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By SMF Hossaini

With the aim of a clearer understanding of the applicability of existing empirical equations for blast induced ground vibration, an investigation has been conducted on three mostly applied forms of such equations. The effect of explosive type on the applicability of these equations has been assessed by analysing 44 sets of data produced by using two types of explosives, namely ANFO and slurry explosive, in an open pit coal mine. The analysis of the data has revealed that the type of explosive affects the applicability of the criteria of the three equations. All three criteria have better correlation with the data of shots in which ANFO was used than the shots with slurry explosive. However, the applicability of one of the criteria is reduced, by far, only by replacing ANFO with slurry explosive for the same ground conditions. It was also found that one of the parameters of these criteria (i.e. “k”) is significantly sensitive to the type of explosive in all the three equations. The degree of influence to the values of “k” obtained by the variation of explosive from ANFO to slurry explosive in the three equations is 76.3%, 811% and 39%. This implies that “k” is not only dependant on ground conditions, as stated in most previous publications, but is also strongly a function of the type of explosive.

Jan 1, 2004

By K. O. Bennington

The thermodynamic properties of two manganese silicates, pyroxmangite and fowlerite (zincian rhodonite), were experimentally determined by the Bureau of Mines. The standard enthalpies of formation were determined by hydrofluoric acid (HF) solution calorimetry, the low-temperature heat capacities by adiabatic calorimetry, and the high-temperature heat capacities by differential scanning calorimetry over the range 322 to 1,372 K. Data for the standard enthalpy of formation (AH298), the derived standard entropy (S298), and the standard Gibbs energy of formation (AGf 298) are as follows: Pyroxmangite [(Mn0.9554Cao,0446)(Si03)J- AHf298 319.668±0.46 kcal/mol AH298 (from oxides)... -7.215±0.11 kcal/mol 5295 23.785±0.048 cal/(mol'K) AGf298 -301.190±7.96 kcal/mol Fowlerite [(Mno.7o3Zno.0884Ca0.2086)(Sio3)]--AHf298 ?... -329.914±0.419 kcal/mol AH298 (from oxides)... -8.400±0.104 kcal/mol 5598 21.949±0.059 cal/(mol-K) AGf298 -310.716±7.99 kcal/mol These experimentally determined values were combined with data from the literature to calculate the Gibbs energies and equilibrium constants of formation over the temperature range of the measurements. Standard enthalpies, Gibbs energies, and equilibrium constants of formation are given as a function of temperature from both the elements and the constituent oxides.

Jan 1, 1987

By C. F. Lucks, W. D. Wood, H. W. Deem

Electrical ad thermal-conductivity measurements have been made on titanium and 6 titanium alloys. The following expression was derived for calculating thermal conductivity from electrical conductivity: K = 0.626 s T x 10-8 + 0.00497 where K = thermal conductivity, cal sec-1 cm-2 cm0C-1 s = electrical conductivity, ohm-]cm-1 T = temperature, deg Kelvin This expression gives calculated thermal conductivities that are not in error by more than 10 pct from the experimental values for A-55 titanium and the 6 alloys measured; namely, A-110AT, C-110M, C-130AM, Ti-6A1-4V, Ti-140A, and Ti-155A, which are representative of the presently available commercial a and a-ß titanium alloys. THERMAL conduction in a gas, liquid, or amorphous solid is accomplished by energy diffusion from molecule to molecule, a relatively slow process. For this reason, such materials have a low thermal conductivity. When a material is crystalline, there is in addition a heat transfer by a vibratory motion of the crystal lattice. It is the contribution of this lattice conduction that makes a crystal a much better conductor than a gas, liquid, or amorphous solid. Lattice conduction, however, does not account for the relatively enormous thermal conductivity of a metal. This is explained by the freedom of movement of valence electrons. These valence electrons drift in a metal in a direction toward a drop in electrical potential and, to a lesser degree, in the direction of a temperature drop in the metal. Since both the electrical and thermal conductivities of a metal depend upon the presence of free electrons, there should be some relatively simple relation between the two. Wiedemann and Franz in 1653 first discovered an approximate empirical relation between the electrical and thermal conductivities of metals at the same temperature. This ratio varies appreciably with temperature, and Lorenz later showed that by adding a temperature factor to the Wiedemann-Franz ratio the value of K/(s T) is constant, where K is the thermal conductivity, a the electrical conductivity, and T the absolute temperature. This Lorenz constant shows a greater variation for alloys than it does for pure metals, the ratio increasing slightly as the proportion of alloying elements increases. It has been found that a closer correlation between electrical conductivity and thermal conductivity can be obtained by means of an equation of the form K - A s T + B [1] where A and B are constants. In this equation the term AsT is the contribution of electronic conduction and B is the contribution of lattice conduction to the total thermal conductivity. EXPERIMENTAL MEASUREMENTS Electrical-resistivity and thermal-conductivity measurements on titanium and 6 titanium alloys serve as the basis for determining an equation of the K = AsT + B type for titanium alloys. Specimens—Table I shows nominal compositions of the 7 metals on which electrical and thermal conductivities were measured. The electrical and thermal-conductivity specimens for each alloy were taken from stock of the same heat and usually from adjacent sections of the same bar. All of the metals measured were in a mill-annealed condition. Methods—Electrical-resistivity measurements

