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By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Carl G. Hogberg

During recent months, the acute shortage of steel scrap has necessitated the use of higher percentages of hot metal in the open-hearth charge. With these higher percentages, the sulphur content of hot metal has become an increasingly important factor in the control of the quality of steel. Thus, the blast-furnace operator is faced with a demand not only for more output but for a higher quality of product. More than go per cent of the sulphur charged into the blast furnace is contained in the coke. With the tremendously increased demand, the trend of coke quality has been toward higher sulphur, higher and more variable ash, and poorer physical characteristics. This has been brought about by less selective coal mining, increased production rates in coke plants and resumption of operations of many beehive ovens. In a single month last year, one blast-furnace plant in the Pittsburgh district operated with coke obtained from 52 sources. The effect of variability and quantity of coke ash on blast-furnace operation is well known. The improved results obtained with furnaces operating on coke made from washed coals compared with results on coke made from raw coals is ample proof of the effectiveness of low and uniform ash. Coal-washing plants, however, require a large capital expenditure, and are impractical for most of the large number of small producers, whose operations are confined chiefly to periods of abnormally high demand. Furthermore, not all coals are physically adaptable to washing. Principles 01 Iron Desulphurization in Furnace Although investigations of the blastfurnace process have not clearly revealed the detailed mechanism of iron desulphuri-zation within the furnace, they have been sufficiently extensive to permit a postula tion of the following general principles: 1. Iron, in its travel from furnace top to hearth, continues to pick up sulphur until it has reached tuyere level. The zone of iron desulphurizatioil is relatively narrow, being confined to a vertical distance extending zapproximately from tuyere level to the iron-slag interface in the hearth.' 2. Combustion of coke is confined to spherical zones extending approximately 40 in. from the nose of each tuyere.= Coke ash is released as the coke bums in these combustion areas. 3. With a constant amount of sulphur in the charge, the sulphur content of the metal product is a function of hearth temperature, final slag analysis, slag viscosity, and slag volume. Both hearth temperature and slag analysis affect slag viscosity. For a slag of constant analysis, viscosity always decreases with an increase in temperature;

Jan 1, 1943

By Dorsey A. Lyon, Robert M. Keeney

Page I. Introduction..........234 I1. Chemistry oF Copper Smelting...235 1. Native Copper Ores.......235 2. Oxide and Carbonate Ores....235 3. Sulphide Ores.......236 (a) Elimination of sulphur ...236 III. Reverberatory Copper Smelting...237 IV. Substitution of the Electric Furnace for the Reverberatory Furnace..................... 238 V. Smelting of Fine Michigan Native-copper Concentrates in the Electric Furnace.................. 239 1. Conclusions.................240 VI. Proposed Process for Electric melting of Fine Native-copper Concentrates.................. 241 VII. OrdINary Copper Blast Furnace 'Smelting......... 245 1. Prerequisites.................. 245 2. Losses .................... 247 VIII. Experimental Data on the Electric Smelting of Raw Sulphide. Oxidized and Carbonate Ores............. 248 1. Vattier's experiment................ 248 2. Wolkoff's experiments................ 249 3. Experiments of Stephan.............. 250 (a) Conclusions of Stephan ............ 251 IX. Smelting of Sulphide Ores in the Electric Furnace...... 251 1. Ores Treated.................. 252 2. Conclusions................... 253 X. ELectric Furnace vs. the Reverberatory Furnace and Blast Furnace as a Melting Agent.............. 253 XI. Smelting of Sulphide Ores without Roasting or Partial Pyritic Smelting............254 XII. The Electric Blast Furnace vs. the Copper Blast Furnace for Partial Pyritic Smelting.......259 1. Metallurgical conditions......259 2. Mechanical considerations......259 3. Comparison of costs.......260 (a) General considerations .....260 (b) Cost of plant........260 (c) Amount of electrical energy...260 (d) Cost of smelting.......261 (e) Cost of electrodes........262 XIII. The Use of the Electric Furnace in the Smelting of PyRITIc ORES : 262 XIV. Summary...................... 264

