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By Edwin T. Myskowski, Alfred H. Hesse

THE development by the U. S. Bureau of Mines of a process for purifying manganese by electrolysis has stimulated interest in manganese alloys. While recent publications have shown some alloys of manganese and copper to possess rather unusual properties, none have included information on tensile properties, which have an important bearing on the usefulness of the alloys. Manganese-copper alloys can be heat-treated, since the single phases that exist at high temperatures may be retained by quenching. According to Persson,1 when quenched alloys containing from about 30 to nearly i00 per cent manganese are reheated, alpha manganese is precipitated (Fig. I). Calculations based on Persson's X-ray data indicate that this decomposi¬tion is accompanied by a change in volume of as much as S per cent. The reason that this large volume change has not been noted probably is the slow rate at which equilibrium is reached by these alloys. In an investigation on hardening by cold-work and heat-treatment, Dean and Anderson3 found that quenched alloys increase in hardness with manganese content and that high-manganese alloys harden very slowly with cold-work, while high-copper alloys harden much more rapidly. Heat-treatment has little effect on manganese-copper alloys containing less than 40 per cent Mn, and affects those alloys containing more than 40 per cent in accordance with their manganese content and heat-treating temperature. Dean and Anderson4 also found that cold-work increased electrical resistance of alloys containing from 50 to 80 per cent Mn, and that heat-treatment of alloys containing from 40 to 96 per cent Mn altered the electrical resistance considerably. Dean, Anderson and Potters have shown that the high vibration damping capacity that characterizes manganese-copper alloys containing 40 to g0 per cent Mn. is affected by cold-work and heat-treatments. Highest vibration damping capacity at low stresses was obtained by heating for 2 hr. at 450°C. (842°F.) after quenching from solution temperatures. Preparation of Alloys.-The alloys for these tests were melted in a 17-lb. basic-lined high-frequency induction furnace using electrolytic manganese, grade A ingot copper and a 70-30 Cu-Mn master alloy (69.80 per cent Cu, 0.12 Fe, 0.04 Si, 0.006 S, 0.07 C, balance Mn). The manganese was heated slowly to expel excess dissolved gases and melted before the addition of copper. No fluxes or covers were used. The melts were cast in tapered iron molds and the ingots were reduced go per cent when forged to ½ in. rounds. These rods were given 2-hr. solution treatments at temperatures that depended upon the composition (Table I). Tensile Tests.-The tensile specimens, 0.313-in. diameter (1.25-in. gauge length), which were enclosed in evacuated Pyrex

Jan 1, 1942

By W. H. Herrnstein, F. H. Beck, M. G. Fontana

Sulfur solubility in a iron was measured in the 750 to 890°C temperature range and was found to be insensitive to ferrite purity within a limited composition range. The permeability of sulfur in ferrite was determined from the internal sulfidation of Fe-Mn alloys. From the solubility and permeability results, the diffusivity of sulfur in ferrite could be calculated. These results are summarized as follows: Dissolved sulfur decreased the lattice parameter of ferrite. The effect of dissolved sulfur on the tensile properties of ferrite at low temperatures was also determined. SINCE sulfur is an important residual impurity in commercial irons and steels, effects associated with the presence of sulfur as a solute in iron are of considerable practical interest. Unfortunately, certain basic information relative to the Fe-S system appears to be lacking in the literature, e.g., the effect of dissolved sulfur on the lattice parameter and mechanical properties of ferrite. In addition, discrepancies exist in previously reported results for the solubility of sulfur in ferrite. These discrepancies raise questions regarding the sensitivity of sulfur solubility to the purity and microstructure of iron. This study was undertaken primarily in an effort to obtain reliable data on the solubility of sulfur in ferrite. Additional objectives included determination of the permeability and diffusivity of sulfur in ferrite by the internal sulfidation method and determination of the effect of dissolved sulfur on the lattice parameter and tensile properties of ferrite. EXPERIMENTAL METHOD Three grades of iron, encompassing a range of impurity levels, were employed in the study. The grades were designated VME (vacuum-melted electrolytic), SPZR (single-pass zone-refined), and MPZR (multipass zone-refined). The composition of each grade is given in Table I. Poly crystalline and single-crystal strip specimens were employed in the solubility experiments. Uniform grain size strip (ASTM 3 to 5) of 0.005 to 0.020 in. thickness was obtained by alternate cold reductions of 60 thickness 60 to 80 pct and recrystallization at 650°C for i hr in pure, dry argon. Single-crystal specimens were produced in 0.010-in.-thick SPZR iron strip by the strain-gradient anneal technique. Recrystallized strip 0.25 in. wide was strained until a Luders band or bands had propagated over the length of the strip; the strip was then annealed by drawing it through a 150°C per in. gradient (890°C peak temperature) at 1 in. per hr in an atmosphere of pure, dry argon. Laue photographs of the crystals produced exhibited no discernible asterism. Specimens were equilibrated with H-H, atmospheres at temperatures between 750" and 890" by one of two methods, each of which makes use of the reaction: The encapsulation sulfurization method was employed in the majority of the solubility experiments. A strip