Jan 1, 1959

By M. Hancer, J. D. Miller

It is known from soluble salt flotation practice that the K, Mg double salts of kainite (KClMgSO43H2O), and carnallite (KClMgCl26H2O) are difficult to float and must be converted to other salts such as schoenite (K2SO4MgSO46H2O) and sylvite (KCl) in order to recover potash values. The flotation characteristics of these double salts have now been confirmed in some detail by carefully controlled laboratory experiments with both cationic and anionic collectors. The experimental results are discussed in view of recent experimental findings regarding the flotation characteristics of simple salts, in which the flotation response was shown to be determined by the interfacial water structure and whether the salt could be considered to be a water structure maker or a water structure breaker. The same approach can be use to explain the flotation response of the potassium double salts ; schoenite, kainite, and carnallite. In addition, the sign of the surface charge of schoenite (K2SO4MgSO46H2O), was determined as a function of pH from nonequilibrium electrophoretic mobility measurements. Schoenite appears to exhibit three charge reversals (CR) which can be explained based on surface hydrolysis reactions. The flotation behavior of schoenite is further considered based on solution chemistry calculations, electrophoretic mobility measurements, and microflotation results.

Jan 1, 2001

By Robert M. Doerr

The purpose of the investigation was to determine the oxidation behavior of selected tungsten-cobalt alloys. Specimens of Wand W-Co containing 0.7, 1.7, 3.4, and 9.7 weight-percent Co were subjected to pure 02 at 1,000° and 1,100° K, and specimens of W-Co containing 29.8 weight-percent Co, at 1,100° K. Reaction kinetics were determined volumetrically. For specimens other than those containing 29.8 percent Co, the reactions proceeded at about a constant rate at either temperature, indicating the formation of a scale of constant protectivity; the reaction rates were essentially independent of the Co concentration. The scales on these alloy specimens consisted principally of WO3 and CoWO4. Specimens of a 29.8 weight-percent Co alloy, consisting primarily of the W6CO7 phase, oxidized with only slight deviations from the parabolic rate law at 1,100° K. The protective scale on these specimens consisted chiefly of Co3O4, CoW04, and W1 8°49; Co3O4 was outermost, and the W18O49 was adjacent to the alloy. The results suggest that the Co-rich outer scale inhibited the inward transport of 0 to an extent sufficient to greatly limit the amount of the nonprotective WO3 formed, so that protective W18O49 formed instead.

Jan 1, 1967

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By D. A. Stanley

The Bureau of Mines is investigating a method of dewatering flocculated fine-particle waste that involves treating the waste with a high molecular-weight polymer such as polyethylene oxide (PED) followed by dewatering on a static screen and/or in a trommel. Dilution of the polymer solution used for dewatering and use of the ion-exchanged form of the montmorillonite clay were found to be major factors determining the amount of polymer required to dewater clay-containing slurries. The amount of polymer, A, required to dewater ion-exchanged montmorillonite can be described by the equation, An = kC + b where n, k, and b are empirical constants and C is the concentration of the polymer solution used for dewatering. Clays that require large amounts of polymer for dewatering also dewater to a lower solids content. The concentration of the polymer solution is important because it affects the radius of the polymer coil in solution and hence its ease of transfer to a bridging configuration by shear. The constant, n, a function of the charge to hydrated radius of the exchange ion, relates to the strength of the bond between the polymer and the surface of the clay through a water bridge. The constant k is related to the hydrated radi-us for sodium or to the unhydrated radius for the other exchange ions.

