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Jan 1, 1969

By Basil Prescott

Resume.—The district of Santa Eulalia lies 12 miles to the southeast of the city of Chihuahua, Mexico. The ore deposits occur in a Cretaceous limestone of unknown thickness, overlain by a series of rhyolitic tuffs and flows. The limestone is very gently folded and is cut by several systems of fissures, of which only those with a general north-south strike are pre-mineral and control the deposition. The deposits are of two main types; the earlier silver-bearing iron sulphide type occurs as high-grade tabular bodies resembling veins and as large masses of relatively low-grade ore, The gangue of this type is composed of lime-iron silicates that point toward a close association with an igneous rock mass which has not yet been encountered. In the later silver-lead-zinc type the ore occurs in vertical chimneys and horizontal mantas, principally as oxides, though at a depth of 1,500 ft. some sulphides have been encountered. During oxidation the ore chambers have increased in size owing to the solution of the walls by the sulphuric acid generated in the process, and a substitution has taken place of nearly one-half part by weight of the original constituents of the ore, by newly introduced elements and radicals. Both types are believed to have come from greater depths than those yet reached by mining, and their ultimate source, from a consideration of similar deposits, is believed to be an igneous rock in contact with the limestone at some horizon below. The deposits are believed to have been formed at unusually great depths, as indicated by the proved great vertical range of the silicate minerals coupled with the absence of the igneous rock, and by the practically unchanged character of the silver-lead-zinc ores as far as developed. The volcanic capping is believed to be distinctly later than the economically important ore deposition. Introduction The Santa Eulalia district is situated in the State of Chihuahua, Mexico, and lies about 12 miles southeast of the capital, the city of Chihuahua. (See map, Fig. 1.) The district embraces the Sierra de La

Jan 1, 1915

By F. R. Hensel

PURE silver and silver-lead alloys have been studied as to their suitability for bearings.1-8 A review of the properties of thallium and the silver-thallium constitutional diagram was made by the author to analyze the possibilities of silver-thallium compositions for antifriction materials.† The silver-rich end of the diagram as reported in the literature9-11 was found to be sketchy and it was necessary to carry out considerable experimental work to arrive at definite conclusions. Some of the results of this work are reported in this paper. TEST MATERIALS In the beginning of the work, only fused alloys were investigated. Later, research [TABLE I. Composition of Fused Silver thallium Alloys Tested for Antifriction Properties PERCENTAGE ALLOY No.OF THALLIUM 15330.48 153406 231 HT2.04 2312.10 232 HT3.83Balance 2324.07Silver 233 HT5.86 2336.38 2349.84 234 HT10.07] was carried out on electroplating methods and diffusion processes. In preparing the fused alloys, care was taken to exhaust the toxic fumes caused by the thallium content. The compositions of the series of fused alloys are listed in Table I. The silver-thallium alloys were melted in clay-graphite crucibles and cast into preheated steel molds of 3/4-in. diameter. In the cast condition, they showed a cored structure, as indicated by the micrographs of Figs. I to 3. The etching reagent used was a mixture of 2 grams K2Cr2O7, 8 c.c. H2SO4, and 100 c.c. H2O. The cored structure is unsatisfactory for the type of corrosion resistance required for bearing applications, and homogenizing experiments were carried out at various temperatures, the results of which are shown in Figs. 4 through 8. The alloys with a lower thallium concentration, which were heated for 2 hr. at 525°C. show an almost completely homogenized solid solution type of structure. With higher thallium concentration, the homogenizing temperature was dropped to 475°C. to eliminate the formation of a liquid phase. It is evident that heating for 2 hr. at this temperature did not result in complete elimination of the cored structure. As would be expected, cold-working of the cast structure is an expedient in establishing equilibrium conditions. The fine homogeneous grain structure shown in Fig. 7 corresponds to the cold-worked area under the Rockwell ball penetration when the hardness was taken before heat-treatment. A detailed structural study was made on a cast silver-thallium alloy containing 3.67 per cent thallium. Three micrographs (Figs. 9, 10 and 11) show the transition

