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By C. R. Hopkins

"The petroleum refiners of the United States made rapid strides in fuel economy in 1928, when the calculated number of B. t. u. required to refine a barrel of crude petroleum was 637,000 as compared with 698,000 in 1927, a decline of 9 per cent. The major portion of this indicated increase in fuel efficiency was undoubtedly due to the gain in use of the pipe-still and the continuous process of refining as contrasted with the old batch method of distillation.,Almost without exception the new refineries are equipped with one or more pipe-stills, and many of the older plants are changing over to this type of equipment. The refineries of the Appalachian area are among the oldest and most conservative of the country, yet a number of them dismantled their old shell and cheese-box stills and installed pipe-stills in 1928.The more extensive use of the pipe-still was not the only way in which the refiners lowered their fuel requirements in 1928. The use of heat-exchangers, in which the heat from hot vapors to be condensed is used to heat the incoming cold oil, also increased in 1928, and in addition the refiners have kept abreast of the times in saving fuel through better insulation and improved burners.For the year 1928 the refiners burned as fuel the following: 46,400,000 barrels of-fuel oil; 3.362,000 short tons of coal; 114,950,000,000 cubic feet of natural gas; 77,313, 000,000 cubic feet of refinery or still gases; and 470,000 short tons of coke, in addition to a little electricity. This fuel was calculated to have produced a grand total of 582,156 billions of B. t. u., as compared with 578,784 billions B. t. u. in 1927.The total of 46,400,000 barrels of fuel oil burned represents an increase over 1927 of about 5,000,000 barrels, which made it about equal to the 1926 figure. Practically all of the refinery districts used more oil as fuel in 1928. The most important increase - over 2,000,000 barrels - occurred in the East Coast district, where greatly expanded throughput of foreign crude was instrumental in increasing fuel-oil production.The use of coal for fuel at refineries again registered a material decline, the total for 1928 of 3,362,000 short tons being 33 per cent below that of the previous year. The outstanding decrease in the use of coal in 1928 occurred in the East Coast district, where coal was probably replaced by oil. The use of coal for fuel at refineries in the States of Ohio, Pennsylvania, and West Virginia declined materially in 1928; the substitute used in the majority of cases was oil burned in pipe-stills."

Nov 1, 1929

By C. P. Kempter, H. L. Brown

Recently Chang determined heat content values of tantalum monocarbide and tungsten monocarbide from 325" to985°Kand 326" to 912"K, respectively, and, using other published data, made certain solid-state calculations for these two compounds. Chang expressed his Cp values in units of cal per "g-atom alloy" OK. We consider this poor usage since l) tantalum monocarbide and tungsten monocarbide are not alloys, and 2) an atom of an alloy does not exist. However, one may convert his values to units of cal per mole OK by merely doubling them. For TaC he calculated a Nernst-Lindemann parameter of 9.07 x lo-' "g-atom per cal". We have refined the calculation of this parameter and have arrived at a much lower value. Rather than approximating the true coefficient of volume expansion, a,, as three times the true coefficient of linear expansion, a, we calculated u, from the TaCo.99, lattice expansion data of Fries and Wahman.38 At 25°C a, = 14.3 x 10s per OC. The molar volume was calculated to be 13.32 cu cm per mole at 25°C. From the lattice compression data of Champion and Drickamer~' for "TaC,.,," we determined the room-temperature compressibility to be 3.5 x 10-l3 sq cm per dyne by plotting l/Vo (aV/ap) vs applied pressure. (Since the lowest pressure at which Champion and Drickamer reported a relative volume was 20 kbars, one may calculate an approximate compressibility only. Chang calculated a compressibility of 3.175 x 10-l3 sq cm per dyne from the same data.) We also used twice Chang's value of Cp = 4.38 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated a Nernst-Lindemann parameter of 5.8 x 10-l4 mole per erg or 2.4 x lo- ' mole per cal, and a Cdil value of 2.3 x 10' ergs per mole OK. In the case of tungsten monocarbide no isothermal compressibility has been reported; however, one may calculate an approximate Nernst-Lindemann parameter by using the adiabatic compressibility reported by Brown, Armstrong, and Kempter." Using the WC lattice expansion data of Mauer and Bolz~l we calculated a, to be 12., x l0-' per OC. The molar volume was calculated to be 12.5 cu cm per mole. We used twice Chang's value of Cp = 4.18 cal per "g-atom alloy" OK for the molar heat capacity at 25°C. From these four values we calculated an approximate Nernst-Lindemann parameter of 2 x lo-' mole per cal, which is much

