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By L. C. Graton

[CONTENTS PAGE INTRODUCTION AND ACKNOWLEDGMENTS. By George M. Fowler2 Question 1-Is Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions, Especially in Limestone or Other Dense Rock? DISCUSSION by: A. M. Bateman 10 S. F. Kelly 15 C. H. Behre, Jr 8, 13 G. B. Langford 13 T. M. Broderick11 H. E. McKinstry6 R. H. Clarke 13 D. H. McLaughlin8 J. D. Forrester for M. H. Gidel . . . 4 W. H. Newhouse13 G. M. Fowler 2, 6, 11 R. H. Sales 6 L. C. Graton 11 Edward Sampson 12 R. D. Hoffman 10 J. S. Stevenson 7 I. B. Joralemon11 L. B. Wright 2 Question 2-What Are Some of the Chemical and Physical Characteristics in Certain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? DISCUSSION by: G. W. Bain 17G. M. Fowler 21 C. H. Behre, Jr21L. C. Graton18 J. S. Brown 16G. F. Loughlin18 E. L. Bruce 19R. H. Sales 19 R. H. Clarke 20A. K. Snelgrove 20 Question 3-Are There Any Criteria by Which One Can Determine When Mining Operations Have Reached the Roots of an Ore Deposit? DISCUSSION by: J. M. Boutwell29G. B. Langford 29 T. M. Broderick28G. F. Loughlin25 E. Y. Dougherty27R. H. Sales 24 G. M. Fowler 22F. A. Thomson 26 I. B. Joralemon 22Edward Wisser 30 General S. F. Kelly35 References36

Jan 1, 1940

By Milton F. Goodrich

The idea of using water-only cyclones to scalp clean coal from the feed to other devices has recently been gaining in popularity. 1,2,6 An indication of this popularity is that water-only cyclone scalping is already employed in a few commercial plants. Water-only cyclones scalp the feed to a heavy media vessel in the Warwick plant,3 to Deister tables in the Rowland plant,4 and to a heavy media cyclone circuit in the Amherst Coal Company's McGregor plant.5 Despite this trend, we found surprisingly little information in the literature on the performance of water-only cyclone scalping. Therefore, we undertook a study of its technical merits, limiting our investigation to a water-only cyclone scalper in conjunction with heavy-media cyclones. We felt this to be a reasonable combination of equipment, since both processes operate well on the same size coal. First, we developed simple mathematical relationships revealing general characteristics of the system. Next, we compared the clean coal yield and quality obtainable by the system on four different coals with that obtainable by heavymedia cyclone circuit alone and water-only cyclones middlings recirculation circuit alone. This was done by using computer program to simulate the operation of the three systems. Finally, we considered the effect that implementation of the system would have on a typical preparation plant circuit. The System The system chosen for study [(shown schematically in Fig. 1)] comprises two stages: a primary stage (PI) consisting of water-only cyclones, and a secondary stage (P2) consisting of heavy media cyclones. The water-only cyclones separate raw coal at a low specific gravity, producing a relatively small amount of high quality clean coal and a refuse containing much good coal. This refuse is then recleaned in the secondary stage, where the sharper separation of heavy media cyclones, operated at a higher specific gravity, reclaims additional clean coal. Finally, the clean coal from both stages is combined as the system's clean coal, while the refuse from the secondary stage becomes the system's refuse output. Theoretical Analysis Two assumptions lie behind the following theoretical analysis. The first assumption is that partition curves can represent not only the performance of each stage but also the performance of the system as a whole. These curves show partition number as a function of specific gravity, where partition number is either the percent or fraction of a raw coal with a given specific gravity reporting to clean coal. The second assumption is that these curves are independent of the raw coal characteristics. At any specific gravity the system's partition number is solely a function of the partition numbers of each stage. For convenience, we use the following variables in describing this relationship: g = specific gravity, PS(g) = the partition number of the system at specific gravity g, P1(g) = the partition number of the primary stage at specific gravity g, P2(g) = the partition number of the secondary stage at a specific gravity g. For this system, we can show algebraically that the relationship is: [Ps (g) = PI (g) + (1- P1(g)) P2 (9)(1)] With this equation the system's partition curve can be determined if the partition curves of each stage are known. By definition, the partition numbers P1(g) and P2(g) must each be less than, or equal to, one. Placing these constraints on Eq. (1), we arrive at the relations: [Ps(g) % P1(g) and Ps(g) % P2(g)(2)] Thus, at any specific gravity the system's partition number is always greater than that of both stages. [Figure 2] shows typical partition curves. Curve I represents the primary stage, which consists of water-only cyclones operating at a separating gravity of 1.3. (The separating gravity or the

