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By W. F. Rochow, W. C. Burke

Numerous designs of linings and accessories, including dams, lifters, and heat exchangers, contribute greatly to kiln efficiencies. Greater conductivity is achieved with basic brick than with fireclay and high-alumina refractories, depending largely upon the use of steel plates in radial joints between adjacent brick to increase heat transfer through the lining. Refractory lifters expose all portions of the load to radiant or convective heat and raise some portions to higher temperatures by cascading the load down through the path of the hot gases.

Jan 3, 1955

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By J. P. Neumann, L. Raymond

At temperatures near 1000°C, only the (112) (111) slip systems are operatire in tungsten. Therefore, the substructure introduced into the billet upon rleforming a single crystal by rolling at 1000 "C can be controlled by proper selection 01. processing ral'iubles. Using a reduction of 10 pct pel- pass, the (001)[110] and the (110)[001] crystals will deform by duplex slip rip to a 50 pet reduction in thickuess. These rolled single-crystal sheels are characlerized by anisotropic hardening, retention of ductility with warm working, lattice bending which is related to the conlacl (angle, and macroscopic dimensional changecs in the length bid not the width of the billet. When several slip systems become operative, a greater degree of work hardening is itztvoducetl into the crystal. This rolling- condition is characlerized by isotropic hardening, loss of ductilily with warm working, complex lattice distortions, and macro-scopic dimensional changes in both the length rind Width of the billel. IN tungsten, the {1 10}(111) slip systems are operative below room temperature,' while above 700°C only the {112{ (111) slip systems are observed.2,3 In the transition region, i.e., room temperature. both systems appear. It is the purpose of this investigation to show that tungsten single crystals deformed by rolling at a temperature where only one slip system is operative generate dislocation substructure which depends on the crystal orientation. For a specific crystal orientation. the resulting dislocation substructure can be further influenced by modifying the rolling procedure. Crystals oriented for multiple slip display less substructural sensi- tivity to modifications in processing techniques than do single crystals oriented for duplex slip. Under simple slip modes of deformation, very little work hardening is introduced into a rolled single-crystal sheet. Mechanical properties such as room-temperature strength. ductility, and hardness are used to confirm the existence of the different work-hardened conditions generated within the crystal by modified warm-rolling techniques. EXPERIMENTAL PROCEDURE Material. Single-crystal billets of four different crystal orientations. grown by the Arc-Verneuil technique. were ground to a size of 0.25 by 0.375 by 3 in. In terms of their rolling plane and rolling direction, the billets had the following orientations: (1101 [001 ] (110) [110] (001) [110] (001) [100] The actual orientation of all crystals was within 5 deg of the ideal orientations. The typical impurity content of the crystals is given in Table I. Polishing and Etching. Polishing was done elec-trolytically in a 20 g per liter aqueous solution of NaOH at approximately 10 v. It was established by the Laue back-reflection X-ray technique that the surface damage due to grinding and cutting operations with a diamond wheel did not exceed 0.001 in. Therefore after each cutting or grinding operation at least 0.002 in. was removed electrolytically from the surface in order to eliminate surface effects. By lowering the voltage to 3 v, subgrain boundaries and individual dislocations are identified in agreement with Berlec 4 where the etch-pit traces on a cubic plane form a square. The etching time was about 5 sec at room temperature. Rolling. Rolling was carried out on a Loma 2-high mill (Model 600). The peripheral velocity of the 6-in.-diameter rolls was 500 in. per min, with the surface temperature of the rolls about 400° to 450° C The billets were heated before each pass for 30 min in argon to 1000 C. Oxidation of the crystals during rolling in air resulted in a thin layer of greenish-yellow WO 3 This oxide was removed after each pass by immersing the crystals for a few minutes in a boiling NaOH solution. Prior to the initial rolling pass, a surface layer of 0.001 in. was removed by polishing. The crystals were then annealed in vacuum (10-4 torr) at 2400 C for 30 min. All crystals were rolled in the same direction; i.e., the same end was always introduced into the rolls. The rolling program was conducted in

Jan 1, 1965

By Sherwin F. Kelly

Twenty five years of exploration has shown that the "geophysical dollar" is worth $1780 in the Orange Free State, $1488 on the Witwatersrand, $85 in Sweden, $28,000 in the Transvaal and $3500 or more in the U.S.