Jan 1, 1969

By Ralph Hultgren, David W. Mitchell

MAGNESIUM alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600° to 1700°F while the casting temperature, which depends upon the mold shape, is usually 200° to 300°F lower. The process of superheating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported' that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results.2 As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted" Project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. MATERIALS AND METHODS The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesium used in these alloys was of both carbothermic3 and electrolytic4 origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200' to 1250°F., portions of approximately one pound each were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21† covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F for 15 min., then cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By Ralph Hultgren, David W. Mitchell

Magnesium alloys usually are superheated before casting in order to ensure fineness of grain. Superheat temperatures in common use range from 1600" to r 7o0°F.; the casting temperature, which depends upon the mold shape, is usually 200° to 300°F. lower. The process of superhcating requires considerable time and seriously shortens the life of the iron pots used. Recently it has been reported1 that if acetylene, carbon dioxide or natural gas is bubbled through molten electrolytic A.S.T.M. No. 4 alloy at 1400°F. for 5 min., grain refinement equivalent to that of superheating will take place. Addition of certain solids such as graphite or aluminum carbide accomplishes the same results? As will be shown in this paper, it is possible to achieve grain refinement in magnesium casting alloys at low temperatures by mechanical stirring of the molten metal for a short time. This process was developed in the course of research work, supervised by the War Metallurgy Committee under the "Restricted' project NRC-550, for the Office of Production Research and Development of the War Production Board. This paper, based on that work, has been released for publication by the O.P.R.D. Materials and Methods The alloys studied were the most common American sand-casting alloys designated as No. 4 and No. 17 by the American Society for Testing Materials. The magnesiun used in these alloys was of both carbothermic3 and electrolytic' origin. Chemical analyses supplied by the producers are shown in Table I. Each heat consisted of approximately 5 lb. of alloy melted in a Tercod crucible. It was refined by fluxing with Permanente No. 7* refining flux at 1300° to 1350°F. After cooling to 1200° to 1250°F., portions of approximately one pound each, were ladled into iron crucibles contained in an electric furnace at about 1250°F. The molten metal was covered with Permanente No. 21 † covering flux and then heated to the temperature to be investigated. Normally each of the four portions was given a different treatment. In a typical case one portion was stirred vigorously for 5 min., acetylene gas was passed through a second portion for 5 min., a third portion was superheated to 1600°F. for 15 min., then . cooled to casting temperature, and the fourth was held for 5 min. at the temperature of stirring or gassing without other treatment. Each portion was then cast into one-inch diameter cylinders in three "nonturbulent" molds of identical shape. One mold was made of cast iron and the other two of baked sand. The cast-iron mold and one of the baked sand molds were heated to 360°F., the other baked sand mold was at room temperature. The freezing times in these molds were