Jan 1, 1986

By R. D. Pehlke, J. V. Gluck

The limiting activity coefficient of zinc in a "binary " solvent has been described for several dilute ternary solutions by combining literature data from recent interaction studies in the terminal regions with thermodynamic data for the central regions. Results are discussed in terms of the Alcock and Richardson random solution model. The observed behavior agrees semiquantitatively with predictions using the model. RECENT efforts in the thermodynamics of dilute ternary liquid metallic solutions have been mainly concerned with the interactions between two dilute solutes, that is, the terminal region at an apex of the composition diagram.'-' A more general case is that of the behavior of a dilute solute over the full range of a ternary system, or, more specifically, the limiting activity of solute i as projected to the k-j binary side of the i-j-k composition triangle. An implication of this is that the interaction between i and j at the k apex should connect in some way to the interaction between i and k at the j apex. A model to characterize various types of expected behavior has been discussed by Alcock and Richardson.9,10 Such behavior can range from a simple linear relation for In yi over the 1-k binary to more complex curved relations which depend on various assumptions regarding the heat of solution in the j-k binary system and the presence or absence of clustering with solute i. Quantitative data to assess these concepts have been limited primarily to the cases of nonmetallic interstitial solutes in ferrous solutions. Alcock, Richardson, and various coworkers9-13 have discussed the behavior of oxygen, sulfur, silicon, or hydrogen in dilute solution over the range of iron + metal systems; however, the only data considered by them for substitutional nonferrous metallic solutions were the results of Elliott and Chipman concerning the activity of cadmium in the Pb + Sn, Pb + Bi, and Pb + Sb systems.9 These data were limited and did not cover the terminal regions in detail. An opportunity to extend the Alcock and Richardson considerations to the dilute solution of zinc in various "binary" solvents has been afforded by combining results of several of the recent investigations of ter-minal-region interactions with previous data from the literature for the same more concentrated solutions. RESULTS AND DISCUSSION The results of the analysis are shown in Figs. 1 to 5 where the log activity coefficient, (In yZn)xzn--o, is plotted vs the composition of the "binary" solvent. In these plots the end points are the values for In yzn in the appropriate binary solution with Bi, Pb, Sn, Cd, or In at the indicated temperature—usually 550°C (823°K). For the terminal regions the slopes were drawn using the first-order interaction parameters taken from various studies reported in the literature. The data points shown in the central regions were obtained by the short extrapolation to infinite dilution of the logarithm of the activity coefficient calculated from thermodynamic studies reported in the literature for the same systems. The sources of the data are indicated on each figure. Second-order effects were not considered. Reasonably smooth curves can be drawn to connect the central region with the terminal regions for the Zn-Pb + Bi system, Fig. 1, the Zn-Pb + Zn system, Fig. 1, and the Zn-Bi + Cd and Zn-Bi + Sn systems, Fig. 2. As shown in Fig. 2, where central region data are available from two independent investigations, the agreement is quite good. The Zn-Pb + Cd system does not appear to be as well behaved as the previous four, Fig. 3; however, this type of behavior has also been

Jan 1, 1970

By E. R. Macgregor, J. Halpern

The kinetics of the reduction of cupric salts in aqueous solution by molecular hydrogen to metallic copper are described. The rate of reduction appears to be homogeneously determined and shows a marked inverse dependence on the hydrogen-ion concentration. Precipitation of copper is more rapid and complete in sulfate than in per-chlorate solution. A mechanism is proposed which accounts for this behavior. IN recent years a number of important hydro-metallurgical processes have been developed in which metallic salts in aqueous solution are reduced by gaseous hydrogen, usually at elevated temperatures and pressures, and thereby precipitated either in metallic form (e.g. Ni, Co, Cu) or as an oxide or salt of lower valence (e.g. VO, and VA).1 ; In connection with applications such as these, most of which involve heterogeneously catalyzed reactions, recent demonstrations"-" that salts of certain metals, e.g., Cu", Ag' , Hg" , and Hg,+ can activate molecular hydrogen homogeneously and thus catalyze hydrogenation reactions in aqueous solution, are of considerable interest. For example, cupric salts catalyze the otherwise slow homogeneous reduction of dichromate and ceric salts by hydrogen, i.e. Cr,O; + 3HL. + 8H1 ? 2Cr'- -- 7H,O [1] 2Ce ' ! H.. ? 2Ce" | 2H . [2] In perchloric-acid solution, where Cu" is not appreciably complexed, the kinetics have been found" " to be of the form -d [H,] _- k,[HJ [CU"]' dt -LCu+' l+ (k ,/k,) [H] [3] where, K = 1x10"' exp [—26,600/RT] 1, mole-' min-' ... [4] and (k ,/k,) - 0.25 at 110°C. This kinetic behavior suggests that the reaction proceeds by a mechanism involving the following sequence of steps kt Cu" +H1CuH' 4-HA [51 k., CUH + CU" ? + 2Cu f H' [GI 6Cu'+ Cr,07 + 14H'+ 2Cr- (¦ 7H,O + 6Cu" ['i] fast The catalytic activities of the undissociated cupric-sulphate and cupric-acetate complexes are somewhat greater (by factors of 6.5 and 120, respectively) than that of the simple hydrated Cu" ion.'" These considerations suggest that, in contrast to the other hydrometallurgical hydrogenation reactions, referred to previously, reduction of cupric salts in aqueous solutions by molecular hydrogen, should proceed homogeneously, and in the absence of an extraneous catalyst. This has already been demonstrated" for acetate-buffered solutions where the product of the reaction is a precipitate of cuprous oxide (Cu,O). In the present paper, an investigation of the reduction of cupric salts in perchloric-acid and sulphuric-acid solutions, leading to the precipitation of metallic copper, is described. Some results for the sulphate system, which is of considerable hydrometallurgical interest, have been reported previously by Ipatieff",' " and by Schaufel-berger' but these do not give a quantitative account, of the kinetics and mechanism of the reaction. Experimental The reduction experiments were conducted in the 1-gal, titanium-lined autoclave described in connection with earlier related investigations," " and using a similar procedure. The solutions were made up by dissolving known amounts of CP grade Cu(ClO,), and HC10, (or CuSO, and HISO,) in dis-tilled water. While in the autoclave, the solution was stirred and maintained at a constant temperature (±loc) and under a constant partial pressure of hydrogen gas. It was ascertained that the agitation (provided by two 3-in., four-bladed stirrers, rotating at 900 rpm) was adequate so that at no time was the rate of reaction limited by solution of hydrogen. During each experiment, samples of the solution were withdrawn periodically, allowed to cool, and the concentration of copper remaining in solution was then determined electrolytically. Some Cu' is formed during the reaction, but undergoes disproportionation when the solution is cooled to room temperature. For purposes of kinetic calcula-

