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By R. W. Heckel

The growth and shrinkage rates of second-phase particles of various size distributions are analyzed in terms of five mathematical models. These models apply to various forms of diffusion-controlled growth (one model) and interjace-controlled growth (four models). The expression for diffusion-controlled growth assumes local equilibrium at the interface between the second Phase and the matrix and through the choice of the proper flux area perrnits the definition of minimum diffusion-controlled growth kinetics. The interface-controlled kinetics models consider the situations where the rate-controlling step occurs at either the interlace undergoing solution or the interface undergoing deposition. In addition, each of these interface-controlled kinetics models is analyzed for interface reaction rates which are independent of the thermodynamic activity gradient across the interface or proportional to the gradient. THE variation of the size distribution of second-phase particles in a solute-saturated matrix has been a stimulating topic for many years. Research has been carried out in this area for situations where the matrix was either liquid or solid. It is well-understood that the over-all process results in an increase in the average particle size, a decrease in the total number of particles per unit volume, and a net decrease in surface area. Greenwood1 has presented a mathematical model based upon the mass balance existing between growing and shrinking particles. His analysis is stated in terms of Fick's First Law using concentration gradients set up between particles of different size as a result of the effect of surface curvature on solubility. Greenwood's analysis indicates that the mean particle size should increase approximately as the cube root of time. Asimow2 has shown that several of the simplifying assumptions employed by Greenwood may be eliminated from this diffusion-controlled model with little increase in complexity. Lifshits and Slyozov3-5 have also considered the growth-shrinkage problem involving diffusion-controlled kinetics. Their analysis was extended to include the effects of interacting particles ("kinetic approximation"), particle shape, and elastic strains. These authors also show that the mean particle size varies as the cube root of the reaction time. wagner6 has formulated expressions for both diffusion-controlled kinetics and interface-controlled kinetics in the growth-shrinkage problem. Wagner's diffusion-controlled kinetics is based upon the same form of mass balance using Fick's First Law as used by others and is shown to be applicable to situations where kr >> D (k is the interface reaction constant, r is the particle radius, and D is the diffusion coefficient). This analysis also yields a mean particle size which varies as the cube root of time, in agreement with other workers. Wagner also developed interface-controlled kinetics to handle kr « D. This model was based upon the fact that the interface reaction rate is proportional to the interface area. Wagner assumed that the rate was also proportional to the thermodynamic activity difference, ?a, existing across the interface. Thus, the specific reaction rate at the surface of radius r was defined as k • 4nr2 . ?a. It is the purpose of the present paper to reconsider the processes of diffusion-controlled growth and interface-controlled growth in the variation of particle-size distributions as a function of time at constant second-phase volume. The analyses are formulated in a manner which permits data obtained

Jan 1, 1965

By E. S. Wheeler

THE conversion plant of the Climax Molybdenum Co. is at Langeloth, Washington County, Pennsylvania, approximately 30 miles west of Pittsburgh. The molybdenite concentrates converted originate in the company's mine and mill at Climax, Colorado.1 They are delivered to the Langeloth plant by rail packed in 175-lb. bags. War production of concentrates at the mill started in 1918 but it was not until about 1920 that any peacetime uses of the metal began to develop. Early conversion of Climax concentrates was mainly into ferromolybden um, produced for the company by a custom smelter. CHRONOLOGY OF PLANT DEVELOPMENT In 1924 a small hand-rabbled roaster was built at Langeloth, the roasted concentrates being used principally in the production of calcium molybdate by a conventional wet method. The size of the original plant is indicated by the fact that during 1925 about 400,000 lb. of molybdenum was converted. In 1925-1926, a multiple-hearth roaster was erected (12-ft. o.d. 8-hearth Nichols-Herreshoff); also the first experimental ferromolybdenum was produced at Langeloth. At this time calcium molybdate was produced in the furnace by a process to be described. With continued interest in and increased use of molybdenum, it was necessary to arrange for enlargement of plant facilities. Although only one 12-hearth 16-ft. o.d. roaster was erected at this time (1929), plans were prepared for a duplicate unit, which was completed in 1935, giving a potential roasting capacity of some 16,000 lb. Mo per day under the then prevailing roasting practice. Shortly after this second unit had gone into production, increased demand overtaxed the plant, and as a result two 12-hearth 18-ft. o.d. roasters were placed in operation in 1936 and 1937. This gave the plant a potential roasting capacity of 40,000 to 50,000 lb. Mo per day, and necessitated major changes in auxiliary handling equipment as well as improved facilities for producing ferromolybdenum. Following the introduction (1938) of a new product-molybdic oxide briquets and because of the constantly growing demand for molybdenum, plant facilities were again enlarged in 1940 and 1941 by the erection of two 16-hearth 18-ft. o.d. roasters. These two new units, along with a change in roasting practice, brought the potential roasting capacity to 150,000 to 190,000 lb. Mo per day, based on about 15 lb. per sq. ft. of hearth area. Other departments of the plant have necessarily grown, until today the plant is modern throughout and completely mechanized, with equipment geared to produce marketable products as follows:

Jan 1, 1944

By P. Ramakrishnan, Ramjilal

Fine powders of lead zirconate titanate have been prepared by three different methods such as ball milling, conventional coprecipitation and spray drying. Different powders have also been prepared by changing the process variables in each method. These powders were analysed for particle size chemical composition and reactivity. DTA, TGA and x-ray analysis have been carried out to study the lead zirconate titanate formation with reference to calcination temperatures. The calcined powders were then consolidated by compaction and sintering. An attempt has bean made to explain the consolidation behaviour of these powders on the basis of powder characteristics.

Jan 1, 1980

By Walter Crafts

Tests carried out at the Union Carbide and Carbon Research Laboratories, Inc., on the effects of grain-refining deoxidizers are in substantial agreement with the data presented by Mr. Comstock. Notable is the observation that, although boron and aluminum increased hardenability, the steel was of poor quality in comparison with the other boron-treated steels to which at least two grain refiners were added. The effect of zirconium in improving the ductility of the chromium-nickel steel is in agreement with our experience that zirconium is specifically beneficial to chromium steels. In order to amplify Mr. Comstock's results and to indicate some of the basic principles of special deoxidation, the primary observations of our study have been summarized. The effect of boron in increasing hardenability was described by R. Walther, U. S. Patent No. 1519388, Dec. 16, 1924, but effective amounts in incompletely deoxidized steel are sufficient to harm hot workability and room-temperature ductility. Work at the Union Carbide and Carbon Research Laboratories, Inc., has shown that in order to obtain deep hardening without using such large amounts of boron as to result in impairment of ductility, the steel must be thoroughly deoxidized. This may be accomplished by a high silicon content or a grain-refining addition of strong deoxidizers. The degree of grain refinement and hardenability are inclined to be erratic when only one grain-refining element is used, although aluminum, zirconium, titanium, and vanadium have been used singly and resulted in increased. although somewhat erratic, hardenability. The ductility likewise was inclined to be inconsisterlt when only one grain-refining deoxidizer was added. By combinations of grain-refining elements, it was found possible to combine the specific virtues and counteract some of the defects of each clement. In addition, the complex deoxidizers gave more consistent grain refinement and hardenability. When used in combinations, each element adds its own specific influence as well as modifying the character of the other elements. The function of aluminum is primarily to give consistent results and to minimize abnormalities resulting from too

Jan 1, 1943

By Walter Crafts

Tests carried out at the Union Carbide and Carbon Research Laboratories, Inc., on the effects of grain-refining deoxidizers are in substantial agreement with the data presented by Mr. Comstock. Notable is the observation that, although boron and aluminum increased hardenability, the steel was of poor quality in comparison with the other boron-treated steels to which at least two grain refiners were added. The effect of zirconium in improving the ductility of the chromium-nickel steel is in agreement with our experience that zirconium is specifically beneficial to chromium steels. In order to amplify Mr. Comstock's results and to indicate some of the basic principles of special deoxidation, the primary observations of our study have been summarized. The effect of boron in increasing hardenability was described by R. Walther, U. S. Patent No. 1519388, Dec. 16, 1924, but effective amounts in incompletely deoxidized steel are sufficient to harm hot workability and room-temperature ductility. Work at the Union Carbide and Carbon Research Laboratories, Inc., has shown that in order to obtain deep hardening without using such large amounts of boron as to result in impairment of ductility, the steel must be thoroughly deoxidized. This may be accomplished by a high silicon content or a grain-refining addition of strong deoxidizers. The degree of grain refinement and hardenability are inclined to be erratic when only one grain-refining element is used, although aluminum, zirconium, titanium, and vanadium have been used singly and resulted in increased. although somewhat erratic, hardenability. The ductility likewise was inclined to be inconsisterlt when only one grain-refining deoxidizer was added. By combinations of grain-refining elements, it was found possible to combine the specific virtues and counteract some of the defects of each clement. In addition, the complex deoxidizers gave more consistent grain refinement and hardenability. When used in combinations, each element adds its own specific influence as well as modifying the character of the other elements. The function of aluminum is primarily to give consistent results and to minimize abnormalities resulting from too