Jan 1, 1969

By F. H. Turan, F. W. Jessen

The gel strength and viscosity of two different suspensions of fractionated montmorillonite clay were measured by using a Stormer viscosimeter and Farm V-G meter. The amount of sodium poly-phosphate (sodium bexametaphosphate, sodium tetraphosphate and sodium acid pyrophosphate) adsorbed by the clay particles was determined. A relationship seems to exist between the amount of polyphosphate adsorbed and the nature of the surface, edge or plate, assumed to be the principal sites for selective adsorption. Reduction in viscosity and gel strength was found to be directly related to the adsorption. Both chemical bonding and physical adsorption seem involved in defloccula-tion Some indication of the axial ratios of particles of .l- to .04-micron average size is possible though study of the adsorption mechanism. INTRODUCTION AND PURPOSE A knowledge of surface areas of clay particles in a suspension and a precise determination of phosphate adsorption should provide a basis for a better understanding of reduction in viscosity and gel strength caused by molecularly dehydrated phosphates. The purpose of this investigation was to study the adsorption of sodium polyphosphates on suspensions of fractionated sodium montmorillonite. Although there is considerable uncertainty regarding details of the structure of montmorillonite, a generally accepted one is that suggested by Hofmann, Endell and wi1m.l The structure shown in Fig. 1 is an idealized one, and Marshall2 has postulated that it is possible for several isomorphous replacements to occur. Thus, aluminum may replace silicon, in which case an exchangeable cation would go along with the aluminum to neutralize what would otherwise be a net negative charge on the structure. There is disagreement among various investigators as to the particle size and shape of montmorillonite clays. Marshall2 reported the following results for the mean lateral dimensions of a Putnam clay (montmorillonite)— 3,730 A° for particles having average diameters ranging from 500 to 1,000 A, and 750 A° for those with an average diameter less than 200 A. The latter particles were estimated at 50A°in thickness, which would correspond to a stack of five unit cell layers. On the other hand, Shaw3 has interpreted micrographs as indicating that particles of montmorillonite ire readilv broken down to the individual cell layers by dispersion in water. Brindley4 and Merings indicate the ultimate particles to be of the order of 300 A° in mean lateral dimension. Van Olphen6 suggested the thickness of particles at four to five unit cell layers. It was suggested also that this number tends to become smaller with increasing dilution. Recently, Kahn and Lewis7 determined the size of sodium montmorillonite particles in aqueous suspension from electro-optical bi-refringence decay curves. The

