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By C. P. Melloy

INTRODUCTION Ventilation practice at Isa Mine has been evolving since underground mining began in 1931. Much fundamental work has been conducted and reported regarding the primary ventilation system [Mathews K.E. et a1 (1967) and Brown J.R., Fisher T.H., Gibson K.L. (1979) 1. However, ventilation networks for subsystems such as open stopes, have evolved with experience. This paper outlines current ventilation practice for open stoping. Mount Isa Mine The mine is located in semi-arid North-West Queensland, Australia, and currently produces 20 000 tonnes of copper ore and 10 000 tonnes of silver-lead-zinc ore daily in each five day working week. Mining extends over a north-south strike length of 3.5 km with a maximum width across dip approaching 1 km, and is to a depth of 960 m (Figure 1). At present approximately 90% of the mine's copper production is from the 1100 Orebody, which contains ore reserves of 121 million tonnes of 3.2% copper. Open stoping is currently the mining method employed, and is used for primary stoping and pillar recovery adjacent to cement fill walls. The development of stoping methods in the 1100 Orebody has been documented by Kirkby R.W., Blair J.R., and Hutton R.C. (19781, Hornsby B. and Sullivan B.J. (1978), and Alexander E.G. and Fabjanczyk M.W (1981). As many as thirteen open stopes may be producing concurrently in the Orebody (Figure 2). The multiple silver-lead-zinc orebodies containing reserves of 54 million tonnes of 150 g/t silver, 6.4% lead and 6.5% zinc, are mined by open stoping, and cut and fill techniques. These methods have been documented by Goddard I.A. and Bridges M.C. (1977 1, and Goddard I. A. (1981 1. Only the ventilation of the 1100 Orebody open stopes will be discussed. However, the same ventilation philosophy is employed in open stope design in the lead orebodies.

Jan 1, 1981

By C. R. Van Hise

[Concluding Contribution of Prof. Van Hise to the Discussion of his Paper, and Others on the Same General Subject, presented at the Washington Meeting, February, 1900 (see Trans., xxx., 27, 177, 323, 424, 5 S); also of the contributions of Vogt, De Launay, Beck, Lindgren, hemp, Rickard, Bain, Keyes, Collins and Adams, presented at the Richmond Meeting, February, 1901, and printed in the present volume.] IN June, 1900, shortly after my paper was published in the Transactions, I made a briefer statement* before the Western Society of Engineers covering the same `round, which, in certain respects, is somewhat of an improvement. For instance, instead of using the terms descending and ascending with reference to the waters resulting in the two concentrations, my modified statement is as follows " The first concentration of many ore-deposits is the work of a relatively deep water-circulation, while the reconcentration is the result of reactions upon an earlier concentration through the agency of a relatively shallow water-circulation. Commonly the deep water circulation is lacking in free oxygen, and contains reducing agents, and the shallow water contains free oxygen. The deep water is therefore a reducing, and the shallow water an oxidizing agent."† Of the papers upon ore-deposits which, in vol. xxx. of the Transactions, follow my own, or which were presented at the Richmond meeting, a considerable number are wholly confirmatory of the conclusions which I have presented. Among these are the Washington paper of Emmons upon the Secondary Enrichment of Ore-Deposits‡ and his discussion at Richmond of other papers,§ that of Weed upon the Enrichment of Gold and Silver Veins,[ ]the discussion of Emmons', and at Richmond of Weed's paper by Collinst and Prof. De Launay,† the paper of Lindgren on Metasomatic Processes in Fissure Veins,¶ that of-Rickard upon the Formation of Bonanzas in the Upper Portions of Gold Veins,** and the remarks of Bain upon the Mississippi Valley lead- and zinc-deposits.†† It is therefore un-