Jan 1, 1979

CONTENTS PAGE INTRODUCTION AND ACKNOWLEDGMENTS. By George M. Fowler 2 Question 1-Is Structural Deformation of Some Character Always Necessary for the Migration of Mineralizing Solutions, Especially in Limestone or Other Dense Rock? DISCUSSION by: A. M. Bateman 10 S. F. Kelly 15 C. H. Behre, Jr 8, 13 G. B. Langford 13 T. M. Broderick 11 H. E. McKinstry 6 R. H. Clarke 13 D. H. McLaughlin 8 J. D. Forrester for M. H. Gidel . . . 4 W. H. Newhouse 13 G. M. Fowler 2, 6, 11 R. H. Sales 6 L. C. Graton 11 Edward Sampson 12 R. D. Hoffman 10 J. S. Stevenson 7 I. B. Joralemon 11 L. B. Wright 2 Question 2-What Are Some of the Chemical and Physical Characteristics in Cer¬tain Beds within a Limestone Formation that Determine Their Favorable or Unfavorable Aspects as Reservoirs for Ore and Other Introduced Minerals? DISCUSSION by: G. W. Bain 17 G. M. Fowler 21 C. H. Behre, Jr 21 L. C. Graton 18 J. S. Brown 16 G. F. Loughlin 18 E. L. Bruce 19 R. H. Sales 19 R. H. Clarke 20 A. K. Snelgrove 20 Question 3-Are There Any Criteria by Which One Can Determine When Min¬ing Operations Have Reached the Roots of an Ore Deposit? DISCUSSION by: J. M. Boutwell 29 G. B. Langford 29 T. M. Broderick 28 G. F. Loughlin 25 E. Y. Dougherty 27 R. H. Sales 24 G. M. Fowler 22 F. A. Thomson 26 I. B. Joralemon 22 Edward Wisser 30 General S. F. Kelly 35 References 36

Jan 1, 1940

By D. Turnbull, J. C. Fisher

ACCORDING to the "reaction-path" modell,2 of martensite nucleation, the shear angle of the embryonic martensite plate must be treated as a variable, and included in any calculation of nucleus critical size. Also, as can be deduced from this model, the interfacial free energy between austenite and martensite does not reach its final value until the shear is completed. It is zero for zero shear angle. However, in order to account for the kinetics of the martensite transformation, some sort of interfacial energy barrier appears to be necessary even with the reaction-path model, for otherwise the volume and the energy of formation of the critical size nucleus both collapse to zero.3 Cohen independently suggested that surface energy could be incorporated into the reaction-path model, with the overall free energy of a martensite embryo being a function of its volume and shear angle.' It is possible to estimate the energy associated with the formation of a critical-size martensite nucleus starting with the reaction-path model and including a surface free-energy barrier. As the dependence of interfacial free energy upon shear angle is unknown, a simple type of dependence will be assumed, with the belief that the true dependence would not lead to appreciably different results. Consider the work required to form a lenticular martensite plate with radius r, thickness t, and shear angle 8. There are three contributions; one being the interfacial free energy, one being the free energy change in the martensite plate, and one being the free energy increase in the surrounding austenite. The interfacial free energy u is assumed to depend upon the shear angle 0 according to the relationship s=s0(?/?0)n [1] where 8, is the equilibrium shear angle and n is an exponent that may lie in the range 0 n 2. The work required to form the interfaces of a martensite plate then is W. = 2pr² s0(?/?0)n [2] The free energy change per unit volume of martensite is composed of two parts, one the ordinary volume free energy ?f1. which is negative, and the other the elastic strain energy G?m²/2, where G is the shear modulus and 7, the shear strain relative to the martensite structure. This expression for the strain energy is valid only when the shear strain ym, is sufficiently small that the martensite is within its linear elastic range. There is no doubt that ym, lies beyond the linear elastic range for embryos that are considerably subcritical. However, for critical nuclei it will be shown that ym, is 1.5 pct or less, within the linear elastic range of martensite. For embryos of nearly critical size, then, the strain energy of the martensite is correctly given by G?m²/2. The shear strain in the martensite is ym, = 8, — 8, and the work required to form the strained martensite is Wm --= (pr²t/2) [?fv + G(?O - ?)²/2] [3] The free energy change in the austenite is entirely that due to elastic distortion. The elastic strain is not uniformly distributed in the austenite, being large near the martensite plate and small elsewhere. Approximately, however, the energy corresponds to a uniform shear strain ya= (?t/2)/r [4] throughout the volume 4pr³/3 surrounding the plate. The work required to strain the surrounding austenite then is Wa = (4pr³/3) (G?a²/2) = (G?²/6) prt² [51 For simplicity, the same shear modulus G is assumed for each structure. The total free energy for forming a plate then is W = W3 + Wm + Wa. = 2pr² s0 (?/p?0)n + (pr²t/2) [?fr+G(?0-?)²/2] + (G?²6) prt2 [6] This expression is correct for nuclei and for embryos of nearly critical size, where, as will be shown, the strain energy in the martensite is correctly given by the expression G (? — ?)². Having W as a function of r, t, and 8, as in Eq. 6, there is a saddle-point where W has a stationary value, W subsequently decreasing indefinitely as the nucleus volume increases along the reaction path. The stationary value of W is the energy of the critical nucleus. The critical nucleus has radius, thickness, and shear angle such that ?W/?r - awlat: = ?W/?p? = 0. Performing these differentiations and calculating the critical nucleus energy, W* = [8192p(G?/6)²;s/27 ?fv4] [7] where a= (?/?0)3n+1[l +G(8"-8)'/2af.]' [7a] and where 8 is to be determined from the equation (1 + 3n/4) + G8(6O - (9)/[Af. +G(6>o-6>)72] = 0 [8] For ?f, near —200 cal per mol or —10" ergs per cc, and 8, near 1/6, as for iron-base alloys, Eq. 8 gives ?0 - ? ~ - (4 + 3n) ?f1./4G0O [9] as the difference between the equilibrium shear angle and the actual shear angle for a critical nu-