Jan 1, 1945

By Henry Fay

LAWRENCE ADDICKS, New York, N. Y., (communication to the Secretary *).-There are two points regarding gun erosion on which I want to say a few words: The first is about the analogy to hardening of wire by drawing and the second the possible role played by thermal conductivity of the metal. The ductile metals do not necessarily become brittle when cold-worked as it is possible to draw copper from 3. in. in diameter soft rod down to the finest hair wire without annealing. This results, as stated in the paper, informing a hardened core with a very hard skin. The electrical conductivity is depressed some 3 per cent. and the tensile strength nearly tripled. A soft copper wire 0.08 in. in diameter and 6 in. long may be twisted 150 or more turns before the wire will snap under torsion. A hard-drawn wire will break after perhaps a dozen twists, the skin breaking down at one spot. Just wiping the wire with a cloth clamp with dilute nitric acid has a remarkable effect in increasing the number of twists without appreciably lowering the tensile strength, showing the skin to be very thin. On the other hand, pickling the rod, from which the wire is to be drawn, in dilute nitric acid also greatly increases the number of twists which can be applied to the resulting wire. This indicates that the copper oxide scale produced when the wire bar is rolled hot is more or less rolled into the rod and may have much to do with the skin effect. We also know that if the conditions of drawing are not correct, the heat of deformation in the die may produce quite an annealing effect. The application of this analogy to what occurs in a gun to produce the effects noted offers some difficulty. The second point is that as the temperature of the surface of the gun bore has undoubtedly a great deal to do with the amount of erosion, one natural remedy would be to conduct the heat away fast enough to keep this temperature within desired limits. This brings up the question of the thermal conductivity of the metal of which the gun is made. We know that the conductivity of pure metals is greatly altered by alloying and that the alloy is usually, though not always, lower in conductivity than the metal before alloying. This is interesting when it is considered that the high-nickel and manganese-steel alloys show greater erosion as stated. Would it not be instructive to study the question from the point of view of heat conducted away from the eroded surface?

Jan 3, 1917

By John Tyssowski

In 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temperatures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several particles had become one unit. From this discovery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the application of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper produced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles. Concurrently, the three metallurgists worked on the problem of effecting a complete union of the cathode particles. Adequate washing was all that was needed to free the particles from electrolyte solution and slimes. A press was designed to produce briquettes of the proper porosity and density, and a method was devised of removing surface oxidation from the particles of cathode, by treatment in an atmosphere of deoxidizing gas at an elevated temperature. The temperature was determined at which the surface cleansing and preheating could be done in one operation, and for this a charging and preheating furnace in which there is maintained a positive pressure of deoxidizing gas atmosphere was designed. And finally, a method of feeding the heated briquettes of deoxidized cathode copper into an extrusion press without contamination from the air was evolved. For the final stage, a press was required because not only heat but pressure was required to obtain complete growth of the new crystals between the cathode particles as well as the elimination of all voids or non-coalesced areas. All essential stages of the process are protected by patents or patent applications in the United States and principal foreign countries, and the copper is produced on a commercial scale.

Jan 1, 1941

By John Tyssowski

In 1925, Harry Howard Stout, then metallurgist for Phelps Dodge Corporation, while investigating the cleaning of cathode copper by various gases at elevated temperatures below the melting point of the metal, observed in the laboratory that particles of pure copper heated in a closed tube filled with hydrogen seemingly "stuck together." By further investigation he found that there was actual crystal growth across the boundaries of the particles of pure metal; in other words, there was a complete new crystal realignment and growth throughout the newly formed copper mass. It was coalescence, not adhesion; the several particles had become one unit. From this discovery has been developed the coalescence process, whereby copper of cathode purity is squirted out in semifabricated form from an extrusion press, by the application of about 3000 tons pressure on a 10-in. piston. Stout decided that cathode copper produced by electrolytic deposition was the logical source of the pure copper required for the coalescence process, but as there was no way of reducing the ordinary tough commercial cathodes to the small particles required he was confronted by a serious problem at the outset. Under his direction, this problem was solved by William H. Osborn and Harry Howard Stout, Jr. They developed the process and technique for producing cathode copper in brittle, friable form, and to them must be given the greater part of the credit for this phase of the development program as well as for that relating to the gas cleaning of the cathode particles. Concurrently, the three metallurgists worked on the problem of effecting a complete union of the cathode particles. Adequate washing was all that was needed to free the particles from electrolyte solution and slimes. A press was designed to produce briquettes of the proper porosity and density, and a method was devised of removing surface oxidation from the particles of cathode, by treatment in an atmosphere of deoxidizing gas at an elevated temperature. The temperature was determined at which the surface cleansing and preheating could be done in one operation, and for this a charging and preheating furnace in which there is maintained a positive pressure of deoxidizing gas atmosphere was designed. And finally, a method of feeding the heated briquettes of deoxidized cathode copper into an extrusion press without contamination from the air was evolved. For the final stage, a press was required because not only heat but pressure was required to obtain complete growth of the new crystals between the cathode particles as well as the elimination of all voids or non-coalesced areas. All essential stages of the process are protected by patents or patent applications in the United States and principal foreign countries, and the copper is produced on a commercial scale.