Jan 1, 1902

By Roland de Wit

Conclusions reached in a paper by weertmanl are amplified in a mathematical and graphical way. It is shown that in a stressed crystal a straight dis-location may be in a position of unstable equilibrium with respect to helix development, and how a small perturbation may start the dislocation off on its helical path. Helix development occurs by diffision; bulk diffusion is necessary for development from a screw, but core diffision is sufficient for development from an edge dislocation. For a mixed dislocation helix development can take place by core diffusion if the helix also climbs; a diffusion reversal takes place when the slope of the helix equals the slope of the Burgers vector. The work done on a crystal by the external forces is graphically shown to be consistent with the direction of motion of the dislocation in helix development. Finally a detailed mechanism for tangle formation from helices is presented. In the course of helix development a glide situation may be reached where a segment of each helix loop lies in a slip plane in which it can expand by glide. Thus is it visualized how a helix can deteriorate into a tangle. A paper by weertmanl proposes dislocation-tangle formation by a helical dislocation mechanism. The present paper amplifies Weertman's arguments in a mathematical and graphical way and presents some further ramifications of the proposed model. The importance of dislocation tangles is discussed in Weertman's paper and the references cited therein. The mechanism of their formation is not yet understood. Weertman proposes that in cold-worked crystals conditions exist suitable for the conversion of straight dislocations into helices and subsequently into tangles. Helix formation occurs by a diffusion process and Weertman proposes that at low temperatures only core diffusion is important. The present paper necessarily repeats some of Weertman's work. Since the mathematical development and notation used are slightly different from his, this was thought necessary for clarity. GEOMETRY OF THE HELIX weertman2 has shown that the equilibrium form of any dislocation line is a helix if it is assumed that the energy per unit length (line tension) of the dis- location is constant. For the special case that no external forces act on the dislocation, the helix reduces to a straight line. We shall assume in this paper that the dislocation has a helical form even when it is not in equilibrium. The parametric equation of a helix is, see Fig. l: where a is the radius of the cylinder tangent to the helix, and 270 the pitch of the helix. The pitch is related to v, the number of turns per unit length (along the axis) by the relation: When a = 0 Eq. [I] gives a straight line in the z direction. The growth of a straight dislocation into a helix is now described mathematically by letting a vary from zero to its final value. The tangent to the helix is given by where is the path length along the helix. This gives the direction of t and since its magnitude is unity we must have So that dcp/ds = (a2 +p2)-"'. The curvature of the helix is given by where n = -(cos + sin) is a unit vector normal to the helix. Note that the vectors k and n always point toward the axis of the helix, Fig. 1. FORCE ON THE HELIX The external force which makes the straight dis-

Jan 1, 1963

By Yves Dardel

The literature concerning the remelting of alunlinum and its alloys is very rich. Unfortunately the majority of the papers on this subject have no scientific value, for the theories or explanations are too often in opposition to the laws of physical chemistry. Furthermore only a few of the methods of purification are considered in the literature. Hence it has seemed necessary to the author to sketch a general theory of the purification of secondary aluminum. The purpose of the purification is to eliminate the impurities that the charges, and the atmosphere of the furnaces bring into the bath during the successive remelt-ings. Indeed scrap as well as metal can be used when soiled with oil, greases, water, or others, if it has been sufficiently dried and contains oxides. At the melting point of the metal, the oils and greases are decomposed into their constituent elements H², O2, H²O, co², CO, CH,, and others. These gases are added to the corresponding gases in the atmosphere of the furnace. The impurities introduced into the metal during the remelting will accordingly be the products resulting from the action of these gases on the liquid bath. The quantity of hydrogen that is soluble in aluminum and its alloys is given by the relation of sieverts3 as a function of its partial pressure PH2 in the atmosphere m = K vPH² [I] where K is a constant, which depends only upon the temperature and increases with it. The experiments of Rijntgen and Braun4, RÖntgen and M611er5, Bircum-shaw6 and Winterhagerl have rendered it possible to determine the value of K, when the temperature is less than 1.000°C. One obtains: log K = - 4,702.5T + o 238 [2] Besides its usual significance, the term Ph~ represents also the internal pressure of dissolved hydrogen, since in the equilibrium, that is1 when no gas exchange Occurs between the two phases, the Pressures of hydrogen in the metal and in the atmosphere must be equal. Eq I shows that when the partial pressure of H2 increases the amount of dissolved hydrogen in equilibrium increases, and that, if the contrary Occurs, the quantity of H² should diminish. However, if for any reason the diffusion of hydrogen is hindered and the total amount of dissolved gas remains constant while the temperature decreases, the internal pressure of H² increases until it reaches the value of the hydrostatic pressure. At this point, bubbles of hydrogen appear in the bath and escape out of it. The amount of hydrogen in the metal is then limited by a a depending On the hydro- static pressure, which is practically equal to one atmosphere. Indeed hydrogen does not accumulate in the form of a hydride appearing as a separate solid phase. However1 even the mechanism of the solubility is not yet elucidated. One does not know exactly as yet, whether the

