Search Documents

By A. B. Kinzel

SILICON and its metallurgical uses have been the subject of speculation since the earliest days of modern civilization. The early philosophers, Theophrastus and Pliny, believed that silica was a special form of ice, an opinion that was not seriously challenged until the seventeenth century. The first comprehensive view of the nature of silica was advanced by Lavoisier in 1787. He assumed silica to be an oxide of an unknown metal. In 1808 Berzelius produced ferrosilicon by heating silica, iron and charcoal. Probably the first produc¬tion of crystallized silicon was in 1854 when H. St. C. Deville accidentally produced the material while electrolyzing a double chloride of aluminum and sodium containing siliceous impurities. It is not strange that the early investigators should have given so much attention to silica and silicon, because of the great natural abundance of the former. Although silicon does not exist in the elemental state in nature, it has been estimated that the lithosphere contains approximately 60 per cent silica; quartz and rock crystal are found in practically every part of the world.

Jan 1, 1933

By W. J. Wrazej

THE measurements on the formation of multi-layered scales on pure iron1 and the metal -lographic examination of the produced layer of FeO, Fe,O,, and Fe2O3 shown in micrographs2 throw much interesting light on this apparently well-known subject. Professor Paidassi announced2 that in a few months7 time further results are going to be published with regard to the growth of Fe2O3 and Fe2O3 layers on an Armco iron as a function of temperature. Because of the very thin layers of Fe2O3 which are shown by Paidassi (Fig. 10 of ref. 2) when samples were scaled in air at 700°C for 4 hr and because this is not in agreement with the present author's previous observations, the following experiment was recently carried out. Polished cylindrical samples 13/64 in. in diam and 1/4 in. long from electrolytic iron used for spectro-graphic work (Hilger, H.S. Iron rods, F.693) and an Armco iron sample 1/4 in. in diam of the same length were suspended in a muffle furnace on Nichrome wire and annealed in air for 4 hr at 700°C 5OC. Because of the known easy peeling off of the Fe2O3 layer which is mainly in the form of powder (purple red dust on the surface) the samples were protected against any draft and shock. After annealing, the samples were cooled in air and placed in the mount-

Jan 1, 1954

Discussion of the paper of F. C. LANGENBERG and R. G. WEBBER, presented at the New York meeting, February, 1915, and printed in Bulletin No. 98, February, 1915, pp. 291 to 300. HENRY M. HOWE, Bedford Hills, N. Y.-The results here given are of great interest and are welcome as forming another rivet to increase the stability of our present theories of the constitution and properties of steel. The important discovery is that the hysteresis increases with the fineness of the structure, that is to say with the extent of contact between the particles of ferrite and cementite. All of the specimens except No. 4 consist of ferrite and cementite of different degrees of intimacy of admixture. If hysteresis represents something akin to surface friction, which retards the rotation of the ferrite on the application and release of the magnetizing force, then it is only natural that it should increase as it does with the intimacy of admixture, because it is at the surface of contact of a given particle of ferrite with the neighboring particles of cementite that this friction is to be expected, and of course the extent of surface must in¬crease with the intimacy of admixture. The somewhat greater hardness of specimen 4 than of the others may perhaps he referred to the principle discussed in my paper, Why Does Lag Increase with the Temperature from Which Cooling Starts?' The furnace-cooled specimens were cooled so slowly that the influence of the initial temperature of heating is effaced. But in the air-cooled specimens we have the suggestion that the high temperature, 1,000°, from which the cooling of No. 4 started has prevented the completion of the transformation, with the result that the metal is slightly harder than any of the others. The difference is not to be explained by difference in the fineness of structure, because the whole range of fineness from No. 1 to No. 6 is accompanied by no change in hardness, the only change being an appreciable increase of hardness following the air cooling from 1,000°.

