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By H. R. Hanley, Charles Y. Clayton

One of the most important contributions to the art of electrolytic zinc production has been the aluminum cathode. This has been used in all major production since its commercial development in 1916. The literature is replete with important contributions, some of which may have been replaced by better ones, but thus far there appears no other metal to take the place of aluminum as cathode material. Credit for this innovation goes to Sherard Cowper Coles, of England. When experimenting on the extraction of zinc from Broken Hill ore at Hayle, Cornwall, in 1893, he introduced the aluminum cathode, and in 1895 obtained British Patent No. 20073. The reason for this dominant position of aluminum as cathode material in zinc sulphate electrolytes is its unique surface, to which electro-deposited metals usually do not tightly adhere. The metal must, be of high purity for best results. It is possible to develop a starting-sheet method by which thin electro-deposited sheets of cathode zinc are made and stripped from a smooth aluminum plate. Such thin sheets of cathode zinc may be used as are the copper sheets in standard electrolytic copper-refinery practice. However, complications arise because of extreme warping of the zinc starting sheet after a few hours of deposition, and thus special arrangements must be made to compensate for this abnormality. Reasons advanced for the ease with which deposits may be stripped from the aluminum surface are: (1) presence of a permanent oxide coating on the metal, (2) failure of aluminum to alloy with the deposit, (3) differences in coefficient of expansion, (4) high position of aluminum in the electromotive scries of metals. Of these reasons for nonadherence, which may have some application in general deposition, probably the oxide coating has the greatest bearing on the subject of zinc deposition. Adherence of zinc deposits has occasionally had serious effect on tonnage and production costs. Opinions have differed as to the specific

Jan 1, 1943

By Carleton C. Long, George F. Weaton

Two years ago the general features of the St. Joseph Lead Company's zine-smelting process were described.' At that time the discussion was limited to a description of the production of high-purity electrothermic zinc oxide. The present paper will describe the commercial production of electrothermic zinc metal. Since a fairly complete description of the plant of the Josephtowlz smelter was given in the earlier paper, the brief recapitulation given here will be limited to mention of additional equip-ment recently installed and a bare outline of the preparatory process. The raw material is zinc sulphide concentrate received from the company's mines in St. Lawrence County, New York. An average dry-weight analysis of this material is: Zn, 58.28 per cent; Pb, 0.56; insoluble, 1.6; SiO², 1.12; Fe, 6.4; CaO, 0.47; MgO, 0.27; S, 31.9; Cd, 0.1; Cu, 0.06; Mn, 0.24. Moisture content is usually about 3 per cent. Three 21-ft. 6-in. diameter, 12-hearth Nichols-Herreshoff furnaces roast the coacentrate to a calcine of average conlposition (first 10 months of 1938): Zn, 67.69 per cent; Pb, 0.06; insoluble, 1.75; SiO², 1.26; Fe, 7.24; CaO, 0.47; MgO, 0.36; S, 1.88; Cd, 0.1; Cu, 0.07'; Mn, 0.27. The sulphur dioxide gas, after passing through a waste-heat boiler, proceeds through a recently redesigned low-resistance gas-purification assembly to the contact sulphuric acid plant, of which the capacity is 200 tons of concentrates per day. The calcine is mixed with a portion of returned furnace residues and sintered on 42-in, by 44-ft. Dwight-Lloyd sintering machines, gas-fired. Wind-box gases pass through air coolers before filtering in a 1440-bag Dracco unit, and thence to stack. The Dracco fume is mixed with Cottrell dust, from roaster gas cleaning, and sent to the leach plant, where it is roasted (SO² to acid plant) and leached with sulphuric acid to recover, as end products, lead sulphate, zinc sulphate and cadmium.

