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By Douglas J. Harvey

The surface tension of lead-tellurium alloys (in the range 0 to 6.70 at. pct Te) ad lead-arsenic alloys (in the range 0 to 10.53 at. pct As) has been examined by the maximum bubble pressure method. The surface tension of high purity lead can be expressed over a range of temperatures (M.P. to 750°C) by the relationship = 512 — 0.133t. Arsenic and lellurium were both found to be surface active in lead. The surface excess concentration at 700°C was .found to be constant at 0.74 x 10-10 moles per sq cm for tellurium. The surface excess of arsenic at 700°C varied between 0.26 x 10-10 moles per sq cm at 0.16 at. pct to 1.5 x 10-10 moles per sq cm at 8.3 at. pet. The surface tension of lead has been investigated sporadically over the last 90 years. The first recorded study was made by Quincke1 who used a rather crude application of the drop-weight method. Hogness2 obtained the first reliable value for the surface tension of lead by measuring the pressure necessary to force the liquid metal from the end of a small capillary of known radius. Hogness gives the empirical formula: ?(surface tension)= 444 - 0.077 (l-327) which describes the relationship between surface tension and temperature ("C); This work was followed by that of Bircumshaw3 who applied the two-capillar maximum bubble pressure method of Sugden.4 The values published by Bircumshaw are in good agreement with those found by Hogness. Matuyama5 examined the surface tension of lead by the drop weight method. However, the values found are somewhat higher than those previously reported. More recent investigations by Greenaway6 and by Melford and oar' have resulted in data which are not in close agreement, but which are well within the expected range at most temperature levels. The study of the surface tension of lead alloys began with Drath and sauerwald8 who examined the lead-bismuth system. They found that the surface tension values of the alloys in this system deviated only slightly from the ideal mixture rule. Matuyarna5 examined the lead-antimony system. Bircumshaw the lead-tin, and the lead-indium system was studied by Hoar and Me1ford.10 The results of these investi- gations are summarized in Fig. 1. It may be seen that the data vary only slightly from the ideal mixture rule. As none of the metals studied and reported in the literature has a very interesting effect on the surface tension of lead,*the next logical step might be to examine the effect of metals of low solubility or nonmetals having some liquid solubility. Baes, and Kellogg11 have pointed out that the elements most likely to be surface active in liquid metals are ones of limited solubility in the liquid state and possessing weak intermolecular bonding forces in the solid state. Therefore, Group V, VI and VII nonmetals are most likely to be surface active. It was decided to examine the effect of a borderline metal, arsenic, and a nonmetal tellurium. Arsenic forms a eutectic with lead having a melting point of 290°C and a composition of 6.9 at. pct As.13 Pure arsenic sublimes when heated above 610°C. Even though alloying with lead lowers the vapor pressure, fumes containing arsenic are evolved at a very noticeable rate when lead-arsenic alloys are heated above 650°C. Tellurium raises the liquidus temperature of lead sharply to 904°C,14 the melting point of PbTe (lead-telluride). The solid solubility of tellurium in lead was determined by Greenwood and worner15 to be 0.0007 at. pct at room temperature. EXPERIMENTAL METHOD Surface Tension Measurement—The two capillary maximum bubble pressure method for measuring surface tension developed by Sugden,4 and used later

Jan 1, 1962

By C. A. Winkler, V. Hospadaruk

PREVIOUS papers from this laboratory have discussed the effect of chloride ion on the cathode polarization during electrodeposition of copper from copper sulphate-sulphuric acid electrolytes, in the presence and absence of gelatin. The steady state polarization'" was found to decrease sharply and pass through a minimum with increasing chloride ion concentration in the presence of gelatin. The minimum shifted to higher chloride ion concentrations and to higher polarization values with increase in current density or gelatin concentration, while an increase of temperature shifted the minimum toward lower halide concentrations and lower polarizations. Since these observations were made in acid-copper sulphate electrolytes that contained no other addend than gelatin, there was obviously the possibility that they were not applicable to deposition of copper from commercial electrolytes that contain a variety of other substances in relatively small amounts. In particular, it was of interest to determine whether the presence of arsenic, antimony, or bismuth in the electrolyte would materially alter the behavior. Experiments have now been made under a variety of conditions with systems containing these cations, and the results are summarized in the present paper. Experimental Polarization measurements were made at 24.5oC in a Haring cell in the manner described previously.' Electrolytes were made with doubly-distilled water, and contained 125 g per liter of copper sulphate and 100 g per liter sulphuric acid, both of reagent grade Eimer and Amend gelatin from a single stock was used throughout. Chloride ion was introduced as reagent grade sodium chloride, and arsenic, antimony, and bismuth by dissolving the chemically pure metal in hot concentrated sulphuric acid and adding appropriate amounts of the solutions to the electrolyte. Each cathode, of 1/16-in. thick rolled copper, was first etched in 40 pct nitric acid and washed thoroughly with distilled water. The surface was then brought to a standard condition4~9 by electrodeposition from an acid-copper sulphate electrolyte containing no gelatin, at a current density of 3 amp per sq dm for 30 min, followed by deposition at a current density of 2 amp per sq dm for l hr. As in previous studies, the cathode polarization eventually attained a steady-state value (15 to 75 min) such that further change in polarization did not exceed 0.2 mv per min. The polarization values recorded are those for the steady states. "Excess weights" were determined with arsenic and antimony present in the electrolyte, as the difference between the weights of the deposits obtained in the presence of these cations and those obtained in their absence, with the two cells connected in series. When gelatin was present along with the arsenic or antimony, it was also added to the electrolyte in the cell in series. Results and Discussion The results of the study are summarized in Figs. 1 to 6. From Fig. 1, top, it is evident that the presence of arsenic or antimony alone results in an increase of polarization, while bismuth alone causes a decrease. The presence of gelatin (25 mg per liter) rather drastically modifies all three cation effects, as indicated in the lower panels of the same figure. The addition of chloride ion, when no gelatin is present, causes comparable decreases in polarization in the presence of antimony and bismuth, but a relatively larger decrease when the electrolyte contains arsenic. It is interesting to note that the decrease in polarization brought about by addition of chloride when both arsenic and antimony are present parallels the behavior with arsenic alone, while the polarization in the electrolyte containing the cation mixture, without chloride added, corresponds to that for an electrolyte containing only the antimony cation. Similarly, the polarization at zero concentration of chloride in electrolyte containing arsenic and bismuth is that corresponding to an electrolyte containing arsenic alone. From Figs. 3a, 4a and 4b, it is clear that, in the presence of gelatin at a level of 25 mg per liter, the effect of chloride in the presence of arsenic and antimony, or a mixture of the two, becomes quite analogous to that observed in the absence of added cations. When both bismuth and gelatin are present (Fig. 5), the decrease in polarization with increased chloride concentration is virtually absent. This is perhaps a reflection of the large decrease in polarization brought about by the bismuth itself in the presence of gelatin. The shifts of the minimum in the polarization-chloride concentration curves brought about by changes of temperature (Fig. 3b), gelatin concentration (Figs. 3c and 4c) and current density (Fig. 3d) when the metal cations were present are all similar to the corresponding shifts observed in their absence." The approximately linear "excess weightv-anti-mony concentration relation recorded in Fig. 6 would seem to indicate that antimony is codeposited with copper to a considerable extent. On the other hand, only very limited amounts of arsenic appear to be adsorbed or codeposited.

