring is 99.9 pct waste energy. Do the laws of comminution deal with energy consumed by mineral breakage or with waste heat energy? There seems to be something wrong. Solid State Theory may provide the answer. The following statement is particularly apt to the situation: "The fundamental fact about metals and indeed all materials, is that they are much weaker than they should be. By this, we mean that if the stress required to cause a given plane of atoms to slip past a neighboring plane is calculated from basic atomic and Solid State Theory, the resulting number is some 1000 times too large to be accounted for by errors in approximations or assumptions. We know now that this is due to dislocations, and we even have a fair understanding of the details of the process by which dislocations make a crystal weak. An intriguing possibility which suggests itself, results from the discovery of very minute metallic crystals which are apparently free of dislocations and which have a strength approaching the ideal value for a perfect crystal." Here we have an extraordinary reversal of the situation. The actual energy for breakage is only one-thousandth the theoretical instead of 1000 times as given by Taggart. But the theoretical energy presented by Solid State Theory is the binding energy between atoms (or ions) in a crystal lattice. This is the kind of energy envisaged by Kick&apos;s law. The surface energy or the other hand corresponds to Rittinger&apos;s law. Comparison of theoretical with actual, on the basis of surface or on the basis of Rittinger&apos;s law, seems to present an absurdity; yet Rittinger&apos;s law is confirmed by an impressive array of experimental evidence. Comparison of theoretical and actual on the basis of Solid State Theory or, in other words, on the basis of Kick&apos;s law seems reasonable; yet there is not a scrap of evidence to verify Kick&apos;s law. The situation appears paradoxical, but the developments in the next section of this paper show that the paradox is a hint to a strange turn of events. ENERGY-WEIGHT FRACTION FUNCTION charles3 has presented a final equation showing the relation of energy consumed in comminution to size of product n{-1) a-n + 1 E is energy, C is proportionality constant, a and n are constants and k is the coarsest size in the ground product (size modulus). In the course of study of a large amount of experimental evidence, Charles discovered that in the general case, a-n + 1 approximated zero. For some reason, a and n differed only by unity. But if a—n + 1 = 0 within experimental error, then it is obvious that Eq. 1 states that it requires an infinite amount of energy to grind any sample to any size. This is a case where nature gives an absurd answer to a man-made mathematical equation, hence something is wrong with the equation. An adjustment must be made to fit the equation with experience. TO reveal the nature of the adjustment, the differential equation preceding the second integration in Charles&apos; group of equations is given When Charles integrated the quantity xa-n it was almost impossible for him to realize that he was dealing with a special case of integration and that

Jan 1, 1962

By F. C. Schora, H. P. Meissner

Both a graphical and an analytical technique are presented for calculating stream compositions and temperatures in adiabatic staged systems in which solids travel countercurrently to a gas stream. Such a system might be a tower containing several plates, on each of which the descending solid is fluidized by the rising gas stream. Examples are presented in which chemical reactions occur, including the oxidation of SO, by a solid catalyst and the gaseous reduction of iron oxides. COUNTERCURRENT staged processes involving reactions between solid and gas streams are becoming more common. These operations are generally carried out in a series of beds of fluidized solids, with each bed or "plate" acting as a stage. Fig. 1 is a schematic diagram of such a series of stages located in a column, down through which a solids stream moves from stage to stage counter to a rising gas stream. Typical reactions carried out in such systems are the dehydration of aluminum trihydrate, the calcining of limestone, and the gaseous reduction of iron oxides. Calculation of the performance of these counter-current systems rapidly becomes more complex with increases in the number of stages and in the number of chemical reactions occurring. Calcula-tional procedures for isothermal operations of such systems have been described.4 Actual tower operations, however, are generally adiabatic, and in consequence far from isothermal. The object here is to present both graphical and analytical techniques applicable to such adiabatic towers operating continuously and in steady state. In this introductory discussion, the graphical techniques presented are of the McCabe-Thiele type, rather than of the Pon-chon type. In all the examples presented, it will be assumed that both thermal and chemical equilibrium are attained in each bed. The assumption that the gas and solid streams leaving each bed are at the same temperature as the bed is in accordance with the familiar behavior of actual fluidized solid systems. Chemical equilibrium, on the other hand, is not necessarily attained in any given stage between these two streams, even with deep beds, since reaction rates may be slow. In the last section of this paper, discussion is presented of methods suitable for use when chemical equilibrium is not attained. The adiabatic tower in Fig. 1 has "n" stages numbered from 1 to n, starting with the bottom stage as number 1. In analyzing this tower&apos;s performance, it is important to express gas flow rates in terms of a key component or element which remains completely within the gas stream throughout the tower. Similarly, solid flow is best expressed in terms of a key compound or element which remains within the solid phase throughout the tower. Thus, in burning limestone with a hot flue gas, the gas flow might be expressed as G, the pound mols of nitrogen flowing through the tower per unit time, while solid flow might be expressed as S, the pound atoms of calcium in all forms in the solid stream per unit of time. Defined in this way, both G and S are constant throughout the tower. The enthalpy of the gas and solid streams are now best expressed in terms of these key components. That is, the gas stream enthalpy H is expressed as Btu in the total gas per mol of the key component in the gas. Similarly, the solids stream enthalpy h is expressed as Btu in the total solid stream per pound mol (or pound atom) of the key component in this stream.