Jan 1, 1949

By Bruce F. Grant, Stefan F. Szasz

During 1947, a Sinclair research team was assigned to investigate thermal methods of oil recovery. The assignment was recommended by a survey of possible research approaches to increase the amount of oil that ultimately can be recovered from oil producing reservoirs. The use of heat to stimulate oil production rates by the melting of paraffin deposited in well bores can be traced back to within one or two decades of the drilling of the Drake well. The application of heat on a larger scale has been discussed by generations of oil producers. Shortly after the turn of the century, one intrepid operator is reported to have injected steam into a Pennsylvania property. After a few weeks, he apparently became discouraged and terminated his experiment. Subsequently, the literature contains references to several well-developed techniques for supplying heat to a producing well bore to melt paraffin or to reduce the viscosity of oil contained in the formation immediately around the well bore.1.?.3.4 Some early references discuss procedures to furnish heat to the reservoir,5,6 with the injection well as the heat source, thus obligating the process to maintain the entire rock mass at a temperature above that at which the desired improvement in oil recovery would occur. Another approach to reservoir heating was reported by a group of Russian technologists in 1935.7,8,9 They definitely demonstrated that combustion can occur within the porous structure of an oil-bearing sandstone. Their field experiments, however, relied less on combustion within the rock than on heat furnished by combustion of oil supplied to the injection well bore. Ignition of the air-oil mixtures in the well bore was found very difficult, and the field tests were carried on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well, on for only short periods of time. Publication of the Russian work spurred at least one independent operator in this country to try firing an air-gas injection well. The Brundred Oil Corp. reportedly obtained combustion in the sand immediately around the injection well bore, but the experiment was abandoned because of interference with normal production schedules. Injection capacity of the experimental well was greatly reduced by firing. The well was reshot and pieces of sand showing partial fusing of the quartz matrix were recovered. To the authors' knowledge no other field experiments utilizing combustion techniques for formation heating were undertaken prior to 1948, although the patent literature evidences continued interest in formation heating."'," CONCEPT OF COMBUSTION-SUPPORTED HEAT WAVE The references cited were in agreement that heat applied to a reservoir would increase recovery, but there

Jan 1, 1955

By C. Ernest Birchenall

As a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.1 In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in. the preceding paper.2 A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken .3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity data given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below.

Jan 1, 1947

By C. G. Dunn

NUCLEI that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,1 that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclassesf of the 36 third- order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of de- formation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a {110} plane in a < 100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is notparticularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1946

By C. G. Dunn

Nuclei that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,&apos; that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclasses† of the 36 third-order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of deformation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a (110) plane in a <100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is not particularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1947

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.&apos; In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By C. G. Dunn

Nuclei that are formed during the recrystallization of a grain following plastic deformation generally have orientations that differ from the original. This aspect of recrystallization may be described in terms of orientation changes. It was shown previously, in an investigation on recrystallization in silicon ferrite,&apos; that the observed orientation changes were highly improbable on a chance basis, and that some mechanism must be involved. Analysis showed that the data could be satisfactorily classified into the smaller of two subclasses† of the 36 third-order twin transformations. No attempt was made at that time to classify the data within the special class of 12 third-order twin transformations, although results did indicate a greater probability for some of them to occur. A classification of this type would be more valuable, of course, with more data on orientation changes per old deformed grain. The present work fulfills this condition to some degree and also extends the scope of the investigation to include the effects of original orientation and the amount of plastic deformation. The effect of original orientation is of considerable interest because of the known effects of orientation on plastic deformation, particularly with regard to degree of fragmentation and the formation of deformation bands, and because the orientations produced by deformation should influence the orientations obtained through recrystallization. Barrett and Levenson2 reported that single crystals of iron deformed in the range 82 to 97 per cent could be put into three general classes; namely, crystals in class I maintained a reasonably sharp single orientation, those in class 2 transformed into two distinct orientations, and those in class 3 changed into a large number of major and minor orientations. Something similar would be expected for silicon ferrite crystals, and verification of this for a few cases of types class I and class 2 deformation has been reported elsewhere3 for single crystals of silicon ferrite cold-rolled in the range 10 to 20 per cent. As an example of class 2 deformation, it was shown that a crystal of silicon ferrite cold-rolled in a (110) plane in a <100> direction developed two layers, or deformation bands differing in orientation. When this happens it is possible to etch away one band and leave a single structure for use in studying the orientation changes that occur during recrystallization. when preferred crystal orientations are obtained in recrystallization, it is not particularly necessary to evaluate groups of common orientation, as was done previously (ref. I, Table 6); but an

