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By R. G. Bowman

DISCUSSIONS of processes for the manufacture of white lead generally open with the statement that white lead is the oldest chemical pigment known to man. This fact is of more than historical interest; in the light of the present extensive use of white lead, ii indicates that the .compound possesses characteristics that make it unique among white pigments, and superior to all ;in its particular field. A greater variety of processes have been proposed for manufacturing white lead than for any other one chemical compound. Only a few of these processes have come into commercial use, however, and a large part of the present production here and abroad is made by the process used in ancient times. The outstanding disadvantages of the old process are that it is slow and laborious, affords no control of the product, and yields at best an impure material lacking in uniformity. Improved processes, sometimes classed all together as "quick processes," have had as their main object the shortening of the time required. Most of them accomplish this and some have yielded a superior product as well, but only two or three are now in use commercially. For centuries the manufacture and mixing of paints has been treated as an art, and the practice has been much influenced by tradition and precedent. There is a reluctance to abandon old materials for this purpose, and as few new uses for white lead have been developed, the adoption of the quick processes has been slow. The electrolytic production of white lead is not-new, a large number of processes and forms of apparatus have been proposed and patented within the past 25 years, all directed toward the, production of white lead, wholly or in part, by electrolysis. One or two of these processes were tried commercially but proved unsuccessful.

Jan 9, 1925

By Norman Braly

THE following is not offered as an extended paper on the subject of shaft sinking, but more as a description of the present practice of shaft sinking in the Butte district. The Anaconda company is sinking at present the following shafts: Badger State, Moose, Mountain Consolidated, Mountain View, Pennsyl-ania and Tropic. At the High Ore and Leonard mines the shafts are being deepened by sinking two compartments and will subsequently be enlarged to the full working size by raising alongside the compartments which are now being sunk. The following other companies are also sinking shafts: Butte-Alex Scott, Butte and Zenith City, Boston and Corbin, North Butte Mining Co. (at the Granite Mountain shaft), East Butte Co. (at the Pittsmont shaft), and the Rainbow Lode Development Co. Shaft Timbering. The shafts of the Butte district, generally speaking, are of three compartments arranged in a straight line, and the pump compartment is usually arranged for the use of an auxiliary hoisting cage, as well as for carrying pipe lines and electric wires. The Rainbow shaft is practically square, and of three compartments. The length of the shafts outside of timber will vary from 17 to 22 ft., and the width from 6 ft. 6 in. to 7 ft. Fir timber is used in all shaft work. This may be obtained from the Coast, when it is known as Coast fir, or from Idaho or Montana, when it is known as native fir. The native fir seems to be the tougher wood, but it is hard to obtain clear lumber in the lengths and sizes necessary for shaft work. Some of the shaft timber of the Anaconda company has been treated with creosote as a preservative, but this practice has not come into general use, as the ground of the camp is so heavy that the timbers usually crush before they rot. The size of timber most .used for shaft work is 12 by 12 in., while 10 by 12 in., 10 by 14 in. and 12 by 14 in. are used for some of the special pieces around the shaft. The new Leonard shaft is timbered with 14 by 14 in. wall plates throughout.

Jan 8, 1913

By J. Szekely, J. W. Evans

A formulation is given for radiant heat loss from the surface of molten steel held in a ladle and numerical solutions are presented for the resultant integrodif-ferential equations. The results are shown on plots of the net rate of heat loss against time, with the geometlry, emissivities, thermal properties of the walls, and Preheat as parameters. It was found that the rate of the vadiant heat loss from the exposed metal surface was comparable to the conductive losses from the Portion of the metal in direct contact with the walls. The radiant heat loss was markedly affected by the geometry and by the thermal properties of the walls the net radiant heat loss from the steel could be drastically reduced by providing a top cover and also by the provision of preheat. The results of this work are thought to be relevant to heat loss calculatious concerned with vacuum degassing and with operatzons in which molten metals are held in ladles. WhEN molten steel is held or transferred in ladles heat losses inevitably occur. The accurate assessment of these heat losses is of importance in process design considerations, as the temperature of the metal may have to meet rigid specifications in certain stages of the processing sequence. As shown in Fig. 1, the principal mechanisms responsible for heat loss are: i) Conduction into the walls and ii) Thermal radation from the top metal surface (possibly augmented by natural convection) The conductive heat loss may be readily calculated as much information is available in the literature on both the general theory1'' and on its particular applications to ladle heat loss calculations. Evaluation of the radiant component of the heat loss is less straight-forward. In two recent papers it has been shown that the presence of a slag layer 2 to 3 in. thick would prevent any significant heat loss for periods up to an hour,5'" however, should bare metal be exposed, constituting the radiant surface, substantial heat losses could occur. This latter case is of considerable practical interest in various degassing operations and in the vacuum processing of certain specialty steels, where the top surface of the metal is not covered by a protective slag layer. Under these conditions a substantial radiant flux is emitted by the top metal surface; part of this flux leaves the system, part of it falls in the ladle walls. The radiant flux incident on the ladle walls is in part absorbed and conducted away, and in part reflected and re radiated. The purpose of the paper is to present a general formulation of the problem, the resultant solution of which should enable computation of the net radiant heat loss from the metal surface. The principal variables, the effect of which will be investigated, include initial metal temperature, geometry, thermal and radiative properties of the wall, and various modes of preheat. FORMULATION Consider a cylindrical enclosure, shown in Fig. 2, with a diameter D, height H, and wall thickness W, the cover at the top of the cylinder having a wall thickness L. If the temperature of the base (representing the top surface of the metal) is kept constant, say, Tb, the problem is to calculate the net rate of heat loss from the base as a function of time, geometry, the initial temperature distribution, and the thermal properties of the system. As customary, the formulation will consist of the mathematical statement of the conservation of thermal energy within the system.