Jan 1, 1941

By W. T. Isbell, Carleton C. Long

Zinc recovery from lead blast-furnace slags has heretofore been an indirect process, involving, first, the fuming off and collecting of an impure zinc oxide, and second, the reduction of the zinc portion of this oxide to metal either by electrolytic or pyrolytic means. (In a variation of this process, blue powder is the intermediate product rather than zinc oxide fume.) In 1940, W. T. Isbell proposed that molten slag from the lead blast furnace or stock-pile slag melted down in a blast or cupola-type furnace be charged directly into an airtight container (i.e., furnace) provided with means to heat further the slag by passage of electric current and means to introduce the carbon (coke) necessary to reduce the ZnO constituent of the slag to zinc as a zinc vapor and CO. He also proposed that the zinc vapors so obtained be condensed in a Weaton-Najariant internal condenser directly connected to the proposed furnace. It was thought that the Weaton-Najarian condenser could liquefy zinc vapor from lean mixtures of vapor and noncondensable gases. Such condensers have been in commercial use! since 1936 at Josephtown smelter, where the source of zinc vapor is a column of coke and zinc-bearing sinter electrically heated (charge resistor). Condenser output when supplied with vapor-gas mixtures containing approximately 45 per cent zinc and 55 per cent noncondensable gases, varies from 18 to 30 tons of slab zinc per day per condenser, depending upon the heat-transfer area (length) of the condenser and the volume of vapor (furnace size) fed to it. Lead-smelting operations at the St. Joseph Lead Company's plant at Hercu-laneum, Mo., produce a slag containing 12 to 16 per cent zinc. For several years this slag has been stock-piled with the object of recovering the zinc values if and when a commercial method was invented. Evaluation of the possibilities of the proposed method was made by pilot-plant operation at Josephtown. The first plant, designed in 1940 and operated in early 1941, consisted of a single-phase, two-electrode furnace. The evolved vapors were burned. Electrical characteiistics of the molten slag, power requirements, coke requirements, and extent of zinc elimination indicated the feasibility of the proposed method. In the latter part of 1941 a second pilot furnace was constructed, to which "was attached a small (6 ft. long) Weaton-Najarian condenser in order to develop an over-all picture of zinc-in-slag to zinc-in-slabs. This furnace was operated in the early part of 1942 and yielded such promising results that a decision was made to design- and construct a commercial furnace. Feed for the pilot-plant furnaces was granulated slag. A suitable deduction (300 to 350 kw-hr. per ton slag) was calculated in estimating power require-

Jan 1, 1944

By Herman Garlichs

The development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870. Lead production in Southwest Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a, V. Wood and galena were placed in the furnace and ignited.. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 it. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 1, 1918