Jan 1, 1943

By George F. Weaton, Carleton C. Long

Two years ago the general features of the St. Joseph Lead Company's zine-smelting process were described.' At that time the discussion was limited to a description of the production of high-purity electrothermic zinc oxide. The present paper will describe the commercial production of electrothermic zinc metal. Since a fairly complete description of the plant of the Josephtowlz smelter was given in the earlier paper, the brief recapitulation given here will be limited to mention of additional equip-ment recently installed and a bare outline of the preparatory process. The raw material is zinc sulphide concentrate received from the company's mines in St. Lawrence County, New York. An average dry-weight analysis of this material is: Zn, 58.28 per cent; Pb, 0.56; insoluble, 1.6; SiO², 1.12; Fe, 6.4; CaO, 0.47; MgO, 0.27; S, 31.9; Cd, 0.1; Cu, 0.06; Mn, 0.24. Moisture content is usually about 3 per cent. Three 21-ft. 6-in. diameter, 12-hearth Nichols-Herreshoff furnaces roast the coacentrate to a calcine of average conlposition (first 10 months of 1938): Zn, 67.69 per cent; Pb, 0.06; insoluble, 1.75; SiO², 1.26; Fe, 7.24; CaO, 0.47; MgO, 0.36; S, 1.88; Cd, 0.1; Cu, 0.07'; Mn, 0.27. The sulphur dioxide gas, after passing through a waste-heat boiler, proceeds through a recently redesigned low-resistance gas-purification assembly to the contact sulphuric acid plant, of which the capacity is 200 tons of concentrates per day. The calcine is mixed with a portion of returned furnace residues and sintered on 42-in, by 44-ft. Dwight-Lloyd sintering machines, gas-fired. Wind-box gases pass through air coolers before filtering in a 1440-bag Dracco unit, and thence to stack. The Dracco fume is mixed with Cottrell dust, from roaster gas cleaning, and sent to the leach plant, where it is roasted (SO² to acid plant) and leached with sulphuric acid to recover, as end products, lead sulphate, zinc sulphate and cadmium.

Jan 1, 1943

By L. P. Davidson

ThE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to stor- age tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching pried, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid—-eithcr as acid or as sulphate sulphur in the calcine—because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60" Bè. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1943

By L. P. Davidson

ThE new electrolytic zinc plant of the American Zinc Company of Illinois commenced operation in April 1941. The simple flowsheet using the standard current density and the economic reasons that dictated it are given herewith. The Evans-Wallower Zinc Co. built an electrolytic zinc plant at Monsanto, Ill., in 1929 and operated it for about two years. The plant stood idle from 1932 and was purchased by the American Zinc Co. in 1940. Because of the condition of the equipment, excepting the motor generator set, a complete rebuilding was necessary. The Fairmont City plant of the American Zinc Co. could treat the leach residues, the purification cake and the skimmings from the melting furnace in its various plants. This possibility permitted a simple flowsheet with good economic results. The flowsheet is shown in Fig. I. The calcined concentrates are leached in mechanically agitated tanks with spent electrolyte and such ferric iron solution as necessary. When the acid has been neutralized and the iron coagulated, the fluid is discharged to settling tanks. The underflow from these thickeners is filtered on a Moore filter; the filter cake leaves the plant for retreatment and the filtrate joins the thickener overflow. Zinc dust is added to this solution until the copper and cadmium are precipitated. The pulp is filtered through Shriver presses, which deliver the purified solution to stor- age tanks, and the copper-cadmium-zinc cake is shipped for retreatment and recovery of these three metals. The purified solution is electrolyzed; the regenerated acid is returned for use in the leaching plant and the cathode zinc, after stripping, goes to the melting furnace, from which it is cast in slabs. The skimmings from the melting furnace are shipped to the Fairmont City plant for reduction to metal in the retort furnaces. The choice of this simple flowsheet was made possible only because of the facilities of the Fairmont City plant. The long leaching pried, with high acid content and high temperature which characterize the high-density process, gives a higher zinc extraction but also dissolves more impurities, which must be removed. The same is true to a lesser degree of the multi-step leaching of the western low-density plants. By the sacrifice of some initial extraction, solutions can be obtained that are relatively easy to purify and give good ampere efficiency. This loss in initial extraction is made up in the retreatment of the residues in the Waelz plant. The impurities that accompany the zinc thus extracted are inconsequential when the Waelz product is treated in a distillation plant. It was recognized that this flowsheet would require a somewhat greater amount of sulphuric acid—-eithcr as acid or as sulphate sulphur in the calcine—because of poorer washing. The sulphuric acid plant at Fairmont City could deliver 60" Bè. acid to compensate for the sulphate loss and the cost would be less than the cost of more intensive washing.