Jan 5, 1915

By C. C. Whittier

PLANS are well matured for the joint meeting of the Coal Division and the Ohio Section of the Institute at Columbus, Ohio, Oct. 27 and 28, at which a large attendance is expected. The proceedings for a day and a half will be devoted largely to the uses of coal, the program providing for two technical sessions in the auditorium of Battelle Memorial Institute (505 King Ave.) on Friday, and various plant inspec¬tions on Saturday morning. By way of diversion on Saturday afternoon arrangements have been made for attendance en bloc at the football game between Ohio State and Northwestern, 100 seats having been reserved for the game at $2.40 each-as long as they last. An inventory of the high lights of the meeting would be incomplete without reference to the informal banquet at the Deshler-Wallick hotel on Friday evening, for which Eli T. Conner, Chairman of the Coal Division, is down for a talk, and Howard N. Eavenson, Vice-president of the Institute, will be the principal speaker. The program in detail is as follows:

Jan 1, 1933

By J. A. Fellows, Earnshaw Cook, H. S. Avery

THE increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni; 16 per cent Cr, 35 per cent Ni; 12 per cent Cr, 60 per cent Ni; etc.) in recent years has been accompanied by continued demands by the consumer for improvement in properties. The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties. To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created. It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloy presented in a companion paper.? The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized. THE CREEP TEST Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure. The creep-test laboratory constructed for the American Brake Shoe and Foundry Co. is designed to permit 1000-hr. tests in the temperature range of 1200° to 2200°F. with a choice of applied stress extending from 50 to 50,000 lb. per sq. in. in increments of 50 lb. per sq. in. To simplify the calculation of weight combinations, the loading beams (Fig. I) are provided with counterweights to eliminate the tare. The precision of the knife-edges (10.1 ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a 1-gram weight attached to the loading shackle. Check of the loading weights proved the maximum error to be 0.06 per cent. Axial alignment is provided by crossed knife-edges in the grip seats. The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U.S. Steel Corporation. An 80 per cent Pt, 20 per cent Rh No. 19 B. and S. gauge wire is used as the heating element. The details of construction are shown in the radiograph reproduced in Fig. 2. The windings are held in place on an alundum tube with alundum cement; the distribution of turns is adjusted to give a maximum temperature gradient of ± 1°F. over a 4-in. gauge length (Fig. 3). To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length. Sixteen-inch coupons are used to reduce the temperature of the threaded

Jan 1, 1942

By F. C. Langenberg, J. Chipman

New data on the distribution of silicon between slag and carbon-saturated iron at 1600oand 1700oC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1700°C for slags containing up to 20 pct Al2O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A1203-SiO2 slags over a range from zero pct A12O3 to saturation with A12O3, or CaO.2A12O3. The upper limit of SiO, is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently, 4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/A12O3 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al2O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al2O3 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al,O3 and of A120,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO, (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2 The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By Charles W. Perry

The options of enhanced oil recovery, coal syncrude, and shale syncrude are compared by approximately equivalent economics. The physical constraints for the major enhanced oil recovery processes are described, followed by new estimates of cost. The range for all three options in terms of light syncrude equivalent are $22 to $40 per barrel in 1980 dollars.

Jan 1, 1982

By L. H. DeWald

During the examination of various commercial brands of copper wire bars, which had exhibited different degrees of adaptability for being drawn into fine gages of wire by the present-day high speed machine, it was found that each brand had a more or less characteristic crystal macrostructure. The extremes of these macrostructures are similar FIG. 1.-EFFECT OF METAL TEMPERATURE IN CASTING ON CRYSTAL MACROSTRUCTURE OF BAR. Reading from left to right, metal temperatures were 1166" C., 1149" C., 1132" C.. 1121" C., 1093" C. to the maximum variation shown in the photomacrographs reproduced in Fig. 1. As the various brands did not differ materially in chemical composition, it was concluded that the differences in structure were the result of variations in casting technique.