Jan 1, 1954

By C. F. Baes, H. H. Kellogg

The effect of dissolved sulphur on the surface tension of liquid copper has been measured by a sessile-drop method at 1120°C. Sulphur is highly "surface active" in liquid copper; the surface tension lowering is about 650 dynes per cm for a sulphur content of 0.6 pct. The degree of adsorption of sulphur on the liquid copper surface has been calculated, and various models of the surface layer have been tested against the results. THE science and technology of surface chemistry and physics at room temperature are relatively advanced, and the engineer possesses a background of information that allows him to predict and control many phenomena—such as frothing, emulsifica-tion, wetting of solids by liquids, flow through capillaries, adsorption, mineral flotation, penetration of porous bodies by liquids—which are related to the behavior at interfaces. Surface phenomena in high temperature systems are probably of equal importance to the metallurgist and ceramist, but at present are incompletely understood. Frothing of liquid slags, penetration of refractories by liquid metals and slags, infiltration of powder metallurgy "skeletons" by liquid metals, bonding of metals to ceramic oxides in the manufacture of "cermets," wetting of one metal by another for purposes of soldering and welding, are but a few of the many phenomena of metallurgy that are controlled by surface behavior. Concerning the most elementary of surface properties—the gas-liquid surface tension—the existing data on liquid metals are inadequate. For the surface tension of "pure" metals the results of different investigators differ by 10 or 20 pct. The role of surface-active agents in liquid metals is relatively unknown, and it is not unlikely that the discrepancy in the values for the surface tension of pure metals is due to the presence of traces of surface-tension-lowering impurities in the samples. Based on analogy to room-temperature systems, the highly surface-active impurities in liquid metals should be elements or compounds of limited solubility in the liquid metal and possessing considerably weaker in-termolecular bonding forces than the metal itself. The nonmetals of the V, VI, and VII groups of the periodic table might be expected to act in this way. The experimental work in this paper represents a study of the surface tension of pure liquid copper in hydrogen at 1120°C, and the effect of dissolved sulphur (which is a strongly surface-active agent in liquid copper) on the surface tension of copper. The Gibbs equation has been applied to the results and an attempt made to correlate the surface tension behavior with two models of the interfacial layer. The sessile-drop method for surface-tension measurement at high temperatures which was used in this investigation has been described by several investigators.1,2 It involves the measurements of the dimensions of a stationary liquid drop on a horizontal surface. From these dimensions and the liquid density, the surface tension of the liquid may be calculated either by means of various approximate formulas, or more accurately by means of the Bash-forth and Adams tables.- or liquid drops which exhibit a contact angle greater than 90°, by far the simplest dimensions to measure are those indicated in Fig. 1, i.e., the diameter of the maximum horizontal cross section (2X) and the maximum height (Z) above this plane. In order to calculate the contact angle and the volume of the drop, the diameter at the base of the drop (2a) and the total height (h) also must be measured. Upon investigation of the literature, the authors failed to discover a concise statement of the accuracy of the method when used in conjunction with the Bashforth and Adams tables, hence a careful examination of the tables was made and the curve shown in Fig. 2 was constructed. The "error factor," plotted as the ordinate, is the factor by which the

Jan 1, 1954

By B. B. Kunkle

The history of this refinery has been one of expansion. It now has the capacity to produce 240,000 tons of cathodes annually. A general flowsheet and descriptions of the plant layout, operations involved, and equipment used at one of the world's largest and most modern electrolytic copper refineries are presented. THE El Paso copper refinery of Phelps Dodge Refining Corp. was originally constructed by the Nichols Copper Co., in association with Phelps Dodge Corp. and the Calumet & Arizona Mining Co., in order to refine anode copper produced at the smelters of the two latter companies. Initial production was obtained from the plant in January 1930 and its annual refining capacity was 100,000 tons of anodes. In order to keep pace with Phelps Dodge Corp.'s increasing copper production in the Southwest, it became necessary in 1937 to increase the El Paso plant's refining capacity to 160,000 tons of cathodes annually. This was accomplished by adding two sections to the electrolytic tank house, increasing the number of anodes placed in each commercial electrolytic tank from 33 to 37, and making changes in the dc circuits which made it possible to put three generators on each of the two circuits instead of two, thus increasing the amperage on each circuit from 10,000 to 14,800 amp. The capacity of the two furnaces from which refined shapes were cast was increased by raising the sidedoor bays on the furnaces 6 in. An increase of 70 pct in the productive capacity of Phelps Dodge Corp.s Morenci Branch in 1942 again made it necessary to expand refining capacity. In order to accomplish this, Defense Plant Corp. set up a project to increase the capacity of the El Paso plant to 240,000 tons of cathodes annually. This project consisted of enlarging the tank house approximately 50 pct, the construction of another wire- bar furnace, and corresponding increases in other departments where necessary. The engineering work on this expansion was begun in March 1942. Actual construction was under way by August 1942, and the work was completed by March 1944. These additional facilities were purchased from Defense Plant Corp. by Phelps Dodge Refining Corp. in August 1949. The plant is in El Paso about eight miies east of the center of the city and near Highway 80 and the main lines of the Southern Pacific and Texas & New Orleans railroads. The plant site covers approximately 494 acres of company-owned land that is ideally adapted for its use, being well-drained sandy soil and having enough slope so that a minimum amount of excavation was required when the plant was constructed. There is still ample room on the plant site for any future plant expansion. The plant is constructed on four different ground levels and so arranged that the unrefined copper is unloaded on the highest level at the north side of the plant and the refined copper is shipped out from the lowest level on the south side of the plant. The receiving or unloading platform, weighing and sampling rooms, main floor of the tank house, acid and condensate storage tanks, and the slimes and copper sulphate plants are on the first or highest level. The tank house basement, yard scales, charging and furnace bays, balloon flue and stack, brick-storage building, substation and power house, boiler feedwater treating plant and pump house, water storage tanks, and change houses are on the second level. This second level also contains ample yard area for setting-up furnace charges, and for storage of custom scrap, cathodes, scrap anodes, blister, coke, and poles. The casting wheels, inspection conveyors, cathode shears, wire-bar scalping machine, slag