Jan 1, 1945

By B. M. Larsen

Jan 1, 1965

By A. W. Gauger

Coal as mined contains varying quantities of inorganic components (mineral matter) which, on combustion, produce the residue known as ash. It has long been realized that the weight of this residue does not equal the weight of the mineral matter originally in the coal, because of the chemical changes that take place during the ashing process. Moreover, the ordinary ash analysis presents the ash as a mixture of oxides with little or no clue to the identity of the mineral species originally present in the coal. It is only for pyritic sulfur that an attempt is made to determine a mineral component. So far as the authors are aware, there are practically no experimental data in the literature as to the percentages of the different mineral species present in coal. The oft-quoted table of Marson and Cobb1 cannot rightly be considered as data, since the authors merely state that the table "shows the probable forms in which these ash constituents exist in coal." In view of the attempts to calculate analyses and determinations of the calorific equivalent of coal to the mineral-matter-free basis, as well as the importance of the mineral species in clinkering, combustion and coking, it seems strange that so few data are available on this phase of coal technology. For example, numerous empirical corrections for use in the scientific classification of coal have been suggested to compensate for the losses from the mineral matter during ignition of the coal to ash. These include multiplication of the ash percentage by various factors such as l 1/10 and 156, the use of the Parr unit coal formula (1.08 A + 22/40 S, where S = total sulfur) as well as certain modifications of the Parr formula that attempt to correct for the organic sulfur present in the coal. Although many experiments have been made to determine the loss on ignition of the clays associated with the coal measures and correction

Jan 1, 1934

By Raymond Ward

Jan 1, 1945

By J. W. Rutter, K. T. Aust

The temperature dependence of the rate of grain boundary migration was measured in bicrystals of zone-refined lead containing from 20 to less than 1 ppm by wezght of tin. The apparent activation energy in the temperature range from 320" to 200oC is markedly dependent upon the solute tin concentration and upon the orientation relationship of the grains adjacent to the grain boundavy. The quantitative experimental observat~ons are compared with the predictions of various theories of grain boundary migration. In previous work.&apos;?&apos; the mobility of individual grain boundaries was studied as a function of impurity concentration and type of boundary. Grain boundary migration occurred at the expense of dislocation arrays which were introduced into the specimen during solidification. Boundary mobility in zone-refined lead at 300°C was markedly decreased by small additions of tin. 0.004 wt pct being sufficient to decrease the rate of grain boundary migration by a factor of 1000. The mobility of grain boundaries having polar orientation relationships near 38 and 22 deg about <Ill>, and 28 deg about <100>, was much less sensitive to tin concentration in the range studied. As a result, these boundaries have relatively high mobilities. The present paper is a continuation of the above study. Data are now presented on the temperature dependence of the motion of individual grain boundaries in zone-refined lead as a function of solute tin concentration and orientation relationship of adjacent grains at the grain boundary. The experimental observations are compared with the predictions of a number of theories of grain boundary migration3-8 which, prior to the present experimental investigation, could not be critically evaluated. EXPERIMENTAL PROCEDURE The striation or lineage structure of melt-grown single crystals of zone-refined lead, containing various additions of tin, was utilized to provide a driving force for grain boundary migration, as previously described.1,2 Each grain boundary under study separated the striated single crystal from another grain which was introduced by localized plastic deformation and recrystallization of a small region of the sample. The speed of migration of grain boundaries in dilute alloys of tin in zone-refined lead was investigated as a function of 1) tin concentration from < 0.0001 to 0.002 wt pct, 2) temperature in the range of 200" to 320°C, and 3) orientation relationship of the adjacent grains at the grain boundary. The substructure driving energy available for grain boundary migration was estimated to be about 4000 ergs per cu cm, within a factor of two, from specimen to specimen.&apos; The specimen dimensions, and growth and alloying procedures for the preparation of striated single crystals of lead of known tin composition, were as described previously.&apos; Each bicrystal was carefully wrapped in aluminum foil, and annealed in a well-stirred salt bath consisting of 50 pct NaNO2 and 50 pct KNO3, for known periods of time at a series of constant temperatures (*2°C). The grain boundary positions, before and after each anneal, were determined by etching lightly in a solution of 5 pct nitric acid in methyl alcohol, in order to follow the motion of the boundary and determine its rate of migration. Thus, the rate of motion of the grain boundary in a single specimen was measured at various temperatures. The above procedure was carried out for each grain boundary in seventeen different bicrystal specimens.