Jan 1, 1943

By D. Walton

The effect of small solute additions of Cu on the activation energies for creep A1 single crystals were determined over the range from 78° to 850° K. Below 240°K and above 800°K activation energies were unchanged. Between 240°K and 400°K strain aging causes the creep rate to become vanishingly small and the flow stress was independent of the temperature. Between 500° and 50°K the activation energy was increased to 41,000 cal per mole. NUMEROUS investigationsL have shown that solid solution alloying invariably increases the flow stress. A typical example is documented in Fig. 1. Such increases in flow stress can arise from two general effects: Alloying can increase the long-range stress fields through which dislocations must move by causing appropriate clustering; modification of dislocation densities, and so forth. Alloying can also modify the short-range stress fields that determine the activation energies for thermally stimulated migration of dislocations, such as occurs in some solute atom pinning processes, and so forth. Actually both long- and short-range stress-field effects can occur simultaneously. It was the purpose of this investigation to evaluate the effect of alloying on the short-range stress fields by determining the effect of alloying on the activation energies for creep. The resulting observations also shed some light on the effect of long-range stress fields on dislocation processes. EXPERIMENTAL TECHNIQUE Single-crystal bars (6 in. long 3/8 in. wide and l/4 in. thick) of dilute solutions of Cu in A1 were seeded, so as to provide extensive single slip, with the pole of the tensile axis located in the standard stereographic projection as shown in Fig. 2. Each crystal was grown under an argon atmosphere in a graphite mold containing a large reservoir of molten alloy for the purpose of obtaining rather uniform composition of Cu along the length of the bar. The nominal compositions of the alloys which were produced from 99.99 pct Cu and high-purity A1 containing 0.001 pct Fe and 0.001 pct Si, are given in Table I. Strains, measured by linear variable transformers attached by quartz rods to a 3 in. gage section were sensitive to and the stresses were ap- plied by direct loading of the specimen. Temperatures were determined by thermocouples attached to the gage section of the specimens. Below 400°K the apparent activation energies for creep, Q, were determined by the effect of small, rapid changes in temperature of about + 10°K from T1 to T2 on the corresponding creep rates ?1 and ?2 during primary creep according to where R is the gas constant.' Above 400°K, Q was evaluated from Eq. [1] for the secondary creep rate using temperature changes of about ±20K. A typical set of results is shown in Fig. 3. RESULTS AND DISCUSSION The previously obtained effect of temperature on the apparent activation energy for creep of single crystals of high-purity A12 is shown by the broken curve of Fig. 4. The datum points on the same graph illustrate the effect of dilute a solid solution alloying with Cu on the activation energy between 600" and 750°K. Each plotted point is the average of not less than five independent test values between 600° and 750°K and not less than three at other tempera-

Jan 1, 1962

By C. S. Smith, E. W. Palmer

For several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some interesting general relationships between the thermal and electrical conductivities for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 † except for the electrical conductivity at 200" C., which is given in the appendix of this paper. Literature on Thermal Conductivity of Copper Alloys The papers referred to above contained a summary of the figures available in 1929 for the thermal conductivity of copper alloys. There is given in Table 1 herewith a selection of the data that have appeared since that time. The measurements of Hanson and Rogers3 are particularly interesting since they cover a series of alloys in the alpha solid solution range and show the effect of heat-treatment. Their alloys were tested as annealed castings, and are not therefore directly comparable to the worked alloys measured in the present investigation, although the difference is small. Bailey's determinations4 were carried out on the alloys used by Lees6 in 1906, and extend his results to higher temperatures. It is most unfortunate that the alloys were not analyzed, for the approximate compositions given are hardly sufficient identification of the material. It is equally to be regretted that neither Hanson and Rogers nor Bailey give data for the electrical conductivities of their samples. Sager6, using the heat-wave method of King, determined the thermal conductivity of copper, nickel and four alloys of the two metals. His results are included in Table 1.

Jan 1, 1935

By C. S. Smith, E. W. Palmer

For several years an investigation has been in progress in the research laboratory of The American Brass Co. to determine the thermal and electrical conductivities of most copper alloys of commercial importance and several of scientific interest. This paper contains such data on the binary alloys of copper with silicon, aluminum, manganese and nickel, and on a large number of ternary or more complex alloys. Some interesting general relationships between the thermal and electrical conductivities for all copper alloys at all temperatures are pointed out. The data for the copper-zinc, copper-phosphorus and copper-tin binary systems have already been published1,2 † except for the electrical conductivity at 200" C., which is given in the appendix of this paper. Literature on Thermal Conductivity of Copper Alloys The papers referred to above contained a summary of the figures available in 1929 for the thermal conductivity of copper alloys. There is given in Table 1 herewith a selection of the data that have appeared since that time. The measurements of Hanson and Rogers3 are particularly interesting since they cover a series of alloys in the alpha solid solution range and show the effect of heat-treatment. Their alloys were tested as annealed castings, and are not therefore directly comparable to the worked alloys measured in the present investigation, although the difference is small. Bailey's determinations4 were carried out on the alloys used by Lees6 in 1906, and extend his results to higher temperatures. It is most unfortunate that the alloys were not analyzed, for the approximate compositions given are hardly sufficient identification of the material. It is equally to be regretted that neither Hanson and Rogers nor Bailey give data for the electrical conductivities of their samples. Sager6, using the heat-wave method of King, determined the thermal conductivity of copper, nickel and four alloys of the two metals. His results are included in Table 1.