Jan 1, 1914

CONTENTS PAGE GEISMER, H. S.-Coal Washing Practice in Alabama. Discussed by William Kelly, H. S. Geismer, H. D. Pallister, L. E. Bryant, Milton H. Fies, Elmer F. Harris, James A. Barr, George G. Crawford, E. C. Wright, George S. Rice, R. V. Norris 1 MILLER, F. W.-Byproduct Coking in Alabama. Discussed by Theodore Swann 4 FIES, MILTON H.-Alabama Coal Mining Practice. Discussed by Milton 11. Fies, R. V. Norris, R. D. Hall, L. E. Bryant, George S. Rice, H. S. Geismer 5 MUSSEY, H. E.-Blast-furnace Practice in Alabama. Discussed by C. A. Meissner, Franklin H. Crockard, H. E. Mussey, W. H. Oldham 14 Coal Washing Practice in Alabama Discussion of paper of H. S. GEISMER, presented at the Birmingham Meeting, October 1924, and issued, as Paper No. 1363-C, with MINING AND METALLURGY, September, 1924. WILLIAM KELLY, Iron Mountain, Mich.-Is the dry-cleaning method used? H. S. GEISMER.-Neither the dry-cleaning process nor the Chance sand-liquid method has been tested in Alabama; but all other methods used for cleaning bituminous coal have been largely brought to perfection in this state. H. D. PALLISTER, Tuscaloosa, Ala.-Have you the results from the recent work on the tables with reference to fine coal? H. S. GEISMER.-None of the iron-producing companies has adopted the tables, though three commercial operators have installed tables within the last six months. I tried to learn the results, but they were not willing to release the data just now. At the mines producing domestic coal, fines present a difficult problem; until within the past six months all the fine coal was wasted. The operators are trying to recover some of it on the table. L. E. BRYANT, Rockwood, Tenn.-Is there any connection between the sulfur content of the sludge and the effect of the sludge on vegetation?

Jan 7, 1925

By C. E. Sims, H. M. Banta, S. L. Hoyt

Over the past few years, metallic arc welding has been extended to steels of the hardenable type. As compared with other methods of fabrication, production has been facilitated, service performance frequently has been improved, and the overall results have been so favorable that engineers and production men have placed great emphasis on this application of welding. The metallurgist and welding engineer, however, have been confronted with new problems, since, for one reason, the harder steels are more apt to crack and special precautions must be taken if sound joints are to be procured. Some of the factors that are pertinent to this problem are metallurgical, and it is an object of this contribution to discuss steel manufacture and processing methods and to show how their control assists in reducing the hazard of cracking. By this time, the problem of cracking— specifically underbead cracking, or "hard cracks," or parent-metal cracks-—is well known, and a large amount of work has been published, both here and abroad, dealing with this subject.' The tests described are made under restraint to facilitate cracking and arc so designed that a semiquantitative, or at least a relative, value of the cracking tendency is obtained. As one would expect, it has been reported that the incidence of cracking increases with the carbon and alloy content of the steel. More specifically, the cracking tendency is said to increase with the hardenability of the steel, though it is now recognized that the situation is not so simple. The phenomenon itself, on the other hand, has been but loosely described, and it is in only broad generalizations that this cracking has been related to steel metallurgy. Thus, while it has been abundantly demonstrated that the hardenable aircraft steel, S.A.E. 4130, must tend to crack when are-welded, the problem still remains of why two lots of the same composition and the same hardenability can vary so greatly in cracking tendency, or what it is about the prior metallurgical history that so strongly affects the results. Further, while the efficacy of preheating and postheating in preventing cracking is recognized and utilized in production, the mechanism by which they function seems not to have been described. These points are thought to be significant in the production of steel for fabrication by metallic arc welding and, hence, of interest to mill and process metallurgists and welding engineers. Consequently, it is another object of this paper to discuss the mechanism of parent-metal cracking, including the influence of the condition of the steel and the control of cracking by manipulation of the time-temperature conditions during and after welding. A new method of rating the cracking tendency is also discussed, and the results of the test are related to steel composition and structure or prior history. The work to be described was the outgrowth of work in 1940-41 at Battelle Memorial Institutc on two projects, one