Jan 1, 1970

By Henry S. Rawdon

The structure of wrought iron as usually described by metallographists and workers in metal in general is that of a fairly pure iron. Impurities, if present, are usually considered as being in solid solution in the crystals of the ferrite matrix or as forming part of the ever present "slag streaks." Attention is herein directed to one type of these dissolved impurities; to the detection of such impurities, particularly in low-grade irons, and to their possible influence on the physical properties of the metal. The attention of the Bureau of Standards was first directed to wrought iron of the peculiar and unusual characteristics to be described later, in material which had failed in service and was submitted for test. The examination was extended to other grades of wrought iron, to see whether such features are of common occurrence in this class of material. MICROSTRUCTURE OF WROUGHT IRON Usual Structure The general microstructure of wrought iron is so well known that a detailed description of it here is needless. There is shown in Fig. 2 the structure of a sample of Swedish iron which illustrates well the matrix of ferrite crystals in which are embedded the slag threads so characteristic of the puddling process and the subsequent working of the material. The usual commercial product contains varying amounts of the impurities commonly associated with iron and steel, i,e,, manganese, phosphorus, silicon, and sulphur together with small amounts of carbon. Of these, the larger part of the phosphorus and some of the silicon present are held in solid solution in the ferrite while most of the remaining impurities, other than carbon, exist in the in closures of slag. Aside from the discontinuities introduced by the slag streaks the ferrite matrix has the microstructure and appearance of a pure metal. No definite orientation of the various crystals or grains is apparent; deep etching of the specimens reveals no intracrystalline features (i.e., within the grains) other than those noted in " pure " metals in general (etching pits).

Jan 1, 1918

By J. Ruzicka

IN creep testing, material is subjected to a constant load, preferably at a constant temperature, and its rate of deformation is measured. The method of loading can be of various types but in this paper only creep testing under tensile load will be considered. The ordinary tensile test is essentially a comparison test in conditions that frequently bear little or no relation to those under which the test material is to be used in service. The purpose of creep tests is to measure the strength of the test material at slow rates of deformation that more nearly approach the rates realized in service. One purpose of this paper is to illustrate that the creep test, in addi-tion to its value as a service test, is superior to the ordinary tensile test as a sensitive tool for the comparison of certain metals in investigative testing. The other purpose is to describe equipment having distinctive features of design that make it especially suitable for such tests. Representative data obtained with this equipment on a group of rolled zinc-base materials are given. These data are compared with those from practical comparison tests of the creep type on weatherstrip fabri-cated from the same group of materials. The comparison illustrates the value of the fast creep test and of the equipment.