THE CHAIRMAN (E. G. SPILSBURY, New York, N. Y.).-The relation of the character of manganese ore to the surrounding rocks was called to my attention very strikingly in a recent investigation in Costa Rica. In the foothills of the main coastal range there is a large deposit of manganese which extends for over 150 miles along the coast. This is in a porphyry district and the occurrences are almost exclusively along the lines of contact between a recent diorite intrusion through the porphyries. Wherever that intrusion appears to have exerted great force, the line of contact is very clear between the porphyries and the diorites. Where the action has been slower and the lifting force of the intrusion more gradual, there has been a zone of fracture of very considerable width. Those ores which occur where the fractured zone has not been very extensive carry a, lower percentage of manganese than where it has been deposited along a wider zone of fracture. In the so-called narrow veins, which are really the predominant ones, the solution carrying the manganese has evidently attacked the silica in the intrusive rock, and the resulting ore is practically a combination of manganese and silica, running froth 20 to 30 per cent. of manganese and from 20 to 40 per cent. of silica: hence those ores are not likely for a long time to become a factor in our manganese supply :for this country. On the other hand, where the disturbance to the porphyritic schist has been more intense; the manganese deposits are not so extensive, but the ore is richer, running from 45 to 51 and 52 per cent. manganese, with a silica content of from 4 to 5 per cent. There seems to be some resemblance in these deposits to those of the Cuyuna range. EDMUND NEWTON, Minneapolis, Minn.-The State Bureau of Mines has been working on the problem of concentrating manganiferous iron ore for two years or more. I should consider hand sorting as the best form of treatment, because it is practised at all of the mines which ship ore for making alloys, but not, however, oil the ore that is being used for pig iron. Hand sorting, assisted by selective mining, is readily applicable to some of this ore because the gangue is practically the original rock and is easily separated. However, it is only in rather limited zones that we find clean patches of rock. Generally the silica exists as a skeleton of the original rock structure, in which the manganese has been precipitated; some of the silica may have been dissolved, but if any of the original rock remains, the silica must be eliminated by ore-dressing processes.

Jan 1, 1918

By R. C. Buehl, J. P. Morris

F. D. Richardson—The authors are to be congratulated on this further contribution to our knowledge of the thermodynamics of the interaction between sulphur and carbon and silicon in liquid iron. As the authors state, the influence of carbon and silicon on the activity coefficient of sulphur in liquid iron is clearly of great importance in the blast furnace, since it must cause a three to fourfold improvement in the partition of sulphur between slag and metal. The influence of increasing temperature in further increasing the activity coefficient of the sulphur in the metal in the blast furnace by increasing the carbon content is also of interest. This effect, however, is probably only part of the reason for the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing temperature. Other contributing factors are the lowering of the oxygen potential in the presence of carbon by increasing temperature and the probable increase in the activity coefficient of the lime in the slag for the same reason. The former of these effects, which works via the (CaO) + [S] = (CaS) + [O] equilibrium, might possibly account for a 70 pct improvement in the sulphur partition and the latter might give a further 50 pct improvement. C. Sherman—I would like to compliment the authors on their very careful research. If I may, I would like to show results of calculations on the carbon-sulphur-iron system similar to the ones that were shown in our paper for the silicon-sulphur-iron system. For Fe-S-C ternary system k=PHgs/PH2 x 1/(f1°) (f2°) (%S) where fs = sulphur activity coefficient fs' = fs for Fe-S system of equal pct S f3° = f2/f2 for Fe-S-C ternary system This same analysis has been used on other systems, but the results shown in fie.- 7 are for carbon and silicon. L. S. Darken—I would like to make two brief comments in addition to complimenting the authors on an apparently very precise and accurate investigation. The first is that the present work is in agreement with a calculation by Larsen and myself." Our calculation (much less precise than the present work) was based on: (1) Unpublished work on the sulphur content of molten iron (1.5 pct at 1500°C) in equilibrium with graphite and an iron sulphide slag; (2) the distribution coefficient of sulphur between slag and carbon-free liquid iron. We expressed the result in a form equivalent to log 7. = 0.18 [%C] which gives an activity coefficient (?s.) of sulphur only slightly higher than the authors find and certainly within the precision of the earlier work. My second comment concerns the correlation of the thermodynamic findings with atomistics. A rough pic- ture of the atomic arrangement in the liquid solution is rather easily conceived for this particular liquid solution containing iron, carbon, and sulphur. Carbon has a very much stronger affinity for iron than for sulphur. Hence we may conclude that a sulphur atom will but seldom be adjacent to a carbon atom—since this would be a position of high energy. From the metallic radii of iron and carbon we know that six iron atoms pack neatly around one carbon atom. Thus each carbon atom in retaining this shell of iron atoms (which latter may not be replaced by sulphur on account of the high energy requirement) decreases the available positions for each sulphur atom by six. Hence each atomic percent of carbon decreases the equilibrium sulphur content by 6 pct (of itself). Or, at low concentration each atomic percent of carbon increases the activity coefficient of sulphur by 6 pct. This is in good agreement with the observed increase (6 or 7 pct at low carbon content). It is indeed gratifying to find a case where, by such simple reasoning, quantitative agreement is found between precise data and the modern picture of the atomistics of the metallic state. J. P. Morris (authors' reply)—We would like to point out that there is an error in the equation on p. 322 of the paper. The third equation should read: ½S2 (gas) + H2 (gas) = H2S (gas) The authors wish to thank everyone for the interest they have shown in the paper. In regard to the general observation in blast furnace practice, that the sulphur content of the metal is lowered by increasing the temperature, Dr. Richardson is correct in stating that the cause can be attributed only in part to the increase in activity coefficient of sulphur resulting from the rise in carbon plus silicon content of the metal with rise in temperature. However, this factor is probably an important one. The results of one experiment, performed since this report was written, indicate that at a constant temperature the addition of silicon to a melt saturated with carbon causes an increase in the activity coefficient of sulphur even though the carbon solubility is lowered. In this test, 2.5 pct silicon was added to a melt saturated with carbon and maintained at 1400°C. Although the carbon content dropped from 4.85 to 4.1 pct, the activity coefficient of sulphur was increased by about 20 pct.