Jan 1, 1943

By Frederic Benard

Recovery of selenium and tellurium at Copper Cliff by the Ontario Refining Co. has been previously described by the writer.l During 1935 a new building was erected to house this operation and description of the new plant and process form the subject of this paper. The building, of modern steel and tile construction, covers an area of 5900 sq. ft. with a volume of approximately 166,000 cu. ft. The large monitored center bay is flanked by two smaller outside bays, one of which is devoted to the tellurium section. All equipment, ceilings and upper walls, are treated with aluminum paint, giving good illumination and facilitating good housekeeping, essential from a health standpoint in handling material of this nature. Equipment Layout and type of equipment conforms to the requirements of the process as described below. In the selenium section, storage tanks, neutralizing tanks and precipitators are of steel construction, lead-lined and arranged for gravity flow (Fig. 1). The neutralizing tanks are equipped with water-cooled lead coils for controlling solution temperature, agitation being accomplished with compressed air. The precipitators are provided with mechanical agitators, and sulphur dioxide is introduced into the solution through 1/2-in. lead pipes leading from a manifold attached to the cover of the precipitator. Each precipitator has internal cooling coils and an air-jet exhauster to carry off fumes. Neutralized solutions are filtered in a 29-plate wooden filter press using heavy cotton duck as a filter medium, forced feed being maintained by a Welmet centrifugal pump. Dilute solutions are concentrated by evaporation in a vacuum evaporator, constructed of cast hard lead. Heat is supplied by an outside steam chest operating under 15 Ib. steam pressure. The solution is circulated through the steam chest by a pump of antimonial lead at a rate approximating 400 cu. ft. per min. The evaporator is evacuated by a water-jet condenser that creates a vacuum of 26 in. of mercury under normal operating conditions. The capacity of the vessel is 60 cu. ft. and the rate of evaporation 25 cu. ft. per hour.

Jan 1, 1943

By Frederic Benard

Recovery of selenium and tellurium at Copper Cliff by the Ontario Refining Co. has been previously described by the writer.l During 1935 a new building was erected to house this operation and description of the new plant and process form the subject of this paper. The building, of modern steel and tile construction, covers an area of 5900 sq. ft. with a volume of approximately 166,000 cu. ft. The large monitored center bay is flanked by two smaller outside bays, one of which is devoted to the tellurium section. All equipment, ceilings and upper walls, are treated with aluminum paint, giving good illumination and facilitating good housekeeping, essential from a health standpoint in handling material of this nature. Equipment Layout and type of equipment conforms to the requirements of the process as described below. In the selenium section, storage tanks, neutralizing tanks and precipitators are of steel construction, lead-lined and arranged for gravity flow (Fig. 1). The neutralizing tanks are equipped with water-cooled lead coils for controlling solution temperature, agitation being accomplished with compressed air. The precipitators are provided with mechanical agitators, and sulphur dioxide is introduced into the solution through 1/2-in. lead pipes leading from a manifold attached to the cover of the precipitator. Each precipitator has internal cooling coils and an air-jet exhauster to carry off fumes. Neutralized solutions are filtered in a 29-plate wooden filter press using heavy cotton duck as a filter medium, forced feed being maintained by a Welmet centrifugal pump. Dilute solutions are concentrated by evaporation in a vacuum evaporator, constructed of cast hard lead. Heat is supplied by an outside steam chest operating under 15 Ib. steam pressure. The solution is circulated through the steam chest by a pump of antimonial lead at a rate approximating 400 cu. ft. per min. The evaporator is evacuated by a water-jet condenser that creates a vacuum of 26 in. of mercury under normal operating conditions. The capacity of the vessel is 60 cu. ft. and the rate of evaporation 25 cu. ft. per hour.

Jan 1, 1943

By W. M. Weigel

The first successful use of the wire saw in slate quarrying in the United States was late in 1926, at the quarry of the Colonial Slate Co. near Wind Gap, Pa. This installation was sponsored and supervised by the United States Bureau of Mines in collaboration with the National Slate Association.' The success of this trial resulted in other installations of wire saws, so that 27 were in operation at Pennsylvania slate quarries2 by October, 1928. Marble Quarrying with a Wire Saw Until recently, little or no attempt has been made to use the wire saw in the quarrying of other stone, but it is believed that its successful use in slate will be followed by attempts to take advantage of its possibilities in other quarrying operations. An example of such a trial is the recent installation of a wire saw at the marble quarry of the Saint Clair Marble Co. near Guion, in the Ozark region of northern Arkansas. This quarry is in a comparatively new district and the decision to open and develop it had to be made in the face of many unknown factors. For this reason, it was essential that the development costs be held at a minimum, and as a wire saw could be installed more cheaply than standard channeling equipment, it was decided to try it out. One factor Largely controlling the decision was that the location was peculiarly adapted to this method. The point of development selected was on the rather abrupt end of a ridge formed on the south by an almost perpendicular bluff along the White River and on the north by a rather steep slope with little or no overburden. By taking advantage of this topography it was possible to place the supporting standards for the sheaves at both the outer and driving end without the necessity of drilling or excavating openings to receive them, and to locate the motive power in line with these standards, which made it unnecessary to deflect the sheaves.