Jan 1, 1952

By Peter R. Drummond

THE final casting of refined copper has been re-J- stricted for generations by the following sequence of operations: Filling the reverberatory furnace, melting, skimming, blowing or flapping, and poling. The hoped-for 24 hr cycle, producing 300 tons or more, has been taken up largely with the necessary bat time-consuming tasks of cleaning the bath, sulphur elimination, and in turn removal of excess oxygen to produce tough-pitch copper. Incidental to comparatively slow melting under combustion gases, copper oxides react with the furnace lining, and the slag so-formed must be completely recycled. The three-phase arc furnace has eliminated some of the cycle stages, and telescoped the remainder into a continuous operation. Electrical energy, supplied to graphite electrodes enclosed in high grade refractories, rapidly melts copper cathodes and sustains a stream of metal, containing approximately 0.01 pct oxygen, without contamination from fuel. The arc was struck on the first large electric furnace for melting copper in the United States on April 13, 1949. The earliest use of this type of furnace was at Copper Cliff, Ont., in 1936, and an admirable description of their installation has been published? Copper, melted in the Baltimore furnace, is used to cast billets, and the installation differs somewhat from the Canadian, as will be described. The arc furnace is a heavy-duty, three-phase furnace, holding 50 tons, the general outline of which appears on Fig. 1. The steel shell is 15 ft ID with a bottom radius of 14 ft 2 in. The roof, separate and distinct from the body, consists of a 15-ft water-cooled, cast-steel ring of the same outside diameter as the furnace. The center line of the furnace lies 9 ft 6 in. from that of the trunnions, permitting a 5" backward tilt for skimming, and a 40" maximum nose tilt forward for complete draining. Normally, the furnace overflows by displacement, and the use of the forward tilt arrangement is restricted to covering charging delays. The charging slot, 3 ft 8 in. x 5 in., lies on the north center line, the tap hole on the south, and the 30x30 in. skim door 45" to the west of the slot. The original 20-in. graphite electrodes were replaced with 14 in. in December 1949. Three conventional direct current winch drives, governed by electrical controls, position each electrode which has individual mast supports and counterweights. An independent circulation supplies cooling water for the electrode glands, the roof ring, charge slot, and the skim door frame. Arc Furnace Refractories Hearth: Fused-in monolithic bottoms had been used in copper arc furnaces, installed prior to April 1949. These consisted of thin layers of periclase, successively fused in place over preliminary brick courses. Heat was obtained from the arc, using a T-like arrangement of broken electrodes resting directly on the periclase to be fused. The operation, taking weeks to perform, was very expensive. The chemically-bonded magnesite-brick bottom, installed at Baltimore, was the first of its kind and a radical departure from previous practice. It consists of a 1 to 6-in. layer of castable refractory laid on the steel shell, modifying it to a 12 ft 2 in. bottom radius. Two courses of 9x2 % -in. fireclay straights and keys follow. The third course is made of 9-in. magnesite blocks of special shape to form circles of an inverted arch. It was started by a four piece keystone with skew-backs forming the outer course. The fourth course also started on a central keystone, or button, of four 90" segments, 12 in. diam x 13 Vz in. deep, and continued with 13%-in. blocks. Skewbacks at the shell completed the course to produce a horizontal surface for the side walls with a single course of No. 2 arch fireclay against the steel. Dry chrome-magnesite cement was brushed over each course after laying, and a 1-in. expansion space between the brick and the shell was filled with the same mixture. The total bottom thickness, excluding the castable material, was 5 in. of clay plus 22% in. of chemically-bonded magnesite. Tap Hole: A 5-in. OD and 3-in. ID silicon-carbide tube constitutes the tap hole and is set tangential to the upper course of the furnace bottom. Molten metal fills the tube when the furnace is level and filled to capacity. Side Walls: The lining, against the shell, consists of a 9x4Y2x3 in. soldier course of fireclay, using straights and No. 1 arches to turn the circles. A second soldier course of 9x4'/2x2'/2-in. fireclay was laid in a somewhat similar fashion. Three courses of 13Y2x6x3 in. and 9x6~3 in. of final magnesite, laid flat, completed the lining, using Nos. 1 and 2 keys to turn the circles. Cardboard spacers were placed between every two bricks in horizontal courses, and a thin coat of chrome-magnesite cement filled the joints between the firebrick and magnesite. A sprung-arch spanned the skim door with jambs of suitable magnesite shapes. Charge Slot: The slot is 3 ft 8 in. wide x 5 in. high. A silicon-carbide sill of special shapes has a 30" slope to allow cathodes to slide easily into the bath. The original arch was flat, and composed of Nos. 1 and 2 wedge magnesite with a 6-ft radius. It projected 5 in. over the sill, and, being a flat arch, gave an 18 15/16-in. opening between the inner edge and the metal line. The whole assembly was later raised 9 in., and the flat arch replaced with an arch, the lower edge of which maintained the 5-in, width from the outer to inner edges as shown in Fig. 2. A water-cooled, cast-copper jacket protects the steel shell behind the slot.

Jan 1, 1952

By K. A. Svanstrom, W. R. Opie

Problems associated with deposition of titanium infused chloride baths using TiCl4 as a feed material are reviewed. A potentially workable cell design using Alumdum diaphragms is discussed. Problems inherent to diaphragm-type cells are emphasized and experiments described which led to the development of a cell without a diaphragm. INVESTIGATORS assigned the problem of developing a commercial electrolytic process for making titanium metal have found that they are faced with the difficulty of overtaking rapidly improving magnesium and -sodium reduction processes. The ultimate goal must be a simple process that can be conducted with low-cost raw materials in equipment that is inexpensive to build and operate. This paper deals with some work of a preliminary nature conducted by personnel of the Research Laboratories, National Lead Co., Titanium Division. Many others have reported on the general subject of depositing titanium from fused salt electrolytes. A partial bibliography is attached. PRIMARY CONCEPTS Anyone attempting to deposit titanium metal from fused chloride electrolytes using TiC14 as a source material is faced with at least the following problems: 1) Getting the titanium into solution in the bath. 2) Controlling oxidation and reduction reactions associated with multiple valency of titanium, which result in low electrical efficiency. a) Prevention of dichloride oxidizing to trichloride and trichloride to tetrachloride at the anode. b) Prevention of trichloride from being reduced only to dichloride at the cathode. 3) Prevention of metal formation away from the cathode thru disproportionation of titanium dichloride to satisfy the equilibrium. 3 TiCl2 == 2 TiCl3 Ti [I] 4) Protection of reduced chlorides in the bath from reaction with oxygen from the bath container or air. 5) Removing from the bath the deposited metal formed without allowing it to become contaminated with oxygen or nitrogen. 6) Selecting cell materials of construction which will not contaminate the metal product or cause cell inefficiencies. EARLY EXPERIMENTS The initial attempts made to electrodeposit titanium from fused chloride baths using TiCl4 as a source material indicated that TiCl4 was essentially insoluble in molten chlorides of alkali and alkaline earth metals. If, however, the TiCl4 was introduced close to a nickel cathode some metal could be formed and appreciable quantities of reduced chlorides would be present. These reduced chlorides reacted with any oxygen present in the atmosphere above the bath and would also diffuse quickly to the anode (graphite) where they would react with chlorine and be evolved as TiCl4. The net electrolytic efficiency of such a cell is essentially nil. The TiCl4 evolves from the anode at almost the same rate that it is introduced in the vicinity of the cathode although a small amount of titanium metal can be formed on the walls of the cathodic pipe. It becomes apparent from the operation of such a cell that: metal can be deposited on the cathode, although of small particle size and a nonadherent nature, and when reduced chlorides are present in the electrolyte, TiCl4 can be absorbed, probably by the following reactions: TiCl4 + TiC12 - 2 TiCl3 [21 2 TiCl3 + 2 faradays - 2 TiC12 + C12 [31 DIAPHRAGM CELLS These facts encouraged the development of cells containing diaphragms to prevent migration of reduced chlorides from the cathode area to the anode. Small-scale cells for process development are described by Alpert, Schultz, and Sullivan.20 A larger brick-lined cell incorporating internal heating by passing ac through the bath is shown in