Jan 1, 1937

By T. J. Smolik, Harman, D. W. Fuerstenau

By means of electrokinetic measurements, the surface properties of the aluminosilicate polymorphs (sillimanite, andalusite, and kyanite) and also mullite have been found to depend on the ratio of A10 bonds to SiO bonds in the surface. The Al-toSi ratio in the surface is dependent upon the crystal lographic properties of the mineral, which in turn determine coordination numbers of A1 and of Si, cleavage characteristics, and density of the various solids. Mullite with a greater bulk Al-toSi ratio has the highest zpc of the aluminosilicates. By treatment in dilute acids or by cycling between acidic and basic solutions, alumina is selectively dissolved from the surface of these orthosilicates. This shifts the apparent zpc to lower pH values as the fraction of SiO groups in the surface increases. Thus, surface properties can be altered by procedures that alter the A l-to-Si ratio in the surface. Flotation of these aluminosilicates results from electrostatic interaction of the collector ions with the mineral surfaces. As a result, flotation response shifts in accord with any shift in apparent zpc by pretreatment. Separation of minerals by flotation is based on differences in the physicochemical properties of their surfaces.'-3 For many minerals, adsorption of flotation collectors results from their functioning as counter ions in the electrical double layer at solid-water interface. In such systems, separation depends on differences in the zero point of charge (zpc) of the various minerals. The zpc is defined as the concentration of potential determining ions in solution at which the surface is uncharged. The potential determining ions for inorganic oxide-water interfaces are hydrogen and hydroxyl.4,5 This work is concerned with the effects of crystal structure, composition, and surface preparation on the surface properties and flotation behavior of aluminosilicates. Differences resulting from crystal structure were studied by measuring electrokinetic potentials and determining the flotation behavior of three different aluminosilicate materials having the same chemical composition (Al2O3 SiO2), namely andalusite, kyanite, and sillimanite. Furthermore, the effect of the Al2O3-to-SiO2 ratio on flotation behavior and surface properties was investigated by including synthetic mullite, 3A12O3 .2SiO2. Gaudin and co-workers 6,7 have clearly shown how crystal structure determines the native floatability of certain minerals. Those solids in which the surface is comprised mainly of broken residual bonds possess naturally hydrophobic surfaces. It was found by Bakakin8 that for a number of oxidized lead minerals, differences in floatability were due to the distance of Pb atom from the surface. Only limited work has been done on relating electrical properties of surfaces to crystal structure and composition. Healy et. a1.9 found that the zero points of charge of various manganese dioxides ranged from about pH 1.5 to pH 7.5, and these differences in the zpc's were interpreted in terms of the atomic packing in the various crystals. The research presented here clearly shows that crystal structure and chemical composition do affect the surface properties of aluminosilicates and, in addition, that these effects can be altered by changing conditions under which the surfaces are prepared. CRYSTAL STRUCTURE OF THE ALUMINOSILICATES Sillimanite, andalusite, and kyanite are composed of regionally metamorphosed rocks differing mainly in degree of metamorphism. All three minerals have the same chemical composition, Al2O3 - SiO2, of which sillimanite is the high temperature polymorph and kyanite and andalusite the lower temperature polymorphs. Andalusite and sillimanite crystallize in the orthorhombic system while kyanite crystallizes in the triclinic system. The structure of these three minerals is essentially chains of aluminum-oxygen octahedra linked laterally by silicon and aluminum. The arrangement of these chains in the three minerals is shown in Fig. 1.l4

Jan 1, 1967

By R. M. Brick

THE etched microstructures of cold-worked alpha brasses, after reduc-tions in excess of about 20 per cent, exhibit dark lines or markings, which have been termed "deformation bands," "etch bands," and "strain markings." The terms will be used synonomously in this report. The markings are similar in their general appearance to etch figures found in cold-worked iron, aluminum and other cubic metals but in certain respects may differ noticeably. At reductions of from about 20 to 50 per cent in brass, they appear as straight dark lines of irregular spacing and at random directions in different grains, but apparently intimately associated with definite crystallographic planes, usually {111}, in each crystal. At higher reductions, the markings on the rolling plane tend to appear in a direction transverse to the rolling direction in all crystals but may bend away at considerable angles, particularly near grain boundaries. Samans,1 on the basis of X-ray and micrographic studies of two single crystals of brass, rolled to a 50 per cent reduction, showed that the lines of deformation were the edges of thin mechanical twins parallel to octahedral planes. Barrett and Levenson2-4 have made comprehensive studies of the deformation of iron and of aluminum. They show that in these two metals the deformation markings originate by division of the original homogeneous crystal into banded areas differing in orientation by an amount that increases with the degree of deformation. The markings thus cannot be twin bands, and Barrett, in a review of this subject,2 attributed Samans' results on brass to an accidental choice of deformation that left the bands in approximately a twinned relationship. On the other hand, Mathewson5 has suggested that in some cases mechanical twinning offers a better rationalization of the coverage of some (111) pole figures of worked brass than the assumption of band rotation into sym-metry positions. Considering next a deformed and annealed alpha brass, the most striking aspect of its microstructure is the multiplicity of twin bands.

Jan 1, 1940

By Cyrus Garnsey

NECESSITY FOR PRICE FIXING DURING the latter part of 1916 and the early months of 1917, clue to war activities, there was a threatened shortage of coal which resulted in panic among consumers and a rush to obtain coal at once at any price. As a result of this insistent demand for immediate delivery, prices were bid up by the consumers to unprecedented heights; spot coal which had previously been selling at from $1.50 to 82 per ton was bid up to $5, $6, and, in exceptional cases, as high as $7.50 or more per ton. Then when the April, 1917, contract period arrived, contracts could be made only at prices ranging from $3 up to $5 and $6 per ton for the year's delivery. This condition caused such a demoralization of the business, and so much complaint, that some action to regulate prices was considered essential by the National Administration. LANE-PEABODY AGREEMENT In May, 1917, a committee under the chairmanship of F. S. Peabody, of Chicago, was appointed by the Council of National Defense, through Mr. Lane, to consider the whole question of bituminous coal. This committee, with the Secretary of the Interior, Mr. Lane, after numerous meetings and long negotiations with the operators throughout the country, announced on June 29 an agreement between the Committee and the producers, fixing a tentative maximum price for bituminous coal throughout the country at $3 per net ton f.o.b. mines, to which was added 25 c. for selling commission to wholesalers. This plan was based on the idea of fixing a maximum price, high enough to greatly-stimulate production, with the expectation that the laws of supply and demand would, with ample production, operate to maintain fair and just prices for coal throughout the country.