Jan 1, 1931

By A. G. H. Anderson, Eric R. Jette

During the period from 1910 to 1920, there was a lively interest in the subject of grain growth and many papers were published, followed by interesting discussions. Questions dealing with the fundamentals of grain growth—why and how it occurs—were treated in papers by Howe,' .Jeffries,² Sauveur,² Chappell,4 Beilby,5 Mathewson and Phillips,6 Mc Adam,7 Carpenter and Elam,8 Stead and Carpenter,9 Ruder,l0 as well as others. Since that decade, much indeed has been done regarding the practical control of grain size, and it is now possible to order material having a size sperified in the American Society for Testing Materials classification. Also, one hears the term "spliced boundaries" used in connection with certain tungsten lamp filamentsl1 wherein it is important to prevent "sagging" between consecutive turns of the helix.12 This practical use of a certain knowledge as to the things that influence or even control grain growth should not be taken as an indication that the subject has been thoroughly explored and that nothing more can be learned from fundamental studies. It is with this thought in mind that a report of some observations and experiments on abnormal grain growth is believed justified. Abnormal grain growth is met with in heat-treating high-carbon steels in the austenitic range,'? in the hardening treatments of high-speed steels,14'15 and in the low-temperature annealing of strained low-carbon steels as in sheet and wire material. Entirely aside from these instances of exaggerated grain growth, which some might consider as freakish, it is thought that abnormal growth is simply a case where the growth forces and the forces tending to prevent growth are almost, but not quite, evenly balanced. Information relative to grain-growth characteristics in general may be obtained from a study of abnormal growth conditions, which may be looked upon as vantage points. Reflection will show at once that if growth forces are great in comparison to inertia or resistance to growth, many crystals start to grow and, for that reason, none becomes very large, whereas if inertia is

Jan 1, 1938

By Eric R. Jette, A. G. H. Anderson

During the period from 1910 to 1920, there was a lively interest in the subject of grain growth and many papers were published, followed by interesting discussions. Questions dealing with the fundamentals of grain growth—why and how it occurs—were treated in papers by Howe,' .Jeffries,² Sauveur,² Chappell,4 Beilby,5 Mathewson and Phillips,6 Mc Adam,7 Carpenter and Elam,8 Stead and Carpenter,9 Ruder,l0 as well as others. Since that decade, much indeed has been done regarding the practical control of grain size, and it is now possible to order material having a size sperified in the American Society for Testing Materials classification. Also, one hears the term "spliced boundaries" used in connection with certain tungsten lamp filamentsl1 wherein it is important to prevent "sagging" between consecutive turns of the helix.12 This practical use of a certain knowledge as to the things that influence or even control grain growth should not be taken as an indication that the subject has been thoroughly explored and that nothing more can be learned from fundamental studies. It is with this thought in mind that a report of some observations and experiments on abnormal grain growth is believed justified. Abnormal grain growth is met with in heat-treating high-carbon steels in the austenitic range,'? in the hardening treatments of high-speed steels,14'15 and in the low-temperature annealing of strained low-carbon steels as in sheet and wire material. Entirely aside from these instances of exaggerated grain growth, which some might consider as freakish, it is thought that abnormal growth is simply a case where the growth forces and the forces tending to prevent growth are almost, but not quite, evenly balanced. Information relative to grain-growth characteristics in general may be obtained from a study of abnormal growth conditions, which may be looked upon as vantage points. Reflection will show at once that if growth forces are great in comparison to inertia or resistance to growth, many crystals start to grow and, for that reason, none becomes very large, whereas if inertia is