Jan 1, 1959

By Philip D. Anderson, Ralph Hultgren

Heat contents of extremely pure iron were measured over the range 300"to 1433"K, using a diphenyl ether calorimeter. Results from three samples containing widely differing impurities agreed with one another and with Previously reported results at higher temperatures (1184 ° to 1809°K) by Olette and Ferrier. From these data a table of heat contents of iron has been Prepared which is believed to be more accurate than those previously available. CP values have been derived which are consistent with these heat contents, with the best experimental Cp data, and with the thermodynamic conditions of equilibrium between bcc and fcc iron. The opinion is expressed that low-temperature extrapolations of presently known Cp values for y-Fe are not reliable. It would seem that the thermodynamic properties of iron, which is by far our most important metal, should have been well established long ago. This is not the case, however. As discussed by Olette and Ferrier,' there is objection to every earlier heat content measurement. While the best true Cp determinations agree well at temperatures below the Curie point, there is wide divergence at higher temperatures. Several investigators have examined available data and attempted to calculate thermodynamic functions for iron that are consistent with the two equilibrium temperatures of bcc and fcc iron. The two primary efforts were those of Austin' in 1930 and Darken and smith3 in 1948. The recommended values differ considerably; integration of Austin's Cp values leads to a heat content at 1100°K which is 300 cal per g-atom higher than the value recommended by Darken and Smith. The compilation of Fisher4 in 1949 was based on the selection of Austin. In 1956, Weiss and Tauer obtained yet another set of values by resolving Cp values into components due to dilation, lattice vibration, electronic excitation, and magnetism. The magnitude of contribution by each component and its dependence on temperature was estimated by semiempirical means. Their values are not self-consistent in that they do not form smooth curves when plotted vs temperature; moreover, their calculations cannot easily be repeated since they do not give the values of some of the parameters used. Clearly, experimental values for iron were in a most unsatisfactory state. The presently described measurements of the heat content of iron were therefore undertaken, covering temperatures as high as 1433°K. While the work was in progress, the high-temperature (1193" to 1789"K) heat content measurements of Olette and Ferrier' were published; in the region of temperature overlap the present results agree with Olette and Ferrier well within experimental accuracy. It is believed that the present results, combined with those of Olette and Ferrier, provide for the first time a reliable set of heat contents of iron from room temperature to the melting point. From these data, guided by available Cp measurements, it proved possible to derive Cp, entropy, and free energy function values for @-iron from room temperature to the melting point, and for y- iron in the temperature region of its stability. Exhaustive study led to the conclusion that extrapolations of y-iron functions to room temperature were not reliable enough to be useful; hence these have been omitted from the tables. EXPERIMENTAL Materials. Three samples of extremely high purity iron from different sources, containing widely different impurities, were measured. The first of these, designated "Chipman", was kindly supplied by Dr. K. K. Kelley of the U. S. Bureau of Mines from a lot which was made many years ago by Dr. John Chipman of the Massachusetts Institute of Technology. The second, designated6'Teddington", was supplied by the National Physical Laboratory, Teddington, England, from a lot zone-refined by them. The third sample, designated "Irsid", was supplied by the Institute de Recherches de la

Jan 1, 1962

By A. S. Emanuel

A correlation has been developed for calculating the phase behavior of, gas-condensate systems at reservoir conditions. The correlation is based on the principle of corresponding states and has been coded for an IBM 7094. Experimental K-values were determined for several gas-condensate systems at reservoir conditions to evaluate various semi-empirical parameters of the correlation. The approximate range of application of the correlation is 150 to 300F and 1,500 to 6,000 psi. INTRODUCTION The rapid development of digital computers during the past several years has made feasible the calculation of hydrocarbon phase behavior by methods based on rigorous thermodynamic principles. Good correlationsl have been developed for low to moderate pressures, but these techniques have not yet been extended successfully to reservoir fluids at high pressures. Consequently, the determination of phase behavior of oil and gas systems at reservoir conditions is still based almost entirely on generalized data correlations or on experimental studies of the fluid in question. While these methods have been used successfully many times, they do have inherent limitations that restrict their applicability. Generalized correlations, such as the NGShlA K-charts, are limited to the range of pressure, temperature and components for which the data were determined. The accuracy of these correlations is often questionable because the effect of total system composition is not well defined. Experimental studies offer a reliable method for determining phase behavior, but usually the studies are costly and time consuming. Recently, Leland and co-workers presented a new approach to calculating phase behavior from the principles of corresponding states.6-8 Corresponding states methods determine the thermodynamics properties of a given system by comparison with a reference substance whose properties are known. The accuracy of this approach depends on close chemical and structural similarity between the reference substance and the system in question and between components within the system itself. For high accuracy, it is usually necessary to correct for chemical and structural dissimilarities. In principle, however, the corresponding states method should be no less accurate at high pressures than at low pressures, provided reference substance properties are known. This paper describes an empirical modification of the basic correlation proposed by Leland, et al.6 for the specific purpose of calculating the phase behavior of gas-condensate fluids at reservoir conditions. The modified correlation, which has been programmed for an IBM 7094, may be used for either approximate or precise determination of fluid behavior depending on the amount of analytical and, experimental data available for the system. BASIC THEORY The basic theory of the corresponding states phase equilibria correlation was first published by Leland, Chappelear and Gamson.6 Subsequently, Leland, Chappelear and Leach published methods for improving the accuracy of the original theory.7-9 The aim of the correlation is to calculate the K-value of each component of a given system as a function of pressure, temperature, and over-all composition, where Once the K-values are known, the phase behavior may be determined directly by an appropriate flash calculation. The basic equation for calculating component K-values was taken from the work of Joffe. 4 For any component i of a mixture, the K-value is given by