Jan 1, 1931

By E. R. Kaiser

ACTIVITY on long-range and on immediate wartime problems shared the attention of specialists in coal research during 1943. Programs of the principal coal laboratories were more adequately financed than in previous years, but all reported shortages of technical personnel. Expansion in coal research in the year to come will depend primarily on the availability of qualified research talent.

Jan 1, 1944

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

Jan 1, 1959

By P. Chiotti, R. J. Hecht

Vapov pressure data of solid and liquid alloys along with phase diagram data WERE employed in calculating the thermodynamic properties for the Ca-Zn system. The relative excess partial molal free energy for zinc in the liquid alloys was fitted to the relation wnvre i is we tvmpvrutiirc in ucgrees neivtu ana in is the tr~ole fvaction. Relations for the standard free energy of fortnation for the eight cornpounds were developed. ThE phase diagram for the Ca-Zn system as determined by Messing et a1.' is reproduced in Fig. 1. Earlier work on the phase diagram has been summarized by Hansen and Anderko2 and the very limited thermodynamic information for this system has been reviewed by Hultgren et a1.3 The heat of fusion for the compound CaZn2 has recently been determined to be 9260 cal per mole.4 Solubility data for calcium in zinc for the temperature range of 650" to 725°C were fitted by the relation and reported by Johnson and Dilloon5 In the present investigation zinc vapor pressure data were obtained by both the dewpoint and Knudsen methods in order to calculate the thermodynamic properties for liquid and solid alloys. The dewpoint method as employed in this work requires that only one of the components be significantly volatile, in this case zinc, and that the vapor pressure of pure zinc be known. For calculation purposes the vapor pressure data for pure zinc3 were fitted to the relations; for temperatures below 692.7K, the melting point of zinc. The corresponding free-energy relations for vaporization and sublimation of pure zinc are respectively. Some of the calculations also required knowledge of the free energy of fusion of zinc and calcium and the free energy for the 721°K allotropic transformation of calcium. The free energy of fusion of zinc was taken to be the difference between Eqs. [4] and [5], or The free energy of fusion and transition for calcium were based on the enthalpy values of 2040 and 222 cal per g-atom, respectively, as reported by Chiotti et al. 4 and the heat capacity data given by Hultgren et a1.3 and are represented by the relations, In the latter expression the difference in heat capacity between the a and 0 forms of calcium was neglected. MATERIALS AND EXPERIMENTAL PROCEDURES The metals used in preparing the alloys were Bunker Hill slab zinc, 99.99 pct pure, and Ames Laboratory calcium. The average impurities in the calcium in parts per million by weight, ppm, were N-17, H—77, Ba—216, Mg-15, Si—7, C—157, and Fe—9. The zinc was cleaned in dilute nitric acid and the calcium was used as received. The calcium was stored and handled in an argon-filled glove box and when removed from the dry box it was kept in an argon-filled desiccator. Tantalum was found to be a suitable alloy container. The alloy components were contained in a 1-in.-diam cylindri-

Jan 1, 1968

By C. C. Whittier

CIVILIZATION'S PROGRESS, which has multiplied man's comforts, conveniences, a n d happiness, is based upon the extensive employment of natural minerals and sources of energy. Mineral resources are basic factors in modern economic development, machine industry, international trade and world power. A survey of mineral consumption shows that the United States leads the world in the production and consumption of energy materials, of metals, and of the large and diverse array of earth materials that fall in the nonmetallic mineral group. The use of nonrnetallic minerals exceeded both the metals and the fuels in the long period before the industrial age, but it is only in the last two decades that consumption of non- metals has kept pace with and approximated in value the output of metals. Although the data of production in the first half of the last century are meager and fragmentary, the record of the past fifty years-the period of most rapid growth-is available, and reveals an astounding growth.

Jan 1, 1933

By Sadtler, C. B.