Jan 1, 1945

By J. W. Eckerd, P. S. Lewis, N. H. Coates

USBM designed, constructed, and operated an 18-in.-diam fluidized-bed combustor for highly caking coals to evaluate the method for possible application to power generation. In initial tests, combustion was carried on successfully, with carbon losses as low as 0.8%+ Coal ash was not satisfactory as a bed material, but mullite proved to be acceptable. Overall heat-transfer coeffients from the bed (-20 t 50 mesh mullite) to a water-cooled tube were about 75 Btuper hr-sq ft. Fluidized-bed combustion is being investigated by the U. S. Bureau of Mines (USBM) as a potentially cheaper method of firing power plant boilers. Lower combustion temperatures in fluidized beds—only 1400" to 1800°F-—should reduce fireside deposition and corrosion and nitrogen oxides production. Fluidized-bed combustion also offers possible advantages in the use of additives to control SO, emissions and amenability to processing of high-ash, high-moisture coals without special preparation. This paper describes development of a fluidized-bed combustor and the results of preliminary tests. Equipment and Procedure Fig. 1 shows the 8-ft-high combustor. A cone-shaped plate perforated by I/8-in.-diam holes supports the fuel bed and admits the fluidizing air; water passing through the 3/4-in. pipe extracts heat from the combustion bed. Fig. 2 is a flow diagram of the system. Coal is fed pneumatically to the base of the fuel bed. Combustion products are passed through two centrifugal separators to remove most of the entrained solids, then to a water

Jan 1, 1971

By G. H. Clevenger

Continuing the discussion of the paper of James Johnston, presented at the New York meeting, February, 1914. See Trans., xlviii, 3 to 32 (1914). This paper cannot fail of being of great interest and value to all who are interested in the cyanide process, on account of the important developzn~ents which it records. Mr. Johnston is to be commended for the large amount of detail which he gives, and the company and its management for permitting the publication of data of this character, which while of great value to others could well be considered private property. It might be discussed from a number of standpoints: First, as an example of recent practice in mill and cyanide plant construction; second, the mill practice; third, the cyanide practice; and fourth, the new features in cyanide treatment involved. Perhaps a more vivid way of expressing it would be: First, the equipment or tools with which the various operations are carried on, are they the best and most efficient which could have been selected for their respective uses; and, second, is the best use in every case made of these tools? It may be well inquired is the highest possible recovery of silver made at the lowest cost per ounce recovered? For after all, the making of the greatest ultimate profit is inseparably associated with successful metallurgical practice; there must therefore be at all limes a careful balance maintained between recovery and cost of obtaining it. I wish to call attention in a very general way to the equipment used and to an anticipation of questions which are bound to arise in this connection. However, the bulk of my discussion will be confined to the presentation Of certain additional data, together with a more or less general discussion showing the line of development which leads up to the present practice and the applicability of certain features of it to similar problems elsewhere. There are a number of vital points of broad general interest involved in Nipissing low-grade practice upon which metallurgists will by no means be agreed to which I wish to call particular attention in the hope that it will lead to the presentation by others of data of practice in other districts which will assist in reconciling this divergence of opinion.

Jan 1, 1915

By J. W. Spretnak, R. Speiser

IT has been suggested that boron in steel may form a film entirely around the austenite grain and that this film is responsible for the boron hardenability effect. In this connection, it is of interest to examine some of the ramifications of the concentration range of boron usually employed in hardenable steels, namely 0.0005 to 0.003 pct in a grain size range of ASTM grain size No. 1 through No. 10. The ratio of the iron to boron atoms and the number of unit cells of y iron per boron atom are listed in Table I. Even at the highest concentration considered, there are 1600 unit cells of y iron per boron atom, assuming a uniform distribution of boron. To investigate the possibility of the boron film formation, the number of boron atoms required to cover the grain surface completely must be calculated. With some transition elements, boron crystallizes in sheets composed of equilateral hexagons very much like graphite.' The selected value for the length of a side is 1.80Å. A simple calculation shows that two boron atoms cover an area of 8.4x l0 -16 sq cm. Table II lists the number of atoms of boron required for the formation of the monatomic film and Table III lists the number of boron atoms per grain. The hypothetical cases of 100 pct and 10 pct adsorption are calculated (all boron atoms in a grain and 10 pct of all boron atoms in a grain are located at the grain surface respectively). In Table 111, all combinations of grain size and composition below and to the left of the solid line (100 pct adsorption) and the dashed line (10 pct adsorption) are excluded as to the possibility of covering the grain surface with a continuous boron film. Thus, even for 100 pct adsorption, the smaller grains can form the film only at the higher concentrations. For the best case, grain size No. 1 and 0.0030 pct B, the required degree of adsorption is 3.9 pct. The above calculations deal only with the number of boron atoms required to form a monatomic film and do not take into account the mechanism of concentration of boron at the grain surface and the possible limitations to the extent of this concentration at a constant temperature, as for example in the austenitizing process. The question next arises as to how this surface concentration can occur during an isothermal treatment. Such surface enrichment of boron must occur through the phenomenon of surface adsorption, i.e., the concentration of solute atoms in solid solution in the vicinity of the surface without precipitation. A solute atom will tend to concentrate at the grain boundary if it reduces the interfacial tension. The possibility of adsorption effects involving both boron and carbon in iron has been discussed.' In general, the tendency for a sol-