Jan 1, 1947

By C. Ernest Birchenall

AS a basis for further progress in several branches of metallurgy, particularly the study of physical properties of solid solutions and the kinetics of solid-solid reactions, a more complete understanding of the structure of solid solutions and the nature of the metallic bond is- necessary. Any investigation contributing to this understanding should be of primary interest to the metallurgist. Since the metallic bond is characteristic of an assemblage of atoms, it can be studied only where this assemblage exists. One of the most promising approaches to this study of the interactions in metals is through the general problem of binary metallic solutions. Although crystal structures of many solid metallic solutions have been determined and solubility limits for many systems are given in phase diagram studies, progress beyond this is irregular. Electromotive force and vapor pressure determinations have provided thermodynamic activity data for small concentration and temperature ranges in the amalgams and a few other systems.&apos; In two systems, however, copper-zinc and iron-carbon, data are available for the calculation of activities over wide ranges of temperature and concentration. This activity data for the brass system is summarized in the preceding paper.= A detailed study of the solubility and distribution of carbon in iron is given by Smith and Darken.3 Their treatment of interaction energies is applicable only to dilute interstitial solutions. The objectives here will be to derive from activity gats given in the previous paper for the brasses and structural considerations as much new and detailed information as possible about the interactions between copper and zinc in metallic solid solution and the effect of these interactions in determining the short range structure of the equilibrium phases; that is, we shall investigate the energy of interaction between pairs of atoms of the same and different kinds, the deviations of the distribution of nearest neighbors from complete randomness, and show that the conclusions found are consistent with the observed behavior of the brass system. The method of treatment is fairly general for substitutional metallic solid solutions and will be applied to other systems. The determination of vapor pressures of the components of alloy systems is being undertaken in this laboratory to supply more data for this purpose. The information obtained from solid solutions may be extended by careful analogy to liquids as long as the metallic type of bonding is preserved. Since it will be necessary to employ the language of thermodynamics, a brief summary defining the terms used extensively in solution theory is given below. Solution Theory4 An ideal solution is one in which the vapor pressure of the constituent molecules

Jan 1, 1947

By Michael Tenenbaum, C. C. Brown

Numerous investigatiolls have been carried out to determine the total oxygen present in the basic open-hearth bath and the results of these studies have clearly defined the factors controlling the bath oxidation during the period prior to deoxidation. On the other hand, very little is known concerning any changes in total oxygen content that may occur during deoxidation, tapping and teeming. The need for such additional data is continually becoming more apparent, since there is no strict technical basis for selecting any particular deoxidation practice. Many steels are made for the same purposes and to the same chemical analyses by widely differing practices. Apparently, each practice is satisfactory. However, it would be desirable to establish more definitely the effects and relative merits of the individual practices. Such information could be used to give a definite foundation for evaluating various types of deoxidation. In order to approach this problem, a study was made of the changes effected in the total oxygen content of several grades of steel by representative open-hearth deoxidation practices. To carry out such studies, it was necessary that a reliable testing procedure for determining the oxygen content of the steel bath and the ingot mold be established. Before entering on any extensive testing program, consideration was given to the available methods of obtaining steel samples and analyzing for oxygen. Testing Procedures It has been shown5-9 that in solidified steel oxygen may ekist in combination with iron, manganese, silicon, aluminum, titanium, chromium and carbon, depending upon the amount of these elements in the sample. In molten steel, however, there has been no direct distinction of the various oxides. Accordingly, the total active oxygen in the molten steel bath is designated by the symbol 0. During deoxidation, various oxides may be present either in solution in the molten steel or as solid or liquid inclusions. Any sample taken from the molten steel for oxygen analysis will include both the dissolved and the mechanically included oxygen. Similarly, samples of the solid steel product will also include the two forms of Oxygen&apos; Methods of Samplirzg the Molten Steel Bath In order to obtain a true oxygen analysis from liquid steel, this element must be completely retained in the solidified sample. Several methods have been proposed whereby this stabilization can be effected. As early as 1915, Kichlinelo proposed a method for testing molten steel, in which the oxygen combined with some added aluminum. The concentration of the resultant aluminum oxide was determined by chemical analysis. This method was