By Herman Garlichs

THE development of the extensive Southeast Missouri deposits greatly preceded that of the Iowa and Wisconsin deposits. It began about 1720 at Mine La Motte and other localities, and has continued uninterruptedly to the present time. It is estimated that this district produced about 184,000 tons of lead in the year 1916, having a value of approximately, $25,000,000. This is a new high record. The Southwest Missouri orebodies were hardly known before 1845 and were not extensively developed until 1870: Lead production in South-west Missouri for 1916 was 38,788 tons. Oklahoma produced 14,399 ,tons and Kansas 2,345 tons, making a total for Southwest Missouri, and the adjoining districts in Oklahoma and Kansas, of 55,532 tons of lead. The first metallurgists in Missouri were the Indian and the hunter. The early settler learned to procure his bullets either by melting ore in his camp fire or by throwing pieces of galena on an old stump and depending on the usual roasting and reaction method to obtain the metal. A little more refined method was to arrange two flat stones in the form of a V. Wood and galena were placed in the furnace and ignited. As heat developed, some of the metal was extracted and molded into bullets. The next step in utilizing the lead ores was the log hearth. All lead in Missouri was smelted in this crude affair before 1820. It was built on sloping ground, and consisted of a hearth of stone, surrounded on the front and two sides by a stone wall. The wall was 7 ft. high in front. The top and rear end were left open and in front an arch or opening was made, forming the eye of the furnace. In front of this a pit was dug in the ground, to receive the molten metal. Large logs were rolled in at the back and made to rest upon ledges formed inside, to raise them from the hearth and to give a draft. These logs filled the entire width of the furnace. Small split logs were then set up around the two sides and the front, and the ore was piled on until the furnace was full. Finally, the mass was covered with logs and fuel until the ore was completely surrounded. A gentle heat was started, which was raised very gradually. After 12 hr. the heat was increased and continued for 12 hr. more, 24 hr. being required, for each smelting. The furnace treated about 5,000 lb. per 24 hr. and the ore yielded about 50 per cent. of its metallic lead. A considerable quantity of the ore was not desulphurized, and fell between

Jan 7, 1917

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By Palmer C. Sweet

Kyanite. andalusite, and sillimanite are anhydrous aluminum silicate minerals, and they have the same chemical formula, Al2SiO3. Dumortierite and topaz are also classified as aluminum silicates although they contain boron and fluorine respectively. Mullite (a rare mineral named for its discovery site, the Scottish island of Mull) is produced when kyanite, andalusite, or sillimanite are heated. Synthetic mullite, also classified as an aluminum silicate, is formed by melting alumina and silica, bauxite, and kaolin or alumina, kaolin, and kyanite, depending on the type of synthetic mullite desired. These materials are either sintered in rotary, periodic, or tunnel kilns, or fused in an electric arc furnace. The world's largest producer of kyanite is the United States. Domestic kyanite is presently produced from one company at two sites in Virginia; Kyanite Mining Corporation mines kyanite from Willis Mountain and adjacent East Ridge in Buckingham County in the central Piedmont province of Virginia. Internationally, kymite is produced in Australia, Brazil, India, Kenya, Sweden, and Zimbabwe; the former USSR also produces kyanite (Fig. 1). Andalusite is produced by Piedmont Minerals Company, Inc. in the Piedmont province near Hillsborough, NC. Andalusite is also produced in France, India, the Republic of South Africa, and Spain (Fig. 1). Sillimanite is produced in Australia, Brazil, India, Spain, and the Republic of South Africa; the former USSR is also thought to be a major producer (Fig. 1). Some of the countries produce only for domestic use. Synthetic mullite, made by sintering and by electric arc fusion, is produced by Mulcoa (Mullite Company of America) in Andersonville, GA, and by Washington Mills Electro Minerals Corporation in Niagara Falls, NY. Annual world production of kyanite, andalusite, sillimanite, and synthetic mullite is approximately 672 727 tons (Potter, 1988). GEOLOGY Mineralogy Kyanite is a blue to light-green, triclinic mineral that occurs in long, thin-bladed crystals and crystalline aggregates in gneiss, schist, and pegmatites. The mineral has a hardness of 5 parallel to the long axis of the crystal and a hardness of 7 across the crystal. Andalusite is a yellow, brown, green, or red orthorhombic mineral that occurs in thick, almost square prisms in schist, gneiss, and hornfels. Gem quality andalusite exhibits a strong pleochroism; brownish-green in one direction and brownish-red perpendicular to it. Andalusite also occurs in placer concentrations where it has weathered out of rock. Sillimanite is a brown, pale-green, gray, or white orthorhombic mineral that occurs in long, slender, needlelike crystals in schist and gneiss. Chemical and Physical Properties Chemical and physical properties of kyanite, andalusite, and sillimanite are noted in Table 1. Kyanite is the only mineral that irreversibly expands when heated (calcined to produce mullite) and may offset the shrinkage of most ceramic or refractory ingredients when heated.