Jan 9, 1918

By D. Harker, M. J. Murphy

The mechanism by which age-hardening takes .place is still not completely understood. The principal theories range from the extreme of "precipitaiion-hardening" to that of "order-hardening," with many intermediate gradations. In the hope of obtaining new data on which to base a choice among the many theories, the authors have made electron micrographs of formvar replicas taken from metallic specimens at various stages of age-hardening. The results so obtained on an alloy of 2 per cent beryllium in copper and one of 20 per cent molybdenum in iron will be described in the following pages, as well as the technique used in preparing the replicas. Preparation of Formvae. Replicas of Metallic Specimens This section is concerned with the techniques that have roved successful in preparing formvar replicas for studying the microstructure of metals with the electron microscope. Because of its simplicity and accuracy, the formvar replica1 method developed in the General Electric Research Laboratory has been used exclusively, since it is much simpler than the silica replica method of Heidenreich and Peck2 and produces as good results. The formvar method to be described requires a technique acquired only by practice, and no foolproof set of rules can be given. it is a rapid method and a replica can be obtained in less than five minutes under favorable conditions. This does not mean that perfect replicas can be produced every five minutes, but rather that one can well afford to take several strippings* in order to produce a replica of high quality. The metallographic technique required for replica work—very fine polishing and etching with very dilute solutions—is described here. It can be said, in general, that almost any surface that has been carefully prepared for a photomicrograph at 1000 or more diameters can be used to obtain a replica for the electron microscope. Preparation of Metallographic Specimens The preparation of the metallographic specimens is somewhat more exacting than that usually given to samples to be used for inspection under the light microscope. After much experimentation, it was concluded that the best method consists in polishing the metal through to the coarse cloth, then etching and repolishing on final cloth until the layer of distorted metal is removed. After this procedure has been completed, a dilute etch—to approximately the depth necessary for a micrograph at 1000 diameters—usually produces a sur-

Jan 1, 1945

By F. Keller, J. D. Edwards

THE anodic treatment of aluminum presents problems of scientific as well as of commercial interest.1-3 Of particular interest is the fact that, during the anodic oxidation process, the oxide continues to form at the metal-oxide interface under any oxide previously formed. This has led to speculation as to the mechanism involved in the formation of the relatively thick oxide coatings that are used commercially for decorative or protective purposes. Furthermore, the ability of certain types of oxide coatings to adsorb dyes and other substances has stimulated research to determine the actual structure of these adsorptive coatings. It has been found that anodic oxide coatings on aluminum are composed essentially of aluminum oxide. They are formed by the action of oxygen ions penetrating to the metal surface during the electrolytic oxidation treatment. These coatings can be formed in a number of different electrolytes, as for example, those which contain sulphuric acid, chromic acid, oxalic acid, or boric acid. These are the commonest and most useful electrolytes employed commercially. Except for certain specific conditions of formation, the coatings in general have been found to be amorphous alumina, as far as can be determined by X-ray or electron-diffraction methods. Anodic oxidation processes can be arranged in three rather general classes if they are grouped in relation to the solvent action of the electrolyte on the coating.4 In the first class, the electrolyte has little or no solvent action on the coating that is formed. In general, coatings produced under such circumstances are nonporous and non- adsorptive. In the second class, the electrolyte exerts an appreciable solvent action on the coating. These coatings are porous and adsorptive. Finally, for the third class, the electrolyte tends to dissolve the coating about as rapidly as it is formed. This action produces electrolytic brightening or anodic polishing of the aluminum surface and at most leaves only a very thin film of oxide. The nonporous and nonadsorptive type of oxide film is represented by the coatings that are formed when solutions of boric acid are employed as the electrolyte. It is especially significant that these impervious films are formed in electrolytes that exert little or no solvent action on the coating. Where a boric acid electrolyte is used, the coating tends to form rapidly, with the result that the flow of current is soon reduced to substantially zero. This indicates that the growth of the coating has stopped. As a rule, the thickness of the coating is roughly proportional to the voltage employed for formation and the coatings of this type are exceedingly thin. In an electrolyte of this type, the coating has a high resistance when the aluminum is made anode; consequently, any current that may flow (leakage current) is very