Jan 1, 1935

By M. E. Wadsworth, I. B. Cutler, R. W. Bartlett

The oxidation kinetics of ZrC was studied between 450" and 580°C in oxygen pressures from 6.5 x 10-to 1 atm using a ther mogravimetric apparatus and sized powder samples. Two parallel rate controlling processes were observed. A surface reaction occurring at the ZrC-ZrO2 phase boundary accounted for most of the oxidation and had an activation enthalpy of 46 kcal per mole. The other process, believed to be diffusion of oxygen into the ZrC lattice partially replacing carbon, had an activation enthalpy of 53 kcal per mole. The enthalpy for chemisorption of O2 on ZrC was determined to be —13 kcal per mole. Water vapor in the presence of oxygen accelerated the surface reaction rate. THERE has been little reporting of formal rate studies or attempts to ascertain the mechanism of oxidation of carbides. MacDonald and Ransley1 studied the oxidation of titanium carbide which has the same structure as zirconium carbide, fcc. They observed an initial increase in rate with increasing temperature followed by a rapid decrease through a rate minimum and a subsequent second increase at higher temperatures. The discontinuity in the rate rise was attributed to a phase change in the oxide which changed the rate determining step from the surface reaction at the carbide-oxide interface to diffusion through the oxide layer. Samsonov and Golybera 2 studied titanium carbide and reported that during the initial period of oxidation a dense film of Tic-TiO was formed followed by the formation of less adhering layers of higher oxides. The purpose of this investigation was to study the kinetics of oxidation of zirconium carbide and to attempt to gain some knowledge of the mechanism by which oxidation occurs. EXPERIMENTAL PROCEDURE Measurement of the weight gain associated with the oxidation of ZrC was used to determine oxidation rates. The principal experimental parameters were surface area, temperature, and oxygen pressure. Although moderately sized crystals of ZrC can be grown by the Van Arkel method, the only commercially available ZrC is a powder. In using powders, the surface area must be controlled either by fabricating the powder into a sintered pellet with a measurable surface area, relatively fixed during oxidation, or by using sized unconsolidated powder and applying appropriate geometric considerations to the shape of the grains to correct for their diminishing surface areas as they oxidize. Both techniques involve some difficulties. pellets of binder-free zirconium carbide can be made by hot pressing, but it is difficult to obtain densities greater than 90 pct of

Jan 1, 1963

By Frank Firmstone

IN the early decades of the past century the method of starting iron blast-furnaces by "scaffolding-down" seems to have been in universal use for coke-furnaces and, at least in this country, for charcoal-furnaces also. It was likewise used at some of the early anthracite-furnaces, as is stated in the important "Reminiscences" printed by the late Samuel Thomas. I It had been generally superseded in Great Britain as early as 1850, by some variations of the plan now used, and was rarely used when Percy wrote.' On the Continent it was still followed in the 60's,3 and was elaborately described by Valerius in 1852. I have never read any statement as to when and by whom '4 scaffolding" was first dispensed with, but the following extracts from journals of my father seem to fix an authentic date for an instance in this country:

Mar 1, 1907

Joseph Esrey Johnson, Jr., had already achieved rare distinction as an able metallurgist, clear thinker, brilliant author, and wise consulting engineer to bankers and operators; he had achieved the essentials of a great career when dcath cut short his activities on Apr. 4, 1919, in the forty-ninth year of his age. He belonged to a family of iron blast-furnace men and mine managers. His father, Major J. E. Johnson, after serving with distinction in the Army of the North, identified himself with the iron mines and blast furnace at Longdale, Va., with which he was connected during almost his entire business life. It is significant, that, during those troublous times of reconstruction in the South, he enjoyed always the affection and respect of his neighbors and associates alike. From him his son obtained not only a thorough training in blast-furnace practice and iron mining, but great personal courage and force of character. His mother, who survives both her husband and sons, possesses rare intellectuality, humor and a tenderness and human sympathy which those who were privileged to know well J. E. Johnson, Jr., recognized beneath his exterior of aggressiveness and will power. In a recently published analysis of the qualities which characterize the world's great men, three traits stand out preeminently; viz., independence, courage, and intellectuality. Each of these characteristics J. E. Johnson, Jr., possessed in extraordinary degree. His early education was obtained under a private tutor at Longdale, and this circumstance probably enhanced a natural tendency to independence of character and individuality which, however, under the control of his unusual power of straight thinking and clear analysis never allowed him to go far astray. It has been said of him that if once he set his mind to a problem, however knotty, he scored a bull's-eye before the subject was dropped. His manner of attacking a subject involved first mastering the details of the available knowledge; then, putting this acquired information to one side, with an untrammeled mind blazing out a path of his own, so clear, so well-defined, and expressed in such simple terms that he illuminated the whole subject without distorting the original data or discussion. His two books, "Blast-furnace Construction in America" and "The Principles, Operation, and Products of the Blast Furnace, "on the iron blast furnace together form the most comprehensive, the most enlightening, and the most useful treatise on the subject ever produced in any language. But his ability did not end with the mastery and elucidation of principles enunciated by his predecessors; his own

Jan 1, 1920

Jan. 7, 1952, AIME, Boston Section, Massachusetts Institute of Technology, Campus Room, Graduate House, Cambridge, Mass. Jan. 8, Society for Applied Spectroscopy, 6 pm, supper, Tosca's; 8 pm, meeting, Socony-Vacuum Training Center, 63 Park Row, New York. Jan. 9, AIME, Chicago Section, Chicago Bar Assn., 29 S. La Salle St., Chicago. Jan. 13-15, Institute of Scrap Iron & Steel, Waldorf-Astoria, New York. Jan. 14-1.6, AIME, Minnesota Section, Hotel Duluth, Minn. Jan. 14-18, SAE, annual meeting, Hotel Book-Cadillac, Detroit. Jan. 1.6-18, Society of Plastic Engineers, Inc., annual national technical conference, Edgewater Beach Hotel, Chicago. Jan. 17, AIME, New York Section, Mining Club, 33 Broadway, New York. Jan. 1.7, AIME, Utah Section, Newhouse Hotel, Salt Lake City.

Jan 1, 1952

By W. R. Shimer

IN his valuable report on Finishing Temperatures and Properties of Rails, I Dr. G. K. Burgess, Chief of the Division of Metallurgy, U. S. Bureau of Standards, has begun a line of investigation which should be continued by those interested in the subject, and who have proper facilities for carrying put the work. For the past year or more the Bethlehem Steel Co. has been conducting experiments to learn the effect of rail finishing temperatures on their physical properties and microstructure and the results are here given for the consideration of those interested in the rail situation. . Considerable differences of opinion have been expressed by various authorities, in the past, as to the effect of large or small grain size and high or low finishing temperatures of steel rails on their physical properties and wearing qualities. Low finishing temperatures and, therefore, low shrinkage, have been advocated on the theory that the wearing qualities would be improved. Others have recommended high finishing temperatures. The generally accepted cause for rail failures, due to the development ,of transverse fissures, is excessive wheel pressure on hard rails. One of the causes advanced for hard rails has been that they contain too high per centages of carbon and manganese; another that the rails were finished at too low a temperature, i.e., at or near the critical point. In the experiments herein described the rails were rolled from reheated blooms. All the rail blooms were charged hot in a reheating furnace and brought up to about the original ingot-rolling temperature before rolling into rails. These rails gave better results in deflection, withstood a greater number of drops before breaking, and showed greater ductility, than. rails of identically the same composition and section which were rolled, direct from the ingot. Rails rolled from reheated blooms, finished at somewhat higher temperatures than when rolled direct from the ingot, have a different microstructure, which the writer does not believe is due so much to the difference in finishing temperatures, as to the difference in