Jan 1, 1951

By William F. Harris, Joseph Easha

FOR many years basic control of refinery operations depended on visual observation of small chill specimens poured at various intervals during processing. The oseto of these samples was related to the physical and chemical properties of the metal. Since the =setn is dependent on many factors other than oxygen content, this method, while giving a general indication of the condition of the copper, does not accurately measure the oxygen content. For the last 3 years a modified vacuum fusion procedure which enables the operator to determine the oxygen content of the copper within 1 5 min of sampling has been in use at the Westinghouse Copper Mill. For use with this apparatus a sampling technique has been developed which gives oxygen values representative of the oxygen content of the wire bar. The sampling technique is based on a statistical study, which compared the oxygen content of the laboratory sample of copper poured at the same time a wire bar was being poured, with the oxygen content of the wire bar. The apparatus used for the determination of oxygen in copper is shown in Fig. 1 and is essentially the same as previously described but with one important modification. A very porous fritted glass disc has been inserted in the tubing between the manom- eter and 40/50 ground glass joint. The fritted disc retains the copper vapor and copper particles in the furnace section and prevents contamination of the mercury in the manometer. Without the disc the manometer became difficult to read after a few weeks of operation. In earlier work1 it had been established that the simplified vacuum fusion apparatus used at the Copper Mill gave essentially the same results as a con-vential vacuum fusion apparatus. However, for this study it was necessary to determine the difference, if any, between the oxygen content of the wire bar and the oxygen content of the small chill sample used for the oxygen analysis. This correlation was established by taking a chill sample at the same time wire bars were being poured. The wire bar being poured at the time the chill sample was taken was marked and removed for further analysis. The copper is sampled at various times during refining and cast into laboratory size samples with the mold shown in Fig. 2. The mold is made of cold rolled steel and is 2 in. high and 2 1/2 in. in diam. The large upper portion of the cast sample is used for measurement of the conductivity of the copper, The lower portion which is a rod about 1/4 in. diam by 3/4 in. long is used for determination of the oxygen content. This portion of the sample weighs about 5 g which is approximately the size sample used for the analysis. The only preparation neces-