Jan 1, 1960

By W. F. Hergert, L. H. Banning

Experimental production of Al-Si alloys, containing from 33 to 55 pct Al, by direct reduction of aluminum silicates in a three-phase arc furnace is described. Advantages of a smelting technique utilizing hogged wood waste as part of the reductant and for temperature control are discussed. WORK on the problem of producing aluminum by smelting has been in progress since the middle of the eighteenth century. Early work met with little success and in 1782 Lavoisier, an eminent French chemist, expressed the belief that alumina could not be reduced by carbon. It was almost a century later when the Cowles brothers developed a process for the production of aluminum alloys by reducing alumina coincident with the reduction of other metal oxides. In practice, the other metal oxide was usually copper. In 1907 it was first shown that alumina alone could be reduced by carbon at a temperature of 2200°C. The metal produced was volatilized and lost or recombined with the oxides of carbon formed in the reaction.' For a number of years after the Cowles brothers abandoned production of Cu-A1 alloys because their product was not commercially competitive with the aluminum produced by the Hall process, there was little interest in thermal reduction processes. After World War I interest in such processes was renewed and a number of patents were issued on processes for the production of A1-Si alloys.' , "he function of the silicon in these processes was the same as the function of the copper in the Cowles brothers process, namely, to prevent the reduced aluminum from recombining with the oxides of carbon and to promote absorption of the aluminum vapors set free at the high temperature required for the reduction reaction. The advantage of using silicon in place of copper for this function is that silicon has a higher boiling point (2600"C) than copper (2310"C) and its oxides, combined with aluminum oxides, occur in nature in almost unlimited quantities. No A1-Si alloys have been produced commercially in the United States, as far as is known. However, considerable experimental smelting of aluminum silicate materials has been done by the TVA at Wilson Dam, Ala.' The most extensive development and commercialization of the electrothermal production of A1-Si alloys took place in Germany before and during World War II.V he furnaces used in the

Jan 1, 1956

By G. H. Kessler

ALTHOUGH considerable attention has been devoted to reaction mechanisms and equilibria of a number of endothermic reactions through which metals or their refractory compounds can be formed upon heated surfaces, only a comparatively small amount of work has been done to develop rate information for these systems. The interestin and very worthwhile work of Holden and Kopelman, Runnalls and Pidgeon,Dijring and Moliere, and Herrick and ICrieble4 is to be noted; however, their work was done under very specific conditions and the rate information which they have developed is not applicable to many systems which have been studied experimentally. That a more generalized approach is needed is shown by the diversity of these systems and of the experimental conditions which they require. These include the preparation of titanium, zirconium, tungsten, molybdenum, chromium, co-lumbium, aluminum, and silicon by decomposition or disproportionation of their halides, in some instances through hydrogen reduction; the preparation of nickel and iron by decomposition of their car-bonyls; and the preparation of copper by decomposition of the acetylacetonate. They may be carried out at temperatures ranging from 100" to over 2000°C and at pressures of from less than one mm Hg to superatmospheric. The physical mechanism of the overall process can be broken down into several steps, any one of which may be rate-determining; and the rate associated with each of these basic physical processes can be predicted. Consequently, by proper application of the present technology of rate processes, it is possible to arrive at a rate of metal deposition in the system of interest and to reach an understanding of the influence of' each major variable upon the deposition rate. It is the purpose of this paper to illustrate how this can be done and to present experimental results for a specific system for comparison with theory. The overall process of deposition of metal upon a heated surface which is immersed in vapors of a compound of the metal can be broken down into the following steps: 1) Transport of the reactant vapors to the surface. 2) Decomposition of the reactant in the immediate vicinity of the surface to a) establish chemical equilibrium if reaction rates are high; or to b) establish a dynamic equilibrium in accordance with the several reaction rates. 3) Diffusion of reaction products away from the vicinity of the surface, with or without simultaneous recombinations to form still other products. The overall process is said to be diffusion controlled if Step 1, or the equivalent Step 3, is slow; it is reaction-rate controlled if Step 2b is slow. When experimental evidence shows the reaction rate to be controlling, the well-known theories of Eyring' and others can be used as a basis for correlating and extrapolating the experimental data. Although these theories give only approximate estimates of reaction rates, they are of considerably greater value in correlating experimental data. Most deposition systems operate at surface temperatures sufficiently high that reaction rates near the surface are very high. Mass-transport rates then become controlling; and it is this regime of diffusion controlled rates which is most often of concern and Which will be considered here. When the system pressure is very low, i.e., in the micron range, then the transport processes are those of molecular movement, and the results of kinetic theory can be applied to specify a rate of arrival of reactant molecules at the heated surface. If the condensation coefficient can be estimated, then the deposition rate will be given by the product (rate of arrival) x (condensation coefficient), Conversely, experimental data can be used to determine a condensation coefficient, as was done by Holden and Kopelman' for the decomposition of zirconium tetraiodide upon a heated molybdenum surface, who found the coefficient for zirconium on molybdenum to be 1.0 at temperatures of 1382°C and above. In this pressure range, the geometry of the system. and in particular the distance between the source of reactant molecules and the heated surface, can exert a considerable effect upon the deposition rate;

Jan 1, 1961

By L. W. Rowe, S. S. Cole

A laboratory bench scale unit is described whereby finely divided chlorinatable residues are held for a short period by a restraining bed of a coarse-grained ore of comparable composition to permit 'flash' chlorination of the high surface area powder. Results on chlorinating a finely divicled titania residue using rutile sand as the restraining bed showed that 92 pct utilization of chlorine and equivalent conversion of TiO2 in the fine residue to Ticl4 were attained with a dust loss of about 3 to 4 pct and an equivalent amount of ch1om'nation of the titanium values in the restraining bed. THE chlorination of coarse grain titaniferous ores; i.e., 20 to 150 mesh sizes in fluidized beds is practiced commercially.' One effective method found for the chlorination of a very fine material in a fluidized bed is the "flash" chlorination technique.' By charging the finely divided charge material into the bottom of an established bed of optimum sized rutile, ilmenite, titanium beneficiate, or even an inert material such as sand, chlorination occurs before the dust can pass through the bed. The major requirement is that the bed be less chlorinatable than the charge. In this process, the charge consists of a finely divided (between one and 50 µ) titania residue obtained from a titaniferous ore beneficiation process. The charge is blended with a 20 pct wt basis addition of 20 to 60 .mesh size low volatile coke (to minimize hydrogen chloride formation) and fed to the bottom of the bed with the chlorine gas stream. A ball check device is used to permit entry of the charge and prevent the bed from discharging when the gas flow is cut off. The coarse pieces of coke serve to reduce compaction in the charge mixture and permit sat]sfactory feeding without plugging or jamming. Feed and gas rates are adjusted to provide for complete reaction of the charge material, with 90 to 95 pct chlorine efficiency, and maintain a gas flow in the range of 0.4 to 0.6 ft per sec. The equipment consisted of a 3-in. diam mullite tube enclosed in an electric furnace. A bow-shaped 3/4 in. Saran tube fed the charge from an air lock type of feed hopper (to prevent the escape of the chlorine gas into feed bin) to the bottom of the bed. The charge rate was set by providing a small awiliary hopper below the feed hopper where a weighed portion of the charge could be discharged in a specified time interval into the main chlorine stream. The chlorine rate was measured by a flowmeter. The reaction tube was filled with a bed of Australian rutile ore, this restraining bed serving two purposes; i.e., it rapidly heated the fresh charge to the reaction temperature and retained the particles in the bed for a sufficient time for selective chlorination to proceed. Due to the fine particle size and open, porous structure of the charge, this reaction was almost instantaneous, and, with proper adjustment of feed and gas rates, very little fine material passed through the bed without reacting and only a very small fraction of the restraining bed was chlorinated. A typical reaction procedure was to fill the bench scale fluidized bed unit with a 1 kg charge of Australian rutile ore analyzing 95.5 pct TiO2, 0.6 pct FeO, a beach sand deposit 40 to 150 mesh size. When fluidized, the bed was approximately 2 ft in depth. The ore was fluidized with a 1:l mixture of chlorine and nitrogen at a rate of 0.40 ft per sec. This gas mixture was necessitated by the comparatively short bed depth; a larger unit, with a deeper bed, could be fluidized with chlorine alone without significant free chlorine loss. Feed rate was 8.0 g per min of beneficiated ilmenite analyzing 85.0 pct TiO2, 2.6 pct FeO plus 1.6 g per min of 20 to 60 mesh petroleum coke. The