Jan 1, 1960

By W. H. Brandt

THERE has been much progress in the last two decades in understanding the hardenability of steel. Roughly, the progress has been along two lines, which may be designated as empirical and fundamental. This empirical work has progressed to the point where steels may be manufactured to the desired characteristics quite closely and heat-treatment and application problems can be approached with considerable confidence. Particularly noteworthy among the empirical work is that of Grossmann,12 who has given formulas for calculating hardenability as a function of composition, and the establishment of the isothermal transformation curve by Davenport and Bain.13 The latter does not fall entirely in the class of an empirical study, for while it provides a means of presenting a tremendous amount of empirical data in the form of a single curve, it also outlines clearly the problems that face the fundamental investigator. The isothermal transformation curve shows clearly that the phenomena occurring in the neighborhood of the knee of the curve are those that limit the hardenability of steel. Above the knee of the curve, the product of decomposition of austenite is lamellar pearlite and fundamental progress has consisted chiefly of a detailed study of structure and formation of pearlite, largely at the hands of Mehl and his collaborators.1-5 They have shown that formation of pearlite proceeds by a process of nucleation and growth and they measured both the nucleation and growth rate. However, there is still a wide gap between our empirical knowledge and fundamental knowledge, owing largely to the fact that there is no satisfactory theory of nucleation rate or of growth rate. This paper is being written in an attempt to fill in a small part of the gap. A method was presented recently14 for calculating the velocity of edgewise growth of pearlite using an expression for the carbon concentration that satisfies the diffusion equation. The edgewise velocity of pearlite growth in a plain carbon eutectoid steel was calculated, using linear extrapolations of the ferrite and cementite solubilities. While the results are in fairly good agreement with the experimental facts, the calculated velocity of edgewise growth is smaller at 600°C. than G, the radial growth velocity of pearlite nodules, whereas one would expect it to be larger. In this paper the calculation will be repeated using a new extrapolation for the ferrite solubility, which gives better agreement between G and V, the calculated velocity of edgewise growth. A calculation will also be made of the effect of carbon content on velocity of edgewise growth, and the problems of calculating the effects of other alloying elements on growth rates will be discussed. It will be assumed that the mechanism of pearlite growth, established by Mehl and

Jan 1, 1945

NORTH AMERICA. CANADA Canadian Army Overseas. Ball, H. D. Bridges. C. Butterill, H. J. If. Ladner, F. E. Lane, H. C. Alillar, W. A. ALBERTA Calgary.-Chonette, W. C. Clark, L. At. Corbett, C. S. de Hart, J. B. Dingman, C. W. Fath. A. E. Fulton. J. If. Cray, J. G. Johnson. R. V. McCutchin, J. A. *Slipper, S. E. Vin Buckirk H. A.