Jan 1, 1994

By E. A. Gulbransen, W. S. Wysong, K. Andrew

INTRODUCTION THE reaction of carbon in solid solution in a metal with the surface oxide film on many metals may be inferred from thermodynamic calculations for high vacua and high temperature conditions. Holm1 has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. Considerable work has been described in the literature on the decarburization reaction. Several general references may be noted.2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides 0n strips of various types of chrome-nickel alloys. Some of the early experiments on the behavior of 13 pct chrome-iron in vacua of the order of 5 X 106 mm and at a temperature of 600°C have been reported.5 These experiments showed a slow reaction with the residual oxygen or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600°C pure enough to reduce Cr203 formed on the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome iron and Nichrome V has been investigated in the thin film range by Gulbransen, Phelps and Hickman,6 and shown to be Cr203. It was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pct nickel and 20 pct chromium was heated to 850°C in a high vacuum, the specimen' lost weight. The rate of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. TYPE REACTIONS Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature, of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type. They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: [I. Metal • (gas) ;--* metal + gas - degassing of the metal 2. xM(s) + y ½ 02(g) tom- M.0„ (s) – oxidation]

Jan 1, 1948

By John I. Yellott

Since the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate producer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. Liquid Fuels Compete with Coal As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal-burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an electrical transmission, found an excellent application in railroad service. The high availability of diesel-electric locomotives, resulting in part from freedom from water

Jan 1, 1947

By John I. Yellott

Since the days of Newcomen and Watt, when men first sought to turn the energy of fuels to useful purposes, coal-generated steam has supplied most of the power needed for both stationary and mobile applications. The low efficiency and large water requirements of the nineteenth century steam-power plant caused many engineers to turn their thoughts toward more direct means of converting heat into power. As far back as 1791, John Barber secured an English patent on a combination' which he might well have called a "gas turbine." He proposed to generate producer gas from coal or charcoal, to burn it under pressure in air obtained from a reciprocating compressor, and to drive a turbine wheel with the resultant hot combustion products. With the optimism characteristic of the inventor, he hoped that the turbine would not only operate his compressor but also perform useful work. There is no record that Barber ever built his machine, but if he had done so he would have learned that useful power can result from such a combination only when both turbine and compressor are highly efficient and when the temperature of the gas entering the turbine is not far below 1000°F. Hot-air prime movers continued to attract attention, and both Stirling in England and Ericsson in America2 built reciprocating engines that operated with some success upon coal-heated air. The internal-combustion engine, burning liquid fuels, supplanted the hot-air type, and, for the first time, challenged the supremacy of both the steam cycle and its familiar fuel, coal. Liquid Fuels Compete with Coal As the increasing use of the automobile multiplied the demand for gasoline, the supply of residual fuel increased rapidly, and heavy oil declined in price to the point where it became competitive with coal. First in the marine field and later in stationary plants in areas adjacent to refineries, oil began to be widely used. Oil's greater convenience and higher heating value per pound of weight or per cubic foot of bunker space have caused it to take over much of the marine field. The introduction of the highly efficient diesel engine, capable of burning a fuel that is cheaper than gasoline, again threatened the position of coal, for the operating costs of the diesel became directly competitive with those of coal-burning equipment. In isolated power plants and smaller marine installations, the diesel provided the medium by which oil again successfully invaded fields formerly dominated by coal. The diesel engine, provided with an electrical transmission, found an excellent application in railroad service. The high availability of diesel-electric locomotives, resulting in part from freedom from water