Jan 1, 1962

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

By Molly Gleiser

The standard free energies of formation of some gaseous metal oxides together with those of their condensed oxides have been plotted against temperature. The heats of formation of the gaseozcs oxides are tabulated. An explanation is given of the use of the data to predict the importance of the gaseous metal oxides at high tenzperatures. RECENT mass spectrometric work1 has resulted in the detection of several hitherto unknown gaseous oxides and the measurement of their free energies of formation. Of especial interest is the fact that several of the refractories in common use either as crucibles or furnace tubes, and metals used in Knudsen cells and in furnace windings, have been found to have one or more stable gaseous oxides. In view of the present emphasis on high-temperature techniques, the development of vacuum metallurgy.z heating by electron bombardment and plasma jets, and the resultant shift to ever higher temperatures, it is no longer possible to plan experiments without taking into consideration the significance of the presence of these gases in the system, the reactions they undergo. and their contribution to the vapor pressure. A good example of what went wrong in earlier work, when the existence of these gaseous molecules was not yet known, is presented by the work of Hoch, Nakata, and Johnston. Hoch and coworkers attempted to measure the vapor pressure of solid ZrO2 by letting the vapor in equilibrium with zir-conia effuse from a tantalum Knudsen cell. The free energies of formation of solid zirconia and tantala are such that a short calculation showed that the reaction

Jan 1, 1962

By M. H. Caron

D. C. Ralston—The fact that none of the organizations that have worked on these ammoniacal leaching processes have contributed discussion of Mr. Caron&apos;s papers today is a matter of some disappointment. Adaptations, modifications and improvements have been made by several organizations or individuals and to complete the record I want to document a number of them. The Nicaro Nickel Co. operated a Government owned plant at Nicaro, Oriente, Cuba, during the past war. A report on the project was written for Reconstruction Finance Corp. and is in the document file collected by the Office of Technical Services, Commerce Department and filed with the Library of Congress, where it can be consulted or bibliofilm or photostat copies obtained by asking for copies of PB 97271. Nicaro Nickel Co. has obtained a series of U.S. Patents, my list (probably incomplete) of which bears the following numbers: 2,400,098; 2,400,114; 2,400,115; 2,400,461; 2,400,612; 2,458,902 and 2,473,795. International Nickel Co. has also studied the problem and U.S. Patent 2,478,942 shows that some of the complications involving occasional low extractions have been unraveled. Forward, Samis, and Kudryk, of the University of British Columbia, have also published a study of copper-nickel sulphide concentrate.&apos; Others are interested and it is evident that this type of hydrometallurgy is likely to find a happy application in the not-too-far distant future. Caron&apos;s two papers practically amount to a summation of his life&apos;s work on the important subject of nickeliferous iron ores and the American Institute of Mining and Metallurgical Engineers is fortunate to have been chosen the medium of publication. M. Rey—The ammonia leaching process has been the subject of certain studies in New Caledonia, but at the present time, the conditions are not very favorable to its adoption. The process is a combination of a thermal and a hydrometallurgical process. As a result, the first costs and the operative costs are rather high. To counteract this unfavorable situation, it would be necessary to make a very high extraction. But unfortunately, the process is delicate and in spite of all of Caron&apos;s valuable work, there are still many unknown factors. It is difficult to obtain regularly a high extraction, exceeding 75 to 80 pct. It would be interesting to have the opinion of Inter-national Nickel on the process and to know what the Dutch are doing in Celebes. M. H. Caron (author&apos;s reply)—I am quite familiar with the different types of nickel and cobalt ores as found on New Caledonia, and it may be pointed out that the Celebes ores are quite the same in their properties. Their behavior when treating the ores by the ammonia-leaching process is also alike and in my opinion, there is no reason why a high extraction of the New Caledonian ores could not be obtained if the process is properly applied. For the sake of completeness I may add that one of my patents has not been discussed in the papers. This patent deals particularly with the treatment of serpentine nickel ores. (Netherlands No. 62693 40a, French No. 965.786 April 21. 1948. and Cuban No. 13.625 Jan. 1950.)

Jan 1, 1951

By J. H. Rushton, L. H. Mahony

Principles of fluid motion and turbulence which have been found to be of use in mixing and agitation problems are discussed, as well as suggested applications in extractive-metallurgy processes. Various types of impellers are described, together with other conditions that affect flow pattern and turbulence. The choice of equipment for particular requirements is considered, and equations for power input are given. Modern heavy-duty mixing and agitation equipment can take an increasingly important part in such extractive-metallurgy processes as solids handling, crystallizing and leaching, chemical operations, and flotation. Application of mixing and fluid-mechanics principles to extraction methods can lead to greater process rates and a resultant saving in time and money. MIXERS are being applied with increasing frequency to problems in the metallurgical industries. The increase represents in part the modernization of mechanical equipment used through the application of unitized drives, modern electric motors and speed reducers, and recently developed materials of construction. Some applications have resulted from process changes and the use of techniques for operations similar to those that have been demonstrated and proven in the chemical industry. Still more applications are being developed through the use of fluid-dynamics principles not previously recognized as applicable to these operations. It is the purpose of this paper to describe those principles of fluid motion and turbulence which have been found to be of use in mixing and agitation problems, and to suggest applications for them in the extractive-metallurgy processes. Modern mixing equipment has been designed to provide the fluid motion consistent with that best suited to different operations.&apos; When properly applied, these more efficient fluid-handling mixers result in lower process-production costs. Metallurgical operations usually involve large amounts of solids. The characteristics of the ore control the process and only enough liquid is added to provide sufficient fluidity for handling and processing. The reactive part of the ore, the mineral value to be extracted, is likely to be low in percentage, and the quantity of reagent required is similarly low, but excessive dilution makes additional reagent necessary and therefore is undesirable. Thus, the primary problems in minerals processing are to handle as high a concentration of solids as possible and to distribute reagents uniformly. These pulps, or slurries, are in a range of solids concentration where hindered settling rates apply, and care must be taken to agitate and mix sufficiently to maintain suspension and flow throughout the equipment. Such slurries have high densities which are the weighted average of the components and viscosities that are spoken of as "effective viscosities" but are difficult to evaluate. It is convenient to separate metallurgical operations involving mixers and agitators into three categories: solids handling, mechanical or physical operations, and chemical operations. In each of these categories fluid motion is required to maintain suspension, to distribute surface-active agents, to blend components and reactants, and to induce high rates of chemical reaction. After a discussion of some basic principles of mixing and agitation, examples of application to the three categories will follow. Fluid Motion The fundamental problems of mixing and agitation of liquids have to do with the mechanics of fluid streams and the means by which they are