Jan 1, 1962

By E. A. Gulbransen, W. S. Wysong, K. Andrew

The reaction of carbon in solid solution in a metal with the surface oxide fim on many metals may be inferred from thermo-dynamic calculations for high vacua and high temperature conditions. Holm has recently shown that oxide films may be removed from ferrous materials by heating in a vacuum at high temperatures and that carbon is the essential element in the reaction. considerable work has been described in the literature on the de-carburization reaction. Several general references may been 2,3,4 However, the nature of the mechanism involved in the decarburization is not well understood. Our interest in this reaction resulted from many attempts to degas and to reduce by pure and dry hydrogen the surface oxides on strips of various types Of chrome-nickel alloys. Some of the early experiments On the behavior Of '3 pct chrome-iron in vacua of the order of 5 X lo' mm and at a temperature Of 600°C have been reported.5 These experi-merits showed a 'low reaction with the residual Oxygen Or water vapor in the system and no reaction with hydrogen. This is in accord with thermodynamic data which would lead to the prediction that it is extremely difficult to maintain a hydrogen atmosphere at 600' C pure enough to reduce Crz03 formed On the surface. The crystal structure of the superficial oxide film formed on 13 pct chrome- iron and Nichrome V has been investigated in the thin film range by Gulbransenr Phelps and Hickman,' and shown to be "203. It Was surprising to us to note that when a specimen of Nichrome V containing approximately 80 pet nicke1 and 20 pet chromium was heated to 850°C in a high vacuum, the specimen lost weight. The rate Of weight loss was very temperature sensitive. A study of this reaction in vacua and in a hydrogen atmosphere is the subject of this communication. Type Reactions Let us consider the various reactions which may occur when a metal is heated in vacua, in a hydrogen atmosphere, or in an oxygen atmosphere. The number and kind of reactions will depend upon the chemical nature of the metal, its alloying constituents and the location of the alloying constituents. The metals used in this study are chrome-nickel alloys of the heater type, They consist essentially of chromium, nickel and iron, small amounts of carbon, silicon and manganese and traces of zirconium, calcium, aluminum and magnesium. The trace elements are added to improve the lifetime and other characteristics of the alloy when used as a heater. Seven of the more important reactions with which we are going to be concerned here are as follows: 1. Metal . (gas) F? metal + gas — degassing of the metal 2. zM(s) + y }i Oi(g) M MIOu(s) -oxidation

Jan 1, 1949

By N. Tiner

IN an article on magnesium and its alloys, Gann and Winston1 stated that manganese has a limited solubility in the liquid state. W. Schmidt2 showed a diagram according to Joseph Ruhrmann indicating that the solubility of manganese in liquid magnesium falls from about 2.65 per cent at 790°C. to about 0.5 per cent at 695°C. The curve was extrapolated to show zero solubility at the melting point of pure magnesium (Fig. I): This work suggested that at the lowest manganese contents it was not possible to detect either a eutectic or the formation of a solid solution, so that manganese was stated to be present in the structure as large individual crystals. Two years after the presentation of these results, Gann3 brought evidence to show that some manganese is capable of dissolving to form a solid solution, any excess of manganese present then assuming chiefly the form of small blue-gray particles scattered throughout the primary magnesium crystals, occasionally in clusters but seldom at the boundaries. He presented micrographs of cast alloys containing o.1, 0.4 and 1.0 per cent manganese that show a small amount of coring around the individual particles due to solid solution, and indicate that the location of the manganese particles is closely associated with the original dendritic structure of the primary crystallization. He also pointed out that the amount of manganese that can be dissolved in magnesium depends on the amount of other alloying elements present, the effect of the second alloying element being to decrease the amount of manganese retained in the alloy. E. Schmid and G. Siebe14 have determined the solid solubility of manganese and its variation with temperature by means of precision X-ray diffraction measurements. They found that the solubility is 3.4 per cent at 645°C and decreases to practically zero at 200°C. It is apparent that the X-ray diffraction measurements of Schmid and Siebel are not in agreement with the results of Ruhrmann as presented by Schmidt. This disagreement, and also the lack of data on magnesium-aluminum-manganese and magnesium-zinc-manganese systems, led the author to the present investigation, to determine accurately the liquid solubility of manganese and its variation with temperature. EXPERIMENTAL METHOD The experimental method for making solubility determinations consists of saturating the molten magnesium or the alloys with manganese at various temperatures and analyzing the dip samples taken from these melts. Melting is carried out in a cylindrical steel pot heated by an electric resistance furnace. The pot had a metallic outside coating to protect the steel against oxidation, and a graphite inside lining to prevent the contamination of the melt by prolonged contact with iron. The inside diameter of the pot was 4 in. and the depth 12 inches.