Jan 6, 1951

By M. Cross

INTRODUCTION The results of the Japanese dissective investigations have [l-4] transformed our understanding of how the blast furnace operates. These studies revealed an internal structure of the furnace burden with five main zones, as illustrated in Figure 1. In the granular zone the charged material retains its structure whereas in the cohesive zone the iron ore particles are at advanced stages of reduction and form a semi-molten mass with a relatively high flow resistance. In the active coke zone molten iron and slag flow through a matrix of loosely packed coke. The raceway is a relatively small void space generated by displacement of coke due to the hot blast momentum, whilst the hearth is packed with coke, slag and molten iron. [ ] It is now well appreciated that furnace control is largely achieved and maintained by using the burden charge distribution to determine the gas glow distribution within the furnace and, hence, the shape and extent of the cohesive zone. In fact, Wakayama et a1 [5] of Nippon Steel Corporation state that optimum furnace operation is synonomous with the formation of a desirable cohesive zone shape, which in turn is almost solely determined by the burden charge distribution and its mechanical properties [6]. Much of the development work on operating furnaces since the dissective investigations has been oriented towards the identification of external furnace measures which reliably predict the shape of the cohesive zone. Currently the most popular measures are top gas temperature, velocity and CO/CO, ratio profiles [5]. More recently pressure distributions as evaluated from a series of wall measurements down the height of the furnace are also being utilised [7] to identify the position and shape of the cohesive zone. A great deal of emphasis has been placed upon achieving a consistent quality in the burden charge materials, establishing a suitable set of operating conditions and only making changes when forced to, ie., the operation for some reason moves outside a desired operating range or the production requirements change. Operational control schemes based upon this philosophy (eg., Kawasaki's GO-STOP system [8]) have been remarkably successful at achieving both high production rates and relatively low fuel costs. Mathematical models have long been used as tools to assist in the analysis of the blast furnace process. Although, the models have been useful in post-operative analysis and for identifying trends, etc., they have not proved reliable for detailed design criteria or as the basis for effective control schemes. Such mathematical models have moved from simple statistical correlation, through overall and stagewise heat-and-mass balance calcu-

Jan 1, 1984

By Rodney L. Stone, David S. Cahn

As part of an over-all laboratory and plant test program to determine mixing ad other techniques for a more economic use of bentonite as an iron ore pellet binder, a settling test for measuring the bentonite content within a pellet or a batch of pellets has been developed. Through this test, it has been shown that dry fracture load is directly proportional to bentonite content in batches of pellets, but inversely propor tional to bentonite content in individual pellets of the same batch. This apparent paradox is explained by a negative correlation between a pellet's size and its bentonite content and the fact that large pellets can withstand a higher fracture load than small pellets. In past attempts to characterize green and dry iron ore pellets, the authors found large variations in the results of strength tests on closely sized pellets from the same batch.' Reasons advanced for such variations in the quality of pellets in which the binder is bentonite were the presence of internal flaws and the nonuniform distribution of the binder. Even when resulting pellet strength is good, there is still the question of whether the same strength could have been attained through a more effective use of a smaller amount of bentonite. The authors' own and other studies 2-3 have pointed out the strong dependence of pellet strength on the degree of "mixedness" of the iron ore concentrate and the bentonite binder. However, before such a relationship could serve as a guide for the development of better mixing techniques and the associated economy of

Jan 1, 1969

By R. G. Burdick, W. R. Peters

Shallow underground voids resulting from early coal mining and other resource recovery activities over the past several decades are now being recognized as a significant cause of ground subsidence problems. Uncertain knowledge of abondoned coal mines also imposes potential hazards in current underground mining operations, since water inundation or the release of methane gas is a serious hazard when mine excavation operations break into an abandoned mine. Requirements for detecting and mapping subversive manmade tunnels in previous work has led to the development of a surface-operated automatic earth resistivity survey system and associated computer data reduction process for military applications. Field demonstration tests of this system have resulted in successful detection of tunnels at depth-to-diameter ratios greater than 10 to one. Under the sponsorship of the Bureau of Mines, a similar high-resolution earth resistivity system was designed and constructed for use as a potential means of detecting abandoned coal mine workings. The hardware and software aspects of third new system are described together with applications of the method for surveying and mapping abandoned coal mine workings. Field tests are presented to illustrate the detection of both air-filled and water-filled mine workings.