Jan 1, 1947

By L. D. Fetterolf, G. T. Mahler, W. M. Peirce, R. K. Waring

Until recently, the only commercial method of producing magnesium has been fused salt electrolysis, despite a considerable amount of experimental work on the direct reduction of magnesium oxide. In this early work, a number of investigators demonstrated that magnesium oxide would react with any one of several reducing agents to produce magnesium vapor, but that the mixture of magnesium oxide and reducing agent must be heated to a high temperature even in a vacuum. In particular, it was demonstrated that silicon and aluminum are effective reducing agents and that when either of these is used the magnesium vapor can be condensed to massive metal. In spite of this knowledge, no successful commercial reduction process was developed, at least in this country, because of the operational difficulties imposed by the requirement of high temperature and vacuum and because of the high cost of the reducing agent. The outstanding experimental work done by Pidgeon, who carefully reviewed all of the known methods of making magnesium and then selected ferrosilicon reduction, overcame some of the operational difficulties. The process developed by Pidgeon comprises briquetting a mixture of calcined dolomite and reducing agent, preheating the briquets to about 600°C. in an externally heated alloy retort, reducing the MgO with silicon in an evacuated horizontal alloy retort heated externally to about II50 C., and condensing the magnesium vapor to a solid in a cold extension of the retort projecting beyond the front of the furnace. A major advantage of Pidgeon's process is that the retort is not cooled down between charges. Earlier investigators had used apparatus that necessitated cooling and reheating of the retort between charges. Early in January 1942, when the War Production Board was considering the Pidgeon process for quickly increasing the production of magnesium, The New Jersey Zinc Co. offered to have a research investigation of the process carried on, with the hope of assisting in its further development. This offer was accepted, and a two-retort pilot plant was built at Palmerton and put in operation on Jan. 29,1942. An intensive investigation of certain phases of the process was carried out in the ensuing four months. This investigation was completed in the last part of May 1942) and the pilot plant was then shut down. Subsequently, The New Jersey Zinc Co. was requested to have further development work done on the process, and a more extensive investigation was undertaken in August 1942 under contract with the War Production Board and under the supervision of the War Metallurgy Committee. This paper describes the ,phases of the investigation that are thought to be of sufficient general interest to merit publication.

Jan 1, 1944

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at sub-critical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.' Westgren, Phragrnén and Ne-gresco2 identified the following carbides in chromium steels: Cementitc............ Fe3C (containing up to about 15 per cent Cr) Trigonal carbide...... Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide........ Cr4C (or Cr23C6) (con- . taining up to about 25 per cent Fe) Orthorhombic carbide , cr3c2 (containing only a few per cent Fe) The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus,4 By means of dilatometric and microscopic stzdies, sections of the diagram were established. This diagram showed the presence of the special carbide CI7C3 in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in I per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7C3 occurs in chromium steels containing more than about I per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. Experimental Procedure The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into I-in. round bars, and all heat-treatments were conducted on specimens of this section size. Sections of the bar stock 8 in. long were hardened in air, oil or water, depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after quenching. The quenched bars were cut into

