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By Leslie Burris, J. C. Hesson

The diffusivity of uranium in liquid cadmium has been measured as a function of temperature by the capillary -bath technique. The diffusivity measurements were made at 4509 500°, 575º, and 650°C, over which temperature range the diffusivity of uranium varied from 1.3 to 2.3 x 10-5 sq cm per sec. The diffusivity of uranium in cadmium was less than that predicted by the Einstein-Stokes equation. VERY little information is available on the diffusivity of uranium in liquid metals. Bonillal has reported a single measurement of the diffusivity of uranium in bismuth. Measurement of the diffusivity of uranium in cadmium was undertaken, not only to supply data in an area in which a dearth of information exists, but also because of a need for this physical property measurement in connection with mass transfer studies now underway in the U-Cd system at Argonne National Laboratory. The capillary-bath method used in this work has been successfully used by other workers2"4 to obtain diffusivities in liquid metal systems. Although considerable experimental technique is required to obtain reliable diffusivity measurements, the basic information required is only that of temperature, capillary tube length, the initial and final compositions of the alloy in the capillary tube, and the composition of the bath into which the solute element is diffusing. From these measurements, diffusivities may be calculated using Fick's law. The diffusivity equations are presented in the Appendix. Equations which are often used to predict diffusivities in dilute solutions5 are the Einstein-Stokes equation: D= (kT)/(6pµr) and the Eyring equation: D = (?,kT/?y?zp), where D= diffusivity (sq cm per sec), k = Boltzman's constant, T= temperature ("K), p = viscosity (poises), r = radius of diffusing molecule or species (cm), and A,, Ay, and A, are the diameters of the diffusing molecule in the three axial directions. For round molecules, the Eyring equation gives values which are 37r times larger than the Einstein-Stokes equation. In this work, the experimental values were compared to the Einstein-Stokes equation. Experimental values of diffusivities in liquid metal systems usually lie between those predicted by the Einstein-Stokes and Eyring equations. The viscosity values for cadmium were obtained from the Liquid Metals Handbook.6 EXPERIMENTAL APPARATUS AND PROCEDURE The general procedure employed consisted of rapidly immersing in a molten cadmium bath containing a negligible amount of uranium a capillary

Jan 1, 1963

By S. Razi

Injection luminescence of single crystals of rare-earth-activated CdS was investigated. Crystals of CdS:Nd, CdS:Er, and CdS:Yb, grown by the vapor transport technique, were suitably etched and hetero-junctions of Cu2S-CdS were fabricated on one side of the CdS substrate by chemical reaction. The device was then heated to 200°C in an inert atmosphere for 5 min. Static V-I measurements show that at low voltages (V < 1 v) the current is controlled by the junction, while at higher voltages the bulk Properties of the CdS substrate effectively control the current. Because of the large thicknesses no negative resistance was found. Reverse breakdown voltage varied from 5 v, for junctions that were not heat-treated, to 100 v, for diodes that received the proper heat treatment. The rectification ratio, measured in the range of 2 to 10 v, varied from 300 to 3000. Capacitance- voltage measurements indicate a weak dependence of the junction capacity on applied voltage. The capacity was found to increase appreciably with room light illumination. The variation of capacitance with frequency is indicative of a p+-i-n structure. An open-circuit voltage of 0.4 v was measured under an illumination of 100 mw per sq cm. Under forward bias, the bluish-green edge emission characteristic of CdS was observed. No sharp rare earth emission line was observed, which is in contrast to our results using ZnS:Tb, where, under high-voltage excitation, the rare earth emission was dominat over the lattice emission. The absence of rare earth emission implies that either the nature of the rare earth ion is different at the het-erojunction than in the bulk or the probability of energy transfer to the rare earth ion is small. RARE earth elements are playing an increasingly important role in the Synthesis of materials for a variety of purposes, e.g., solid-state lasers, color television screens, and so forth. Interesting systems result when wide-band-gap photoconducting lattices are activated with rare earths. A study of the lumines-