Jan 1, 1954

By L. M. Pidgeon, W. Curlock

FREE energies of formation of zinc sulfide and magnesium sulfide had previously been estimated to an accuracy of ± 5.0 kcal per g mol. In the present work, these values were determined experimentally. As the determinations of the free energies of formation of zinc sulfide and magnesium sulfide presented different problems, separate experimental procedures were employed for each. ZINC SULFIDE It is difficult to measure the free energy of formation of either zinc sulfide or magnesium sulfide by measuring their decomposition pressures directly, as they are very stable compounds. An attempt was made by Jellinek and zakowski3 to study the equilibrium. zns(s) + H2(g) = Zn(g) + H2S(g) [I] They passed hydrogen over zinc sulfide and analyzed the gases leaving the reaction zone for H2S. They were unable to determine the true partial pressures of the H2S by this method, as some of the H2S on being cooled from the reaction temperature, reacted with the zinc in the gas to produce ZnS. Consequently, they were unable to establish any true equilibrium data for reaction [I]. More recently,' the equilibria ZnS(sphaledte) + Fe (s) — FeS(s) + Zn(g) [2] and ZnS(sphalerite) + 2Cu(s) — Cu2S(S) + Zn (g) [3] were studied. As the standard free energy of formation of Cu2S is known to * 3.0 kcal, and of FeS to ± 1.0 kcal, it should be possible upon performing equilibrium studies on reactions [2] and [3] to deduce the standard free energy of formation of ZnS (sphalerite). However, as both of these equilibria involve 2 solid sulfides, and as it is possible for these sulfides to dissolve in one another, it is necessary first to ascertain the activities of the various sulfides in these solid phases.

Jan 1, 1959

By Philip B. Bucky

CONTENTS [PACEPACE r. What Is a Rock Burst?2 4. How Can Rock Bursts Be Predicted? . 35 Jack Spalding2Jack Spalding35 A. F. Robertson 2, 5A. F. Robertson35 W. R. Crane 2A. B. Yates and P. J. Shenon. . . . 35 G. S. Rice 2W. R. Crane 35 P. J. Shenon 2G. S. Rice 35 L. C. Graton 2B. F. Tillson 36 2. What Are the Causes of Rock Bursts? 6 5. How Can Rock Bursts Be Controlled?. 36 Jack Spalding6Jack Spalding36 A. B. Yates and P. J. Shenon . 7, 12, 29A. F. Robertson 36 A. F. Robertson 12, 28W. R. Crane37 W. R. Crane 15A. B. Yates and P. J. Shenon. . . . 37 G. S. Rice 15Oscar Weiss38 Oscar Weiss15G. S. Rice37, 42 P. B. Bucky21R. D. Hoffman42, 43 P. H. Bird 21, 26, 28R. D. Hall 42 M. K. Hubbert26R. H. Cromwell42 G. Wheeler 26. J. Shenon 42 B. F. Tillson26, 28P. B. Bucky42, 44 T. T. Read 27B. F. Tillson 42, 44 A. B. Yates 43, 44 3. How Can Rock Bursts Be Prevented? . 30P. H. Bird 43 Jack Spalding. . . . • . • • • • . 306. General Discussion . A. B. Yates and P. J. Shenon. . . . 31Jack Spalding44 A. F. Robertson32R. D. Parker49 W. R. Crane 35C. Baring Horwood 51 G. S. Rice 35P. B. Bucky 52] FOREWORD THIS symposium brings together points of view, experiences and ideas on rock bursts from a goodly portion of the globe. Some conceptions, particularly those regarding the necessity of depth, have been fairly well shattered, as we find that they are present in the water tunnels of New York, on the surface at marble quarries in Vermont, and in the coal mines of the United States, as well as in the deep mines of the South African and Kolar gold fields, and in the nickel, copper and gold mines of Canada. Their occurrence under such a variety of conditions is, therefore, a challenge,