Jan 1, 1942

By George F. Weaton, Carleton C. Long, H. I. Najarian

Partial descriptions of the operation of the St. Joseph Lead Company's Joseph-town smelter have been published. In, 1936 the electrothermic production of zinc oxide was described;' in 1939 appeared a description2 of the electrothermic method of producing zinc metal. Inasmuch as the plant capacity has more than doubled, and in view of the fact that operating practices have improved greatly since these publications, it seems worth while to prepare a fresh description of the present-day elec-trothermic zinc plant and practice. Josephtown smelter is situated on the south side of the Ohio River about 3 miles below its confluence with the Beaver River. In addition to river barge, the smelter is served by Pennsylvania state highway No. 18 and by a spur line of the Pittsburgh and Lake Erie Railroad (N.Y.C.). A recent extension of this spur line connects with the Pennsylvania Railroad. As originally contemplated the plant was to handle only the product of the com-pany's own mines in St. Lawrence County, New york, but owing to the incessant demand for zinc and zinc oxide, it has been necessary to supplement New York concentrates with foreign ores (principally from Quebcc and the Argentine). The general operational procedure followed comprises roasting the sulphide con-centrates, converting the sulphur dioxide into sulphuric acid, preparation of a strong-structure sinter from the calcine, crushing &lid sizing of coke, reduction of coke-sinter mixture by electrothermic means, condensation of the evolved zinc vapor to make zinc metal or burning of the zinc vapor to make zinc oxide, collection and packing of the zinc oxide. Dusts recovered by the roaster and sinter Cottrells are treated in the leach plant for separation of lead sulphate, cadmium metal and zinc sulphate. The general flowsheet is shown in Fig. I. Principal Items OF Equipment Roaster Plant Concentrate drier, 6-ft. 'ia. by 4O ft. 5 in., countercurrent, direct gas-fired. 3500-~on concentrate storage in three vertical steel tanks. Five modified Nichols-Herreshoff twelve-hearth roasters, 21 ft. 6 in. in diameter. Four fans for shaft-cooling air. One threedrum Stirling water-tube waste-heat boiler, 4'8 hp., 200 1b. Per sq. in., with connections to upper and lower balloon flues. Direct gas-fired countercurrent rotary-kiln roaster for Cottrell dust. Necessary conveying equipment, described below. Instrumentation consists of: draft indicators, (3d hearth); various manometers; pyrometer served by thermocouples in each hearth, entrance and exit of waste-heat Joseph. entrance and exit of each hot Cottrell; roaster draft recorder and shaft air-pressure controller; temperature recorder and controller (10th and 12th hearths); SO* recorder (waste-heat boiler n

Jan 1, 1944

By Walter Crafts, C. M. Offenhauer

IN the course of study of the heat-treatment of low-alloy steels, the behavior of alloy carbides at subcritical temperatures was found to vary from that indicated by published investigations. In order to establish the ranges of formation of carbides in low-chromium steels, a series of steels containing up to 0.60 per cent carbon and 7.5 per cent chromium has been investigated with respect to the type of carbide formed after quenching and tempering at subcritical temperatures. The types of carbide formed as products of austenite transformation to pearlitic and pseudomartensitic structures have also been determined. There have been numerous investigations of the carbides in chromium steels and diagrams of the iron-chromium-carbon system.1 Westgren, Phragmén and Negresco2 identified the following carbides in chromium steels: [Cementite Fe3C (containing up to about 15 per cent Cr) Trigonal carbide Cr7C3 (containing up to about 55 per cent Fe) Cubic carbide Cr4C (or Cr23C3) (containing up to about 25 per cent Fe) Orthorhombic carbide . Cr3C2 (containing only a few per cent Fe)] The most complete information on the iron-chromium-carbon system was supplied by Tofaute, Sponheuer and Bennek3 and by Tofaute, Küttner and Büttinghaus.4 By means of dilatometric and microscopic studies, sections of the diagram were established. This diagram showed the presence of the special carbide Cr7Ca in steels containing about 2.5 per cent to 12 per cent chromium in low-carbon steels and from about 5 to 20 per cent chromium in r per cent carbon alloys from A1 to room temperature. The present investigation has shown that a carbide inversion from Fe3C to Cr7Ca occurs in chromium steels containing more than about 1 per cent chromium after hardening and tempering at subcritical temperatures above about 500°C. The type of carbide observed to be more stable in quenched and tempered specimens was also found to be produced by direct austenite transformation in corresponding ranges of temperature and composition. EXPERIMENTAL PROCEDURE The steels used in these experiments were made in magnesia-lined crucibles in high-frequency furnaces and were poured into 2-in. ingots. The ingots were forged into 1-in. round bars, and all heat-treatments were conducted on specimens of this section .size. Sections of the bar stock 8 in. long were hardened in air, oil or water depending on the composition, after heating to a temperature sufficiently high to dissolve the carbides. The low-carbon and low-chromium steels were not entirely martensitic after quenching, and contained some ferrite and pseudomartensite. No pearlite was observed in the microstructures after auenchine. The quenched bars were cut into

Jan 1, 1942