Jan 1, 1969

By J. D. Price, W. M. Bertholf

A. C. RICHARDSON*—First of all, [ think that the paper represents a lot more work, study, and correlation than has been indicated by the brief talk by Mr. Price. I like the way he started out and described the areas from which the samples were obtained, the locations of the washing plants, the available tonnages, and other background information with which to evaluate the data he submitted later on. Then I like the way in which he described the various types of washing plants, the tonnages handled and the difficulties of the washing problems; showing the amount of material that lies close to the specific gravity at which the washing separation is made. Later he gave figures from washing plant operations showing recoveries and cleaning efficiencies. He then discussed his own plant at Pueblo. It is the same old plant, I think, that I worked around a good many years ago. It is unusual to find a plant treating nearly 5000 tons of coal a day on tables. But this table plant is, I believe, more efficient than is indicated by the figures that Mr. Price gave. To determine the efficiency of a cleaning operation or to compare it with another it is necessary to consider the quantity and character of the material close to the specific gravity at which the separation is made. It is not fair, I believe, to penalize the table operation by something like 4 pct of out-of-place-material as he has done here. The variety and difficulty of the coals that he has to wash, the continuous shift and change in their composition make a very difficult cleaning problem and the table performance is excellent. I believe that the information in this paper will be of interest and value to anyone operating or planning to build a coal cleaning plant in this or other areas; particularly where the cleaning of fine coal is a problem. The data may be used for comparative purposes in determining the relative efficiencies of other cleaning plant separations. E. D. HAIGLER*—What is a Baum jig? J. D. PRICE (authors&apos; reply)—A Baum-type jig is one in which the pulsations of the water is secured by means of a pulsating air current applied on top of the water. I imagine you are all familiar with the old plunger-type jig which is in effect a U tube in which a plunger on one side of the U, moving up and down, causes a corresponding pulsation on the far side of the jig. In the Baum jig, the pulsating air current is applied on the surface of the water on one side of the U tube of the jig and gives a corresponding pulsation on the other. It is also commonly known as a pneumatic jig. The control of the rise and fall of the water in the jig body proper is under much better control than it is in any of the other type jigs. Mr. Richardson could enlarge on that feature, for I know that he has had considerable experience with these jigs. A. C. RICHARDSON—You have asked how to control a Baum-type jig. The pulsations in a Baum jig can be modified and regulated to a marked degree by the amount of water admitted to the jig and by the adjustments of the valve which regulates the manner in which air is admitted. The number of pulsations per minute is controlled by the number of cycles of the air valve. Thirty to forty cycles per minute is a good speed for large jigs treating coarse sizes of cod. With an air valve it is possible to modify the time-velocity curve of the pulsating water to some extent which in turn determines the action in a jig bed. Within limits the following parts of the air valve cycle may be regulated: (1) the rate and period of air admission, (2) the period of air expansion, (3) the rate and period of air exhaust, and (4) the period of air compression. The rate and period of air admission determines the acceleration of the water at the beginning of the pulsion stroke and the amplitude of the stroke. The period of air expansion, after inlet port is closed, is one in which the water has reached the desired velocity, positive acceleration reduced, and the bed held in a mobile condition. The rate and period of the air exhaust can be adjusted to modify the degree of suction and so modify the manner in which the particles in the bed stratify. The compression period, alter the exhaust port closes and before the intake port opens may be used to advantage in retarding the downward velocity of water during the suction stroke. An ideal jig stroke is one in which during the up stroke the bed is lifted slowly in a mass and opens up like an accordian with the bottom layers dropping away first. With the bed open and mobile the particles adjust themselves according to their hindered settling rates. During the down stroke, while the bed is still open the particles of high specific gravity are accelerated toward the bottom layers. It is possible to approach this stroke with all types of jigs but it is less difficult to approximate it with a Baum jig.