Jan 1, 1984

A New Ingersoll-Rand Turbo Blower The Ingersoll-Rand Co. has added to its Turbo Compressors and Blowers a low-pressure machine t o handle volumes from 3,000 to 35,000 cu. ft. per minute at from 1-2 ½ lb. These are particularly adapted to such service as foundry cupola blowing, atomizing oil for oil burners, supplying blast to heating and annealing furnaces of various kinds, blowing air for water-gas generators, pneumatic conveying and ventilating. They are of the single stage, double flow type and are furnished either electric motor, steam turbine or water wheel driven.

Jan 6, 1916

By J. R. Stone, J. T. Roy

ASARC09s continuous tapper for lead blast furnace is described. Its use throughout the company's plants has resulted in higher production rates, lower labor costs, and better working conditions. It has also permitted wide latitude in blast pressures, as well as in charge and slag compositions. The practice of tapping a lead blast furnace has remained essentially unchanged for many years. In principle, it is a batch operation discharging the products from the continuous smelting of lead-bearing materials. As such, it imposes certain restrictions on the proper functioning of the smelting operation. First, it calls for a highly developed sense of timing, and a considerable amount of physical effort on the part of the operator. Dirty and hot working conditions, as well as the hazards of flying metal and slag, usually prevail. These conditions have resulted in higher labor costs, both in rate and in amount. Labor turnover has also been high. Secondly, rigid control of mechanical and metallurgical factors must be maintained. Frequent oxygen lancing of the tap hole is needed to permit tapping, thereby increasing operating costs. Rapid increases in smelting rate, plugged tap holes, or forgetfulness on the part of the operator may permit the molten material to rise above the tuyeies and freeze the furnace. Also, the operator will often blow out the tap hole after draining, filling the area with fume. Composition of charge also vitally affects the tapping. The type of lead-bearing material being smelted will naturally affect the smelting rate, and thus the frequency of tapping. The amounts and types of fluxing materials, which determine the ultimate fluidity of the slag, must be regidly controlled. Finally, the batch tapping of a continuous smelting operation of this type appears to be wrong in principle. The molten material drains into the crucible at the bottom of the furnace where it starts cooling immediately and continues to cool until tapped out. While keeping the lead molten is no particular problem, maintaining a fluid slag at all times is often difficult, and sometimes impossible. These factors all point to the desirability of a method for the continuous tapping of a lead blast furnace. The expected advantages would be more desirable working conditions, lower labor costs, increased production, and a much wider latitude in both blast pressure and charge composition. CONTINUOUS TAPPING Historical. A number of devices, e.g., mechanical tappers, siphons, and lead wells, have been tried in the past in attempting to effect continuous tapping. None proved to be entirely satisfactory for tapping lead and slag simultaneously. It was not until 1955, however, that ASARCO designed and put into operation a successful tapping unit at its East Helena, Mont. lead smelter. This unit is described in detail in U.S. Patent NO. 2,890,951. Continuous Tapping Unit—See Figs. 1 and 2. Fig. 1 is a schematic drawing of the unit in place, showing front and side views. The component parts are identified in the caption. Fig. 2 is an actual photograph, front view, of the tapping unit attached to the base of the blast furnace. Operation. The operation of the tapping unit is quite simple. Essentially it consists of a narrow tapping bay surrounding the furnace tap hole, with a deep notch in the front wall. When the blast furnace is started this notch is open down to the level of the tap hole. Starting the furnace may be accomplished in several ways but the most satisfactory method is to plug the tap hole with clay, permitting metal and slag to build up inside the furnace. Before the liquid reaches the tuyeres, the plug is removed and the furnace is drained to the settler. The blast is then stopped momentarily while the notch in the front wall of the tapping bay is dammed with chrome brick and plastic chrome ore. The blast is again started, and the height of the dam is adjusted so that the liquid in the bay will counterbalance the internal pressure of the furnace. When the desired level is reached the slag and metal will overflow to the settler. It should be noted that the molten material ,is not siphoned from the furnace and that the metal 'acts as a liquid valve controlling the flow of slag through the tap hole. During normal operations the tapping bay is filled primarily with lead, covered with a thin layer of slag. Thus, the heavier lead plays the major role in compensating for variations in furnace pressures. Due to the high specific gravity of lead, changes in the liquid level in the tapping bay will never exceed a few inches. For this reason it is seldom necessary to change the height of the dam due to minor variations in operating conditions. Some turbulence of the liquid in the bay is essential at all times. This indicates that the level of the