Jan 1, 1955

By D. R. Spink

In the preparation of zirconium and hafnium metals, there are many indications that impurity levels control the physical and chemical properties of the metal. The purpose of this work was to develop methods of producing pure raw materials that could be reduced to highly pure metals. Early work by the Carbomcndum Metals Co. and others indicated that certain fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. We have developed workable fused salts along with a continuous and higly efficient scrubber design which can be used to produce very pure zirconium tetrachloride. Metal made from the purified tetrachloride has been shown to approach crystal bar metal in purity. Scrubber designs are discussed with recommended materials of construction. VARIOUS methods have been used to purify zirconium (and hafnium) tetrachloride. Most of these methods involve thermal degassing initially (the removal of more volatile compounds at temperatures below that where zirconium tetrachloride exhibits a significant vapor pressure) followed by a sublimation step (which conveniently leaves the nonvolatiles behind.) While these procedures effect definite purification, such processing is batchwise and does not result in optimum purification. Early work by The Carborundum Metals Co. and others indicated that fused salts were highly efficient in the removal of impurities from gaseous zirconium tetrachloride. The objective of this work was to develop a continuous fused-salt scrubbing process that would yield high-purity zirconium and hafnium tetrachlorides. The term "fused salt" refers to the molten state of ionic compounds and as used here, specifically refers to alkali metal and alkaline earth halides. Fused salts, because of their many valuable properties, are becoming increasingly im- portant industrially. These valuable properties of the fused salts are: 1) stability at elevated temperatures; 2)low vapor pressure; 3) low viscosity; 4) ability to dissolve many different materials; and 5) good elctctrical conductivity. All but the last property enhances the use of fused salts as scrubbing agents for zirconium and hafnium tetrachlorides. Fused-salt scrubbing may be defined for our purpose as the intimate contact between a gaseous compound and a molten salt with the purpose of removing impurities from the gaseous compound. In this case, the gaseous compound is zirconium tetrachloride which submlimes at 331°C. When this gas is contacted with a molten salt, impurities such as aluminum, iron, and titanium are removed and the resulting product is considered fused-salt scrubbed. Zirconium and hafnium are sold to a purity specification. Generally speaking, normal production without scrubbing is capable of meeting specifications. There are, however, several considerations That make the knowledge of methods of additional purification highly desirable. These are: 1) the control of product analysis; 2) the production of a pure product for special applications; 3) the salvaging of off-specification material; and 4) the use of raw materials with higher impurity levels than 1 he present raw materials. You will note that items 1 and 2 are somewhat complementary to each other and that item 4 assumes that The present process has impurity removal limitations. To better understand the part that fused-salt scrubbing of zirconium tetrachloride plays in the manufacture of zirconium, Fig. 1 contains an illustrated flow sheet of the industrial production of zirconium metal. In referring to Fig. 1, we can point out the specific benefits derived from our ability to purify zirconium tetrachloride. Purification of the crude (hafnium-containing) zirconium

Jan 1, 1962

By J. B. Cohen, B. W. Howlett, M. B. Bever

The partial molar heats of solution at infinite dilution in tin of aluminum at 300° and 350°C and of gallium, indium, and thallium at 240°, 300°, and 350°C have been measured by tin solution calori-metry. Aluminum, gallium, and thallium are endo-thermic on solution; indium is exothermic. Any temperature dependence of the heats of solution lies within the experimental scatter. Over the dilute ranges investigated, only aluminum has a measurable change in its heat of solution with composition. HEATS of solution of one element in another reflect the interaction between them. The investigation of partial molar heats of solution in dilute alloys is of particular interest as the properties of the solvent are altered to only a limited extent by the presence of the solute and also as the interaction between solute atoms is small. When the heats of solution of a related series of elements in a solvent are known, a systematic comparison may be made. In the investigation reported here, the partial molar heats of solution of the Group III elements aluminum, gallium, indium, and thallium in dilute solution in tin were measured. This work follows an investigation of the heats of solution in tin of the Group IB elements.&apos; EXPERIMENTAL PROCEDURES Materials. Samples of gallium, indium, and thallium were obtained from Johnson, Mathey and Co., Ltd. Indium and thallium were supplied as wire, 1.6 mm in diam; gallium was in the form of irregular pieces. The supplier reported the following minimum purities: gallium—99.95 pct; indium—99.99 pct; thallium—99.99 pct. The aluminum, obtained from Alcoa Research Laboratories, was reported to be 99.995 pct pure. The tin was supplied by Baker and Co., Inc.; the reported analysis indicated a tin content of at least 99.96 pct with lead as principal impurity. Calorimeter. this description will cover only the essential features of the calorimeter with special attention to modifications made since an earlier description was published.&apos; A Dewar flask containing the tin bath was held in a constant-temperature bath of a near-eutectic mixture of lithium, sodium, and potassium nitrates. This bath, which was stirred vigorously, was heated by a primary resistance winding in the container wall and by a secondary winding immersed in the salt. The voltage supplied to both windings was stabilized. The temperature of the salt bath was controlled by means of a platinum resistance thermometer in one arm of a Wheatstone bridge. The light from a mirror galvanometer in the bridge circuit fell on a photocell which controlled the current in a saturable reactor in series with the secondary winding. In this manner, the temperature of the salt bath was controlled to ±0.003°C and that of the tin bath to at least ±0.002°C. Each of these temperatures was measured by two iron-constantan thermocouples in series, coiled in a helix to minimize heat loss and immersed in the salt and tin baths in protective sheaths. The temperature of the laboratory was kept constant to ± 1°C during a run. Specimens were dropped into the tin bath from an addition arm held at O°C which was part of the cal-orimetric system. The system was evacuated to about 0.02 1 to minimize oxidation and to reduce transfer of heat. The bath was stirred by a glass stirrer introduced through a double Wilson seal. The samples were scraped clean before weighing, which was carried out as rapidly as possible. Each sample was immediately placed in the evacuated addition arm to minimize contamination. These precautions were especially necessary with aluminum. After the runs with gallium and thallium at all temperatures and with indium at 240° and 350°C (Series I) were completed and before the runs with indium at 300°C and aluminum at 300° and 350°C (Series 11) were begun the following changes were made. The shape of the Dewar flask was changed so as to result in a lower surface to volume ratio of the bath and at the same time the amount of tin was reduced from 500 to 400 g. The paddle type stirrer was replaced by a helical screw and the rate of stirring was increased to about 150 to 200 rpm.