IT is generally assumed that in most metals and alloys a given tensile stress produces a given deformation irrespective of the length of time during which the stress is applied. This assumption is justified in most of the important engineering applications of metallic materials; however, in the case of some metals and alloys used or tested at temperatures over or slightly under that at which recrystallization can occur the assumption is not warranted.1 This paper deals with the variations of deformation produced by a constant tensile stress acting for varied lengths of time in the special case of thin aluminum alloy sheet of the duralumin type, which had been subjected to different thermal and mechanical treatments. The material investigated was in the form of a sheet approximately 0.002 in. thick, which had been cold-rolled from a thickness of 0.020 in. It has been found that at a sufficiently high constant tension such material deforms continuously with the elapse of time and that the rate at which this deformation occurs is greatly influenced by the previous thermal and mechanical treatments.

Jan 1, 1927

By Carl Wagner

AT elevated temperatures. most metals react with oxygen, sulphur, or halogen rather rapidly, although a coherent layer of the reaction product is formed and separates the two reactants from each other. The reaction proceeds, since one of the reactants or both dissolve and diffuse across the reaction product. In many cases the rate is diffusion-controlled as is indicated by the validity of the parabolic rate law of Tammann' and Pilling and Bed-worth. wott and Gurney' have suggested that diffusion processes also play an important part in the case of reduction reactions. This is confirmed by observations reported below. In general, however, the rate of reduction reactions is determined not exclusively by diffusion processes. Reduction of Silver Sulphide Above 179°C silver reacts with liquid sulphur very rapidly. Since the volume of silver sulphide is much greater than that of the equivalent amount of silver, a coherent layer of silver sulphide is formed in accordance with a rule established by Pilling and Bedworth.' According to Wagner','' silver ions and electrons migrate from the Ag-Ag,S interface across the silver sulphide layer to the Ag,S-S interface where the following chemical reaction takes place: 2 Ag +2 e + S Ag,S If silver sulphide is reduced by means of hydrogen, the equivalent volume of the reaction product, silver, is less than that of the initial substance. Accordingly, no coherent layer of silver is formed. Instead, fine filaments of silver grow from the silver sulphide surface into the ambient gas. This phenomenon has been investigated by many authors, especially by Kohlschiitter," who has also reviewed previous literature. Kohlschiitter has interpreted the observed phenomena by migration of "silver" dissolved in silver sulphide. According to Wagner,' silver ions and electrons are the migrating particles. The sequence of consecutive steps involved in the reduction of silver sulphide is shown in Fig. 1. Every- where at the silver sulphide surface, hydrogen reacts with sulphur so that excess silver ions and electrons are formed, which migrate at random until they are captured by a nucleus of metallic silver. If such a nucleus lies on the surface and material is furnished only from the base, the original nucleus is pushed outward and thus a filament grows. Removal of sulphur and formation of metallic silver may also take place at different points when silver sulphide is reduced by copper. The reaction is usually formulated as: AgL,S + 2 Cu = Cu.S + 2 Ag but the actual reaction products are silver and a solid solution of the two sulphides. Primarily, excess silver and electrons dissolved in silver sulphide are formed. After a certain degree of supersaturation has been reached, nuclei of metallic silver may form. If, however, a silver foil is in contact with the silver-sulphide phase, as is shown in Fig. 2, silver ions and electrons will migrate to the Ag,S-Ag interface where they are captured. To confirm this scheme, a composite sample, with the geometry shown in Fig. 2, was made by pressing silver sulphide tablets 0.6 cm in diam and 0.4 cm high together with a copper cylinder and a silver foil in crucibles of iron, which does not react appreciably with silver sulphide at 400°C. After heating for 3 to 7 hr at 400°C. the specimens were cut normal to the phase boundaries. It was found that the thickness of the silver foil had increased from 0.01 cm as initial value to a maximum value of 0.06 cm. In the interior of the silver sulphide tablets only traces of metallic silver were observed. These observations show clearly that silver ions and electrons may migrate over distances of several millimeters before they form metallic silver. Reduction of Cuprous Sulphide by Iron The behavior of cuprous sulphide is very similar to that of silver sulphide, since the lattices of the high temperature modifications are identical, but in Cu.S there is a variable deficit rather than an excess of metal. To investigate the displacement of copper by iron, cuprous sulphide powder covered by a copper foil was pressed in iron crucibles and heated up to 800 °C for 3 to 7 hr. The thickness of the copper foil increased from an initial value of 0.005 cm to a nlaximum value of 0.029 cm. In the interior of the