Jan 1, 1942

By N. A. Gokcen

EQUILIBRIA in the reactions between gases and liquid metals have been the subject of many interesting investigations. The experimental realization of true equilibrium, however, is questionable in certain cases due to the lack of conclusive studies in reaction rates. It -will be shown here that a systematic interpretation of rate studies with the analysis of prevailing experimental conditions leads to valuable practical information. The reactions of particular interest are: H2(g) +S(inFe) - H2S(g) [1] H2(g) +O (inFe) =H2O(g) [21 2H2(g) + SiO2(s) = 2H2O(g) + - (inFe) [3] The usual and perhaps the most convenient method of investigation may be illustrated with reaction 1. A stream of gas mixture consisting of H2 + H2S is passed over or bubbled through the liquid metal at constant temperature. The ratio of H2S/H2 in the entrant mixture is fixed in each experimental run, and, therefore, the composition of melt varies until the establishment of equilibrium. The purpose of this paper is to derive a formula expressing the minimum time required for the establishment of equilibrium and to compare the calculated values from such a formula with the available data. Equations Reaction 1 is used for the purpose of illustrating the derivation. Let E represent the equilibrium and X the nonequilibrium sulphur in weight percent at any time t in minutes. For the sake of simplicity, it is first assumed that E > X although the results are of general applicability without restriction. It has been shown by Morris and Williams' that within a difference of 1 pct S or less, i.e., E-X5 1.00, the value of K'1 = Ph2s/Ph2.S% is very nearly constant. The maximum ratio of available Ph2s/Ph2 = H,S/H,, from which sulphur can be absorbed by metal, is equal to H2S/H2 in equilibrium with E (which equals H2S/H2 in the entrant gas), minus H,S/H, in equilibrium with X. Thus: Available H2S/H2 = EK'1 - XK'1 [4] Eq. 4 expresses that sulphur can be absorbed by metal from the H2S/H2 in the entrant gas until the gas leaving the metal assumes a value of H2S/H2 which is in equilibrium with the dissolved sulphur X at that time. H,S constitutes up to approximately 1 pct of the gas mixture. Its disassociation into H2 and SL is about 1 pct at 1600°C, hence, the H2S/H2 impinging on the surface of metal is very close to that in the entrant gas. The rate of flow of hydrogen entering the reaction chamber is kept constant experi-

Jan 1, 1954

By W. A. Anderson, R. F. Mehl

RECRYSTALLIZATION of cold-worked metals has long been known to proceed by a process of nucleation and growth.1 When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.' Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrystallization is thus analyzed into its two component rates.2 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;* values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of N and G over appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By M. J. Ginsberg, N. A. Gokcen

THE preliminary study of electrochemical desul-furization performed by Ohtani and Gokcen1 left a number of points concerning the process to be investigated. Two of these were i) the determination of the effect of greater current and voltage on the desulfurizing Flower of acid slags (% CaO/% SiO2- 1) and ii) the possibility of the loss of silica in slag by the reactions 2C (in metal) + SiO2 (slag) = Si (in metal) + 2CO(g) and C + SiO2 (in slag) = SiO(g) + cO(g) proceeding to a point at which the composition of the slag was sufficiently altered toward the basic side so a1.s to noticeably affect the rate of de-sulfurization. The apparatus and the procedure used in the present investigation were the same as those used by Ohtani and Gokcen, except the control circuit was connected to 120 v dc instead of 24 v dc and thereby allowed greater freedom in choosing the values of both current and voltage. The graphite crucible containing the melt and serving as the cathode was 3-in. high, and was of 1 1/2-in. ID with a graphite bar of 3/8-in. diam and 8-in. length threaded into the bottom for electrical connection. This was placed into a magnesja outer crucible with a hole in the bottom and alumina insulation was packed between the two crucibles. A charge consisting of 180 g of

Jan 1, 1962

By J. Chipman, T. P. Floridis

The equilibrium of gaseous H2O-H2, mixtures with liquid iron is used to establish the activity coefficient of dissolved oxygen as log f o = — 0.20 [%O]. Discrepancies in earlier work are explained or eliminated. Additions of cobalt, molybdenum, tungsten, and platinum increase the activity coefficient of oxygen whereas copper and gold decrease it. THE importance of dissolved oxygen as a refining agent in liquid steel has led to a number of studies of its thermodynamic properties. It is the purpose of this paper to examine the effects of a number of alloying elements on the activity of oxygen in the steel bath. As a preliminary to the study of the effects of alloying elements, it seemed desirable to examine certain minor discrepancies in the published data on the properties of oxygen in simple iron-oxygen solutions. The activity and free energy of oxygen in liquid iron were studied by chipman1 in 1933 by means of the reaction h2(g)+-o = H2O (g);K; = PH2O/PH2[% O] [1] The data were in fairly good agreement with calculations from results on the similar reaction CO (g) + O- = CO2 (g); K2 =P CO2/P CO [% O] [2] which had been obtained by Vacher and Hamilton2 as an incidental part of their study of the reaction of carbon with oxygen dissolved in the melt. It was found that the equilibrium ratio k1 was not a true constant but varied with the oxygen concentration in the manner shown in Fig. 1, which is copied from the original paper. This early observation has been refuted in subsequent work but is confirmed in the present paper, and an explanation of the discrepancy can now be presented. In Fig. 1, the two points on the extreme right were disregarded in drawing the