Jan 3, 1915

By D. M. Schuster, E. Scala

The elastic effects occurring in the matrix of a composite reinforced by discontinuous fibers were studied by means of photoelastic techniques. A hirefringent plastic was employed as the matrix material with high-strength a Al2O3 whiskers as the reinforcing fibers. It was found that for whiskers aligned parallel to the tensile load direction: (I) Matrix reinforcement occurred along the length of the whisker to within about 5 diameters of the whisker tip for a length to diameter ratio, L/D, of 40. (2) Significant stress concentrations were created in regions immediately surrounding the tips; the fine as-formed tapered ends exhibited the minimum stress concentration whereas the square-ended whisker produced relatively high values, K r 2.5 for L/D = 40. (3) The axial and radial stress distributions could he determined quantitatively; the stress distribution at the whisker-matrix interface was in general agreement with theoretical calculations. (4) The highest source of stress concentration occurred at points of fracture in whiskers which had ruptured after incorporation into the composite. Whiskers aligned perpendicular to the load direction neither reinforced nor caused appreciahle stress concentrations in the matrix. ThE properties of composites have generally been formulated empirically on the basis of macroscopic tests. There are still many questions concerning the mechanical and chemical interactions occurring at the interface between the reinforcing fiber and its matrix. Continuously reinforced plastics and dispersion-hardened metals represent the two extremes of composite reinforcement. Whether artificially produced or formed in situ, the whisker composite falls between these two extremes and is an example of discontinuous fiber reinforcement. The effect of fiber shape, size, surface condition, and end configuration on the stress distribution in the matrix is important since the presence of stress concentrations, especially in any high-strength, thin-wall structure, could become the cause of catastrophic failure. DOW,' in his theoretical discussion of discontinuous fiber reinforcement, has pointed out that appreciable stress concentrations occur at the tips or ends of the reinforcing fibers. It is the purpose of this study to examine directly, by means of the photoelastic technique, the stresses which occur in the vicinity of a discontinuity or whisker tip and to measure qualitatively and quantitatively the effects of whisker geometry when embedded in a birefringent matrix material. The use of sapphire (a A1,O3) whiskers was decided upon as the reinforcing agent because of their high elastic modulus (E- 60 X 106 psi) and in some cases strengths in excess of one and a half million psi. Sapphire whiskers are of further practical interest since they retain large fractions of their strength up to temperatures approaching the melting point (3720oF).2 The whiskers were grown, by the vapor-phase reaction commonly employed,3 as part of this study to insure a physically uniform supply. Tensile and bend tests were performed to verify that the whiskers were of the expected ultra-high strength. The high-strength whiskers can be identified and selected from the combustion boats by surface perfection, shape, and size; otherwise, strength values can vary by a factor of ten or more. Macroscopic defects are quite common on the surface of large bladed whiskers and the principal experiments were conducted with hexagonal whiskers of about 0.002 in. diameter and lengths ranging from 0.1 to 0.4 in. Upon completion of these two phases of the experiment, several birefringent resins were evaluated. A plastic, developed by Zandman,4 which is supplied by the Budd Co., was found most suitable and was used as the matrix material for the whisker composite throughout the study. It has a sensitivity of 60.5 lb per in. order, calibrated in tension and cures without introducing residual stresses. Young's modulus for this matrix material is 430,000 psi in the fully cured condition. Since good wetting and bonding between the sapphire and the matrix material is essential to the interpretation of the results, a wettability test was performed. The contact angle was measured to be 168 deg where perfect wetting is defined as 180 deg; therefore, the Budd Plastic wets the sapphire

Jan 1, 1964

De la pirotechnia. Libri .X. dove ampiamente si tratta non solo di ogni sorte & diuersita di miniere, ma anchora panto si ricerca intorno á la prattica di quelle cose di quel the si appartiene á l'arte de la fusion ouer gitto de metalli come d'ogni altra cosa simile I questa. Composti per it S. Vanoccio Biringuccio]

Jan 1, 1942

By V. Apraxine, J. Lakaye, J. J. Saquet, P. Troch

Union Minière du Haut-Katanga owns concessions for extracting copper and associated metals in the high plateau region of Katanga. The concession is about 188 miles long by 44 miles wide and has three principal areas: Southern area-The Prince Leopold mine is an underground operation from which a copper-zinc sulfide ore is extracted. The mine and associated concentrator are at Kipushi. Copper concentrates are smelted and converted to blister copper at the Lubumbashi smelter at Elizabethville.

Jan 12, 1962

By Sidney A. Swensrud

The writer has been interested for some time in trying to appraise our industry's prospects for gasoline consumption over the next half dozen years or so. Anyone who has even approached the problem knows the intimate relationship to it of the number of automobiles in use— by automobiles I mean both passenger cars and trucks. Probably at least 90 per cent of our gasoline is used in automotive vehicles. Some recent estimates secured from the Department of Commerce show the following breakdown: Per Cent Passenger cars............................................ 60.0 Trucks................................................... 27.4 Busses................................................... 2.9 Taxicabs................................................. 2.2 Subtotal............................................... 92.5 Aviation, motor boats and railroads......................... 0.5 Agricultural: farm tractors, etc.............................. 3.3 Balance (manufacturing, government use, construction, etc.)... 3.7 100.0 Up to the beginning of the depression there was, of course, a constant annual increase in the number of automobiles in use, for each year the industry added to the total inventory or ''population" more new units than were being scrapped, as may be seen in Fig. 1. Few of us in the oil industry needed to give much attention to the detailed figures, although the automobile industry seemed to interest itself in all sorts of calculations of replacement demand vs. new car demand, the average life of the car, the number scrapped, and the like. Probably many people in the oil industry, as well as outside it, were surprised at the way in which automobile registrations and gasoline consumption held up during the early years of the depression. Nor were they greatly perturbed when, as in the last two years, both registrations and consumption began to fall somewhat. That was natural enough; it