Jan 1, 1938

By Carl E. Swartz

In the course of a recent investigation1 to develop a more satisfactory white-metal bearing alloy, a number of alloy systems were studied. The cadmium-nickel system showed characteristics desirable in a bearing alloy, and the system was therefore studied in some detail. Experimental Method Alloying cadmium with nickel offered no serious difficulty. After melting the cadmium, clean sheet nickel was added while the temperature was maintained at 500" to 600" C. A few crystals of ammonium chloride2 served to clean the nickel when the latter did not "wet" readily. In preparing the individual alloys for thermal and microscopic investigation, a "hardener" containing about 10 per cent nickel was used. Thermal Experiments and Apparatus Time-temperature cooling curves were made by standard methods. Globe electrolytic cadmium was added to the hardener to make a melt of the desired composition weighing between 100 and 200 grams. This charge was placed in a Pyrex test tube, 1 by 10 in., closed with a rubber stopper carrying a thermocouple sheath and quartz stirring rod. The assembly was lowered to a depth of about 4½ in. into an electric resistance pot furnace containing a No. 0000 clay-graphite crucible (to catch the melt in case of a break in the test tube). After the tube was clamped in this position, an asbestos-magnesia mixture was loosely packed in the furnace around the tube and a "halved" cover of transite placed on top. This left at least 5 in. of the test tube protruding from the furnace. When the alloy had melted, the thermocouple was adjusted so that the hot junction was l! in. from the bottom of the test tube. The melt was stirred thoroughly for several minutes to insure composition homogeneity and absence of thermal gradients.

Jan 1, 1934

By Wm. Reuben Webster

Brass is an alloy of copper and zinc. The brass containing 70 per cent copper and brasses (using this term to denote all useful 30 per cent zinc. Fig. 3 shows the effect of proportions of the two constituents) are the annealing at various temperatures on the most valuable and widely employed of all same alloy. This effect is somewhat modi- nonferrous alloys, because of their high resistance to ordinary corrosive agencies and the very wide range of properties that may be imparted to them by variations in the proportions of the constituents and by variations in mechanical treatment and heat-treatment. Fig. I shows the normal physical properties, as determined by standard tensile tests, of the series when in the annealed condition. Fig. 2 shows the effect of varying amounts of cold-working on an almost pure fied by the degree of cold-working to which a brass has been subjected, as shown by Fig. 4. A fourth test, which is empirical, has been found useful because of its simplicity —the hot hammer test. Samples 1/2 in. in diameter and 3/4 in. long are placed in a suitable furnace. These are withdrawn one at a time. at successively higher temperatures and are subjected to the blow of a drop hammer weighing 50 lb. with a drop of 4 ft. The percentages of reduction in length of the cylinders are plotted against temperatures and give a camparative measure of plasticity at different temperatures. The results of this test on several

Jan 1, 1942

By Wm. Reuben Webster

Brass is an alloy of copper and zinc. The brass containing 70 per cent copper and brasses (using this term to denote all useful 30 per cent zinc. Fig. 3 shows the effect of proportions of the two constituents) are the annealing at various temperatures on the most valuable and widely employed of all same alloy. This effect is somewhat modi- nonferrous alloys, because of their high resistance to ordinary corrosive agencies and the very wide range of properties that may be imparted to them by variations in the proportions of the constituents and by variations in mechanical treatment and heat-treatment. Fig. I shows the normal physical properties, as determined by standard tensile tests, of the series when in the annealed condition. Fig. 2 shows the effect of varying amounts of cold-working on an almost pure fied by the degree of cold-working to which a brass has been subjected, as shown by Fig. 4. A fourth test, which is empirical, has been found useful because of its simplicity —the hot hammer test. Samples 1/2 in. in diameter and 3/4 in. long are placed in a suitable furnace. These are withdrawn one at a time. at successively higher temperatures and are subjected to the blow of a drop hammer weighing 50 lb. with a drop of 4 ft. The percentages of reduction in length of the cylinders are plotted against temperatures and give a camparative measure of plasticity at different temperatures. The results of this test on several

Jan 1, 1942

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: d= Zlxl(xl - P) + Zsxs(P - xs)/Zl(xl - P) + Zs(P - xs) [1] where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, Xl and 28 are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The 6 equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid- to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By Morris Cohen, William P. Kimball

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expression for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: d= Zlxl(xl - P) + Zsxs(P - xs)/Zl(xl - P) + Zs(P - xs) [1] where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, Xl and 28 are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The 6 equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid- to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling, the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By William P. Kimball, Morris Cohen