Jan 1, 1963

By Edward J. Felten

THE oxidation resistance of chromium and Fe-Cr alloys is increased by small additions of yttrium or other rare earth metals.1,2 In addition, the presence of the additives increases the resistance of these alloys to spalling of the external oxide above 1000°C. This ability to prevent spalling appears to be related to the formation of an internal oxide in alloys containing yttrium or the other rare earth metals. The internal oxide is found in the form of a filamentary growth concentrated in the grain boundaries of the unoxidized metal. In alloys containing yttrium this internal oxide was found to be either Y2O3 Or YCrO3.' In an earlier report,' the growth of the external oxide was found to be controlled by diffusion through the oxide layer. Thermal balance studies were used to establish the kinetics of external oxide formation. In this related study the rate of growth of the internal filamentary oxide has also been studied. The results obtained indicate that the growth of the internal oxide is also diffusion controlled. Internal oxidation appears to occur in at least two ways. Using copper alloys containing small amounts of silicon, Rhines 3 found that between 600" and 1000oC a subscale was formed which consisted of particles of silica dispersed in the metallic matrix. The conditions requisite to internal oxidation as suggested by Rhines are: 1) a solubility of oxygen in the alloy, 2) the ability of oxygen to diffuse at an appreciable rate into the alloy, 3) the possibility of the formation by the alloying element of an oxide more stable than the oxide of the host metal, and 4) a relatively low solubility of this oxide in the metal. These conditions are fulfilled for a number of other copper alloys.3-5 Furthermore, the relationship between the depth to which the internal oxide is formed and the oxidation time follows the simple parabolic law.6 The activation energy for copper containing small amounts of silicon, germanium, iron, or manganese as calculated from Rhines data6 is about 48 kcal per mole. In some cases the internal oxide is found segregated at the grain boundaries, especially near the the surface. Observations of this type of oxide formation have been reported by stead,7 Rhines,* and Lustman. Evans" cites these cases as examples of the simultaneous movement of anions and cations during oxidation. Furthermore, Evans states that the presence of a minor constituent with a high

Jan 1, 1962

By H. H. Dreissen, F. J. Fontein

The operating principle of the classifying cyclone has been described often but some special aspects of the cyclone receive further clarification here. In addition, several uses of the classifiers are summarized and made clear by means of practical examples. In coal and ore washeries, the washing cyclone is widely used for the separation by specific gravity of sizes up to about 12 mm. This application has lately been extended to the separation by specific gravity of particles up to about 50 mm. This use makes special demands on the construction and wear resistance of the cyclone. The sieve bend, a development of the Dutch State Mines which is less well known than the hydrocy-clone, is dealt with at some length. The sieve bend is an apparatus designed for wet screening. Attention is given to the variables influencing the performance of the sieve bend. Hydrocyclones are now so widely applied that it would be difficult to find an industry not, directly or indirectly, using them or knowing how to use them since publications on this subject abound.1-3,5,9-11,13-15 However, because of the large number of variables influencing the operation of classifying cyclones, it is not entirely possible to calculate the results of this type of cyclone. Therefore, a number of lesser known variables will be discussed here along with some special applications of the classifying cyclone. FACTORS INFLUENCING CYCLONE CLASSIFICATION Shape of Particles: The shape of particles may cause a much coarser classification than the one expected, considering the sieve analysis and the cyclone dimensions chosen. This was clearly shown by feeding a mixture of spheres and disks in water into a cyclone. The spheres were 0.36 mm diam and the disks, 3 mm diam and 0.03 mm thick. These dimensions were chosen in order that the disks and spheres might have the same rates of fall under gravity. Both spheres and disks had a specific gravity of 1.05. The results obtained with these particles in a cyclone are summarized in Table I. Test No. 2 shows that the catch of spheres was

Jan 1, 1963

By A. T. Yu

On March 18, 1964, the 52,000 dwt ore carrier M/S Houn Maru called at the port of Coquimbo, Chile, on its maiden voyage to take iron ore to Japan. This marked the first time a vessel of this size ever arrived at Coquimbo, and the event promises to drastically accelerate henceforth iron ore exports from Coquimbo province. This was made possible by the use of a versatile shiploading system recently installed by Cia. Minera Santa Fe. Coquimbo has no mechanized loading facilities other than six conventional 5-ton cargo cranes. Limited space on shore further complicates the stocking problems. To make the best of what is available, a meticulously organized semi-hand-loading system has been developed through the years.