Jan 1, 1950

By M. Metzger, J. C. Bilello

Microyielding in 99.999 pct Cu occuwed in two distinct parabolic microstages and was substantially indeoendent of grain size at the relatiz~ely large grain sizes stzcdied. The strain recouered on unloading was a significant fraction of the forward strain and was initially higher in a copper-coated single crystal than in poly crystals. Results were interpreted in terms of cooperative yielding and short-range dislocation motion activated otter a range of stresses, and a formalism was given for the first microstage. It was suggested that models involving long-range dislocation motion are more appropriate for impure or alloyed fcc metals. THERE are still many unanswered questions concerning the degree and origin of the grain size dependence of plastic properties. In the microstrain region, a theory of the stress-strain curve proposed by Brown and Lukens,&apos; based on an exhaustion hardening model in which the grain boundaries limit the amount of slip per source, accounted for the variation with grain size of microyielding in iron, zinc, and copper.&apos; This theory assumes N dislocation sources per unit volume whose activation stress varies only with grain orientation. Dislocations pile-up against grain boundaries until the back stress deactivates the source, which leads to a relationship between the axial stress and the strain in the microstrain region given by: where G is the shear modulus, D the grain diameter, a the flow stress, and a, is the stress required to activate a source in the most favorably oriented grain.3 If this or other grain-boundary pile-up models are correct, then the reverse strain on unloading would be much larger for a polycrystalline specimen than for a single crystal. Also, the microplasticity would become insensitive to grain size if this could be made larger than the mean dislocation glide path for a single crystal in the microregion. These questions are examined in the present work on polycrys-talline copper and a single crystal coated to provide a synthetic polycrystal. EXPERIMENTAL PROCEDURE Tensile specimens 3 mm sq were prepared from 99.999 pct Cu after a sequence of rolling and vacuum annealing treatments similar to those recommended by Cook and Richards4-6 to minimize preferred orientation. Grain size variation from 0.05 to 0.38 mm was obtained by a final anneal at temperatures from 310" to 700°C. Dislocation etching7 revealed pits on those few grains within 3 deg of (111). For all grain sizes dislocation densities could be estimated as -107 cm per cu cm with no prominent subboundaries. The single crystals, of the same cross section, were grown by the Bridgman technique with axes 8 deg from [Oll] and one face 2 deg from (111). An anneal at 1050°C produced dislocation densities of 2 x 106 cm per cu cm and subboundaries -1 mm apart in these single crystals. A Pb-Sn-Ag creep resistant solder was used to mount the specimens, with a 19 mm effective gage length, into aligned sleeve grips fitted to receive the strain gages. All specimens were chemically polished and rinsed8 to remove surface films just prior to testing. The synthetic polycrystal was made by electroplating a single crystal with 1 µ of polycrystalline copper from a cyanide bath. Mechanical testing was carried out on an Instron machine using two matched LVDT tranducers to measure specimen displacement, the temperature and the measuring circuit being sufficiently stable to yield a strain sensitivity of 5 x 107. At the crosshead speeds employed, plastic strain rates were, above strains of 10¯4, about 10¯5 per sec for polycrystalline specimens and 10-4 per sec for the single crystals. Plastic strain rates were an order of magnitude lower at strains near l0- &apos;. A few checks at strain rates tenfold higher were made for reassurance that the initial yielding of polycrystalline copper was not strongly strain-rate dependent. Test procedures followed the general framework outlined by Roberts and Brown.9,10 An alignment preload of 8 g per sq mm for polycrystals, and 2 to 4 g per sq mm for single crystals, was used for all tests. These gave no detectable permanent strain within the sensitivity of the present experiments; although at these stress levels, small permanent strains are detectable in copper with methods of higher sensitivity.11 12 stress and strain data are reported in terms of axial components. RESULTS General. The initial yielding is shown in the stress vs strain data of Fig. 1. For polycrystals, cycle lc, the loading line bent over gradually without a well-defined proportional limit, and almost all of the plastic prestrain appeared as permanent strain at the end of the cycle. The unloading curve was accurately linear over most of its length with a distinct break indicating the onset of a significant nonelastic reverse strain at the stress o u, indicated by the arrows. The yielding in subsequent cycles, Id and le, had the same general character. The single crystal behavior, shown to a different scale at the right of Fig. 1, was different in that initially the nonlinear reverse strain was unexpectedly much greater than for polycrystals. It should be noted that these soft crystals had a small elastic