Jan 1, 1944

By Dell H. Adams

COAL EXPLORATION Coal exploration may be defined as the acquisition of data necessary to define and acquire a block of coal which can be mined at a profit. Unlike ore minerals, coal resources are widespread and relatively abundant with supply exceeding demand in almost every case. Thus simple discovery of coal is generally not enough. The chemical and physical variability of individual coal seams, the capital intensive nature of coal mine development, and the changing patterns of utilization require that a multiphase, three-dimensional evaluation be made of each potential reserve. Factors which must be investigated include not only the quantity and quality of the coal but also the geologic, hydrologic, and engineering characteristics of the seam and its surrounding strata. Acquisition of property to provide a secure base for exploration and mine development is equal in importance to the geologic and engineering programs. The successful development of a coal reserve requires that control of coal and, in the case of a strip mine, the surface be in the form of contiguous blocks of sufficient size to support mining. PHASES OF EXPLORATION The high capital risks of coal exploration and land acquisition dictate that a multiphase program be utilized to minimize initial risk. In such a program, phased development of the data insures that each increase in capital expenditures will be justified by a corresponding increase in the level of confidence in the ultimate success of the project. Each phase is designed to provide sufficient data and property control to facilitate the decision whether to proceed to the next phase of development or to discontinue the program (Table 1). The first phase of a typical exploration program consists of a pre-

Jan 1, 1981

By W. A. Doble

Opinions differ as to whether the water-wheel almost universally known as the Pelton type belongs to the impulse, the tangential, the reactive, the jet or the percussion class, or to a cross between two or more of these classes. The fact is, that for an almost infinitesimal part of a second the axis of the jet of water strikes the bucket of this wheel at a true tangent to its base-line. The percussion of the water, striking the bucket, imparts an impulse to the wheel, causing rotation; and generally the bucket is so shaped that the direction of the jet is

Jan 1, 1900

This is a most interesting paper and some data in it are corroborated by work I did at Watertown Arsenal some time ago with iron powder. I would like to ask Dr. Wulff to say just a little more about the compressive and tensile stresses on the surface of compacts. JOHN WULFF (author&apos;s reply).-Our work has not yet been completed; although enough data have been obtained with cylindrical compacts of iron to permit some conclusions. Briefly, in a compact 3/4 in. high and 1/2 in. in diameter pressed at 48 tons per sq. in., the residual stresses on the surface measured by X-ray diffraction techniques are as follows: The radial stresses on top center and bottom of compacts are practically zero; the longitudinal residual stresses on the side walls are near the top quarter of the compact about seven tenths that of the yield point of mild steel in tension; at the center surface of the compact they are in compression and in magnitude about 0.3 that of mild steel in tension; near the bottom, they are practically zero. F. V. LENEL.?- I was particularly interested in the work that Messrs. Wulff and Seelig reported on the influence of lubrication on the density of parts. In connection with the work of the American Society for Testing Materials on determining the green density of a compact, we ran into considerable difficulty in getting reproducible results of green density determinations. It was much easier to get a reproducible green density when the lubricant was mixed with the powder than when the lubricant was applied to the die walls; particularly when the die was not perfect-i.e., if it was somewhat rough or out of round. In this case, it was almost impossible to get reproducible green densities when the die walls were lubricated, while it was not too difficult to get reproducible

Jan 1, 1946

By P. W. George

This paper presents geological data regarding deposits of over 7,500,000 tons of fine-grained sulphide ore in barite gangue. A series of pyroclastics and arkoses was intruded by sills of quartz porphyry in connection with batholithic intrusions of granite 3 miles from Buchans. Gentle folding, with fracturing acid shearing of tuff beds and intruded quartz porphyry, accompanied and followed the intrusion of granite and porphyry. The sulphide-barite mineralization is localized primarily in fractured and sheared tuff beds, but also in the sheared quartz porphyry. Two structures have proved particularly favorable for mineralization-one, the center of an anticline; the other, a series of weak, incompetent tuff beds intruded by thin sills of quartz porphyry and located between strong beds of arkose. During the folding the weak tuff with intruded quartz porphyry was intensely sheared and contorted and subse-quently mineralized by sulphides and barite.

Jan 1, 1937

NORTH AMERICA ALASKA Anchorage.-Strandberg, H. Tuck, R. Coal Creek.-Moore, E. G. Spencer, W. W. College.-Hance, J. H. Henricksen, R. Henton, H. M. Comet.-Albertson, F. E. Cordova.-O&apos;Neill, W. A. Douglas.-Cahill, W. E. Fairbanks.-Crawford, J. D. Earling, R., B. Fowler. D. A.