Jan 5, 1964

By Ove Alm

Wet and dry specimens of three rocks of approximately granitic composition were deformed at different experimental conditions. These experiments were carried out in order to study the extent to which water, either added or released from mineral reactions, may affect the mechanical properties and the microstructure of these rocks. The experiments were conducted in a Griggs&apos; hot creep apparatus at temperatures and pressures up to 900ºC and 1000 MPa respectively; and most of them were performed in the constant strain rate mode [(1.10-6 < t < 1 • 10-4 s-1 )]. All three rocks were low porosity rocks, and the wet specimens never contained more than 0.9 wt % of added water. The experimental results are, however, quite unequivocal: They show that wet rocks are weaker than dry ones. A significant difference is even found for rocks tested in uniaxial compression at room temperature. A few experiments carried out on specimens obtained from larger prestressed rock cores indicated that the central parts of these cores were more likely to contain more microcracks than the ends. Optical microscope examinations revealed that extensive microcracking takes place even at the highest temperatures, where other mechanisms such as slip and dislocation creep also become important. Very little partial melting could be observed except for the specimens deformed at 900ºC.

Jan 1, 1982

CYRIL STANLEY SMITH, Chairman CARL E. SWARTZ, Past-Chairman ARTHUR PHILLIPS, Vice-Chairman E. E. SCHUMACHER, Vice-Chairman H. A. MALONEY, Treasurer FRANK. T. SISCO, Secretary 9 West 39th Street, New York, N. 1. Executive Committee 1944 1945 WILLIAM C. ELLIS C. S. BARRETT ALAN MORRIS T. A. WRIGHT KENT R. VAN HORN L. L. WYMAN

Jan 1, 1943

By J. M. Toguri, K. Grjotheim

It is known 1,2 that the equilibrium between titanium metal, TiCl2 , and TiCl3, in a solvent of molten metal chlorides, is influenced both by the total amount of dissolved titanium and by the type of solvent. Assuming that the trivalent titanium forms the complex ion Ti111 Cl4, the equilibrium reaction may be expressed by the following equation, (Me) TiIII cl4+ 1/2 Ti = 3/2 TiII cl2+ (Me) Cl The ideal ionic equilibrium constant for this reaction is, Where the N&apos;s are the molar ionic fractions in the equilibrium melt, and (Me) the different types of cations present in the equilibrium mixture. The following thermodynamic relation is derived between Kand the concentration of cations in the equilibrium melt, mix The N"S are the equivalent ionic fractions, and so forth are constants corresponding to the standard changes in free energy for reactions in melts where only the cation indicated is present, and f (y1) is a function of the activity coefficients in the equilibrium mixture. When this term vanishes, a simplified linear relationship between In Kideal and the concentration is obtained. The simplified relationship has been applied with satisfactory results to the experimental data of Mellgren and pie,&apos; and Kreye and Kellogg.2 MANY existing methods for the production of light metals involve the reduction of their respective metal halides in the presence of salt melts composed of alkali or alkaline earth chlorides. In such a solution phase, the light-metal halide may undergo stepwise reduction from a higher, to a lower valence, and finally to a zero valent state. In this connection, the disproportionation equilibrium is of great interest. In the case where the higher valence is three and the lower valence is two, the disproportionation equilibrium may be written as follows, 3 Me11 = 2 Me111 + Me [I] If this equilibrium occurs in a salt melt containing a large excess of alkali chlorides, a typical ionic melt is obtained. It is then possible to formulate the cation equilibrium: 2 Me+h&apos; + Me = 3 Me++ [II] Reaction [11] is analogous to a cation exchange reaction. It has been shown thermodynamically that the equilibrium constant for such a reaction in 2