Jan 1, 1970

By Michael Shaughnessy, O&apos

The outstanding features of the Coloinbian situation for the year 1929 were legal and political. The passage of Law 84 and the promulgation of the Regulatory Decree 150 were recounted in the review for 1928, as was also the Presidential proclamation suspending this law and its accompanying decree until decision could be reached in the suits filed against them before the Supreme Court and the Council of State. Early this year the Minister of Industries, Jose Antonio Montalvo, announced the appointment of a commission of foreign experts to aid in drafting a new petroleum law. He requested all of the foreign experts employed not to consult with the oil company representatives in Bogota, and these experts were therefore shut off from receiving any suggestions from those who had actually operated in the country and knew the conditions under which operations would take place. It was to be expected that the provisions of a law suggested under such circumstances would not meet operating conditions satisfactorily. The specific objections are stated in O&apos;Shaughnessy&apos;s South American Oil Reports (April, 1929). An especially qualified commentator observes that one of the curious provisions of the proposed law was the high royalty on gas—5c. per 1000 cu. ft. of gas produced. There was also a provision requiring 20 per cent. of the stock of the company operating in Colombia to be offered for sale to Colombians. The bill failed to pass Congress in the closing hours of the session. The Supreme Court, in the meantime, handed down its decision on Law 84 of the previous year and Regulation 150 covering the enforcement of that law. Contrary to expectation, the majority opinion of the Court practically affirmed the constitutionality of both the law and the regulatory decree, with the exception of Article 20 and parts of Article 21 of the decree which referred specifically to the registration of private properties. At the time the suit was filed against Law 84 and Decree 150 the operation of these measures was suspended by the Executive. Law 84 and its Regulatory Decree 150 still remain suspended as the Council of State has not yet brought in a decision upon the questions raised in the suits instituted by the various companies against the law and decree, and at the moment of this writing it appears unlikely that such a decision will be reached by that body.

Jan 1, 1930

By Walter R. Hibbard, George H. Eichelman, William P. Saunders

INTEREST in the various products of the austenite eutectoid transformation in iron-carbon alloys, particularly as produced by the isothermal sub-critical techniques introduced by Davenport and Bain,1 has resulted in the application of similar heat treatments to other eutectoid transformations. Studies2.3.4 of the beta copper-aluminum alloy eutectoid transformation revealed microstructures very similar to those found in iron-carbon alloys. Investigations5,6 of the kappa phase in the copper-silicon alloy system have established the eutectoid type transformation of this phase into terminal alpha and intermediate gamma phases. This transformation has been reported&apos; as forming a eutectoid type structure in a very sluggish manner by a long time isothermal treatment. The purpose of the present investigation is to study the products of the kappa eutectoid transformation as affected by transformation temperatures by means of microscopic and hardness methods. PREPARATION OF ALLOYS The copper-silicon alloy equilibrium diagram is shown in Fig I. The kappa field converges to a minimum silicon solubility at the eutectoid composition and all other completely kappa alloys are hypereutectoid. Thus, kappa decomposition involves first the proeutectoid precipitation of gamma, followed by the eutectoid transformation of a lower silicon content kappa (5.2 pct). Smith5 has indicated that alloys containing between 5.4 and 5.7 pct silicon could be hot rolled, but that the latter composition was desirable in order to permit a wider kappa temperature range. The alloy was prepared by adding Baker&apos;s commercially pure silicon to an ingot of copper-silicon alloy containing 2.34 pct silicon remaining from the investigation of Brick, Martin and Angier.7 Following the casting techniques of Krynitsky, Saunders and Stern,8 the ingot was melted under a heavy layer of dried charcoal in a clay-graphite crucible in a gas-fired pot furnace. Small lumps of silicon were held under the melt surface with a graphite rod. After the silicon had dissolved, the alloy was chill-cast and then remelted without a cover, stirred thoroughly, skimmed and poured into a preheated cast iron mold. The cast microstructure is shown in Fig 2. The casting, 10 X 4 X ¾ in., was annealed at 750°C for 21 brand furnace cooled. About 1/16 in. was milled from all surfaces. The plate was cut in half longitudinally and the bottom half analyzed by A.S.T.M. methods.9 The composition by weight was as follows: copper 94.24 pct, silicon 5.56 pct, iron 0.11 pct.