Jan 1, 1954

By J. H. Mallery, J. H. Keeler

THE crystal structure of Zral, the compound richest in zirconium (91.03 pct Zr by weight) in the system Zr-Al, has been found to be ordered face-centered-cubic. This compound is of particular interest, since it is encountered as the precipitated phase in potentially useful zirconium-rich alloys. It forms peritectoidally from body-centered-cubic zirconium and Zr,Al at about 975°C. The Zr-A1 constitution diagram has been reported by McPherson and Hansen.' For the primary determination a 100 g ingot was prepared by arc-melting in a water-cooled copper crucible under purified argon. The raw materials were crystal-bar zirconium (a purity of better than 99.7 pct) and spectroscopically pure aluminum. The ingot was double melted, examined metallographi-cally, and found to be quite uniform as shown in Fig. 1. The hardness of the as-cast button was VHN 390 to 445. A 20 mil diam specimen was prepared from annealed (900°C) filings of Zr,Al. The specimen was mounted in a 5 cm radius powder camera and an 8 hr exposure was taken using copper radiation with a nickel filter. The structure of the compound Zral was found to be ordered face-centered-cubic of the Cuau type, with an a,, value of 4.37220.003A. Its calculated density is 5.976e0.013 g per cu cm. The relative intensities for the lines were calculated using the formula 1+cos2 20 I oc----------------- • p • /F7 sin2 0 cos 0 1 + COS' 20 where----------------is the Lorentz polarization fac- sin2 0 cos 0 tor, p is the multiplicity factor, and F is the structure factor. The X-ray data are given in Table I. The compound has exhibited plasticity when present as particles in a matrix of a zirconium. During hot working at about 900°C, the compound has been found to deform plastically to the extent that some of the particles exhibit a length-to-width ratio greater than 4:1 as shown in Fig. 2. In answer to the discussion of ref. 1, McPherson and Hansen pointed out that the compound may be cold rolled and reduced as much as 33 pct. Zr,Al has also been found2 under certain conditions to precipitate in lamellar form at grain boundaries of the a phase of hexagonal-close-packed zirconium. Acknowledgment This work was carried out under Contract W-31-109-Eng 52 for the United States Atomic Energy Commission.

Jan 1, 1956

By R. W. Gurry

IN the course of a series of measurements of the rate of diffusion of carbon in austenite at about 960°C. (1760°F.) and 1110°C. (2030°F.), it became necessary to determine carbon concentration when austenite is saturated with graphite, because of indications that the hitherto accepted value of the solubility of graphite in this temperature range is too low. Specimens of carbonyl iron were saturated at temperature in a hydrogen-toluene atmosphere which was in equilibrium with graphite. The carbon content of the steel was measured either by combustion or by the loss of weight after substantially complete decarburization in an atmosphere of hydrogen saturated at room temperature with water vapor. The absence of carbide or graphite as a phase at temperature was demonstrated by microscopic examination of saturated specimens that had been drastically quenched. The mean result of concordant measurements is that gamma iron saturated with respect to graphite contains 1.39 per cent carbon at 957°C. (1755°F.) and 1.89 per cent at 1110°C. (2030°F.). These two values, plotted along with what appears from the literature to be the best value (0.69 per cent) at the iron-graphite eutectoid temperature (738°C. or 1360°F.), yield a curve that is almost linear, and which, continued upward through a short interval, leads to a limiting solubility of 1.98 per cent at the iron-graphite eutectic temperature 1135°C. (2075°F.) instead of the commonly accepted value of about 1.7 per cent. EXPERIMENTAL PROCEDURE The samples of carbonyl iron, with the exception of those for microscopic examination, were cylinders 3.8 cm. long, 0.475 cm. in diameter. They were placed in a graphite holder and suspended in a vertical furnace, the temperature of which was controlled precisely by means of the resistance of the platinum winding.1 In the empty furnace the range of temperature over a distance of 4 cm. at the heat center was 9°C. (16°F.) but at a given location the temperature remained within ±0.5°C. (0.9°F.); it was measured by inserting a platinum-rhodium couple calibrated at the melting point of palladium, 1555°C. Since the presence of the sample probably improved the uniformity of temperature, it was decided to consider the average temperature of the sample to be 3°C. lower than the maximum measured in the empty furnace with the same setting of the controller. Data were obtained in the vicinity of two temperatures, 960°C. (1760°F.) and 1110°C. (2030°F.). The samples for microscopic examination, 2.2 cm. long, 0.475 cm. in diameter, were suspended individually on pure iron wire; for these no temperature correction was applied. The carburizing gas passed into the furnace was dry, oxygen-free hydrogen saturated at room temperature with