Jan 1, 1953

By H. Y. Hunsicker

A graphic method has been devised for three-di-mensional analysis of hot deformation and for correlating the amount and directionality of the deformation with resulting directional properties. Deformation is evaluated in terms of dimensional change ratios referred to three orthogonal axes. Since all combinations of the three ratios can be represented in a triangular coordinate field with logarithmic scales, a two-dimensional chart of extent of deformation and degree of asymetry is possible. The entire gamut of shape changes from upsetting through flat-rolling to rod-rolling is accommodated. The resulting coordinate system is a base upon which can be represented the properties of the wrought products measured in the directions of the axes employed fir evaluating the deformation. When property data are available for many types and amounts of deformation, a three-dimensional figure can be constructed, and the projection of this figure is referred to as a ''3d'' chart. Experience in using such charts to plan fabricating operations for a variety of thick-section forged and rolled products of heat-treated aluminum alloys has verified its practical value for optimizing directionality relationships. MechANICAL anisotropy of thick section products of heat-treatable aluminum alloys is recognized by producers and users of these products, and the extent of the directional differences is apparent in property tabulations included in handbooks, standards, and specifications.' Attention has also been directed to the existence of important directional differences in the resistance of these products to stress-corrosion cracking. Metallurgical structure factors responsible for these directional differences include, among other possibilities, shape and alignment of grains, voids and nonmetallic inclusions (when present), volume fraction and spatial distribution of secondary phase particles and solid-state precipitates, crystal-lographic textures, and Bauschinger effect. The contributions of the individual factors vary with alloy composition, heat-treated temper, type of working process (forging, rolling, extrusion), and the amount and directional nature of the deformation. In general, the cast ingot used as the starting material for producing these wrought products exhibits only a modest degree of directionality. A monotonic and continuous transition from this nearly isotropic state with progressive hot deformation would appear probable, assuming that the working temperature is sufficiently high to cause continuous dynamic recovery. Several years ago a project was undertaken to evaluate the effects of hot deformation and metallurgical structures on the directionality of thick wrought aluminum alloy products, and the method to be described was developed as an analytical tool in this investigation. DIRECTION NOMENCLATURE The nomenclature system adopted by industry for the three mutually perpendicular directions employed in testing aluminum alloy products includes four terms: "longitudinal", "transverse", "long transverse", and "short transverse". These terms are conventionally related to the external geometry of the product but also by implication to the deformation and resulting metallurgical structure. Occasions arise in which through use of unusual fabricating methods, intentional or otherwise, the structure does not have the usual relationship to external geometry or may be very complex because of inhomogeneity of deformation throughout the piece. The longitudinal direction is generally parallel to the primary rolling direction or to the direction of extrusion. In the case of forging, it is parallel to the direction of maximum extension (not maximum "working" or "flow", as frequently stated). The term transverse is applied to any direction perpendicular to the longitudinal direction in a product having symmetry about the longitudinal axis, and generally, although not always, the deformation to produce these forms is nearly symmetrical in the transverse plane. This term then may be applied to a round, square, hexagon, or other polygonal, symmetrical shape produced by extrusion or rolling or by forging, if produced by a simple, symmetrical drawing procedure. The type of microstructure generally associated