Jan 1, 1959

By C. E. Birchenall, H. M. Schadel

THE purpose of this study was to measure the vapor pressure of silver as the first step in the determination of activities in silver alloys and to test the limitations of the method adopted. In order to work at low pressures, below 2x10-2 mm of mercury, the orifice effusion technique was employed. To shorten the time of collection of silver from the atomic beam, radioactive silver (Ag110) was used as a tracer. The rate of effusion of a monatomic vapor from an "ideal" orifice, where the thickness of the orifice edge is negligible compared with the orifice diameter, can be readily calculated from the kinetic theory of gases, G = vM a p/v2pRT where G is the weight of material effusing from the orifice per unit time; p is the vapor pressure at oven temperature, T; R is the gas constant; M is the molecular weight of the vapor; and a is the orifice area. Consolidating constants and expressing as the weight of material effusing from the orifice in a period of time, t, (5.83)(10-2) (vM) (a) (t) (p)/vT where GT is total weight of monatomic vapor effused (g); M is molecular weight of the effusing tracer vapor; a is orifice area (cm2); t is time of effusion (sec); p is vapor pressure of effusing material (mm of Hg); and T is oven temperature (OK). The vapor effuses from the orifice in a hemispherical pattern, and the intensity of the beam in any direction is given by the cosine distribution law.' Considering this, the weight of effused material can be calculated from the amount of material passing through a circular collimator intersecting the beam. If such a collimator is in a plane parallel to the plane of the orifice and with center on the normal to the orifice center, GT = G?/1-cos2? = G?/sin2? where G? is the weight of effused material passing through the collimator, and 0 is one half the apex angle of the cone defined by the collimator circumference and the orifice center. Reducing eq 3 to the more directly measurable quantities of orifice to collimator distance, d, and collimator diameter, D, the expression becomes,

Jan 1, 1951

By H. L. Gilbert, W. W. Stephens

Production of anhydrous zirconium tetrachloride by direct chlor- ination of a zirconium oxide carbon mixture in a silica-brick-lined chlorinator is described. Theory and thermodynamics of reactions are discussed. A pilot-model chlorinator and full-scale production equipment are described and operating data are included. ANHYDROUS zirconium tetrachloride required as a starting material in the Kroll process for production of ductile zirconium has been produced in this country principally by chlorination of the carbide or "carbonitride" made by reduction of zircon sand concentrates with carbon in the arc furnace. This process and the equipment used have been fully described.'.' It is well known that zircon or badde-leyite ores may be chlorinated directly with chlorine in the presence of carbon, and this one-step approach would seem at first glance to be preferable to the two steps involved in the carbide-chloride operation. As previously discussed1 considerations leading to adoption of the longer process were: 1—Chlorination of the carbide proceeds rapidly at temperatures below 500°C, whereas temperatures above 900°C were considered necessary for chlorination of zircon-carbon mixtures. 2—The highly exothermic nature of the carbide-chlorine reaction makes it self-sustaining, while heat must be supplied continuously in direct chlorination of the ore. 3—Silicon was thought to be chlorinated along with zirconium in the direct chlorination of zircon, leading to high chlorine consumption. In production of carbide in the arc furnace, silicon is driven off as silicon monoxide and does not enter the chlorinator. 4—For efficient direct chlorination, the ore must be finely ground and intimately mixed with carbon, and the mixture briquetted. 5—Direct chlorination requires a much larger chlorinator for a given production capacity than chlorination of carbide. Recently it has become necessary to produce large quantities of zirconium metal from a chemically purified zirconium oxide. Since the cost of the latter is high, the relatively high losses encountered in production of carbide in the arc furnace could not be tolerated, and a graphite resistor furnace5 was developed for production of carbide, which was then chlorinated in equipment previously used for chlorinating arc-furnace carbide. This method of operation was quite satisfactory, and losses in the carbid-ing step were minimized. However, operating costs were relatively high, and the process did not lend itself particularly well to large-scale operation because of the multiplicity of small units required and the hand labor needed to load, unload, and maintain the furnaces. To chlorinate the carbide, a vertical-shaft chlorinator was used in which the charge was heated with a central split graphite-rod resistor.' Operation of this chlorinator was somewhat less satisfactory with the resistor furnace carbide than it had been with the arc-furnace carbide due, principally, to the differences in physical properties of the carbide. The arc-furnace carbide is obtained as a fused metallic-appearing mass which can be crushed to -1/4 in. with production of a minimum of fines, whereas the resistor-furnace product is lightly sintered and produces a large proportion of fines in crushing and handling. These fines tend to pack in the chlorinator and promote channeling. which results in poor chlorine efficiency and low capacity. Data based on production of 22,000 lb of chloride from resistor-furnace carbide in this equipment are shown in Table I. Necessity for increasing production of chloride from about 2,000 to 15,000 lb per week led to further investigation of possible methods for direct chlorination of the oxide or oxide-carbon mixtures. Direct chlorination of the pure oxide presents much less difficulty than chlorination of zircon sand or oxide ores. The oxide is easily ground to —200 mesh, and no silica is present to cause excessive consumption of chlorine or contamination of the product. Theoretical Considerations The principal chemical reactions involved in chlorination of mixtures of zirconium oxide and carbon may be written as follows: ½ ZrO2 (c) + C(c) + Cl2(g) = ½ ZrCl,(g) + CO(g) [I] 1/2 ZrO, (c) + CO(g) + Cl2(g) = ½ ZrCl,(g) + CO2(g) 121 ½ ZrO2 (c) + ½ C(C) + Cl2(g) = 1/2 ZrCl4(g) + ½ CO2(g) [3]