Jan 1, 1960

By A. T. Miesch, L. B. Riley

Distribution of minor elements in sandstone-type uranium deposits of the Colorado Plateau is being studied by the USGS on behalf of the A EC. A primary objective has been to provide basic data which could be useful in geo-chemical exploration for new deposits. The basic statistical measures — similar to those used in sedimentary petrology—are described. The underlying principle is that the frequency distributions fit or approach the log-normal form. Since 1952 the U. S. Geological Survey on behalf of the U. S. Atomic Energy Commission has conducted a study of the distribution of minor elements in sands tone-type uranium deposits of the Colorado Plateau. A primary objective in this study has been to provide basic data which could be useful in geo-chemical exploration for new deposits. Among the basic data considered important are estimates of the abundance and habit of each element in the ore and in the host rocks. It has been found that a few basic statistical techniques, and variations of these techniques, are useful in this type of study. Some of the basic techniques have been used to advantage by researchers in geochemistry and in other fields of geology, especially sedimentary petrology; others have been used to only a limited extent. Among the latter is the linear correlation coefficient, which has proved useful in assessing the element associations in a particular rock type without analysing individual mineral separates. In computing the basic statistical measures a scale has been used which is, in some ways, similar to the phi ($) scale used by sedimentary petrol-ogists in grain-size studies.&apos; FREQUENCY DISTRIBUTIONS It has been recognized for some time that the results of analyses for a given minor element in a suite of samples of rocks or ores yield frequency distribution curves which are approximately normal when the curves are plotted on logarithmic or geometric scales. In other words, the analytical results give an approximate lognormal frequency distribution. A classical example is given by D. G. Krige2 in the study of the distribution of gold values from a mine on the Witwatersrand. Another example is shown in Fig. 1, the distribution of barium concentrations in samples of uranium ore from the Chinle formation. The geochemical data are analogous to grain-size data gathered by the sedimentary petrologist. Both types of data, after simple logarithmic transformations, may be treated by conventional statistical methods based on the normal distribution. This is not to say that other types of transformations may not serve equally well or better for particular element distributions.3 Spectrographers and other analysts are quite aware of the dependence of their precision on the concentration of the element present.4 For example, in the part per million range the variation may

Jan 1, 1961

By W. H. Bassett

THE ease and value of the application of spectrum analysis to industrial chemistry appears to be appreciated in few of the large works laboratories of this country. For 8 years, this analysis has been of great value to the authors in both analytical and metallurgical work. To the analyst the complete qualitative analysis of an unknown alloy, revealed by a spectrogram, is a sure basis for the planning of the most direct and rapid method of attack. As the determination of each element proceeds, the purity of precipitates may be checked as often as desired. The spectrograph proves invaluable in the recognition of impurities, the separation of which would entail a lengthy and difficult procedure, or when the weight of an unknown is less than is necessary to complete the desired determinations. A few hundredths of a gram will usually suffice for spectrographic analysis. In the separation of the rarer elements, the spectrograph will show, with precision, the point where each step has been successful. In zinc of certain classes, indium, gallium, and germanium have been isolated in this way; the presence of antimony in lake coppers has been proved; and bismuth has been detected in zinc and in alloys where the presence of a few thousandths of a per cent. would be harmful. An antimony precipitate in a delicate determination may contain a considerable proportion of tin or arsenic, both of which will be revealed. The spectrograph is consequently important to the metallurgist as well as to the analyst.