Jan 1, 1948

By Floyd C. Kelly

There is an ever-increasing demand for furnaces with controlled atmosphere, due to the large quantities of steel being used in the automotive industry, such as the high-chromium stainless irons, the 18 Cr, 8 Ni stainless iron and low-carbon steel sheets. The difficulties involved in the annealing of such materials, if they are to be kept absolutely free from oxidation, are many. It is possible to bright-anneal these steels in small laboratory hydrogen furnaces, using specially purified hydrogen and taking some additional precautions. In the first place, the insulation, usually of alumina or magnesia, holds small amounts of water vapor, which it is almost impossible to remove completely. Secondly, there is always condensataion of water vapor in the cooling chambers of such furnaces, and with the continuous circulation of the hydrogen gas in the furnace, the water vapor is carried from the cooling chamber back into the heating chamber. This water vapor oxidizes the charge. Lastly, the supply of moisture is made sure by the diffusion of small amounts of air from the atmosphere into the furnace against the pressure of the hydrogen. The oxygen combines with the hydrogen and forms more water. Under such conditions there is little gained by using specially purified gas, because it becomes contaminated after reaching the furnace. Low-carbon Steel If a sheet of low-carbon steel is annealed in such a furnace at 750" C. and allowed to cool with the furnace, an adequate flow of purified hydrogen being maintained all of the time, the steel will come out with a very thin coating of blue oxide. If a similar sheet is annealed at the same temperature and quickly pushed into the cooling chamber, it will come out nearly bright, or perhaps with only the edges slightly discolored. It is difficult to get a piece of steel through a furnace of this type with an absolutely bright surface. This is due to the fact that there are always traces of oxygen or water vapor in the furnace. When the steel is allowed to cool with the furnace, it reaches a critical temperature where the affinity of iron for oxygen is greater than that of hydrogen for oxygen, and the steel comes out discolored. If the steel is pushed from the hot zone

Jan 1, 1931

By S. W. Parr

FRom a study of sulfur with reference to its specific combination in coal, published as University of Illinois Bulletin No. 111, 1919, it is now possible to determine the various forms of this constituent with a good degree of accuracy. This fact suggests two questions: (1) Are the same analytic methods applicable to coke? (2) Is there any correlation between the forms of sulfur as it occurs in coal and the residual sulfur found in the finished coke? The answer to the second question might be helpful in answering a still further question as to what chemical route the sulfur travels during the carbonization process. While the special studies along these several lines are by no means complete, a few preliminary statements are herewith presented. They may, at least, prove suggestive of further possibilities from a continuation of research along these lines. There is no reason, chemically, why the analytic methods devised for coal should not apply to coke and a fair amount of experience in connection with such use affords confirmation of this statement. The procedure in the case of coal may be briefly outlined as follows: Combinations of sulfur as sulfate, or sulfides other than FeS2, are readily dissolved without disturbing either the pyrite sulfur or the sulfur that is in organic combination by means of dilute hydrochloric acid— 1 part of concentrated HC1 to 10 parts of water or approximately 3 per cent. acid. Digestion at 60" C. for 24 hr. insures the complete removal of the sulfur thus combined. In freshly mined coal the amount of such sulfur is very small; weathering processes, however, may very materially increase the amount of sulfate present. Sulfur in the form of iron pyrites, or marcasite, may be quantitatively removed without oxidation of the organic sulfur as follows: A dilute solution of nitric: acid is prepared having 1 part of concentrated HNO3 to 3 parts of water or with an approximate specific gravity of 1.12. The coal sample, ground to 100 mesh, is digested with this solution at room temperature for 3 or 4 days, filtered and evaporated to dryness, taken up with water, and acidified with hydrochloric acid. It is now ready for precipitation with barium chloride in the usual manner. If sulfate is present in the original sample to an appreciable amount, it should be removed by the procedure outlined above. It is not necessary here to give the methods for determining the two