Jan 1, 1970

By P. K. Koh, H. A. Lewis, H. F. Graff

New data on the distribution of silicon between slag and carbon-saturated iron at 1600Oand 1700OC are presented which, in combination with previously published data, permit the determination of silica activities over a broad range of compositions in the CaO-Al2O3-SiO2 system. The distribution of silicon between graphite-saturated Fe-Si-C alloys and blast furnace-type slags in equilibrium with CO has been described in previous publications.1"3 In this past work the silica-silicon relation was established at temperatures of 1425" to 1'700°C for slags containing up to 20 pct A12O3. This paper presents the results of additional studies at 1600" and 1700° C which extend the silicon distribution data at these temperatures for CaO-A12O3-SiO, slags over a range from zero pct Al2O3 to saturation with Al2O3, or CaO.2Al2O3. The upper limit of SiO2 is set by the occurrence of Sic as a stable phase when the metal contains 23.0 or 23.7 pct Si at 1600" or 1700°C, respectively. The activity of silica over the expanded range is determined directly from the distribution data.3 Recently4-7 other investigators have studied the activities of SiO, and CaO, principally in the binary system, using different methods and obtaining somewhat different results. EXPERIMENTAL STUDY The experimental apparatus and procedure have been fully described in previous publications.1, 3 Six new series of experimental heats have been made, four at 1600° and two at 1700°C. Master slags of several fixed CaO/Al203 ratios were pre-melted in graphite crucibles, and these were used with additions of silica to prepare the initial slag for each experiment. Slag and metal were stirred at 100 rpm and CO was passed through the furnace at 150 cc per min. The initial sample was taken 1 hr after addition of slag at 1600°C or 1/2 hr after addition at 1700°C. The run was normally continued for 8 hr at 1600°C or 7 hr at 1700°C, and the final sample was taken at the end of this period. Changes in Si and SiO2 content indicate the direction of approach to equilibrium, and in a series of runs where the approach is from both sides this permits approximate location of the equilibrium line. Fig. 1 shows the results of such a series of 15 runs at 1600°C for slags of CaO/Al,O3 = 1.50 by weight. Figs. 2 and 3 record other series at 1600°C and Fig. 5 a series at 1700°C with fixed CaO/Al0 ratios. The results of the experiments at 162003°C have been reported in part in a preliminary note.3 In the experiments recorded in Figs. 4 and 6, the slags were saturated with A12O3 (or with CaO.2A12O3 within its field of stability) by suspending a pure alumina tube in the melt during the course of the run. The final slag analyses were used to establish the liquidus boundaries8 in the stability fields of CaO.2Al2O3 and of Al20,. ACTIVITY OF SILICA The free-energy change in the reaction has been calculated by Fulton and chipman2 from recent and trustworthy data including heats of formation, entropies, and heat capacities. The more recent determination by Olette of the high-temperature enthalpy of liquid silicon is in satisfactory agreement with the values used and therefore requires no revision of the result which is expressed in the equation: SiO2 (crist) + 2C (graph) = Si + 2CO(g.) [1] &F° = + 161,500 - 87.4T The standard state for silica is taken as pure cristobalite and that of Si as the pure liquid metal. Since the melts were made under 1 atm of CO and were graphite-saturated, the equilibrium constant for Eq. [I] reduces to K1 = asi /asio2. The value of this constant is 1.77 at 1600°C and 16.2 at 1700°C. Through K1, the activity of silica in the slag is directly related to the activity of silicon in the equilibrium metal.