Jan 1, 1945

By Pradeep K. Rohatgi, Clyde M. Adams

Dendritic aggregate of ice formed on freezing of aqueous soluitions has been studied. Chlorides of sodium, potassiutn, lithiunz , and hydroget1 were used as solutes. The spacing between ice platelets or den-drites was experimenlally found proportzonal to the square root of freezing time when the freezing rate was constant from beginrting to end of solidification; the constant freezing rates were obtained during freezing of small droplets of aqueous soliitions surrounded by relatively large heat sinks. The transverse growth velocity of the ice platelets is proportional to the square root of the freezing rate. During unidirectional freezing from a constant temperuture chill, the solution at each location is subjected to a spectrum of freezirtg rates. The freezing rate is ini- FREEZING of solutions has been a subject of investigation in many disciplines. Aqueous solutions offer the advantage of transparenty; their study is of special significance due to the increasing interest in freezing processes for desalination. In addition dendritic solidification of aqueous solutions is in many ways analogous to freezing of metallic solutions. Aqueous solutions of most ionic salts freeze with tially low, passes through a maximum, and then decreases until solidificatimz is complete. The den-drite spacing increases linearly with the distance from the chill surface; it is inversely profiortional to the square root of the maximum freezing rate. The dendrite spacings in the two systems (the constanl freezing rate and the varying freezing rate) are equal, when the maximum freezing rate of the varying freezing rate system equals the average freezing vale of the constant freezing rate system. Mass transport in interdendritic liquid duriug solidificatiotz is analyzed; the experimental observations indicate that maximum concentration difference (AC) and supercooling (AT) in the interdendritic liquid are indepexdent of freezing rate. the separation of practically pure ice crystals from the liquid phase; with very few exceptions there is no solid solubility of ionic salts in ice. As an ice crystal grows there is rejection of solute from the moving interface into the liquid. Since the rejected solute moves primarily by diffusion, concentration gradients are established in the liquid. The highest solute concentrations are found in liquid immediately adjacent to liquid-solid interfaces and lowest concentrations farthest from the interface. Two-phase equilibrium obtains only at the solid-liquid interface; at other locations the liquid becomes supercooled because temperature gradients are negligible compared to concentration gradients. This is an immediate consequence of the fact that thermal diffusivities are considerably higher than mass diffusivities.