Jan 1, 1953

By W. C. Kelly, E. J. Essene, A. M. Affifi

Occurrences and associations of natural tellurides are constrained by the relative fugacities of Te, in specific mineralizing environments. Some are rare (e.g., FeTe2) and others absent (e.g. MoTe , ZnTe) m nature because high f-Te2/f-S2 ratios are rare or unattainable , whereas others (e. g . , Ag2Te,HgTe) require lower ratios and are common. Complex and seemingly chaotic sulfide-telluride associations are, in fact, highly systematic and depend both on temperature and fugacity ratios. Some older sulfides act as buffers via reactions such as PbS + Te2 = PbTe + S2, thereby affecting the deposition and paragenesis of younger tellurides and the combined or uncombined mode of occurrence of precious metals. Thermochemical calculations of telluride-sulfide-oxide equilibria can have pragmatic value. The thermochemical approach tells us little about the Te "source", but is beginning to unravel the systematics of telluride mineralogy and controls at the precipitational end of the line.

Jan 1, 1985

By W. A. Anderson

Recrystallization of cold-worked metals has long been known to proceed by a process of nucleation and growth.' When a cold-worked metal is heated to a temperature at which recrystallization will ensue, nuclei of new grains, essentially strain-free, appear and grow. As the process proceeds, nuclei continue to appear and to grow, until the cold-worked matrix has been entirely consumed and recrystallization has been completed (Fig. I). Conducted isothermally, a measurement of the fraction of the matrix recrystallized plotted against time, yields an isothermal recrystallization curve, showing the time course of the recrystallization process (Fig. 2).2 Evidently, then, the rate of recrystallization is determined by the rate at which nuclei form and the rate at which they grow. The rate of nucleation N is the number of nuclei that form in unit time in unit volume of the unrecrystallized matrix, and the rate of growth G is the increase in radius of the recrystallized grain per unit time. In recent years attempts have been made to determine N and G as these vary with the well-recognized variables affecting recrystallization: time, temperature, degree of deformation, etc.1 Such studies yield information that is more fundamental than that conveyed by the conventional recrystallization diagram,' since the rate of recrvstallization is thus analyzed into its two component rates3 Methods are now available by which N and G can be measured, and analytical expressions have been developed for the interrelationships among N, G, the isothermal recrystallization curve, and the final grain size, which greatly facilitate analysis.2-4 The application of these methods has been demonstrated recently for the recrystallization of silicon ferrite.2 Data on N and G in dependence upon the recognized recrystallization variables are, however, very fragmentary;" values of N and G have been determined for some metals, but the effect of temperature, which would yield the fundamentally important activation energies, has been too little studied. Thus far there has been no detailed study of the recrystallization of any one metal in terms of X and G ovcr appreciable ranges of the variables time, temperature, degree of deformation, and original grain size. It is the purpose of the present paper to provide such a study, employing aluminum.

Jan 1, 1945

By A. Mitchell, T. Bagshaw

A recent paper by Thomas1 has presented new data on the solubility of hydrogen in solid silver at 1 atm pressure in the temperature range 600° to 963°C. However, no data is reported in the literature on hydrogen solubility in liquid silver. The Sieverts technique which has been described previously2,3 was used in the present work. Charges of approximately 160 g were melted in Morgan "purox" recrystallized alumina crucibles and purified helium was used for the determination of the "hot volume" during each experiment. A chemical analysis of the silver indicates that the impurity content (Cu + Al) is less than 0.02 wt pct. Hydrogen solubility in the temperature range 963° to 1200°C was investigated. The results of three experiments are shown in Table I. Fig. 1 shows an Arrhenius plot of the present work together with the solid-state data of Thomas, Steacie, and johnson,4 Eichenauer et al.,5 and Siegelin et al.6 The following expression has been derived from the Arrhenius plot of the present data: log (solubility of hydrogen, cm3 per 100 g) = 2.154-3512.0/ToK The heat of solution derived from Fig. 1 is 31,150 cal per g mole H2 compared with the value of 33,020 cal per g mole H2 obtained by Thomas and 12,000 cal per g mole H2 obtained from the data of Steacie. It was observed that hydrogen evolution took place when the silver melts were solidified under 1 atm of hydrogen, which would not be expected from an extrapolation of the results of Steacie. Schenck and Lange7 have observed that, for several transition metals at their melting points, the ratio of the hydrogen solubility in the liquid to that in the solid lies in the range 2.1 to 3.1. The present results and those of Thomas are in accord in this respect having a ratio of 2.8. 'C. L. Thomas: Trans. TMS-AIME, 1967 vol. 239, pp. 485-96. 2T. Bagshaw and A. Mitchell: I. Iron Steel Inst., 1966, vol. 204, p. 87. 'M. Weinstein and J. F. Elliott: Trans. TWS-AIME, 1963, vol. 227, p. 382. 'E. W. R. Steacie and F. M. G. Johnson: Proc. Roy. Soc. (London), Ser. A, 1928, vol. 117, pp. 662-79. 'W. Eichenauer et al.: Z. Metallk., 1958, vol. 49, pp. 220-25. 6W. Siegelin et al.: Z. Elektrochem., 1957, vol. 61, pp. 359-66. 'H. Schenck and K. W. Lange: Arch Eisenhuettenw., 1966, vol. 37, no. 9, pp. 739-48.