Jan 1, 1933

By Robert D. Pehlke, Weldon L. Daines

The reduction of manganese oxide from a basic slag by silicon dissolved in liquid iron at steelmaking temperatures was studied to determine the rate-controlling step for the process. The experiments were carried out under an argon atmosphere in a resistance-heated vertical-tube furnace. The two liquid phases, slag and metal, were held in zirconia crucibles. Sampling and chemical analysis of the slag phase led to time-concentration curves for the system. Results obtained by varying parameters such as temperature, stirring rate, concentration, and melt geometry defined the limiting reaction mechanism. The reduction of manganese oxide by silicon is a fast reaction and reached equilibrium within 90 min. The rate of stirring has a marked effect on the reaction rate, while, on the other hand, the effect of temperature is very small. This identifies the rate-controlling step as diffusion rather than interfaciul chemical reaction. The variation of other parameters revealed that a) diffusion of manganese in the iron phase is the slow step, b) the value of D/6 for manganese in iron at 1550°C is 7x 10-4 cm per sec, c) the energy of activation for the apparent rate constant is 7 kcal per mole, and d) increasing the amount of silicon in the iron decreases the diffusion coefficient of manganese. THE equilibrium relations pertinent to the reduction of manganese oxide from a steelmaking slag by silicon dissolved in liquid iron have been studied, but little is known about the mechanisms that control the rate of the process. The purpose of the present investigation was to study the rate of reduction by silicon and to determine the rate-limiting step. The effects of stirring rate, temperature, composition, and melt geometry were investigated as a means of identifying the controlling step. On the laboratory scale, relatively little work has been done in the area of slag-metal kinetics, primarily because of the problems confronted in attempting to contain liquid slags and metals in laboratory crucibles at steelmaking temperatures. Since graphite is an ideal material for a crucible, several investigations have been carried out on the reduction of various oxides from a slag by carbon in graphite-saturated iron and on the transfer of sulfur between a slag and graphite-saturated iron. Most of this work has been performed in induction furnaces. Studies where the container was not graphite are extremely limited. A single kinetic study of manganese transfer between molten iron and basic slags was carried out by Sano, Shiomi, and Matsushita.' These investigators prepared calcium oxide and titanium oxide crucibles to contain the two-phase system. Only a few experiments were carried out and the results had to be treated qualitatively. Despite the paucity of kinetic data, a large quantity of information is available in the literature concerning the thermodynamics2-12 and physical properties'3-21 of the slags containing manganese oxide and the dilute liquid iron alloys containing manganese and silicon which were involved in this research program. EXPERIMENTAL METHOD A vertical-tube resistance-heated furnace was used in this investigation to study the slag-metal reaction Although most previous slag-metal studies were carried out in induction furnaces, a resistance furnace has several advantages including better control of temperature and stirring rate. Hence, a resistance furnace was selected for this study, and its design is shown schematically in Fig. 1. Slip-cast, fine-grained, low-porosity, lime-stabilized cubic zirconia crucibles were used for the kinetic experiments. The crucibles were 4 1/2 in. high and 2 1/8 in. OD with a 1/16-in. wall. The crucibles were only slightly