Jan 1, 1942

By R. W. Hyde, S. E. Eaton, B. S. Old

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides' In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949

By R. W. Hyde, B. S. Old, S. E. Eaton

One of the most important problems facing the steel industry at the present time is that of maintaining at a minimum the sulphur content of many grades of steel where sulphur is known to have harmful effects On both quality and yield. The present outlook in this struggle to reduce the amount of sulphur in steel is rather gloomy since the sulphur content of the raw materials available in the United States is gradually rising, with little relief in sight. A flow sheet of sulphur in the steel process is shown in Fig I. The values used here were obtained by averaging coke oven and blast furnace data at No. 5 furnace in Cleveland and are considered typical for high top pressure practice. The sulphur evolved in the blast furnace top gas was obtained by difference and since the amount is relatively small, little significance should be attached to this particular value. From Fig I it is apparent, however, that coals used in the production of metallurgical coke represent by far the largest single source of sulphur in steel-making. As an indication of the decrease in quality of these coals as regards sulphur content the weighed average annual sulphur analysis of the coals supplied to two different steel plants, since 1925, is plotted in Fig 2} The sharp rise since 1940 is strikingly apparent. Another indication of this trend is found in estimates of coking coal reserves. Thus in the case of Pittsburgh seam coals available in Allegheny, Fayette, Greene, Washington, and Westmoreland Counties in Pa. as of Jan. 1937 only 25 pct of the coal reserves would contain less than 1.50 pct sulphur after washing.2.3 Many of these lower sulphur reserves have been seriously depleted in recent years because of accelerated war demands. still another demonstration of the increasing sulphur content of coals on a country-wide basis is found in a report by the Bureau of Mines4 which shows a steady increase in the sulphur content of coke made in the United States. It should be noted that this increase continues in spite of the wider use of coal washing in recent years. Sulphur occurs in coal in three forms, pyritic (FeS2), organic sulphur, and a small amount of sulphate sulphur (CaS04). The sulphur is subsequently found in the coke in combination with carbonaceous material of is composition and as calcium and iron sulphides' In considering the general problem of sulphur elimination, the Republic Steel Corp. was interested in determining which, if either, of the two major forms of sulphur in coal contributes the greater portion of sulphur to the coke. Since the ratio of pyritic to organic sulphur varies widely in different coals, it was thought that if it could be shown definitely that the major part of the sulphur occurring in coke originates from one of the two ""jar forms of sulphur in the coal, it would then be possible to select with confidence coal which, although high .in total sulphur, would yield coke of fairly low sulphur content. Using the new