Jan 1, 1969

By J. Serra, M. Turpin, R. Alberny

A new method is proposed to obtain automatically an unbiased estimate of the interdendritic spacing A. It is shown that the structure can be built by a random distribution of a rectangular basic unit. The usual definition of the interdendritic spacing yields a value 1 which, coupled with A, gives the shape of the basic rectangular unit. A study of the relationship between dendrite arm spacing and solidification rate was conducted as a part of a research program on dendritic solidification. For any comparison between theory and experiments to be meaningful, it is necessary to measure reproducible and clearly defined spacings. Fig. 1 shows clearly that even in a fairly simple structure such measurements are difficult. if we compare photos (a) and (b), we can hardly assess which one shows the larger spacing. Moreover, the quantity to be measured can be defined in several ways. On a small scale, dendrites seem to be distributed in a very regular and ordered way. However, on a larger scale, this regularity no longer exists. The usual way to measure spacings is to pick up some rows of dendrite stalks; such measurements are obviously biased since less orderly regions are not taken into account. A more objective method is to section the picture with randomly oriented straight lines and average the measured interdendritic spacings. The purpose of this paper is to show that such measurements, which can be conducted automatically, yield objective and reproducible results which are directly related to characteristic features of the dendritic structure. I) THEORETICAL ANALYSIS 1-1) Mathematical Morphology and Function of Co-variance. Matheronl and Serra2 enlarced- the definition and geometrical meaning of the notion of covariance to encompass problems in mathematical morphology. A brief review of part of their theory can be stated as follows. Let A' be an isolated particle, and let us consider a group of two scanning points h is the vector joinlng these points, h its modulus, and a its direction. Let us also define a boolean function, k(x), whose value is 1 if x lies inside the particle and 0 if it 1s outside. The total number of events in which both points are inside A' IS the covariance Ii',(h): is the measure of the intersection of A' with the particle ALh obtained by translating A' of -h Obviously K,(O) is the volume of the particle A', or its area if A' is a two-dimensional body. The average value of K,(h), when the direction of a vector h of constant modulus is rotated, is: An important property of the covariance is illustrated on Fig. 2: if the shape of a particle shows some regularity along a direction a, K,(h) generally presents a maximum. We now consider a group A, made of many particles A' distributed in space; then k(x) is taken as the realization of a stationary random f~nction.~ The volume fraction (or fraction of area if the problem is two-dimensional) occupied by A equals the average value q of k(x): meaning "average value of"). We also replace