Jan 1, 1969

By J. Chipman, M. N. Dastur

The importance of dissolved oxygen as a principal reagent in the refining of liquid steel and the necessity for its removal in the finishing of many grades have stimulated numerous studies of its chemical behavior in the steel bath. From the thermodynaniic viewpoint the essential data are those which determine the free energy of oxygen in solution as a function of temperature and composition of the molten metal. A number of experimental studies have been reported in recent years from which the free energy of oxygen in iron-oxygen melts can be obtained with a fair degree of accuracy for temperatures not too far from the melting point. Certain discrepancies remain, however, which imply considerable uncertainty at higher temperatures; also several sources of error were recognized in the earlier studies. It has been the object of the experimental work reported in this paper to reexamine these sources of uncertainty and to redetermine the equilibrium condition in the reaction of hydrogen with oxygen dissolved in liquid iron. The reaction and its equilibrium constant are: H2 (g) + Q = H2O (g); K1 _ PH2O / [1] Ph2 X % O Here the underlined symbol Q designates oxygen dissolved in liquid iron. The activity of this dissolved oxygen is known to be directly proportional to its concentrationl,2 and is taken as equal to its weight percent. The closely related reaction of dissolved oxygen with carbon monoxide has also been investigated:3,4,5 co (g) +O = CO?(g); K _ Pco2___ [2] K2= pco X % O [2] The two reactions are related through the wat,er-gas equilibriuni: H2 (g) + CO2 (g) = CO (g) + H2O (g); K2 = PCO X PH2O [3] PH2 X PCO2 and with the aid of the accurately known equilibrium constant of this reaction, it has been shown5 that the experimental data on reactions [1] and 121 are in fairly good, though not exact, agreement. Experimental Method Great care was taken to avoid the principal sources of error of previous studies, namely, gaseous thermal diffusion and temperature measurement. The apparatus was designed to provide controlled preheating of the inlet gases and to permit the addition of an inert gas (argon) in controlled amounts, two measures found to be essential for elimination of thermal diffusion. A known mixture of water vapor and hydrogen was obtained by saturating purified hydrogen with water vapor at controlled temperature. This mixture, with the addition of purified argon, was passed over the surface of a small melt (approximately 70 g) of electrolytic iron in a closed induction furnace. After sufficient time at constant temperature for attainment of equilibrium the melt was cooled and analyzed for oxygen. GAS SYSTEM A schematic diagram of the apparatus is shown in Fig 1. Commercial hydrogen is led through the safety trap T and the flowmeter F. The catalytic chamber C, held at 450°C, was used to convert any oxygen into water-vapor. A by-pass B with stopcocks was provided so that the hydrogen could be introduced directly from the tank to the furnace when desired. From the catalytic chamber the gas passed through a water bath W, kept at the desired temperature by an auxiliary heating unit, so that the gas was burdened with approximately the proper amount of water vapor before it was introdvced into the saturator S. All connections beyond the catalytic chamber were of all-glass construction. Those connections beyond the water bath were heated to above 80°C to prevent the condensation of water vapor. After the saturator, purified argon was led into the steam-hydrogen line at J, and finally the ternary mixture was introduced into the furnace. THE SATURATOR The saturator unit comprised three glass chambers, as shown in Fig 1, the first two chambers packed with glass beads and partially filed with water and the third empty. Each tower had a glass tube with a stopper attached for the purpose of adjusting the amount of water in it. The unit was immersed in a large oil bath, which was automatically controlled with the help of a thermostat relay to constant temperature, ± 0.05ºC, using thermometers which had been calibrated against a standard platinum resistance thermometer. The performance of the saturator over the range of experimental conditions was checked by weighing the water absorbed from a measured volume of hydrogen; the observed ratio was always within 0.5 pct of theoretical.

Jan 1, 1950

The Nominating Committee desire to submit the following nominations. President and Director: SIDNEY J. JENNINGS District 0 Vice-President and Director: H. S. DRINKER District 2 R. M. RAYMOND District 0 Directors: G. C. STONE District 0 HENNEN JENNINGS District 9 S. A. TAYLOR District 2 F. G. COTTRELL District 6 ARTHUR THACHER District 3 These nominations were unanimous. By order of the Committee J. V. N. DORR, Chairman. Oct. 10. 1917.