Jan 1, 1960

By W. E. Rice

The ceramic industry has to do with forming or molding articles of clay, and imparting to them their characteristic properties of permanence, strength and color by subjecting them to heat treatment in kilns. This heat treatment is commonly known as "firing" or "burning." The art of firing clay ware antedates the industrial use of coal; hence wood was the fuel first used, and the earliest kilns were built to burn wood. The majority of the clay ware produced today is fired in periodic kilns that are essentially enlarged structures similar to the earliest enclosed kilns; a kiln consists of a large chamber 16 to 32 ft. dia. (or rectangular) in which the ware is charged and fired either in direct contact with flame or hot gases from the fuel, or in saggers which shield the ware from direct contact with the gases. The fuel is burned in a number of small furnaces built in the thick wall that encloses the chamber; these furnaces are from 16 to 36 in. wide and from 3 to 5 ft. long; some of them have horizontal or sloping grates, but many have no grates; the last are called "dead-bottom" furnaces. The temperature necessary to mature the charge in the kiln varies for different clays; for some it is as low as 1800°, and for others as high as 2700" F. Wood was an ideal fuel for the low temperatures that were used in early kilns; it burns freely and produces a long, clean flame, which promotes uniform distribution of the heat in the kiln; it does not coke and so restrict the passage of air through the fuel bed; the ash does not melt in the fuel bed to form clinker; and the ash that is carried into the chamber and deposited on the charge does not contain iron and sulfur to discolor the clay. The extent of the ceramic industry now precludes the general use of wood in kilns, so that today this industry is one of the large users of bituminous coal, burning more than eight million tons annually in kilns. Manufacturing plants usually are at or near the source of clay, with deposits of coal suitable for kilns occurring near the clay. The cost of coal is the largest single item of expense in the manufacture of clay ware, and, because all coals are not equally suitable for the process, the careful selection of coal is important. In this selection the desidera-

Jan 1, 1932

By E. T. Turkdogan, L. S. Darken, R. J. Fruehan

Further consideration is given to the application of the quadratic formalism to evaluate the thermodynamics of binary metallic solutions from experimental data. The use of the thermodynamic relation, in(r1/r2) dN2= 0, in the evaluation of activity data is discussed. The empirical correlations derived previously for enthalpies and entropies of solutions in Part II are shown to be predicted theoretically for a special case. The applicability of the quadratic formalism to the activity coefficients for binary organic solutions is demonstrated. DARKEN&apos; introduced a quadratic formalism describing the composition dependence of the activity coefficient in the terminal regions of binary metallic solutions. In a subsequent paper (Part II) Turkdogan and Darkeen2 extended this formalism to the enthalpy and excess entropy of binary metallic solutions, and showed that the available data for the activity coefficients and heats of mixing of many solid and liquid binary metallic solutions confirm reasonable applicability of the quadratic formalism. Much variation was noted, however, in the extent of the terminal regions from one system to another, commonly from about 10 to 70 at. pct. For the present purpose, equations derived previously need be given only for one of the terminal regions, e.g. region (I), 0 < N2 < N&apos;2: where subscripts 1 and 2 indicate quantities for components 1 and 2 and superscript ° the values at infinite dilution; other terms are: N = atom fraction, y = activity coefficient, = partial molar enthalpy of solution, ?HM = molar heat of solution, ?Sx = excess partial molar entropy, ?Sx = excess molar entropy. The heat and entropy like terms (constants) el, and S12 are defined in the following expression for the temperature dependence of a12, thus a12 £12 — s12 rnl 2.303RT 2.303 R l J Using this formalism, the thermodynamics of binary systems in the terminal regions may be described over a temperature range of experisental interest in terms of eight quantities: Lº1—Lº2, ?Sx1,?Sxº2 , £12 ,£21,fiai, S12, and S21. In the previous paper, these quantities were evaluated for many solid and liquid binary solutions, and two significant correlations were observed between these thermodynamic quantities pertaining to the terminal regions, thus [10] and [11] Combining Eqs. [9], [l0], and [ll] and rearranging gives a12 -a21 = 1.382R log rº2- 0.08(?S2xº- ?S1xº) [12] Since the second term involving entropies is small and Eqs. 1101 and [ll] are empirical relations, the above equation may be simplified to a12 = 2.74 log rº2 [13] Using the values of a&apos;s and y°&apos;s compiled in Parts I and 11, a12 - a21 is plotted against log(rº2/rº1) in Fig. 1; the line drawn has a slope of 2.74. For Hg-K at 300°C, log(yº2 /yº1)= —5.10, not shown in Fig. 1, and from correlation [13], a12 - a21 = -13.97; this is to be compared with -10.76 derived from the activity data (Part II).