Jan 1, 1970

Mr R. C. J. Goode (President) was in the Chair. There were also present one hundred and thirty-six Members, including Messrs R. J. Adamson, Dr J. M. Bereza, Messrs M. Barcza, H. Britten, H. E. Cross, J. K. E. Douglas, G. W. Holl, Dr J. P. Hugo, Messrs C. J. Irving, P. Lambooy, Prof J. de V. Lambrechts, Mr D. G. Maxwell, Dr J. T. McIntyre, Prof R. P. Plewman, Messrs J. F. Reid, V. C. Robinson, H. Simon and P. W. J. van Rensburg (Council Members), G. Abdinor, C. B. Anderson, H. F. Allan, E. L. Atkinson, V. C. Barnes, J. F. Bennet, W. W. Bath, R. E. Barnes, C. L. Berrange, J. P. Buds, Dr W. Bleloch, Dr L. A. Bushell, Messrs D. L. Carson, D. D. Cornier, R. S. Cooke, R. R. M. Cousens, J. P. Coetzee, W. L. Cousens, J. Daniel, R. Daniel, D. G. Davies, S. K. de Kok, V. S. Dillon, B. S. Dykhouse, Dr H. G. Denkhaus, Dr R. S. J. du Toit, Messrs J. I. L. Edwards, R. C. Espley-Jones, J. C. Ferguson, D. T. Fourie, A. Frost, W. R. Flook, Dr N. P. Finkelstein, Messrs D. F. H. Grave, J. M. Gosnell, E. K. Gibson, R. W. Grout, E. W. Gray, J. S. Hay, F. G. Hill, H. N. Hepker, J. P. Hoffman, C. G. Hodges, D. M. Jamieson, Dr D. G. Krige, Dr N. P. Lategan, Messrs J. E. Laschinger, J. Levin, C. P. Linsell, J. O. Kempe, F. Q. P. Leiding, A. I. Lee, D. G. Malan, W. Malan, H. W. McCulloch, R. D. R. Munro, C. S. Macphail, Dr T. F. Muller, Dr A. J. Nel, Messrs S. C. Newman, G. G. Nicolson, G. Y. Nisbet, J. A. Papenfus, E. Pavitt, W. H. Pittie, P. C. Pirow, P. G. D. Pretorius, N. F. Peverett, R. P. Plaskett, M. P. Pearse, W. Pilkington, T. K. Prentice, Dr R. E. Robinson, Messrs R. B. Richardson, R. St. J. Rowland, R. J. Rouillard, F. O. Read, W. T. Ruhmer, D. Savile Davis, E. F. Statham, K. Smith, H. Simon, G. B. Stern, C. D. Storrar, Dr N. B. Strydom, Messrs J. H. Talbot, A. H. Taute, J. H. Taylor, G. W. Thiel, K. A. Tweedie, W. E. Vance, Dr H. J. van Eck, Messrs L. W. P. v. d. Bosch, P. A. von Wielligh, N. B. Vinson, S. J. Venning, W. M. Walker, D. T. Watt, Dr H. J. R. Way, W. T. L. Wayman, R. G. Williams, L. G. S. Wright and C. F. Ziervogel. Thirty Associate Members, including Messrs E. Collier, G. Douglas, D. H. Gray, H. G. Gericke, R. Hemp, N. M. Hayne, A. Hazell, P. M. Johnston, D. E. Love, Miss V. E. Marting, Messrs R. G. Matthews, P. Malpage, D. Nicolle, R. Pendreigh, J. J. Rosslee, R. W. Shearer, R. F. Taylor, G. C. Thompson and D. A. Viljoen. Three graduates, Messrs G. S. Giles, J. P. Hatfield and J. A. Jones. Five Affiliates, Messrs A. C. Collie, E. Collier, A. B. Cook, W. Jacobs and G. M. Thain. Two Students, Messrs C. J. Bircher and R. P. Henrard.

By J. A. Cahill, A. D. Kirshenbaum

Using an alumina or zirconia crucible with an alumina sinker or a molybdenum sinker coated with zirconium dioxide, the density of liquid iron was determined by the immersed-sinker method over the temperature range of 1800" to 2500°K. The density, with respect to temperature, is ex-Dressed by the equation Dg/cm = 8.523 - 8.358 X 10 T'K The molar Volumes and thermal coefficients of expansion were calculated. Iron, upon me1ting, was found to expand 3.5 pct. A basic knowledge of the physical properties of materials at high temperatures is becoming increasingly important. A check of the literature shows, that in spite of the importance of iron, very few measurements have been made of its physical properties in the liquid state. Density measurements have been made by Benedicks and his collaborators1g using the method of balanced columns, by Desch and smith4 using the immersed sinker method with an alumina sinker, by Lucas using the maximum bubble method5 and by Stott and endall' who used an alumina pyknometer. In the method of balanced columns, the difference in level of molten iron in two arms of a U-tube, together with the corresponding difference of pressure had to be measured. The formation of gas bubbles in one or both arms was a great source of error. These values are very erratic. They vary from 6.83 to 7.45 g per cm3 at the melting point (1805"~) and from 6.45 to 7.15 g per cm3 at 1890°K. Stott and Rendall determined the density at 1837"K, with a reproducibility of *0.2 pct. They used an alumina pyknometer fired to 1973°K. The vessel was filled in a vacuum furnace by immersion in the liquid metal. When thermal equilibrium was attained, the pyknometer was withdrawn, cooled, the ingot removed and then weighed. The chief disadvantage of the method was the difficulty of inserting the pyknometer without cracking it. The authors have been able to determine the density of liquid iron from its melting point up to 2500°K, by using the immersed-sinker method, with A1203 or ZrOz crucibles and A1203 or molybdenum sinkers coated with Zr02, Fig. 1. EXPERIMENTAL Apparatus. In these studies the source of heat was the carbon tube resistance furnace with an argon atmosphere described previously.7 Experimental runs were made using either Ala3 or ZrOz crucibles. The sinkers used were 1) pure A1a3 and 2) molybdenum coated with ZrOz. The crucible, 2 1/8 in. in diam and 3 in. high, was centered in the furnace on an Ala3 of Zr02 pedestal. The sinker, 1/2 in. in diam and 1 1/2 in. long, together with a counter weight, was suspended from an analytical balance into the melt by a molybdenum wire. Procedure. The procedure, as described previously,' consisted in measuring the weight loss of the sinker in the liquid iron while determining simultaneously the liquid iron temperature by means