This paper deals with the calculation of the composition of the infinitesimal trace of alloy that transfers from the liquid to the solid state at each temperature during the equilibrium solidification of a binary solid solution, and which thereby enables the compositions of the coexisting liquid and solid phases to follow along the liquidus and solidus lines respectively during the cooling. A general expressioll for the composition (6) of the liquid-to-solid transfer at each temperature has been derived: , = Zlxl{xl - P) + ZsXsiP - xs) [I] Zl(xl -P)+ Zs{P - xs) where ZL and Zs are the slopes of the liquidus and solidus lines at the given temperature, xl and xs are the compositions of the stable liquid and solid phases at the same temperature, and P is the composition of the alloy under consideration. The d equation is valid for the process of equilibrium heating as well as cooling, and may be applied to vapor-to-liquid, vapor-to-solid, liquid-to-liquid, and solid-to-solid transfers if the corresponding equilibrium diagrams are known. The d-versus-temperature curves for two alloys P1 and P2 are shown in Fig. I. In each case, the liquid-to-solid transfer has the same composition as the stable solid phase only at the temperature of the beginning of solidification, and has the same composition as the stable liquid phase only at the temperature of the completion of solidification. At each intermediate temperature, the composition of the liquid-to-solid transfer differs by a finite amount from those of the two coexisting phases. Therefore, during equilibrium cooling. the transfers must merge into the solid phase from the liquid without forming a transition phase; otherwise the condition of equilibrium would be violated. At any given temperature during solidification, the composition of the liquid-to-solid

Jan 1, 1941

By Eric R. Jette

In order to control a chemical process by other than empirical, rule of thumb methods, two types of knowledge concerning the reactions involved must be available: (1) the thermodynamics of the reactions, and (2), by no means less important for efficient operation, the mechanisms and kinetics of the reactions. Information on the thermodynamic side enables the operator to decide upon initial and final conditions, whether heat must be added or removed from the system, whether the reactions proceed farthest in the desired direction at high pressure or low, etc. Knowledge of the mechanisms involves the determination of the individual steps by which an initial set of reactants, under given conditions, proceed to give the desired final products and kinetic studies upon which the mechanisms are based give the speed at which each of these reactions or steps take place. Thus thermodynamic studies of a reaction enable the operator to control the direction and extent to which the reaction can proceed, while kinetic studies enable him to control rates and thus the time efficiency of the operations. The thermodynamics set the limit to which the reacting system approaches; the kinetics tell how fast the system actually approaches this limit. The two types of information are complementary and not antagonistic even though in discussing the mechanism the introduction of thermodynamics is entirely needless and generally of no assistance, while in thermodynamic studies mechanism need not even be mentioned. Heterogeneous Reactions The thermodynamic side of metallurgical reactions has received much attention in the past; the mechanisms, relatively, very little. The main reason for our present lack of information on the mechanisms of these reactions lies in the fact that every one of importance is a heterogenkous reaction; i. e., the substances involved in the reaction exist in more than one phase, while, if we neglect the large amount of work which has been

Jan 1, 1931

By J. J. Egan, A. B. Kinzel, W. Crafts

Advances in the production of quality steel have emphasized the need for greater knowledge of the amount and distribution of oxygen in the steel. Control of inclusion content and quality is largely dependent on such knowledge. While many analytical methods have been devised for the accomplishment of this end, few are without serious limitations in accuracy, convenience, or skill required in application. Usually at least two methods are necessary to determine total oxygen and constituent oxides. Because of the great importance of this problem and the specific interest in the application of such methods of analysis, the various procedures were carefully reviewed at the Union Carbide and Carbon Research Laboratories, with the view of developing a method free from the limitations mentioned above. Intensive experimentation finally led to an improved iodine extraction analysis described by Cunningham and Price.1 After this had been thoroughly checked from the standpoint of the analytical chemist, it was rechecked from that of the metallurgist. This involved preparation of a number of small heats of varying composition with determination of total oxygen in the molten metal by the alumina method2 and an analysis of the solidified material without the aluminum addition by means of iodine extraction; the oxides of iron, manganese, silicon and aluminum also being determined by the iodine analysis. The report of this work constitutes the subject of this paper. The Iodine Method Fundamentally the iodine method is well established. It is based on the procedure first described by Eggertz3 and depends upon the fact that iron, manganese, silicon and aluminum, as well as the metallic constituents of the pertinent sulfides, carbides and nitrides of these metals

Jan 1, 1933