Jan 12, 1917

By S. G. Proctor, D. L. Baaso, W. V. Conner

A double crucible system was developed for I-g scale plutonium reductions. The equipment consists of an inner MgO crucible, an outer MgO crucible, and a stainless steel pressure vessel. The reduction charge is PIaced in the inner crucible and the annulus between the inner and outer crucibles is filled with a mixture of calcium and iodine. The exothermic reaction between the calcium and iodine in the annulus supplies the heat required for complete reaction of the reduction charge ana' good metal coalescence. Metal yields of 80 to 85 ,pct were obtained from I-g scale reductions and yields as high as 97.5 pct were obtained from 0.5-g scale reductions. The system was used to reduce charges containing as little as 0.1 g of Pu resulting in metal yields up to 90 Pct. THIN metal foils of highly enriched plutonium isotopes are used as targets for cross section and other measurements. The isotopes are separated in the calutrons at Oak Ridge and are very expensive to prepare. Often, only 1 or 2 g of material are available thereby emphasizing the need for a method of preparing these small quantities of metal. Procedures for 1-g scale plutonium reductions have been described, but these procedures require elaborate or expensive equipment. For example, the procedure described by Anselin et al.1 requires an inert atmosphere glovebox and induction heating equipment. The procedure described by Baker2 also uses induction heating equipment to obtain the recommended heating rates and liner temperatures. Baker's procedure also requires high purity PuF4 with very little PuO2 present. The procedure described in this paper resulted from a search for a simple and inexpensive method for making 1-g scale plutonium reductions. EXPERIMENTAL Equipment. The equipment required for the double crucible system consists of a pressure vessel, two MgO crucibles, a MgO crucible lid, and a resistance-heated, vertical crucible furnace. The crucibles were slip cast from high purity MgO and were supplied by the Coors Porcelain Co. and the Norton Co. The pressure vessel and lid were fabricated from 316 stainless steel. Materials. The PuF4 used for this study was obtained from the P1utoniu:m Metal Production Department at Rocky Flats. The PuF4 was prepared in a con- tinuous hydrofluorinator by reacting Pu02 with HF at 650°C. The isotopic composition of the plutonium was approximately 93 pct 239PU, 6 pct 240PU, and 0.5 pct 241PU. Some of this PuF, contained less than 1 pct Pu02 (Batch No. 6 and 7), while other batches contained up to 15 pct Pu02 (Batch No. 3). The chemical analyses of all the PuF4 used for this study is given in Table I. The calcium was 99 pct pure, AEC grade, and only that fraction which would pass through a 20 mesh screen was used. The I2 was USP grade re-sublimed I2 which was ground before being used. Procedure. Various charge compositions and methods for loading the double crucible system were tested. The optimum conditions for 1-g scale reductions are described below. The double crucible system was loaded as shown in Fig. 1. The outer crucible was placed in the pressure vessel and the annulus between them was filled with MgO sand. The inner crucible was placed in the outer crucible, supported by a layer of MgO sand in the bottom of the outer crucible. A mixture of 5.2 g of Ca and 25 g of I2 was placed in the annulas between the two crucibles. The upper portion of the annulas was filled with MgO sand. Next, a layer of a mixture of calcium and I, equal to 20 wt pct of the calcium and I2 used in the main charge was placed in the bottom of the inner crucible. The PuF, to be reduced was mixed with a 30 pct excess of calcium and 1 mole of I2 per mole of Pu and this mixture was placed in the inner crucible. The charge was topped with a layer of a mixture of calcium and I2 equal to 20 wt pct of the calcium and I2 used in the main charge. The pressure vessel was sealed with a flat copper gasket and was purged by alternately evacuating and filling with argon. The purge valve was closed and the vessel was placed in a vertical crucible furnace which was preheated to 950°C. The furnace was turned off after 20 min of heating and the vessel allowed to cool. Experience has shown that. this amount of heating is sufficient to assure complete reaction of the charge. RESULTS AND DISCUSSION The double crucible system has been used to produce plutonium metal on a 0.1- to 1-g scale. Reduction

Jan 1, 1970

By M. N. Shetty

LARGE copper whiskers (-100 p) of 11111 orientation were tested in a floor-model Instron testing machine, at liquid nitrogen temperature. (Testing methods will appear elsewhere.) Whiskers deformed by twinning after some initial deformation. A load-elongation curve at the onset of twinning is reproduced in Fig. 1. Twinning was confirmed by taking a back-reflection Laue picture, using a slit colli-mator, which showed distinct splitting of reflections. The tensile stress reached just before twinning is about 1.4 x 107 g per sq cm (-7.0 x106 g per sq cm—resolved shear stress) which drops to 1.2 x107 g per sq cm (-6 x 106 g per sq cm—resolved). This twinning stress is about five to ten times larger than the value for bulk single crystals of copper deformed at 77°K (-106 g per sq cm—resolved). Twinning models based on Cottrell-Bilby's pole mechanism are discussed in detail by Venables.' In the present work a mechanism based on the idea of failure of a Lomer-Cottrell barrier by recombination will be proposed. An L-C barrier may fail either by recombination or by dissociation.3 Fig. 2 provides the necessary information. It shows that the stress necessary to break such a barrier is about 1.8 x 107 g per sq cm by recombination and 4 x 107 g per sq cm by dissociation at 77°K. The twinning stress reached by whiskers is comparable to the stress level required for failure of an L-C barrier by recombination. (Stroh himself points out that his calculations should not be taken too literally.) We consider a segment of the L-C dislocation which has recombined (AB in Fig. 3) over a length to form the total dislocation which then glides in the

Jan 1, 1965

By R. Stratton-Crawley

Flotation-related processes utilizing an oil phase for processing fine mineral particles have been described and various applications discussed. The problems associated with the techniques are varied, but may be summarized by the following areas; (1) applicability to fine particle beneficiation, e.g. collector extender and emulsion flotation. (2) major 'mechanical' problems, e.g. emulsion breakage and oil recovery in oil flotation. (3) complex interfacial chemistry, e.g. empirical nature of pigment flushing .

Jan 1, 1979