Jan 1, 1962

By D. E. Hartman, J. M. Roberts

A detailed study of the temperature dependence of the critical stress, TB . necessary to cause a damping loss of 1.41 x 10-6 g mm per mm3 in pre-strained magnesium single crystals has been carried out in the temperature range 82" to 320°K. Tb is found to be linearly related to the reciprocal of the ahsol~cte temperature in this temperature range. The temperature dependence of the anelastic limit, TA, defined as the stress necessary to form open unidirectional stress-cycle damping loops has been measured between 82" to 320°K. ta is found to be independent of temperature in this range. It is suggested that TA is determined by the stress necessary to activate Frank-Read dislocation NUMEROUS studies1-9 have been reported concerning the details of yielding and microstrain near and below the generally discussed macroscopic flow stress. The work of Kramer and coworkers10-13 is helpful in determining certain qualitative facts. concerning preyield phenomena. The absence of a stress-dependent delay time in annealed copper and aluminum single crystals between 83" and 298 suggests that the preyield mechanism is temperature-independent in this range. This is not sources. The temperature and stress dependence of the effective activation volume (Veff) has been measured in the damping-loop region in prestrained magnesium single crystals. The data suggests that Veff/kT is approximately constant, equal to 2 4.5 sq mm per g in the temperature range 130°to 298°K, and that Veff is almost independent of stress at stress levels greater than 10 g per sq mm. A restricted model is developed to predict the stress (rb) necessary to cause a small fixed damping loss as a function of temperature, effective activation volume, and dislocation density. Various possible dislocation mechanisms controlling TB are discussed. true for zinc, p brass, and iron crystals in the same temperature range, however, since the existence of a stress-dependent delay time suggests a thermally activated preyield mechanism in these materials.10-13 The work by Vreeland et a1.14 confirms the work by Liu et al.ll on delayed yielding in zinc single crystals. A stress-dependent delay time between 82" and 298°K was found12 in prestrained aluminum and copper crystals. These results suggest that the preyield phenomena may be different between prestrained and unstrained or annealed crystals. The temperature dependence of the yield point at 2 x 10-8 plastic strain found by Rosenfield and Averbach3 in annealed copper and aluminum is not in agreement with the delay-time data, unless possibly the delayed yielding experiment only de-

Jan 1, 1964

By Peter W. Scott

Feldspars have major uses in glass manufacture and in ceramic products. About 6 million metric tons (6.6 million short tons) are used annually. Feldspars are desirable because of their high aluminum and alkali contents. Na feldspars are favored for glass, while K feldspar is often preferred in the pottery and tile industries. Economic deposits occur in a variety of geological environments. Most are in granites or granite-like bodies, pegmatites being a common source worldwide. Alkali granites, particularly those some- times called alaskites, are mined directly as a source of feldspar and associated minerals. Some other igneous bodies, such as aplites, rhyolites, and partly altered granites (for example china stone) provide alternative feldspar-rich products. Nepheline syenites and phonolites are other sources of feldspar and contain higher amounts of alkalis. Feldspar-rich (arkosic) sediments derived from the weathering of pegmatites and granites are widely extracted and processed for use in ceramics. The present study reviewed the various sources of feldspars throughout the world. Data on the quality of products has been taken from literature, and samples have been obtained from a large number of producers. The mineralogy and chemistry of the samples has been determined and, as far as possible, have been related to the geology of the source area. Feldspar products show a wide range of chemical and mineralogical compositions. Some are pure Na feldspar (albite), others are made up entirely of K feldspar (microline and orthoclase), but many are mixtures of Na and K feldspars. Significant quantities of quartz are often present, and many products contain mica and kaolinite. Fe203 con- tents are very low, typically less than 0.1 percent. Detailed mineralogical studies show that four groups of products can be recognized on the basis of feldspar mineralogy. These are albite, albite with microcline, microcline with orthoclase, and orthoclase with albite. Products containing microcline and orthoclase together are mostly sedimentary in origin. Those with albite only, or albite with microcline have a pegmatitic or granite origin. Those containing orthoclase as the dominant K feldspar are derived from aplites or rhyolites. There does not appear to be any relationship between the feldspar mineralogy and the quartz content. Peraluminous S- type granites and pelite-dominated high-grade metamorphic rocks, in which there is a significant volatile component, are likely to be the most important feldspar sources. Partial kaolinization of feldspar-containing rocks often improves minability, decreases crushing costs, reduces iron content, and increases the K2O/Na2O ratio.