Jan 1, 1937

By J. Campbell

Various models are discussed for the evaluation of the negative pressures which may occur in solidifying materials which exhibit various deformation modes: elastic-plastic, Bingham, viscous, or creep flow. The inadequacy of the previously proposed elastic-plastic solution for solidifying metals is revealed by comparison with the more reliable creep results which are given graphically for aluminum, copper, nickel, and iron. The maximum tensions experienced in the liquid phase of solidifying spheres ranging in size from large castings to submicron powders are in the range from —10&apos; to —105 atm for these metals. THERE has been much recent interest in the negative pressures associated with the volume change on solidification and in the possibility of the occurrence of cavitation. Considering the freezing of a highly supercooled liquid, an attempt to evaluate the stresses in the liquid ahead of the rapidly moving solidification front has been made by Horvay1 on a microscale and by Glicksman2 on a macroscale. In a casting of a wide freezing range alloy, the pressure differential due to viscous flow of residual liquid through the pasty zone has been discussed by Piwonka and Flemings,3 In a previous publication4 the author has attempted to estimate the negative pressure occurring in the residual liquid of a spherical casting, employing an elastic-plastic model to describe the collapse of the solidified shell under the internal tension. An earlier model assuming a rigid shell was shown to be inaccurate by many orders of magnitude. The elastic-plastic model is critically reviewed here, and other models are developed which are thought to be more closely related to metals and other materials near their melting points. The spherical geometry (Fig. 1) is chosen because the highest shrinkage pressures would be developed, although the analyses are readily adaptable to cylindrical geometry. A parallel sided casting experiences little internal tension because of the relatively easy dishing inward of the sides. (This commonly observed phenomenon has previously been attributed solely to atmospheric pressure.) Furthermore, small regions of confined liquid in a large solidified volume of a casting approximate reasonably well to spherical geometry. ELASTIC-PLASTIC MODEL The author has shown4 that as solidification proceeds the internal hydrostatic tension builds up until the elastic limit of the shell is exceeded. At this point the internal pressure is closely -2Y/3. Subsequently a plastic zone spreads from the inner surface toward the outer surface of the shell. When the whole casting is deforming plastically a rather more generalized analysis taking account of the externally applied pressure PA + 2y/b gives the internal pressure as: P = Pa + 2y/a + 2ys/b - 2 Y In(b/a) [1] The 2y/a and 2ys/b terms result from the tendency of the liquid-solid and solid-vapor interfaces to shrink, reducing their energy, and thereby helping to collapse the solid phase and compress the liquid phase. The 2y/b term would be important only for powders. The last term arises because of the plastic restraint of the solid, resisting collapse and so effectively expanding the residual liquid. From Eq. [I] it is easily shown that there is a minimum in the pressure at the radius amia= y/Y [2] which is of the order of 103K for the metals aluminum, copper, and iron, and corresponds to the minimum pressure Pmin = 2 Y[l-ln(bY/y [3] The results of a fully worked out elastic-plastic solution are given in a previous reporL4 The main criticism which may be leveled at this analysis when applied to metals at their melting points is the strong dependence of the yield stress on the strain rate. The strain rate varies with both solidification conditions (e.g., whether chill-cast or slowly cooled) and during solidification, as is indicated in the following section. Thus an appropriate choice of Y is very arbitrary. Before proceeding to a discussion of models which are strain-rate-dependent, it is necessary to evaluate the strain rate as a function of the rate of solidification. SOLIDIFICATION RATE Various empirical relations have been deduced5 for the rate of thickening of the solid shell by pour- out tests on partially solidified spheres. These, however, are unsatisfactory for our purposes since they become very inaccurate when the liquid core is very small. A theoretical approach is therefore necessary, and some solutions are set out below. Making the assumptions of constant surface temperature of the casting during freezing, no superheat, and a material freezing at a single temperature, Adams8 deduces the approximate solution: which becomes when b » a: Employing a semiempirical approach vallet6 finds:

Jan 1, 1969

By Joseph E. Pogue

The writer visited the Muzo emerald mines in July, 1915, and spent six days in their study. This paper embodies the results of his observations, plus information personally communicated by Robert Scheibe, Professor of Geology in the Mining Academy of Berlin, who at the time of the visit was completing a detailed field investigation of nearly a year&apos;s duration of the emerald deposits of Colombia. An elaborate account of this valuable work may be expected at a future date from the pen of Professor Scheibe.