Jan 1, 1969

By Henry A. Wriedt, John Chipman

Equilibrium in the reaction of hydrogen gas with oxygen in liquid nickel, iron, and their alloys has been studied at temperatures of 1500° to 1700°C. The equilibrium con^stant, 0/p, [% O], is greater in nickel then in iron by a factor of 45 at 1594 C. In the alloy steel range, the activity coefficient of oxygen is slightly increased by the presence of nickel. NICKEL is more resistant to oxidation than is iron, in both the solid and the liquid state. The solubility of oxygen,' however, is greater in nickel than in iron. The two metals and their liquid alloys constitute an interesting series of solvents in which the chemical behavior of oxygen can be studied by methods similar to those used for liquid iron.' Experimental Method The furnace assembly, including the tube for preheating the entrant gas, was the same as that described by Gokcen and Chipman. " controlled mixture of water vapor, hydrogen, and argon preheated to approximately the melt temperature impinged upon the surface of the liquid metal. The charge, weighing about 35 g, was held in an alumina crucible at constant temperature in the gas stream for a prolonged period, then quenched in a stream of cold helium, sampled, and analyzed for oxygen by the vacuum fusion method. The temperature of the liquid metal was measured by a Leeds and Northrup optical pyrometer which had been checked against a similar instrument certified by the National Bureau of Standards. The freezing point of electrolytic iron in hydrogen, taken as 153j°C, was used for frequent checks. This point and the emissivity determined by Dastur and Gokcen" established the transmissivity of the optical system. The emissivities of Fe-Ni alloys at 1535" are known from the experiments of Smith and Chipman,h nd it was assumed that the variation with temperature is parallel with that of iron. Recorded temperatures are probably accurate within k5"C. Preparation of Gas Mixtures—Since the ratio H,O:H, had to be much higher for nickel than for iron, it was found convenient to construct two separate systems for gas preparation. In both cases, the ratio of argon to the sum of the other two gases was at least 4, the proportion of hydrogen and water vapor being varied to produce H,O:H, ratios from 0.2 to 70. The primary purpose of the argon was to diminish the errors caused by thermal separation' in the gas phase. In addition, its presence lowered the saturation temperature required for a given H,O:H, ratio and minimized the difficulty of preventing condensation. Both systems were modifications of the one used by Dastur and Chipman.' For H,O:HI ratios greater than 2, welding-grade argon purified by passage over magnesium chips at 620°C was mixed with hydrogen produced in the electrolytic cell shown in Fig. 1. The design was based on a cell used by Bodenstein and Pohl," the important features of which area nickel wire cathode and sodium hydroxide solution as the electrolyte. The rate of hydrogen evolution was controlled by a calibrated ammeter and a rheostat in the circuit, the current efficiency being taken as 100 pct. Precise control of the argon flow rate at about 300 ml per min was achieved by means of a capillary flowmeter having a controlled pressure drop. The molar flow rate was measured volumetrically before each run, and a constant flowmeter setting was maintained thereafter. The A-H, mixture passed through a water saturator of the type previously described," the saturation temperature being maintained automatically with a fluctuation of k0.04"C. The tube between saturator and furnace was heated by a resistance winding. The system was of all Pyrex construction with the exception of the stainless steel tube containing magnesium chips. This was connected with the glass tubing at the upstream end by

Jan 1, 1957

By John F. Elliott, John R. Rawling

The rate of reduction of silica to silicon by carbon at 1550° to 1700°C in iron blast-furnace type slag-metal systems has been investigated. In the tower portion of the temperature range oxygen transport in the metal boundary layer at the slag-tal interface is probably rate limiting. A second step, which apparently involves a chemical process in the slag at the slag-metal interface, appears to be rate limiting when the oxygen-transport limitation is avoided. Above 1650°C rate control of the reduction by carbon probably is mixed between the two steps. INVESTIGATIONS1.2 into the equilibrium distribution of silicon between graphite-saturated slags and metals typical of iron blast-furnace practice show that, under the experimental conditions specified, the reduction of silica to silicon is relatively slow compared with the rates of other slag-metal reactions under similar conditions. For this reason, the reduction of silica in blast-furnace slag-metal systems was considered to be an interesting subject for further study. Investigations of the kinetics of the reaction3-5 suggest that several possible steps may be rate controlling, and that the rate-controlling step depends not only on the physical state of the systems but also on the configuration of the apparatus. The main objects of the investigation reported here were to sug- gest plausible reaction paths for the reduction of silica under the experimental conditions chosen and to determine the step or steps which control the rate of reduction of silica. EXPERIMENTAL Two types of experiments involving the reduction of silica from the slag were carried out. In the first, the only reducing agent present was carbon (graphite), for which the over-all reaction is (SiO2) +2C(gr) —Si + 2Co(g) [l] The second type was a graphite-saturated ferro-silicon-iron concentration cell. In it silica in the slag could be reduced either by carbon according to Eq. [I], or by a reaction of electrochemical nature in which silicon was oxidized at the ferrosilicon-slag interface and silica was reduced at the slag-iron interface without the formation of CO. The two types of experiment are described below. Reduction of Silica with Carbon as the Only Available Reducing Agent. The reduction of silica was accomplished by allowing a liquid lime-alumina-silica slag and graphite-saturated iron to react in an induction-heated graphite crucible. The crucible was 2.25 in. diameter and 5 in. deep; it was fitted with a graphite stirrer which penetrated through the slag and into the metal, Fig. 1. The slag and metal charges weighed 350 g each. Pure carbon monoxide at a pressure of 1 atm was maintained above the melt by passing the purified gas through the crucible at a rate of 0.5 liter per min. The gas did not stir either the slag or metal. Temperature measurements were made by sighting an optical pyrometer down the hollow stirrer rod into a 1/4-in. hole drilled in the stirrer blade. The crucible temperature was maintained within *15"C of the required value by manual control of the power supply to the

Jan 1, 1965