Jan 1, 2001

By R. W. Gurry, L. S. Darken

The solubility of cementite in austenite is computed by thermodynamic methods from the observed solubility of graphite. It is found that the solubility of cementite is greater than that of graphite in the entire austenite temperature range. Thus the prior discrepancy between this portion of the phase diagram and the observed metastability of cementite is partially resolved. FOR several years it has been apparent that a serious discrepancy exists in certain observations pertaining to the Fe-C system. Direct experimental data indicate: 1-That the curve representing the solubility of graphite in austenite'" crosses that for cementite4 at about 945°C as shown in Fig. 1. 2— That graphite and austenite saturated therewith are stable1 relative to cementite at all temperatures between the eutectoid, about 723°C, and the eutectic, about 1153°C. These observations are mutually incompatible in view of a well-known consequence of the second law of thermodynamics, namely, that the stable phase (presumably graphite at all temperatures) has a lower solubility than the metastable phase (presumably cementite). Hence either 1 or 2 above must be in error; either the measured solubility of graphite or of cementite, or the observation as to the stability of graphite, is in error. Our present purposes are: 1—To collate the available data on cementite and prepare a table of HO — HO° and of (Fa— HO°)/T. This tabular method seems the best and most convenient way to represent the heat and free energy of formation. 2—To determine whether the measured solubilities of cementite and graphite in austenite are in accord with the above table and the measured thermodynamic properties of austenite, in order to resolve, if possible, the existing paradox of these two solubilities. Enthalpy of Cementite The enthalpy of cementite at 273 °K, H279 — HOcem, was computed by integration of the low temperature heat capacity as measured by Seltz, McDonald, and Wells" 68" to 298 °K) and as given by the Debye functions recommended by them (0" to 68°K); the result is included in Table I. At higher temperature HCem — H,,"" is given by Kelley who used the data of Naeser7 (298" to 1037°K) and of Umino8,9 (273° to 1923°K). We have recalculated Hcem — H273 cem from the data of UminoO in the following way. In the equilibrated alloy at temperature the weight fraction of cementite Pct c -Pct cr is PctC -PctCr designated f(C), and the

Jan 1, 1952

By M. J. Ferrante

Relative enthalpies of high-purity disodium hexatitanate (Na2Ti6013) were measured at the Bureau of Mines to provide new thermodynamic data needed to advance the technology of materials. Measurements from 298.15 to 1,478 K were made by drop calorimetry with a copper block. Tabulated values are listed for the standard relative enthalpy, heat capacity, en-tropy, and Gibbs energy function between 298.15 and 1,500 K. Enthalpy data are also given in equation form and are combined with thermodynamic data from the literature to derive values of standard enthalpies of formation, Gibbs energies of formation, and logarithms of the equilibrium constants of formation. Similar calculations were made for the reaction of Na20 with Ti02.

Jan 1, 1986

By H. Al-Kazzaz

The effects of laser power and joint gap on the welding quality of 2-mm butt joints of ZE41A-T5 sand castings were investigated using a continuous wave 4 kW Nd:YAG laser system and 1.6-mm EZ33A-T5 filler wire at a welding speed of 6 m/min and surface defocusing. The smooth weld profiles with the minor welding defects were obtained at a laser power of 4 kW and joint gap of 0.3-0.4 mm. The hardness values in the fusion zone are similar to those of the base metal but there is a drop in the heat-affected zone after a natural aging of 18 months.

Jan 1, 2006

By B. Balamurugan, D. J. Sellmyer, J. E. Shield, G. C. Hadjipanayis, Damien Le Ror, R. Skomski

"Rare-earth transition-metal (R-TM) alloys show superior permanent magnetic properties in the bulk, but the synthesis and application ofR-TM nanoparticles remains a challenge due to the requirement of high-temperature annealing above about 800 °C for alloy formation and subsequent crystalline ordering. Here we report a single-step method to produce highly ordered R-TM nanoparticles such as YCO5 and SmCO5, without high-temperature thermal annealing by employing a cluster-deposition system, and we investigate their structural and magnetic properties. Nanoparticles of size = 10 nm are monodispersed (s /d ~ 0.15) and have Hc values at T = 300 K of 8.0 and 4.5 kOe for YC05 and SmC05, respectively. Alignment of the easy axes is performed via a field applied to the clusters before deposition. These processing steps are highly desirable to create and assemble R-TM nanoparticle composites for future permanentmagnet applications.IntroductionMagnetic nanoparticles with high magnetocrystalline anisotropies (Ki > 1 MJ/m3) are required for permanent-magnet, recording-media, and other significant applications [1-3]. In this regard, bulk rare-earth transition metal alloys (R-TM) especially RC05 (R = Y and Sm) crystallized in the hexagonal CaCu5-type structure have shown a large Ki = 5 MJ/m3 (YC05) and 22 MJ/m3 (SmCo5) along with an appreciable saturation-magnetic polarization (Js, > 10 kG) and high curie temperatures (Tc > 1000 K) [2]. The challenges in controlling the size, sizedistribution, phase purity and crystalline ordering, however, limit the research on RCo5 nanoparticles [4,5]. The conventional arc-melting technique requires high-temperature annealing for alloy formation and subsequent crystalline ordering, which causes excess growth and thus results in nanocrystalline powders of particles sizes larger than 30 nm [6, 7]. Low-temperature wet-chemical techniques yield SmC05 nanoparticles of sizes smaller than 20 nm [5], but the control of phase purity is challenging due to the presence of surfactants and formation of other secondary phases [8]."

Jan 1, 2012