Jan 1, 1920

Jan 1, 1938

Jan 1, 1928

Jan 1, 1951

Jan 1, 1942

Jan 1, 1949

Jan 1, 1894

By C. E. Sims

THE carbon-oxygen reaction without doubt is the basic reaction in steelmaking. It is important on several counts: In the first place, carbon is the element that distinguishes steel from iron. It is the principal element controlling properties, and its control is of prime concern. Although the principal objective of the carbon-oxygen reaction is to oxidize excess carbon, the accompanying boil should not be underrated. The mechanical agitation, stirring, and mixing resulting from the boil are so useful in the distribution of heat and in promoting uniformity of composition in the bath that, were it not a natural accompaniment of the carbon-oxygen reaction, it is probable that something would have to be invented to replace it. The open-hearth operation, for example,, with the bath heated from above by radiation, would be impracticable without the carbon boil. The electric-arc furnace is somewhat less dependent on it, but every melter knows how much easier it is to gain temperature with minimum damage to refractories during the boil than with a dead bath. The motor action of the induced current of the induction furnace makes the carbon boil unnecessary but even there a severe oxidation has been found useful in giving greater freedom from porosity in certain steels. The quantitative aspects of the carbon-oxygen reaction have been given considerable attention by a large number of investigators, and the principles of physical chemistry have played an important part in these studies. Physical chemistry is the science of the mechanics and mathematics of chemical reactions. It is possible to study the mechanisms of reactions in a qualitative manner without reference to mathematics and thus obtain valuable concepts as to the manner in which the wheels go around. When it is desired to express quantitative relations in these reactions, however, resort to mathematics is not only convenient but necessary. Mathematics may also be regarded as the shorthand language of physical chemistry. A basic relation whose description requires numerous words may be expressed very simply by a mathematical formula or equation. A good example of this is the equilibrium constant for a chemical reaction. Expressed verbally, it is: When a chemical reaction has reached a condition of equilibrium, the product of the concentration of the reacting substances on one side of the equation, divided by the product of the concentration of the reacting substances on the other side, gives a quotient that is a constant at constant temperature. For the carbon-oxygen reaction C + 0 [=] CO this is expressed simply as [ ] where K (from the German Konstant) is the equilibrium constant for the reaction. Although mathematics is such a necessary and useful tool, it is also a potential pitfall. Mathematics in itself is an abstract science, which is not inhibited by consideration of mechanisms or materials.

Jan 1, 1947

By R. W. Smashey, B. J. Piearcey

The structure, composition, and morphology of the carbide phases present in the nickel-base superalloy, Mar-M200, hare been determined and three carbide phases observed. The MC carbide is a solidification product, and the M23 Co and M6C carbides are both prod~icts of solid-state precipitation. The identity of each phase usas determined by both X-ray and electron-diffraction techn~ques. Compositions of all three carbides were studied using the electron beam micro-probe analyzer and by unalyszs of electrolytically extracted residues. Optical and electron microscopy were employed in order that the time/temperature -dependent behavior of the carbides might be observed. Supplementary studies were completed on thin foils and oriented single crystals to determine the mor-phology and orientation relationship of each phase with that of the matrix. MAR-M~OO* is a high-temperature, creep-resistant superalloy designed for use in the as-cast condition. The "as-cast" microstructure consists of a solid-solution matrix, referred to as gamma (y), which contains a general, coherent precipitate of the inter-metallic Ni3(A1,Ti) referred to as gamma prime (?). As a result of dendritic segregation during solidification, a degenerate, spherulitic ? -?&apos; eutectic constituent is present at the grain boundaries and the in-terdendritic regions, which is nucleated by the y on the dendrite tips. A primary carbide phase, a solidification product, is also present at the grain boundaries and in the interdendritic areas, and an additional carbide appears at the grain boundaries as a fine discontinuous precipitate. The alloy is particularly susceptible to heat treatment. For example, the mechanical properties of the columnar grained mater- ial are substantially improved by solution heat treatment, followed by an intermediate temperature age. Metallographic examination of heat-treated material reveals, however, that exposure to elevated temperatures has a marked effect on the microstructure of the alloy; in particular, it is observed that precipitation of considerable amounts of various carbide phases occur. The following investigation was carried out to determine the morphology, composition, and behavior of the carbides in Mar-Ma00 as an aid to the determination of their effect on the mechanical properties and stability of the alloy. THE PRIMARY MC CARBIDE The MC carbide phase appears in the interdendritic interstices and the grain boundaries. In directionally solidified Mar-M200 the carbide appears as very small particles in the chilled region, Fig. l(a), whereas in material less affected by the chill, it becomes larger and develops a dendritic morphology, Fig. 1(b). Step polishing of metallographic specimens from this region shows that in directionally solidified material the individual carbide dendrites are connected in a dendritic network within the metallic interdendritic interstices, whereas in material from the chilled region and in conventional Mar-M200 they are discontinuous, isolated dendrites. No orientation relationship exists between the primary carbide and the matrix.