Jan 1, 1944

By Eli T. Conner

My connection, under a commission from the Councils and Board of School Control of the city of Scranton, Pa., with a recent investigation of mine-caves and the resultant damages to surface-improvements, has led to the preparation, at the invitation of our Secretary, of the present paper. It is notorious that there are, in the anthracite-fields, frequent subsidences of the surface, due to the removal of the coal beneath. No particular attention is paid to such occurrences, unless they happen to injure surface-improvements. Many caves have happened in Scranton and its viciuity, which hare excited but little remark, since they have generally caused no serious damage. In August, 1909, a cave occurred in the Hyde Park section of the city, generally known as the West Side, which nearly destroyed school-house No. 16 and considerable adjacent property. Fortunately, there were no pupils in the building at the time; but the thought of the possible result, had the usual number of pupils and teachers been present, aroused the public to the gravity of the situation; and the School Board employed engineers to investigate the case. Two reports were made by separate sets of engineers, which differed in some particulars. These differences were pointed out in the public press and magnified, and the consequent agitation of the subject was taken up and greatly exaggerated by some of the metropolitan newspapers, giving to uninformed people the very erroneous impression that the whole city of Scranton was in danger of sinking into the bowels of the earth. All this tended to affect the credit of the city and to depress real-estate values. The matter was considered at a joint meeting of the Board of Trade, the Councils, and the School Board. The Hon. J. Ben. Dimmick, a former Mayor, suggested that it

Jan 1, 1912

By Smith Bracewell

First evidence of bauxite in Jamaica resulted from an analysis of a soil sample collected at Bull Savannah in 1938 during a systematic local investigation of the island's soil types. Results of subsequent work indicated the possibility of the occurrence of deposits of commercial grade and dimensions, and in 1942, with a view to emergency development of the deposits as a war measure, the Jamaican Government declared all bauxite in the colony to be Crown property.

Jan 10, 1958

By E. W. Dewing

The nature of solid solutions of sodium in non-paphitic carbon at temperatures near 1000°C has been investigated by an electrolytic technique. The activity coefficient is found to vary strongly with the heat-treatment temperature of the carbon, and an analysis of the energy terms involved suggests that this is due to variations in the Fermi level. The diffusion coefficient for sodium is in the range implying that the sodium atoms (or ions) are not bound to specific sites on the carbon, in agreement with lack of evidence for specific compounds in the activity -composition curves. In the light of These results phenomena occurring in aluminum reduction cell linings are dis-cussed. It is concluded that sodium migrates by diffusion through the carbon lallice and not the pores, and that A14C9 is formed within the lining hy The excess of NaF invariably found in used linings is formed by this reaction and by air oxidation: There has recently been much interest in the swelling of carbon which occurs when it is made cathodic in an aluminum electrolysis cell, and there is general agreement that the phenomenon is due to the penetration of sodium atoms, derived from the reaction on the carbon lattice. (NaF and AlF3 are constituents of the fused-salt electrolyte.) The low-temperature lamellar compounds of potassium with graphite are well-known, and one compound between sodium and graphite has been reported.4 There is, however, virtually no information on the basic chemistry of the interaction of sodium with nongraphitic carbon at high temperatures, although Dell3 has made some fundamental studies of rates of penetration. At the time the present work was carried out these were not available. Rapoport and samoilenkol had measured rates of physical expansion in a dilatometer, using the fractional increase in length of a carbon specimen after electrolysis in a cryolite bath for 2 hr as an index of susceptibility to cathodic swelling. Work here with a similar apparatus showed that expansion (of a 1.5-in.-diam cylindrical specimen) ceased in less than 20 hr, and that the final expansion was much more reproducible than the value at some intermediate time. This suggested that an equilibrium was being set up, and that a thermodynamic approach was required. The results obtained are not as accurate as had been hoped, but they are the only ones of their type available and have enabled useful conclusions to be drawn. The experimental work was divided into two parts: an investigation of the activity-concentration diagram for sodium in carbon, and a rough determination of the diffusion rate. For the former, most of the experiments were made with petroleum coke even though this is not a form of carbon used in cell linings. It has the advantages, however, that it is a homogeneous material, that it is low in ash, and that its structure is reasonably well understood. Anthracites and coal cokes gave results of the same type as obtained with petroleum coke, but the reprodu-cibility from specimen to specimen was extremely poor. EXPERIMENTAL 1) The Activity-Composition Diagram for Sodium in Carbon. The petroleum coke was ground, pressed at 40,000 psi into plates 19 by 9 by 2 mm without added binder, and heat-treated. The sodium activities were established by an electrolytic technique. The carbon was made anodic in a cryolite bath with an aluminum cathode, and a controlled potential, E, applied so that the sodium activity at the anode was given by ln Na = 1n asa - EF/RT [21 where as, is the sodium activity generated by Reaction [I]. The relative activity is sufficient for many purposes and is simply given by The value of Na not at present known, but when the thermodynamics of the Na-A1 system have been worked out it can be derived from the equilibrium