Jan 1, 1970

By M. F. Williams, L. G. Hendrickson

IN classification of pulps bearing magnetized ferromagnetic particles, depolarizing is of great importance. If size separation is to be effective, particles must be individual rather than in floes. Depolarizing is also practiced in heavy medium separations in which ferrosilicon or magnetite is the medium. When particles of ferromagnetic material have been removed from a magnetic field, residual magnetism causes agglomeration. The term depolarizing refers to the operation of reducing or eliminating this residual magnetism and may thus be considered magnetic deflocculation. The terms demagnetizing and randomizing are also used. At the Research Laboratory of Oliver Iron Mining Div. in Duluth a method was developed for measuring depolarization of the pulp of ferromagnetic material. Experiments were made with Mesabi taconite,&apos; a natural magnetite of low coercive force. Ferromagnetic materials of higher coercive force, such as lodestone or the artificial magnetite produced by reduction roasting of hematite, present a more difficult problem, which was not within the scope of this investigation. It is possible, however, that some of the techniques evolved for measuring and calculating electrical characteristics of alternating current coils would be of use in depolarizing high coercive force material, particularly in conjunction with high-frequency alternating current, as proposed by Hartig and others.&apos;," Properties of Ferromagnetic Materials:&apos;7 Experimental work, described below, has shown that if a sample in the magnetized state is heated above the Curie point and cooled, much of the preferred orientation is destroyed and the sample is substantially depolarized. It has been thought that when the sample cools below the Curie point the domains cancel each other, leaving a zero net moment. However, such particles still exhibit a tendency to cohere, and undoubtedly this is caused by the forces of residual magnetism. -AS measured by the percent depolarization, this tendency is reproducible for any sample upon repeated heating above the Curie point and subsequent cooling and is independent of the initial state of magnetization. It is postulated, therefore, that as the material is cooled below the Curie point the domains in any particle do not completely cancel each other, but rather are preferentially oriented to some extent. Mechanism of Depolarizing with Alternating Current Magnetic Fields: It is believed that when ferromagnetic material is passed through an alternating magnetic field, depolarizing occurs in the decaying portion of the field. As the particles pass through the portion of highest intensity they become magne- tized. If the particles are not free to move, the polarities of the particles will be reversed (by a mechanism similar to that described above for magnetism) at a frequency equal to that of the applied field. As the material moves through the decaying field, intensity levels become such that a domain does not completely reverse, but stops on an axis of easy magnetization. By the time the material reaches the point of zero field intensity, a state of fairly random orientation of domains is achieved. If conditions are such as to give a completely random orientation, the particle will have little or no external magnetic field, and a pulp of such particles will be depolarized. Previous Work In 1918 E. W. Davis was granted a patent for demagnetization of magnetite pulps.&apos; His method consisted of passing the pulp through a tapered coil, activated by alternating current of normal frequency (60 cycle). This method, with minor modifications, has been used almost universally in all pilot plants and commercial installations in which depolarization of low coercive force materials has been required. Hartig, Onstad and Foot2,3 avd made a detailed study of the factors involved in depolarizing both low (below 100 oersteds) and high (above 100 oersteds) coercive force material. They developed a method for evaluating the relative degree of depolarization of any pulp based on the settling characteristics of the pulp. Their standard of comparison was a sample heated to above the Curie point and cooled in a zero field, all in a neutral atmosphere.* For low coercive force material they found treatment.Thisprocedure is subsequently called, in this report,theCurie that results equivalent to Curie treatment could be

Jan 1, 1957