Jan 1, 1968

By M. W. Dumais, E. P. Abrahamson

In a paper by Abrahamson and Alexander concerning a series of correlations between electronic structure and property changes, it was hypothesized that each solute atom in a dilute solution had a characteristic volume of solvent atoms over which some form of electronic interaction occurred. From this description it is possible to picture the solute atoms as occurring in an ordered array for the most efficient arrangement. A recent review article2 has shown that some form of anomaly exists for a whole series of properties when dilute additions of tungsten are made to iron, of. Fig. 1. Any mechanism to fit one property must also be amenable to mechanisms for the other properties. The possibility of some structural change in this region appears to offer the best hope. The system chosen for investigation was the iron tungsten system. Zone-refined iron with zone-leveled tungsten additions were supplied by Materials Research Corp. as 3/8-in.-diam bars. Transmission electron microscopy was used to study the structure. One-quarter inch specimens of each alloy were cold-rolled to 10-mil sheets, cleaned, punched to electron-microscope specimen-holder size, and annealed in vacuum for 2 hr at 800°C and 2 hr at 700°C followed by a furnace cool. The specimens were attached to a platinum wire and the specimen edge and wire were painted prior to thinning in a solution of 10 pct perchloric acid in glacial acetic acid. It was believed that if ordering were present due to electronic interactions the polishing procedure chosen would provide a simultaneous combination of chemical attack and electropolishing to exhibit the ordered structure. The chemical attack would be expected to penetrate those areas equidistant from the tungsten atoms, while the electropolishing would serve to "plane off" the volumes where the chemical attack had taken place. If one of the ordered tungsten planes were parallel to the specimen face at the edge of the thinned hole, a plate or micalike structure would be expected. A typical result of this polishing is shown in Fig. 2. Here a series of plates can be seen lying one upon the other. In several other specimens the plates parallel to the electron beam have been observed, behaving like slices of bread in a loaf. These edge views coupled with moire patterns indicate that the minimum plate thickness is 37 to 42A. This is equivalent to a concentration of 455 at. ppm of W if a simple cubic superlat-tice exists, or one tungsten atom every twelve iron atoms on the ordered plane. It was further noted that the base iron exhibited no signs of platelike structure. As the concentrations increased above 100 at. ppm W the amount of plate material increased. Among the specimens investigated was that shown

Jan 1, 1967

By Lawrence K. Jetter, Robert F. Mehl

SOME advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory.? Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selected for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatometric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system-a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation ;2,3,4 there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type-the ideal case which Becker5 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1942

By Cyril Smith

ALTHOUGH alloys of copper and silicon were examined several years ago,1 and their excellent mechanical properties were shown, it was not until C: B. Jacobs2 introduced manganese in small quantities to the alloys that they became of commercial importance. A few years ago The American Brass. Company took over the patents and commenced to manufacture the alloy under the name "Everdur." The present study of the constitution of the ternary system was undertaken in order to reach a fuller understanding of the behavior of the alloy. REVIEW OF PREVIOUS WORK ON, THE BINARY SYSTEMS There have been no papers published dealing with the constitution of the ternary system, although some tests of the mechanical properties have been described,3 which indicate that there is a change insolubility with temperature.

Jan 1, 1930

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By Lawrence K. Jetter, Robert F. Mehl

Some advances have been made recently in the theory of the kinetics of precipitation from metallic solid solution despite the complexities of the problem, but there is surprisingly little quantitative information available on rates of precipitation with which to test present theory or upon which to build new theory. Attempts to measure rates of precipitation have been beset with difficulties which originate both in the anomalies that attend the changes in the properties selectcd for measurement, as, for example, in electrical conductivity or mechanical properties, and also in the complexities in the structural changes in some systems, as in the aluminum-copper system. If the functional relationship between the quantity of precipitate and the value of the selected property is uncertain, measurements of that property are obviously of uncertain utility in determining absolute rates of precipitation. If the precipitating system passes through one or more transition stages, the interpretation of measured rates lacks definiteness; in such cases, it is necessary to measure the rate of reaction in each separate stage, if the rate measurements are to have any significance from the kinetic point of view.* These difficulties cannot be wholly avoided, for at least in some measure they are characteristic of the process of precipitation from solid solution, but they can be minimized both by the selection of a simple system and by the use of a method of measurement relatively free from anomalous behavior. The present paper reports dilatome tric measurements on the rate of precipitation of silicon from the aluminum-rich solid solution in the aluminum-silicon system—a study that approaches the desiderata of simplicity. The aluminum-silicon system offers advantages from these points of view: there are no known anomalies in the property changes accompanying precipitation; there are no known transition stages; the precipitate is an element, not a compound, and both matrix and precipitate are cubic, and while the structures are not identical (the solid solution is face-centered cubic and the precipitate is diamond cubic), the system at least approaches the ideal case of a crystal precipitating from a matrix of the same crystal type—the ideal case which Becker6 assumed in treating the precipitation process theoretically. The dilatometric method, while not free from disturbing effects, as the subsequent dis-