Jan 1, 1962

By R. F. Rolsten

VAN Arkel 1 prepared ductile tantalum by the thermal decompoiition of tantalum pentachloride on a resistively heated wire (2000° C) in an evacuated bulb maintained at 100°C. Burgers and Basart2&apos;3 observed the formation of a mixture of tantalum carbide and free metal when a carbon deposition base was used. campbel14 suggested the thermal decomposition of the iodide if a lower decomposition tem- perature was desired. To date, the details for preparing high-purity iodide tantalum have not been disclosed. EXPERIMENTAL The tantalum to be purified was symmetrically placed around the clear quartz deposition surface centrally located within a 64 mm cylindrical Vycor bulb. The deposition vessel usually employed5 was modified6 by incorporating a reentrant fin,mer in place of the customary metal filament in the head

Jan 1, 1960

By A. Berghezan, E. Bull Simonsen

A simple and general method is described for melting and zone refining refractory metals by induction heating on a specially shaped water-cooled copper crucible. The crucible is the essential part of the apparatus and is placed horizontally. It consists of either a copper plate, or a flattened tube, or of several parallel small diameter tubes all water cooled. The charge lies on the crucible, or whenever possible, is suspended above it. This assembly goes into a transparent quartz tube and the whole is passed through the coil of a radio frequency generator. Vaarious atmospheres can be used. No contamination is detected from the copper crucible. purification is obtained both by selective evaporation of impurities and by zone refining. METHODS of melting and refining relatively large ingots of all reactive and refractory metals as well as some semiconductor materials have been developed in this laboratory during the past several years using induction heating and cold crucibles. These methods are simple and permit the use of a variety of starting materials in preparing ingots of suitable shapes. Among these methods, two are of particular interest. One deals only with the problem of melting without contamination. In this method the induction coil has a specially designed shape and acts simultaneously as heating element and crucible. The second goes one step further, being designed for both melting and further purification of the refractory metals. The aim of this paper is to describe the second method which is of more general interest and of greater applicability to metallurgical problems. A) THE PRINCIPLE OF THE MELTING AND PURIFICATION METHOD As originally proposed by one of us1 the method consists of heating a charge of any refractory metal or semiconductor material to the melting point on a water-cooled copper crucible by passing both the charge and the crucible through the induction coil of a radiofrequency generator. Although both are subjected to the same induction field, one achieves the melting of a refractory metal on a copper crucible even when the refractory metal has a melting point of more than 2000°C above that of the crucible. This seemingly "odd" method works effectively for the following reasons. Because of its high electrical and thermal conductivity as compared with the material being melted, copper can be used as the crucible and kept at a low temperature while the material is heated by induction to its melting point. With water Silver and other highly conducting materials can also be used. If a nonconducting material is contemplated, e.g. SiO or a high polymer, a very thin wall should provide efficient cooling. cooling through ducts in the crucible its temperature can be kept between 40" to 70°C; thus its electrical resistivity is kept low, while the resistivity of the charge increases rapidly as its temperature is increased. B) APPARATUS The crucible is the essential part of the apparatus. It has been designed in various shapes depending on the atmosphere used, whether vacuum or an inert gas or hydrogen. In all crucible designs an effort was made to reduce its volume to "nothing but the cooling water" in order to avoid shielding the ingot from the induction field. In practice it is either a

Jan 1, 1962

By E. A. Slover

THE usual reverberatory system of smelting cop--1- per concentrate or calcine has for its component parts a furnace and one or two waste heat boilers. These parts are operated on a basis of compromise, since the furnace can send gas to the boilers at too high a temperature and the boilers by plugging, due to dust or slag, can place a definite limit on the amount of fuel the furnace can burn. Over the years the copper concentrate smelting furnace has had few advances in design. The simple rules of design such as the flame should wipe the bath and the speed of the gases should be reasonably low for dust carrying purposes seem to cover the main features. In the construction of the individual furnaces some innovations are always being introduced. Among these are charging so that the work of smelting is a complete bath process, the use of suspended brick arches in place of sprung arches, the use of basic brick, not only in the crucible, but also in roof and sidewalls, the use of various means to feed the charge, the use of magnetite or other heavy material to construct the hearth, water cooling of bridgewall and slag skimming bay, the smelting of raw charge instead of calcine, the use of preheated air, and possibly the use of oxygen-enriched air for combustion. But the general outlines of the furnaces have not changed much except as to size. Furnaces at Hurley As shown on Fig. 1, the furnace at Hurley is 126 ft long between the longitudinal buckstays and 32 ft wide at the skewback plates. The foundation is a concrete retaining wall with piers at intervals that go deeper into the earth. Purposely the wall at the burner end of the furnace is not backed-up as tightly as the other parts of the foundation so that movement due to expansion may take place here rather than into the boiler foundations. Within these foundation retaining walls of concrete, the earth has been removed to allow the placement of the crucible brick base inside of which a silica hearth is laid 4 ft 6 in. in depth. No expansion is left in the brick base and crucible where they are in contact with the hearth. The hearth itself is of quartzite crushed to 1 in. size with fines left in the product. An 8 in. layer is laid and tamped with paving tampers to about 6 in. in thickness. Then a layer of silica flour is spread and vibrated into the hearth. This operation is repeated until a depth of 4 ft 6 in. is occupied by the silica mass onion-skinned in layers of approximately 6 in. Before firing the entire hearth is covered with broken slag to a depth of 4 in. so that a seal may be formed on the hearth. The crucible is completely faced with magnesite chemically bonded brick while the outside, against the foundation, is made of silica brick. The side-walls are carried up with silica brick in which expansion joints are left at intervals. Above the crucible the sidewall is corbelled to form a shelf on which the charge may build up along the side-walls, see Fig. 2. The arch of the furnace is sprung 20 in. silica brick, with the longitudinal centerline horizontal the length of the furnace, and some 9 ft in the center above the bath. Both straight and wedge brick are used in the construction and a thin silica mortar is troweled for joints. After the arch under heat has assumed its permanent shape, a silica slurry is spread over the arch to fill any cracks that have formed, thus giving bearing surface to the brick and preventing dust from entering the body of the arch to act as a future fluxing agent. The uptake of the furnace slopes up to the boiler entrance where a brick pilaster divides the gas stream for the two boilers. Over this flared uptake is a suspended flat arch of firebrick. The pilaster and sidewalls are constructed of firebrick but the bottom of the uptake is lined with silica brick and fettled through holes in the roof with siliceous fettling. Close to the entrance of each boiler is a brick covered slot through which water-cooled dampers may be lowered in event of boiler trouble. These water-cooled dampers are hung permanently in position ready to be lowered when needed. Flexible hoses to follow the dampers as they are lowered are connected at all times and individual chain blocks are used to lower the dampers. A pump supplying water is started before the dampers enter the heat. Charging of the furnace along the sidewalls for some 80 ft from the bridgewall is accomplished by electric vibrating conveyors fed by belt from charge storage bins above the furnace. These conveyors