Jan 1, 1917

By F. A. Schaufelberger

Early work on chemical precipitation of metals from metal salt solutions is reviewed. The chemistry and thermodynamics of precipitating copper, nickel, cobalt, and cadmium metals by reaction with hydrogen are discussed. Mechanisms of metal precipitation, nu-cleation, growth, and agglomeration are reviewed, as well as some solubility phenomena of cleation,gases and solids at elevated temperatures. Experimental data presented deal mainly with the reaction of copper sulfate solution with Hz. METAL can be recovered from a leach solution either indirectly by precipitation as a compound that is later reduced or directly by electrolysis, cementation, or chemical reduction, for example, with hydrogen. The widely used electrowinning processes suffer from the inefficiency of converting fuel to low voltage dc and from low current efficiency when complete recovery is attempted. With the batch hydrogen reduction methods outlined here, a unit of fuel converted to hydrogen in modern gas reform plants will make two to three times as much metal as can be obtained with electrolysis. With continuous hydrogen reduction, four to six times as much metal is obtained. Precipitation by reducing a metal salt solution with H, has been known for almost 100 years.&apos; Commercial use of the process, however, awaited the research and development program initiated by Chemical Construction Corp. Within the last few years this program has brought about construction of commercial plants, listed on p. 701. Ideal hydrogen reduction will precipitate a pure metal from a solution obtained by commercial leaching methods at a rapid rate without excessive temperatures and pressures. The metal precipitate will be of desired size and density, less than a percent left in the vessel being deposited on the wetted parts. The present discussion will outline Chemical Construction Corp.&apos;s early development program and will discuss the chemistry and mechanics of reducing copper, nickel, cobalt, and cadmium from solution by H2. Work on selective reduction of nickel from cobalt has been described earlier.2 The article is not concerned with precipitation of copper by disproportionation of cuprous solutions where yield is limited" to 50 pet.* It does not discuss use of gaseous reducing agents other than hydrogen, such as SCV which may lead to contamination with sulfur, or CO," which is considerably more expensive than hydrogen and produces a gaseous reaction product, CO2.† The article does not include use of other nongaseous reducing agents: which are far more expensive than CO. Also, notes on the history, engineering design, and performance of commercial plants have been given elsewhere." It will be shown that a pure metal can be precipitated by reduction with hydrogen from solutions obtained by commercial leaching methods when the solution cohposition is controlled and proper acidity, proper metal ion concentration through controlled complex formation and hydrolysis, and adequate agitation for suspension of metal and for transfer of reducing gas are maintained. Reasonable temperatures and pressures are used which are less excessive than those used by previous workers, although they are maintained at above equilibrium values because of process kinetics.&apos; It has also been found necessary to induce nuclea-tion and to control growth and agglomeration in order to get a powder product of suitable physical properties. Review of the Literature Muller, Schlecht, and Schubardt of I. G. Farbenm claimed a successive reduction of silver, copper, nickel, cobalt, and zinc from ammoniacal solution by applying progressively higher temperatures and hydrogen pressures. Metals produced by this technique were not pure, since no attempt was made to adjust the solution composition between the different reductions. It is doubtful that the zinc product contained any metallic zinc. The major contribution to the literature" was made by the Ipatiews,12 who prepared platinum, iridium, copper, nickel, cobalt, lead, tin, arsenic. antimony, and bismuth at often extreme conditions, up to the critical temperature of water (373"C), at 1500 to 7500 psi, for as long as several days. Even cadmium and zinc were claimed to have been observed in trace quantities precipitated together with basic salts. In the early experiments solutions were not stirred. Extensive formation of oxides and basic salts occurred. probably long before sufficient hydrogen could be supplied in the unstirred liquid to decrease the metal concentration in solution by reduction. The importance of hydrogen pressure was