Jan 1, 1968

Jan 1, 1918

By Gerhard Derge

THE extension of metallurgical control of steelmaking processes has always made it desirable to have some quick method for determining the oxygen content of molten steel. To meet the practical demands of the steel industry, this method must also be simple enough so that the sampling can be done by the regular furnace crew. This requirement was kept in mind continually in the work to be described. An oxygen value is required for proper control, whether it be of a rimming steel or of a fully killed steel. However, two factors have discouraged the development of such direct methods: I. The reaction C + FeO -+ Fe + CO is rapid enough to make the correct sampling of the bath a difficult problem. The most generally accepted means of circumventing this difficulty have been the aluminum-killed bomb test of McCutcheon and Rautio1 and the aluminum-killed spoon test of Herty.2 The theory of these tests is that all of the oxygen in the iron is converted to A1203, which can then be determined by chemical methods. Even when simplified so that the analysis is made by a measurement of turbidity, this method is too slow to be used in routine control. Furthermore, the results obtained have never been entirely satisfactory, and some of the reasons for this will be discussed later in this paper. 2. The ordinary chemical methods of analysis for oxygen in steel are not reliable. The only analysis that seems to possess sufficient dependability to be of value is vacuum fusion,3 and the apparatus and technique developed for this have been too complex and slow for routine work. INDIRECT METHODS Indirect methods of estimating the oxygen have been resorted to in mill practice. Generally these depend upon the chemical equilibria involved. The oxygen in the bath is related to other components in the slag or metal that can be analyzed more readily. These methods have many difficulties in common. Steelmaking processes involve a complicated set of interrelated reactions, all of which tend to approach equilibrium at varying rates. The degree to which any particular equilibrium is approached, is not , well established. Moreover, a proper use of theoretical equilibrium constants requires a more extensive knowledge of the activities of the reactants than we now have. This is well illustrated by the irregularities observed when trying to determine the oxygen in the metal by its ratio to the iron oxide in the slag. Equilibrium relations may be used more readily if they are evaluated by plant experience, but the extent of approach to equilibrium remains an undetermined variable and lack of an entirely satisfactory means of determining oxygen for the calibration is felt keenly. For example, the statistical analysis of the relation between carbon and oxygen4 5 illustrates that even in a single plant wide variations exist under normal conditions of operation. Nevertheless, this is one of the best methods now

Jan 1, 1943

By James H. Hance

Discussion of the paper of JAMES H. HANCE, presented at the New York meeting, .February, 1916, and printed in Bulletin No. 110, February, 1916, pp. 299 to 326. FREDERIC P. DEWEY, Washington, D. C. (communication to the Secretary*).-I wish to congratulate Professor Hance and to thank him for his extremely valuable addition to the fund of data upon this subject. It presents clearly conclusive and incontrovertible proof of the unreliability of drill samples of this class of metal for determining the value of such bullion. I am afraid, however, that his hope that some one in the mint service might continue such an investigation upon a more elaborate and exhaustive scale is, for the present at least, doomed to disappointment. As a practical matter, the mint service is not now particularly interested in segregation in crude bullion. So much trouble and friction arose, -both in the original purchase and in the transfer from one institution to another, in handling segregated bullion, that it became necessary to adopt drastic measures and now it is seldom attempted to determine the value of such bullion in the service. When bullion known or even suspected of being segregated is presented for purchase, it is at once strongly refined in the pot and the disturbing elements so far removed that concordant assays may certainly be obtained from the dip samples and a reasonably fair agreement obtained from drill samples. The mint service prefers that the owner should refine his bullion himself, but if he does not we will do it at his expense and return the slag to him when desired. Much work has been done in the mint service trying to arrive at the value of deposits of segregated bullion without strong refining. It was no unusual thing for such deposits to be melted three times at the purchasing office and to have 30 to 40 assays on the metal made before buying it. Yet when shipped to a mint it was found necessary to melt two or three times more and to make 15 to 25 assays before the mint would accept the bar, and there were considerable differences between the valuations of the two offices. In what was undoubtedly the worst case ever investigated, the purchasing office melted the deposit, 953 oz., three times, with a loss of 105.5 oz., and made 46 assays; the mint melted three times, with a loss of 6.6 oz., and made 28 assays. The mint allowed the purchasing office 1.178 oz. of fine gold more than the purchasing office claimed, while an extensive investigation of the mint samples by the Bureau, in which over 100 independent assays were made in various service laboratories, indicated that the metal carried 0.7 to 0.9 oz. more of fine gold than the mint allowed. Preliminary assays on the original metal