Jan 1, 1962

By L. M. Burman

The phase-boundary pressure required to maintain a natural hydrocarbon fluid in a single phase must be considered in planning the recovery of reservoir liquids by miscible-phase processes. The change in the phase-boundary pressure at reservoir temperature that results when a light component or a mixture of light components is added to a reservoir fluid is an especially important consideration. The cricondenbar pressure (maximum phase-boundary pressure) and the critical pressure are unique correlated pressures that have been utilized to calculate the change in phase-boundary pressure that may result when the composition of a reservoir liquid is altered by an additive. In this study one reservoir oil and three gas-condensate fluids are used as examples. Correlations pertaining to the critical and cricondenbar states in chapters 4 and 5 of Bureau of Mines Monograph 10 (3)5 were used to demonstrate how butane and lighter components added to these reservoir fluids affect their phase-boundary pressures.

Jan 1, 1962

By C. R. Montgomery

Coal companies in order to supply their customers En the metallurgical market, both home and abroad, must be able to control their production in order to meet carbonization specifications over and above those of the proximate analyses which has been the prime consideration of purchases in the past. It is the purpose of this paper to review in brief some of the tests used and give data to show the application of such as it applies to the customers needs. It is now recognized that coal is not homogeneous in any of its properties and an amazing fact is that it has been used for so long a time as the principal raw material for the manufacturing of coke without more emphasis having been placed on the variation between coals; yes, even from coals in the same seam at different geographical locations, Recently Kuchta and Clendenin pointed this fact out In a study of the(1) carbonizing behavior as related to chemical and plastic properties of Alabama medium volatile coal.

Jan 1, 1962

By Y. C. Liu, R. H. Richman

Deformation and recrystallization textures of the a solid solutions of Cu-P, Cu-As, and Cu-Sb alloys are examined as a function of composition. It is found that the deformation texture of copper is unckanged up to a composition of 0.43, 0.41, and 0.24 at. pct of phosphorus, arsenic, and antimony, respectzvely, and then the transition to the 70 : 30 brass type of deformation texture proceeds linearly as the logarithm of the solute content. Recrystallization textures consist of strong, new components that do not all bear the usual<111> rotational relation to the deformation components. The dependence of the deformation texture transitions and the recrystallization orientations upon composition and solute-element type is discussed. A systematic evolution of individual recrystallization components in the annealing texture of copper was portrayed as a function of germanium or tin content in a previous study.&apos; Similar patterns of tex-tural change have been observed with copper-zinc alloys,2 and in less detailed studies of other systems.3,4 In fact, most of the literature dealing with preferred orientations in copper alloys indicates that the influence of solute elements upon textures in copper is of one general type. As the alloy content of copper is increased, the deformation texture changes from the copper type to the 70:30 brass type, and the annealing texture undergoes a comparable change from the (001) [ loo] orientation of unalloyed copper to the {113} <211> type of 70:30 brass, with the notable exception of copper alloyed with Periodic Subgroup V-B elements.4-8 In almost every case it is possible to describe the reorientations after annealing as 30 to 40 deg rotations about <1ll> poles of the deformation components. Since there is apparently not much difference in the final textures of the copper binary systems already investigated, only a limited variety of preferred orientations has served as the basis for current theories of the origin of annealing textures. In order to test the validity of the proposed theories, and the possibility that the <111> rotations are not unique, it would be most desirable to study the reorientation relationships of additional, and heretofore unanalyzed, recrystallization components if such components exist. Examination of the literature reveals a good deal of uncertainty concerning preferred orientations in copper alloyed with elements in Subgroup V-B of the Periodic Table. Phosphorus is known to inhibit the cube texture in copper when present in amounts as low as 0.01 wt pct,8 but the recrystallized matrix that occurs instead of the cube orientation was reported as either random or weakly textured, with orientations not observed in Cu-Zn, Cu-Ge, or Cu-Sn alloys.4-9 A Cu-0.75 at. pct As alloy apparently contained, along with the (001)[100] and (113) <211> type of recrystallization components, {110} <112> and (110) <001> components, whereas an almost random distribution of orientations was found in alloys of higher arsenic content.4 A {110} <001> component also appeared in rolledand annealed Cu-Sb alloys, but otherwise the recrystallization textures of Cu-Sb alloys seem to con-

Jan 1, 1962