Jan 1, 1949

By J. Brett, S. Friedman

A study of the diffusion of nickel into both fibrous and recrystallized 0.065-in.-diam silica-alumina doped tungsten wire at 1200°C has been conducted. The diffusion profiles were determined by chemical dissolulion of successive circumferential layers and spectro-photometric determination of nickel in the etchant. It was shown that the diffusion of nickel into tungsten is markedly structure-sensitive. No significant amount of nickel could be introduced at 1200°C into tungsten which had first been recrystallized at temperatures of 2300°C, leading to an upper limit estimate for the bulk diffusivity of nickel in tungsten of 10-11 sq cm per sec at 1200°C. However, nickel did diffuse into initially fibrous wires, caused re crystallization, and was alsays present at the advancing recrystallization front. The accumulation of nickel in an initially fibrous region ceases when the recrystallization front arrives. The characteristics of the resulting diffusion profiles are explained in terms of the relation between diffusion processes and micro structural changes. WHILE it is well-known that the presence of nickel and certain other metals causes low-temperature recrystallization of the cold-worked fibrous structure of doped tungsten,''' the character of the phenomenon is not well understood. Recently it was shown that the recrystallization reaction can be induced at low temperatures by the presence of solid nickel on the surface of doped wire, but not by exposure to nickel vapors.3 Once recrystallization was initiated, a continued source of nickel was required for propagation of the recrystallization front. The phenomenon appeared to be a complicated solid-state reaction since, in addition to the change in structure of the tungsten from fibrous to equiaxed grains, diffusion of nickel from the surface into the recrystallized and fibrous structures was occurring with possible chemical reaction between nickel and tungsten at the surface and interaction of nickel with the dopants which ordinarily stabilize the fibrous structure within the wire. The objective of the present work was to study the diffusion of nickel into fibrous and recrystallized tungsten structures in order to clarify the relationship of the diffusion process to nickel-induced recrystallization. Studies of interdiffusion in the Ni-W system4"7 have been principally concerned with the mobility of tungsten in nickel. Information on diffusion of nickel in tungsten is meager, and there seem to be no studies of the mobility of nickel in tungsten which elucidate the structural aspects of the phenomenon. The present experiments were designed to determine the diffusivity of nickel at 1200°C in fibrous tungsten, in large-grained tungsten prerecrystallized at high tem- perature, and in tungsten recrystallized at 1200°C due to the presence of nickel. Although the concentration profiles were determined in these experiments, unexpected changes in boundary conditions or complex diffusion paths complicated the analysis of these profiles so that the interpretation could not be readily expressed in terms of simple diffusivities. EXPERIMENTAL PROCEDURE The experiments were conducted on Sylvania 0.065-in.-diam silica-alumina doped commercial tungsten wire, hereafter designated as ordinary doped wire. A special lot of 0.065-in.-diam silica-alumina doped low-nickel wire was also used. Impurity analyses of the wire are given in Table I. The experimental design is shown in Fig. 1. All heat treatments were conducted in vacuum. Two groups of ordinary doped wire were prepared for diffusion with nickel. One group in the as-received (fibrous) condition was elec-tropolished, nickel-plated, and annealed at 1200°C for 20 and 40 hr, or was exposed to nickel vapor at 1200°C for 20 and 40 hr. The second group was recrystallized to an equiaxed grain structure at 2300°C for 3 hr, electropolished, nickel-plated, or exposed to nickel vapor for anneals at 1200°C for 20 and 40 hr.

Jan 1, 1969

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By C. R. Kuzell

INTRODUCTION KNOWLEDGE of the thermal capacity of gases is of great importance in making metallurgical calculations. The metallurgist is, frequently called upon to investigate and determine furnace efficiencies in which the heat carried into or out of the furnace by gases is a large item in the heat balance. Not only do such problems present themselves in the determination of furnace efficiency, but also in the study of the application of heat is accessory apparatus, such as stoves, regenerators, waste-heat boilers, driers,.etc. The thermal effect of the use of excess air in the combustion of fuel, the theoretical temperatures of combustion, the quantity of heat in hot blast at various temperatures, the effect of hot blast on furnace temperatures, are a few more examples of frequently occurring calorific problems involving gases. So many are the applications of the data on the heat capacity of gases that the subject merits careful study. The heat in a gas maybe due to its heat of combustion, if it is a combustible gas, and to its temperature. The latter is called its sensible heat and is the heat absorbed or evolved by a gas as its temperature is raised or lowered. The heat of combustion of gases is well established and is commonly known. The values can be found in almost any mcdern treatise on metallurgy. The sensible heat of gases has not been so well established because it is in most cases a function of the temperature, and the values of specific heats of gases over a wide range of temperatures have only recently been determined. It is the purpose of this paper to deal with the sensible heat of gases.

Jan 8, 1914

By PAUL DYER MERICA

PAUL DYER MERICA, who has been awarded the James Douglas Gold Medal for his achievements in non-ferrous metallurgy, is a Hoosier, having been born at Warsaw, Ind., in 1889. His father, a clergyman and educator, was president of the University of Wyoming from 1908 to 1913. After graduating from the University of Wisconsin in 1908, young Merica (not yet twenty years of age) went to China, where he was professor of chemistry in Chekiang Provincial College, Hangchow, until 1911. He then went to Germany to s t u d y and was fortunate enough to receive his Ph.D. from the University of Berlin just a few months before the outbreak of the World War in 1914. Returning to America, his first position was as special investigator at the En¬gineering Experiment Station of the University of Illinois, but before the year was out he joined the staff of the U. S. Bureau of Standards as associate physicist. Since 1918, he has been superintendent of research for the International Nickel Co. His work during those years is excellently summarized in the following quotation from the statement of Zay Jeffries recommending him for the award.