Jan 1, 1957

[NORTH AMERICA UNITED STATES ALABAMA AUBURN Sturm & O&apos;Brien, Consult. Engrs. °Sturm, Rolland G. BESSEMER Granger, W. C. BIRMINGHAM Air Reduction Sales Crockett, John M. Amer. Cast Iron Pipe Co. Carter, Sam F., Jr. Donoho, C. K. Anderson Elec. Corp. Davis, Moss V. J. B. Clow & Sons Neptune, Maurice D. Connors Steel Div. °Sandelin, Robert W. Hayes Aircraft Corp. Ricketts, W. E., Jr. Willhelm, A. Clyde, Jr. McWaine Cast Iron King, O. H. Worthington, B. W. Shook & Fletcher Sup. Co. Gearhart, Thomas A. Southern Res. Inst. Dismukes, Edward B., Wheelahan, Edmund J. Thomas Foys Miller, Ralph M. Union Carbide Metals, Co. Brandler, Edgar A. U. S. Pipe & Fdry. Co. Clay, Donald H. Unaffiliated Berg, H. A. Caldwell, H. A. Gilmer, H. U. Harris, Thomas H. Templeton, J. B.]

Jan 1, 1961

By E. Bicknese, R. Clark

The mechanism and rate of reduction of FeO at conditions similar to those in the stack of a blast furnace have been determined for temperatures from 980" to 1165°C. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal in a static system (no flow of reducing gas) have shown that the CO2-CO ratio of the product gas depends upon the relative reactivities of the Fe2O3 and charcoal. In a systern with a "hot blast" of CO and Nz (simitar to dry bosh gas), synthetic FeO, and actiuated coconut charcoal, the rate of reduction was not sensitive to the flow of reducing gas, and the rate-controlling step alas the chemical reaction at the metal-oxide interface. Wherz solid carbon was not present, a critical flow rate of reducing- gas had to be met in order to prevent a lowering of the reduction rate. The effect of a less-reactive carbon (blast-jurnace coke) and of a "natural" FeO on the mechanistn and rate, and the mininum amount of carbon necessary in the charge to tnaintain the reducing potential of the gas phase, have been determined. THE importance of iron oxide reduction processes has encouraged many studies of the process reaction kinetics. Despite this, the mechanism is not well-understood and three main theories have evolved, which can be stated as follows: A) the rate-controlling step is diffusion, either gaseous diffusion of the reductant or product gas through a porous solid,&apos; or solid-state diffusion of iron and oxygen atoms through the so1id.2 B) The slow step is diffusion of reducing gas through a stagnant boundary layer. C) The reaction rate is controlled by the chemical reaction occurring at the metal-oxide interface and is proportional to the area of this interface.3 By increasing the velocity of the reducing gas to a flow rate beyond which no increase in the reduction rate is observed, critical flow rate, it may be possible to eliminate B as the slow step. However, as warnere points out, the establishment of a critical flow rate may only assure that the reaction is not limited by a reduction in the reducing potential of the gas and that B may still be the rate-determining step. Edstrom and Bitsianes and Seth and Ross8 show that A and C may both be correct for the reduction of the same oxide, depending upon the stage of the reduction, and that the relative importance of the two mechanisms varies with the porosity of the oxide. Themelis9 has derived expressions which express A, B, and C in terms of the fraction reduction, Rx, of a spherical particle. Thus, in the case of A a plot of In (1 - Rx) vs time must be linear and the time to reach a given reduction is proportional to the square of the particle diameter. For B a plot of (1 - Rx) vs must be linear and the time to reach a given reduction is proportional to the square of the diameter. For C a plot of 1 - (1 - RX)1/3 vs f must be linear and the time to reach a given degree of reduction should be proportional to the diameter. In the case of mixad controlled reactions, none of the plots are linear over their entire length. The results of previous studies, in which the rates of gaseous reduction of iron oxide were measured in the absence of carbon, may not correspond to blastfurnace practice because they ignore the effects of the Boudouard reaction. CO2 +C — 2CO The presence of carbon may alter the mechanism or the rate of iron oxide reduction through an enrichment of the gas phase by Eq. [1]. In this case, the presence of and reactivity of carbon become important. If the Boudouard reaction has no effect on the rate of reduction, the reducing gas could be supplied by some means other than the gasification of carbon at the tuyeres and carbon could, theoretically, be eliminated from the burden. Preliminary studies of the reduction of Fe2O3 with activated coconut charcoal were made to determine if the reactivity (surface area) of the Fe2O3 had any effect on the product gas composition. Two size fractions of Fe2O3 were reduced with charcoal in a static system (no flow of reducing gas). In each case the charcoal was -100 + 325 mesh and was 25 pct of the total charge. One fraction of the reagent-grade Fe2O3 was submicron in diameter. The other fraction was -100 + 200 mesh and was prepared from the former by compacting, sintering at 1300°C, crushing, and screening. In each experiment, the reaction vessel was filled with a mixture of CO and CO, which would be in equilibrium with FeO and iron at the reaction temperature. A furnace was heated to the desired temperature, the vessel was placed in the furnace, and the gaseous products of the reaction were collected and analyzed. The results of these experiments, Fig. 1, show that the gas phase associated with the submicron oxide is more oxidizing than that with the -100 + 200 mesh oxide. Therefore, in a static system, the relative rates of the reduction reaction and the gasification of carbon depend upon the reactivities of the Fe2O3 and charcoal. The reduction of FeO to iron is the most important reaction occurring in the blast furnace and is probably the slowest of the several reduction steps. The mechanism and rate of reduction of FeO in a system containing carbon and a flow of dry bosh gas have been studied. TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AlME