Jan 1, 1963

By Eugene A. Mizikar

A mathetnatical model of heal transfer in continuously cast steel slabs is described. The model, consisting of a unidimensional transient conduction equation and boundary condition equations, has been pvogrammed for computer solution. Temperatuve and solidification profiles calculated for a 6-in. slab, being cast under several conditions of secondary cooling, are presented and compared. Calculated solidification profiles are in agreement with reported expevinle~ztal values. For the mold zone, the predicted slab shell thickness can be described by: Resuilts of the study indicate that multibank spray cooling followed by radiant cooling should be employed when solidifying thick slabs with minimum surface temperature of 1600°F. Under these conditions, a 6-in. slab can be expected to solidify in about 8.3 min. Computer results also indicate that radiant cooling can replace spray cooling during solidification of the final 30 pct of slab with little increase in overall solidification time. CONTINUOUS casting has come to the forefront of the steel industry in recent years because of economic advantages resulting from increased yields and elimination of several processing steps. Considerable work, however, remains to be done regarding modifications to the process and operating procedures. Both a lack of operating plants in this country and the experimental difficulties associated with direct measurements on moving castings have made determination of solidification rates and temperature distributions difficult. An alternate approach is to mathematically simulate heat transfer in a continuously cast section, and then calculate the temperature distributions as a function of the controllable variables of the process. Simulation of heat transfer during solidification requires that a nonlinear mathematical problem be solved. As pointed out by Ruddle,' there are two mathematical approaches to the problem- the analytical approach and the numerical approach. While the analytical approach is certainly the more elegant of the two, it does require a number of inexact assumptions because of the complexity of the problem. For example, noteworthy analytical treatments of heat transfer in continuous casting have been developed by Savage Hills,3 and pehlke4 only by making one or more simplifying assumptions such as invariant thermophysical properties, constant heat-transfer coefficients in the mold, and linear temperature profiles in the shell. Simplifying assumptions such as these can introduce considerable uncertainty in the validity of results calculated with analytical solutions. Numerical solutions, which are considerably more versatile, appear to be better suited for solving solidification problems. Complex variations in the boundary conditions and variable thermophysical properties can be handled readily with this technique. Whereas numerical computations can be long and tedious when done by hand, results can now be obtained quite rapidly with the use of either the digital or analog computer. Several numerical models of heat transfer in continuous casting have been published. In 1963, Adenis, Coats, and Ragones published a numerical model used to calculate temperature distributions in direct-chill-cast magnesium billets. More recently, Donaldson and Hess 6 presented results obtained with a numerical computer model of heat transfer in continuously cast steel billets. In the present study, a model of unidimensional heat transfer in continuously cast slabs is presented. The method of solution on a digital computer is also included. Calculated temperature distributions and solidification profiles for various schemes of secondary cooling along with attempts to verify the model are also discussed. MATHEMATICAL MODEL The schematic representation of the slab continuous casting process in Fig. 1 illustrates that the slab passes through three distinct zones of cooling. Accordingly, the mathematical model consists of three parts: 1) solidification in the mold; 2) solidification in the spray cooling zone ; 3) solidification in the radiant cooling zone. Heat-Transfer Equations. The model was developed bymaking a heat balance on a horizontal slice of slab over the time period required for the slice to proceed from the liquid metal meniscus in the mold to the cutoff station. As shown in Fig. 2, the imaginary slice extends from the center line to the surface of the slab. As the slice moves downward, heat is conducted from the center line to the surface of the slab at a rate governed by the surface boundary condition and thermophysical properties of the metal in the slice. The following partial differential equation describes the conduction of heat in a medium moving at velocity U in direction Z:

Jan 1, 1968

By K. M. Myles

The vapor pressure of palladium over a series of Rlz-Pd alloys has been measured by the torsion-effusion method. The thermodynamic properties of the alloy system at 1575=K have been calculated from the vapor pressure data. The activities and the free energies of formation exhibit large positive deviations from ideal behavior. The enthalpies of formation are endother-mic. The entropies of formation are positive and larger than the ideal entropy of mixing. All of the thermodynamic properties suggest that a strong tendency toward phase separation exists in the solid solutions. The possible origin of the phase instability and the various factors that influence the thermodynamic properties are discussed. RECENT studies of the thermodynamic properties of alloys of palladium with nontransition elements have indicated that a significant contribution to the enthalpy of formation is related to the redistribution of the conduction electrons upon alloy formation.'-' The present work was undertaken to ascertain the importance of this contribution in Pd/transition-metal alloys. The Rh-Pd system was chosen for this investigation for several reasons: 1) The thermodynamics of the system were unknown. 2) Rhodium and palladium are completely soluble at high temperatures; below 1118OK the solid solution becomes immiscible.', 3) The difference in magnitude between the vapor pressures of rhodium and palladium permitted the use of an existing effusion apparatus. 4) Additional information was known about the alloy system that would facilitate the interpretation of the thermodynamic results. EXPERIMENTAL PROCEDURE The thermodynamic properties of the Rh-Pd alloy system were calculated from the vapor pressure of palladium over solid palladium and over several solid Rh-Pd alloys. The vapor pressure was measured by means of the torsion-effusion apparatus that has been described previously. In this method, an effusion cell is suspended from a tungsten filament inside a high-temperature furnace. Two orifices are located eccentrically such that the effusion of the vapor creates a rotational torque in the filament. The angle of rotation is directly related to the total vapor pressure within the cell. As the vapor pressures of rhodium and palladium are approximately five orders of magnitude apart," the total vapor pressure was considered to be effectively equal to the equilibrium vapor pressure of palladium. The effusion cells were made from high-purity alumina since auxiliary experiments indicated that essentially no reaction occurs between alumina and solid Rh-Pd alloys. Unfortunately, because the orifices were irregular, an accurate calculation of the Free- man-Searcy correction factors" could not be made. The constants were determined in an independent experiment where the vapor pressure of copper, as measured in the alumina cell, was compared with an accurate value of the vapor pressure, which had been determined previously.4 Depletion of palladium from the surfaces of the specimens was minimal as the deflection of the cell remained constant, for at least 15 minutes, at each of the experimental temperatures. Lattice parameter measurements of the postrun alloys also indicated that no changes in the composition of the surfaces had occurred. The alloys were prepared by arc melting the requisite amounts of the 99.99 pct pure elements. The four most palladium-rich alloys were remelted in a levita-tion furnace since complete melting of the components had not occurred in the arc furnace. All of the alloys were subsequently homogenized at elevated temperatures in sealed alumina thimbles. After heat treatment, the alloys were analyzed chemically and were in essential agreement with the nominal compositions. The thermal histories and nominal compositions of the alloys are given in Table I. Lattice parameters of the heat-treated alloys were computed, by means of the method described by Mueller et a1. ,I2 from X-ray diffraction powder patterns obtained with filtered copper radiation in a 114.6-mm-diam Straumanis-type Debye-Scherrer camera. The results, which are tabulated in Table I, exhibit a slightly greater negative deviation from Vegards' law than the values reported by Raub et al.13 The diffraction lines were sharp and well-resolved and thus indicated that the alloys were homogenous. RESULTS The logarithms of the individual values of the vapor pressure of palladium were fit, by the least-squares method, as a linear function of the reciprocal of the absolute temperatures. The constants of the equations are given in Table I along with the temperature range over which the data was accumulated. The latent heat of vaporization at 298.15"K for pure palladium, calculated by the third-law method,14 showed no systematic temperature dependence. The average value of 88,920 * 20 cal per g-atom agrees favorably with the average of the results obtained in the most reliable previous investigations.15"19 The activities of palladium were computed from the vapor pressure data at 1525', 1575", and 1625OK. Consistent with the mass spectrometric study of the atomicity of palladium vapor,lg the vapor was assumed to be monoatomic. The activities of rhodium were determined by integrating the Gibbs-Duhem equation with the aid of the a function.20 In the calculations, the activities of the pure solid metals were assigned the value of unity. From the activities, the partial and integral free energies, entropies, and enthalpies of formation at 1575° K were computed; they are assembled in Table 11.

Jan 1, 1969

By E. C. Pechin

THE Lucy furnace, owned by Messrs. Carnegie, Kloman & Co., and located on the Alleghany River, on the outskirts of Pittsburgh, is a splendid modern furnace, 75 feet high, and 20 feet bosh. She had been working well on low grade ores of about 50 per cent., producing daily 68 to 75 tons. There was on stock 500 tons of Republic ore, one of the purest and best of the Lake Superior ores, averaging over 68 per cent. of iron, which had been procured for the purpose of making a trial for Bessemer iron. This was charged by itself, and Mr. Skelding, the founder, reports that he did not succeed in getting a single cast when it came down, before the furnace chilled from the hearth to the top of the boshes, some 25 feet. Every effort was made to save her, without avail, and the disagree-

Jan 1, 1874

The Institute maintains a dual relationship with students: (1) an individual relationship with a Student Associate; and (2) a relationship with local organizations of students, known as Affiliated Student Societies or Student Chapters. 1. The conditions of Student Associateship are set forth in Section 9, Article I, of the Bylaws of the Institute (see page 64 and following pages). During 1934, sundry amendments were made for the purpose of improving the student relationship. Postgraduate students are now eligible; and associateship can be maintained, with the payment of the regular dues of $2 per year, for 18 months following graduation in June. With his regular dues, each Student Associate is entitled to receive during the year his choice of MINING AND METALLURGY, METALS TECHNOLOGY, MINING TECHNOLOGY, PETROLEUM TECHNOLOGY, or two "classes" of Technical