Jan 1, 1929

By F. L. Wolf

The catenary system of line construction possesses so many desirable characteristics from the operating standpoint that it has wide application for all types of electric traction. Many steam roads are electrifying sections of their lines, and in most cases are operating both steam and electric locomotives over the same track. This means that the overhead catenary system is subjected to the severe corrosive action of locomotive smoke, and data concerning the resistance of various alloys to this form of corrosion are very desirable from every point of view. Reliable and specific information and data on the subject of corrosion due to steam and smoke from locomotives are extremely meager and, on this account, extensive service tests, together with accelerated tests, have been made on a number of commercial metals and alloys. The observations and data recorded in this paper are the result of a preliminary test which was started in 1923 and which has been carried on to the present time. The recognition of the need for even more detailed and accurate data has resulted in the undertaking of another test which has been in progress for about a year. The result of this test will be published in due course. Some years ago The Ohio Brass Co. was asked by one of the large steam railroad companies to furnish data on construction details for a catenary system which it was considering for one of its divisions. The selection of materials which would give the necessary physical characteristics as well as withstand the severe corrosive action of locomotive gases caused electrical railroad engineers considerable concern. At that time, there were available no specific or authentic data on these important questions: no systematic investigation of the problem appeared to have been made, even though it's importance was generally recognized. Such observations as had been made were crude in that they had been limited largely to visual inspection which too frequently is most misleading. However, the scattered information which was collected gave important clues as to how best to start an investigation. Technical literature was studied, metallurgical experts were consulted, and the problem was discussed with engineers who were in close contact

Jan 1, 1930

By J. T. Crawford

Although nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth-Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal bri-quetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the world's largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis., waterfront and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned, General History In the summer of 1871 a small sailing vessel entered the harbor of Duluth-Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1949

By S. W. Miller

Most of the steel welding done at the present time is in material containing not over 0.3 per cent. carbon, and the tests here described were in similar material. These tests are not as yet completed but it is hoped that more results and more reasons for the conclusions may be presented at the meeting in February. From the time the author found the peculiar structure in electric welds referred to in a previous paper,' that is, needles or plates in the grains and similar material, in larger spots, at the grain boundaries, he has felt that these plates which may be iron nitride and probably contain some carbon, were at least partly responsible for the brittleness of electric welds. He has found but few traces of similar lines in oxyacetylene welds until the last 2 mo., he has since found large numbers under certain conditions. In the top of these welds, they are quite numerous. In the body of heavy oxyacetylene welds, they appear at times, but not nearly to the extent that they do in electric welds; the author has never seen them in the body of welds in material less than % in. (19 mm.) thick. They are shown in Fig. 82. The reason they were not noticed before is undoubtedly due to the fact that in making tests of welded pieces the weld was always ground off level with the plate, and as this structure only appears in the top 1/16 in (1-5 mm.) of the weld, they were removed by the grinding or machining; also, welds 3/4 in. thick had not been examined. It did not appear, in making bending tests, that this structure had much influence on the strength of oxyacetylene welds; while electric welds are noticeably brittle. Further, oxyacetylene welds made with certain special materials were exceedingly brittle even after the tops of the welds were removed; this was true in cases where there was no sign of the plates whatever and where the welds were remarkably free from oxide and the other usual defects. It appeared, therefore, that this brittleness did not depend on any variable that had been noticed so far, and it was decided to find where the rupture occurred in various kinds of welds made

Jan 1, 1920

By Paul D. V. Manning

MAGNESIUM is an exceedingly strategic material but the importance of its production at the time this war started was not realized. Our Government then suddenly became much alive to the need of a tremendous increase in magnesium output, and became a participator in the industry. In this paper an attempt will be made to given an over-all picture of the industry as it has been, and is being, developed. The present war is giving a great acceleration to the use of lighter metals. Development of facilities for production of great tonnages of aluminum and magnesium is bound to bring about some interesting changes in later peace times because costs will be low and production capacities high. As our knowledge of the metallurgy of magnesium alloys increases, this metal will become of vital peacetime importance and will be used in ways we do not now imagine. Household refrigerators, furniture, automobiles, even houses will all be lightened through the use of magnesium.

Jan 1, 1943