Jan 1, 1967

By R. M. Caves

High-purity dense tungsten coating is obtained by means of a modified de Boer-van Arkel iodide process using tungsten bromides. The all-glass reaction system is pumped, baked, and sealed (pinched-off) at about 10-7 mm Hg pressure. The bromides then formed in situ are decomposed, depositing tungsten on heated tungsten surfaces. Heating of the specimen is done inductively in a novel arrangement that avoids electrodes of glass-to-metal seals. The tungsten, deposited at specimen temperatures from 2000° to 2800°F and bulb (halide) temperatures of 225" to 725°F, was adherent and uniform, and ranged in thickness to 1/8-in. REFRACTORY metals are of interest at NASA for use in hypersonic aircraft, in rocket engines, and in other thrust devices where very high temperatures are encountered. Tungsten, with a melting point about 6100° F, is potentially very useful for some of these applications. Considerable research on tungsten and its alloys is currently being conducted at the NASA Lewis Research Center. In this tungsten research program, there is need for a method of depositing high-purity, nonporous tungsten coatirlgs. Metallurgical bonding of the coating both to itself and to the substrate is required. In addition, it is necessary to be able to deposit thin, uniform coatings on substrates of a variety of shapes and sizes for laboratory test purposes. A survey of the methods previously used for depositing tungsten coatings indicated that none would likely meet these requirements for high purity, good uniformity, and high density except thermal decomposition of the halides. The method for coating that was selected for investigation was the thermal decomposition of tungsten bromide. This is a variation of the van Arkel and de Boer iodide process established years ago and recently reviewed.1,2 This process is applicable to the transition metals in general. More recently, the application and techniques were extended with chlorine3 and fluorine,4 and included the coating of tungsten. This is believed to be the first report on the use of the bromide for tungsten coating. Bromine was chosen over the other halogens because it promised a lower temperature for tungsten

Jan 1, 1962