Jan 1, 1943

By HENRY FA

HENRY FAY (communication to the Secretary*).-In reply to the discussion of my paper, I wish to take this opportunity to express my appreciation to the Chairman and the various gentlemen who have taken part. I regret that others have not offered criticism, for honest differences of opinion often lead to the truth, and suggest new lines of work. An experiment has been made which bears on Prof. Sauveur's discussion and which helps to emphasize the conclusion that cementation is not a factor in the hardening of: the surface. Dr. Langenberg, of the Watertown Arsenal, has heated for me, in vacuo at 1,000° C., a piece of the metal containing a hard surface. The microstructure shows uniform distribution of carbon throughout the metal, showing that no carbon has been added to .the surface and heating in vacuo has prevented any oxidation of the surface.

Jan 6, 1917

By W. J. Taylor, H. J. Mutz, A. F. Brock

THE International Kickel Co. of Canada Ltd. operates five underground mines and an open pit. Four of the mines, the Frood-Stobie, Creighton, Murray, and Garson, are on the south range of the Sudbury Basin, map above, within a radius of 10 miles of the city of Sudbury, Ontario. The fifth mine, the Levack, is on the north range of the Sudbury Basin, 30 miles to the northwest of the city. The open pit is operating on surface ores of the Frood-Stobie orebody. Two pits were opened at the Frood-Stobie mine; the Frood section was started in 1938 and the Stobie section in 1942. To meet the heavy demand for nickel during World War 11, open-pit production was accelerated until it constituted over 40 pct of Inco's total tonnage. As a consequence open-pit ore was depleted considerably alhead of schedule; the Stobie pit was completed in the summer of 1951, and it is expected that mining at the Frood pit will be completed in 1953. The major program launched 10 years ago to develop additional underground production as a replacement of open-pit tonnage thus had to be greatly speeded up. This conversion to all-underground mining will be completed within the next two years, and the underground mines will then have an annual hoisting capacity of 13,000,000 tons. One of the new mines in the underground expansion program, the Murray, was brought into production in 1950. Ore production from the new Stobie section of the Frood-Stobie mine was commenced on a limited scale in 1951 and will be increased as the program progresses. Delivery of ore to the new Creighton mill was started in the summer of 1951 from the caving project launched at Creighton mine. When mining was started in the Sudbury district 65 years ago the ore deposits were opened on a small scale and mining methods conformed to a general pattern of small open cast pits, followed by open stopes as mining was extended below the pits. The open stoping methods used were heading-and-bench and shrinkage. In certain cases a type of cut-and-fill mining was used with drywall tramways and dry-wall chutes in the fill. As the mines were deepened,

Jan 1, 1954

By Frederick Prime

The first catalogue of Geological Reports of the United States was prepared by Prof. 0. C. Marsh, and published in the American Journal of Science and Ark for 1567, vol. xliii, second series. Since then the list has more than doubled, and it was thought that the publication of a new catalogue, brought clown to date, would be useful to many of the members of the Institute of Mining Engineers. The compiler will be most thankful to have any omissions or inaccuracies in the list sent to him, to be published as a supplement in the next volume of the Transactions. Especially to have the correct title, number of pages, plates, and maps of any volume on the list to which an * is prefixed, as he has been unable to personally consult such works. A preliminary list was issued last February, which has been almost doubled by the kindness of many friends. The writer desires more especially to express the obligations he is under to the following gentlemen : The Chief of Engineers, U. S. A.; Principal Dawson, Mr. G. M. Dawson, Drs. R. J. Harrington and T. Sterry Hunt, of Montreal; Mr. H. Engelmann, of La Salle, Ill.; Dr. F. V. Hayden and Prof. J. W. Powell, U. S. Department of the Interior; Prof. E. W. Hilgard, University of California; Prof. Henry Y. Hind, Windsor, N. S.; Prof. C. H. Hitchcock, of Dartmouth College; Mr. Henry A. Holmes, State Librarian, Albany; Maj. Jed. Hotchkiss, Staunton, Va.; Prof. W. C. Kerr, Raleigh, N. C.; Dr. J. S. Newberry, of Columbia College ; Prof. W. H. Pettee, of the University of Michigan ; Dr. Samuel H. Scudder, Prof. N. S. Shaler, and Prof. J. D. Whitney, of Harvard College; Mr. Sanderson Smith and Prof'. J. J. Stevenson, of New York; Mr. Addison Van Name, of Yale College, and Lieut. Geo. M. Wheeler, U. S. Engineers.

Jan 1, 1879