Jan 1, 1943

By A. U. Seybolt, R. A. Oriani

The pressure and composition of the solid solution of nitrogen in chromium has been investigated as a function of temperature. The partial molal heat of solution, the activity of nitrogen in solid solution, and the partial molal free energy have been computed. The enthalpy of three reactions is summarized: N + 2Cr(3) = Cr2N(4), H° = —28,500 cal per mol 1/2N2(p) + 2Cr(8) = Cr2N(3)1 ?HO = —23,500 cal per mol 1/2N2(p) = N, ?H° = 5,000 cal per mol. WORKERS who have investigated the problem of the preparation of ductile chromium have been concerned with the effects of minor amounts of impurities upon this refractory metal. In particular, gaseous impurities such as oxygen and nitrogen have been suspected of causing trouble because of many known cases where brittleness in transition elements has been definitely traced to these elements. In order to evaluate the possible effects of the nitrogen impurity in chromium, it appeared desirable to learn something of the dependence of the nitrogen solubility upon temperature and pressure. Previous Work Maier3 in 1942 in his treatise on sponge chromium reviewed the thermodynamics of the chromium nitrides Cr2N and CrN, both of which are well-estab- lished compounds, but which apparently have not been studied in much detail. Maier presented some free energy-temperature expressions for the reactions 2 Cr,N = 4 Cr + N2 [1] and 4 CrN = 2Cr2N + N2 PI based mainly on the work of Satoh2 and Sano." Pearson and Ende3 in 1953 briefly reviewed the thermodynamics of Cr-N using the same data available to Maier, and also derived a free energy-temperature expression for reaction 1. Of the two nitrides mentioned previously, the present investigation was only concerned with Cr,N, since this nitride is in equilibrium with the metal phase, at least over most of the temperature range, Blix4 in 1929 established the structure of Cr2N (close-packed-hexagonal) by X-ray diffraction methods, and indicated that its homogeneity limits extend from 11.2 pet to 15.1 wt pet N. At a temperature of 1200°C, 38 mm Hg from the Maier expression and 43 mm Hg from the Pearson

Jan 1, 1957

By Henry S. Munroe

THE earliest accounts we have of Japan represent the country as having great mineral wealth, especially of precious and useful metals. Marco Polo, the Venetian traveller, in the thirteenth century, writes of "Zipangu:” "They have gold in greatest abundance, its sources being inexhaustible. The king does not allow of its being exported. To this circumstance we are to attribute the extraordinary richness of the sovereign&apos;s palace. The entire roof is covered with a plating of gold. . . . The ceilings of the halls are of the same precious metal ; many of the apartments have tables of pure gold of considerable thickness, and the windows also have golden ornaments." Marco Polo also gives an account of an unsuccessful Tartar expedition against Japan, prompted by the supposed great wealth of the country. Columbus also, as well as many other explorers, were attracted and encouraged by these prevalent reports of the wealth of the islands of Zipangu. Kaempfer, writing in 1727, speaks of the great mineral wealth of Japan, and especially of the abundance of gold, which, he says, is found in many provinces. The Portuguese and Dutch, while they had trading-posts in Japan, furnished tangible evidence of the truth of the early reports. Between 1550 and 1639 the Portuguese merchants sent home from Japan nearly three hundred million dollars&apos; worth of bullion, most of which was gold. As the relative value of equal weights of gold and silver was then six to one, while in Europe, at the same time, it was nearly twelve to one, the exchange of silver bullion for gold was by no means an unimportant part of their business. After the Portuguese, the Dutch continued the exportation of bullion, and the exchange of silver for gold, though with less profit, as the relative value of gold increased with the demand. Between 1649 and 1671 the Dutch traders sent home over two hundred million dollars in bullion, of which, however, nearly two-thirds was silver. In 1671 the Japanese government, alarmed at the rapid rate at which the precious metals were leaving the country, issued an edict forbidding the exportation of gold or silver, under heavy penalties, which had the immediate effect of stopping this trade. Besides bullion, copper formed at this time a most important article of export. According to Dr. Geerts,* who has examined the old * Transactions Asiatic Society of Japan, vol. iii, p. 41.

Jan 1, 1877