Jan 1, 1954

By K. W. Nelson, John N. Abersold

INDUSTRIAL hygiene has been defined by Patty&apos; as "the science and art of recognizing, evaluating, and controlling potentially harmful factors in the industrial environment." This definition implies thorough study of operations, evaluation of potentially harmful factors through air sampling, micro-analyses and other means and finally, appropriate medical and engineering control wherever indicated. The prevention of industrial health injuries is a vital part of operations of American industry today. Progress and interest in this field has increased steadily for many years, the most rapid progress having been attained, perhaps, during the last three decades. It is significant to note that there are now official agencies in 46 states actively concerned with industrial health problems and that a western field station has been established recently in Salt Lake City by the U. S. Public Health Service to augment its industrial hygiene services directed from headquarters of the National Institute of Health, Bethesda, Md. Many of the larger industries have found it advantageous to establish their own industrial hygiene departments. The American Smelting and Refining Co. is a world-wide organization engaged in the mining, smelting, and refining of lead, copper, zinc, silver, gold, by-product metals, including cadmium, arsenic, and others. In the United States there are 13 smelters and refineries, 11 secondary smelters or foundries, and a number of mines. Approximately 9000 workers are normally employed. It has long been the established company policy to seek out occupational hazards and provide safeguards for employee health. Protective equipment has been supplied to individual workers and exhaust ventilation installations have been in use in some operations for more than 40 years. All of the major units have their own medical departments which provide employees with excellent medical and hospital care. In 1937 full scale industrial hygiene studies were undertaken at the Selby Plant and were extended to most of the other smelters during the next three years. In 1945 the Department of Hygiene was organized with Professor Philip Drinker of Harvard University as Director and with Dr. S. S. Pinto as Medical Director. The department is responsible for coordinating and maintaining a program for the good health of all employees from top management down to the lowest paid day worker. It is essentially a service organization serving all of the United States plants regardless of location or size. Full and part-time physicians employed in all of the company&apos;s American plants and working in close cooperation with the Medical Director are responsible for de- termining the state of health of all the employees and giving treatment when necessary. In general, medical care is confined to accidents or illnesses occurring while the men are on the job. Among the duties of the doctors is the making of careful physical examinations of new employees and routine check-ups of old employees. In addition to medical care a primary responsibility of the department is the prevention of occupational illnesses. In this the main concern is with the working environment in relation to its effect on the worker. Environmental factors may be dusts, fumes, gases, toxic materials, heat, humidity, radiation, or noise. The objectives are: (1) Immediate control of these factors through the education of the worker, through providing the wearing of respirators or other protective devices, and through careful medical examinations and regular analysis of urine specimens; (2) a long range control program which may be accomplished by local exhaust ventilation, wetting of materials, changes in metallurgy, changes in methods of handling, or by use of special devices and special equipment. To accomplish these objectives a fine industrial hygiene laboratory was built in Salt Lake City and equipped to do routine and experimental work. Trained and experienced industrial hygienists obtain the facts by making frequent hygiene surveys. These surveys include tests of the air, studies of all processes, and careful investigation of ventilation, lighting, and general working conditions. Except in emergencies, the air contaminants and often the substances handled by the worker are sent to the laboratory for analysis by chemists and technicians specially trained in industrial hygiene methods. The findings are evaluated in terms of limits recommended by various State and Federal agencies, and in light of all available medical data. The methods used for studying the working environment involve all of the usual chemical and physical procedures employed in industrial hygiene. The Impinger, electric precipitator, thermal pre-cipitator, and filter paper sampler have been used to collect atmospheric dust and fume samples. Of special interest here is the filter paper sampler, shown in Fig. 1, which was developed by Dr. Silver-man at Harvard University. The instrument has been improved and is used very extensively in field studies. A water manometer connected behind an orifice is used to determine the rate of air flow. Calibration is effected by use of a standard gas meter or rotameter. The dust or fume is collected on a filter paper clamped between two rings, as shown in Fig. 2. The filter paper, such as Whatman No. 52, collects both dust and fume with a very high efficiency. The instrument is very convenient and easily transported. The solids collected on the filter paper are analyzed in the laboratory usually by use of a polar-ographic procedure. By this procedure it is possible to measure quantitatively in a single analysis the

Jan 1, 1952

By Luiz C. Correa da Silva, Robert F. Mehl

A. D. Le Claire and R. S. Barnes (Atomic Energy Research Establishment, Harwell, Didcot, Berks., England)-—This much awaited paper admirably confirms that the Kirkendall effect is a true diffusion phenomenon and likely to be found in all diffusing systems. The most likely explanation put forward so far to account for the shift of interface is that the two components of the system, diffusing in opposite directions, do so with unequal rates so that there is a net loss of material from that half of the diffusion zone rich in the more rapidly diffusing component. This loss is accompanied, and at least partly compensated for, by a closing up or decrease in volume of this latter half of the diffusion zone and an expansion of the other half so as to tend to keep constant the overall volume per atom. This is manifest as a movement of the original interface. If this is a true picture of what is taking place then there are at least two important matters requiring further study."1—The quantitative relating of the observed shift with the independently measured separate diffusion coefficients of the two diffusing species."2—A detailed study of the mechanism and characteristics of the closing up process."We would like first to make a few remarks pertinent to these topics. In connection with the first of these, it is a pity that more and detailed measurements were not made on the Au-Ag system, the only one for which the separate diffusion coefficients of the two species have been measured.&apos;" One of us (A. D. Le C.) has calculated from Johnson&apos;s results the shift to have been expected in samples D.2 and D.3. Darken4 showed that the velocity v with which the markers move is related to the separate diffusion coefficients Dau, Dag, by the eauation:"dN"v = (Dag — Dau "dx"dN"where .is the concentration gradient at the mark-ax"ers. Under certain conditions,4, 20 it can also be shown that:"Xm"v = "2t"where x, is the total marker shift after time, t:"dN". . xm = 2t (Dag — Dau) [9]"dX"Johnson measured Dag and DAu in a chemically homogeneous alloy and so his reported figures represent the true or ideal diffusion coefficients"; the same quantities in eq 9 represent the actual diffusion coefficients as would be measured in the presence of a chemical concentration gradient, so we need to multiply Johnson&apos;s reported values of Dag and Dau by the"1 before insert-dlogN "ing them in eq 9. 7 is the activity coefficient of Ag at the concentration prevailing near the markers which we shall assume to be - 50 pct. The values of the thermodynamic factor for N = 0.5 and the temperatures at which D.2 and D.3 were annealed were obtained from thermodynamic data quoted by Darken.&apos; aN/ax was computed from the coefficient of inter-diffusion of Au and Ag given by Johnson on the assumption that in the samples D.2 and D.3, the concentration distance curve could be represented by the standard equation:""No is the original difference in concentration between the two halves of the couple, and + is the error or probability function."aN/ax at x = 0 is then given by:"adN/dx "2/nDt"and we assume that this represents the concentration gradient at the markers, although it is probable that the figure is slightly high."When all the appropriate quantities are inserted in eq 9, we find that the expected shifts are: for D.2, 0.0134 cm and for D.3, 0.0119 cm."The agreement between these results and those

Jan 1, 1952