Jan 5, 1916

By William C. Sleppy

The nmgnetic susceptibility of heat-treatable aluminuin alloys is sensitive to chanyes such as solution or dissolution of solute and the precipitation of mew phases. By measuring the change in the magnetic susceptibility of aluminum alloys caused by various heat treatments, an empirical relation was found from which atomic arrangements in dilute binary alloys of copper, zinc, and magnesiutn in aluminum have been delineated. The relation predicts the ultimate formation of C1LA12 when copper is precipitated from solid solution in aluminum. Euidexce joy silovt- range order is found for copper in solid solution in aluminum in the sense that copper atoms avoid being nearest neighbors to an extent greater than would result from a purely random arrangertzeizt. Hume-Rothery has predicted such short-range order joy solid solution of copper in aluminum The Al-Zn system agrees with evidence obtained from X-ray scattering at small angles and predicts a tendency for zinc atoms to cluster in solid solution in aluminum. In the Al-mg system, the empirical relation indicates an approach to randor distribution of magnesium in solid solution in aluminum with a tendency for magnesium segvegation which increases with incveasing temperature. ThE magnetic properties of metals are complicated by the fact that contributions are made to them both by electrons of a "metallic" type which belong to the crystal as a whole, and by electrons in states localized on particular atoms. An expression1&apos;2 for the bulk magnetic susceptibility of aluminum may be written as the sum of three contributions: where XA1 is the bulk susceptibility of aluminum per gram of material (in the cgs system, the units are those of reciprocal density); Xa1+3 is the diamagnetic contribution of the electrons localized in ion cores; Xa1 is. the paramagnetic spin contribution of conduction electrons often called Pauli paramag-netism: Xa1 is the diamagnetic contribution of the conduction electrons often called Landau diamag-netism. Ion core diamagnetism arises from the precession of the electron orbits which occurs when a magnetic field is applied to a system of electrons moving about a nucleus. Its contribution to the magnetic suscepti- bility is small, temperature-independent, and unaffected by alloying. The conduction electron diamagnetism is also temperature-independent and arises from the translatory motion of the electrons. For perfectly free electrons this contribution should be exactly one-third of the Pauli spin paramagnetism, but this relation is seldom even approximately true. Blythe2 determined the conduction electron diamagnetism in pure aluminum and found it to be extremely small. Any change in the conduction electron diamagnetism caused by alloying is neglected in this work. The Pauli paramagnetic contribution3 to the magnetic susceptibility of aluminum depends upon the number of electrons that occupy excited states and whose spins can be turned parallel to an applied magnetic field. The number of electrons free to turn in the field is proportional to the temperature and each spin contribution to the susceptibility is inversely proportional to the temperature. A slight temperature dependence of Pauli paramagnetism occurs when the number of electrons occupying excited states cannot increase sufficiently to balance the inverse dependence on temperature of each spin contribution. The decrease of the magnetic susceptibility of aluminum with increasing temperature is attributed to a temperature dependence of the Pauli paramagnetism. Estimates of the Pauli paramagnetism of aluminum have been made by several workers.2,4,5 All of the values are in reasonably good agreement with each other. In this work Xal at 17°C is taken as 0.761 X 10-8 cu cm per g. An expression similar to [I] can be written for the magnetic susceptibility of an aluminum base alloy containing a fractional weight percent x of solute:&apos; Xa = (1 -x)XAl+3 +xXsoluteion * XaPauli +Xadia) [2] where X, is the magnetic susceptibility per gram of alloy, Xal&apos;3and Xsolute ion are the ion core diamag-netic contributions, and xpauli and xdia are the Pauli and diamagnetic contributions of conduction electrons in the alloy. If the components of a mixture are not alloyed but simply mixed together in their pure states without producing a new phase, then the magnetic susceptibility of the mixture is given by the Wiedemann additivity law: Xm =x1X1 +x2x2 + ..xnxp [3] where X, is the susceptibility per gram of mixture and xnXp are the weight fractions and susceptibilities, respectively,-. for the pure components. The additivity law is not applicable to alloys because the outer electronic structures of the components are changed by alloying.&apos; Both the Pauli paramagnetism and Landau diamagnetism are affected; hence the magnetic susceptibilitv of an alloy is usually different from that calculated using the additivity law. In this work the difference, X, -X,, is taken as a measure of the change caused by alloying.

Jan 1, 1968