Jan 2, 1922

By R. W. Bartlett

DISILICIDE coatings, MeSi2, on refractory metals are usually grown by a solid-state diffusion reaction similar to the parabolic oxidation of metals. Two or more silicide compounds occur in each of the binary silicon-refractory metal systems. When an adequate source of silicon is available during the coating process, the lower silicide compounds are usually not formed.1 However, during service application of the coated refractory metal, continued heating causes further diffusion and growth of the lower silicides. A study of the growth kinetics of the lower silicides in the molybdenum and tungsten binary systems with silicon was previously reported.2 The present study is concerned with the growth kinetics of Ta5Si3 and Cb5Si3, formed as conjugate layers between TaSi2/Ta and CbSi2/Cb diffusion couples, respectively. Diffusion couples consisting of disilicide-coated tantalum and columbium sheet coupons were subjected to diffusion heat treatments, cross-sectioned, and scanned by an electron-microprobe analyzer to determine the relative X-ray intensity profiles. These profiles correspond closely to concentration profiles for the constituents, and were used to identify phases and locate phase boundaries. The analysis of a single specimen after a diffusion-anneal provides only one value for the Me5Si3 phase thickness, corresponding to the time and temperature of the diffusion treatment. Consequently, each isothermal curve showing the rate of accumulation or depletion of silicide phases required several samples with identical diffusion temperatures but different diffusion times. The disilicide coatings were prepared by pyrolizing commercially pure silane in a hydrogen carrier gas. The hydrogen was purified by passage through a palladium membrane. Commercially pure tantalum and columbium sheet metal coupons, 0.005 by $ by 2 in., were used. All of the coated specimens for each system were prepared together in a single group in order to minimize coating variations among individual specimens. During pyrolysis, the brightness temperature was maintained at 1200°C. With suitable flow rates at this temperature, only the disilicides of tantalum and columbium were formed in detectable amounts. Coated specimens were subjected to diffusion an-neals in a tube furnace with automatic proportional control within ±10°C. A H2-Ar mixture, deoxidized and dried over anhydrous magnesium perchlorate, was used to prevent oxidation during the diffusion anneal. Diffusion couples were cross-sectioned, polished and examined with an A.R.L. electron-microprobe X-ray analyzer. Both metal constituents in each specimen were simultaneously scanned using a 1-p beam spot size and either 1- or 2-µ steps. Analyses were performed using the Ka radiation of columbium and silicon, and the La, radiation of tantalum. For all specimens, an acceleration voltage of 30 kv was used, and integration was made against the specimen current. LiF and A DP monochrometers were used to isolate characteristic radiations. Three or more traverses were made on each specimen. The intensity scales were adjusted using the constituent metals and standard samples of the silicide compounds which had been verified by X-ray diffraction. The relative intensity profiles were used directly, in conjunction with the standard samples, to identify compounds and phase boundaries. The stoichiometries differ considerably between the silicide compounds in both systems, and the homogeneity range for these silicide compounds is narrow. These characteristics result in marked differences in relative intensities of the fluorescing elements—differences which permit ready identification of phases and phase boundaries. Projections of both electron back-scattered images and characteristic

Jan 1, 1967

By E. Hornbogen

The deformation mechanisms of a iron-phosphorus alloys were compared at 20oand —196°C. Alloying with phosphorus increases the resistance to slip, but has little effect on the resistance to twinning. The stress for onset of twinning is nearly independent of temperature, but there is an increasing tendency for cleavage along (112) twin boundaries with decreasing temperature and increasing phosphorus content. FIVE iron-phosphorus alloys and one high-purity iron (0.004 pct C, 0.004 pct N, 0.05 pct O) were vacuum melted and cast, then homogenized for 6 hr at 1100oC and water-quenched. Single crystals were cleaved from the coarse grains produced in this manner. The hardness was measured* on polished (100) surfaces of the crystals at 20" and -196°C. Laue back-reflection patterns indicated a deviation of not more than 3 deg from coincidence of the {100} plane with the surface. The deformation mechanisms were studied by relief effects on the polished surfaces. Yield points in compression (0.5 pct offset) were measured with polycrystalline material. At 20°C the addition of phosphorus to a iron leads to a change from slip to twinning as the main deformation mechanism, Figs. 1(a), (b). Between 2 and 4 at. pct P slip and twinning occur simultaneously. In alloys with more than 4 at. pct P twinning is the main deformation mechanism and slip was observed only in the neighborhood of twin intersections. All cracks at 20oC were on (100) planes, some initiated by twins.&apos; From measurements made at-196oC, hardness and yield points of all the alloys were nearly constant and the same as the hardness of high phosphorus alloys that deformed by twinning at 20°C, Figs. 2 and 3. In the high-purity iron, plastic deformation at -196°C occurred by both slip and twinning, but deformation in the iron-phosphorus alloys appeared to be entirely by twinning. In the high phosphorus alloys a large number of cracks formed along the (112) twin boundaries and at intersections of twins, in addition to the (100) cleavage, Fig. 1(c). DISCUSSION In , iron, plastic deformation can occur either by slip or by twinning, depending upon composition,

Jan 1, 1961

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to flocculation of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves.

Aug 1, 1956