Jan 1, 1945

By A. G. Guy

IN the course of a research on steady-state diffusion it became necessary to make diffusion calculations for a finite solid. This problem was found to be sufficiently different from the corresponding problem for the semi-infinite solid for an entirely new approach to be necessary in obtaining a useful solution. The assumption of an exponential variation of the diffusion coefficient with concentration' was no longer a practical necessity, so that the new solution offered the possibility of handling diffusion in semi-infinite solids for arbitrary variations of the diffusion coefficient with concentration. In discussing the principle on which this method of calculation is based, it is convenient to consider the relatively simple problem of one dimensional diffusion into a matrix that initially contains none of the diffusing substance. The solution of the set- ond Fick Law,?C/?t=D0?2C/?x2, for diffusion into a semi-infinite solid is3 C/C=1-F(x/2vD0t [1] where C is the concentration of the diffusing substance at a depth x cm below the surface after dif- A. G. GUY, Member AIME, and M. GOLOMB are Professor of Metollurgicol Engineering and Professor of Mathematics, respectively, Purdue University, Lafayette, Ind., A. S. YUE, formerly with Purdue University, is now with the Research Laboratory, Dow Chemical Co., Midland, Mich. TP 4505E. Manuscript, July 18,1956. fusion has occurred for t seconds; C, is the concentration of the diffusing substance at the surface of the matrix; Do is the diffusion constant, expressed in sq cm per sec; and + represents the Gauss error function. The corresponding solution for diffusion into a finite solid of thickness, 1, is conveniently written for the change in concentration, C+, at a point midway through the matrix and for times, t, great enough for the following equation to be used4 c1/2/C1=(1/2-2/?e-?2D0t/l2) [2] In Eqs. 1 and 2 the diffusion coefficient is represented by the symbol Do (rather than by D) to emphasize that these equations are valid only for constant values of D. To understand how these equations can be modified to take account of actual variations of D, such as that shown in Fig. 1, first consider the fact that for a given time of diffusion theconcentration at a given point is determined, not by the D value alone, but by the ratio x/vD0 in Eq. 1 and by a similar ratio, l2/D0 in Eq. 2. Even though in fact D varies, it is possible to keep this ratio constant by using a special coordinate system, x,, that varies with D in the appropriate manner. The necessary character of this special coordinate system can be easily visualized by imagining that

Jan 1, 1958

By J. K. Stanley

It has been known for many years that the magnetic properties of a ferromagnetic material are very sensitive to internal strain. Any structure-sensitive property such as ferromagnetism, which is a function of the regularity of the atomic arrangement, and discontinuities such as grain boundaries must show deviations from an equilibrium state when the regularity of the lattice is disturbed. Experience has shown that such distortions have a marked effect on the magnetic properties of a ferromagnetic material. The purpose of this paper is to show the feasibility of using magnetic methods in detecting internal strains. More specifically, it will be shown how such properties as permeability, rema-nence, and coercive force change on cold-working of aluminum iron and how these magnetic properties change during the annealing below the recrystallization temperatures. This work was conducted for two reasons. One was the desire to see in what manner strains are relieved in aluminum iron at low temperatures—a subject of practical importance in soft magnetic materials—and the other was the feeling that a study of cold-working and strain relief might shed some light onour understandingof what takes place in the deformation of metals. Definition of Terms It is necessary to define the terminology used in this Paper because magnetic nomenclature is usually unfamiliar to the metallurgist, and certain other terms, such as recovery, have been used ambiguously by metallurgists and others. Magnetic terms are best explained by reference to the common hysteresis loop of ferromagnetic materials (Fig. I). In Fig. 1 the coordinates are magnetic induction, B, (ordinate) and magnetizing force, H. (abscissa). The c.g.s. unit for the magnetic induction is the gauss, the number of flux lines per square centimeter, and the unit for the magnetizing force is the oersted, the number of lines of force per centimeter in air or vacuum. If one starts with a completely demagnetized specimen and magnetizes it, a typical virgin magnetization curve beginning at the origin is obtained. This curve is also the locus of tips of a family of smaller hysteresis loops. From this curve it is to be noted that the induction is not proportional to the magnetizing force, and that it appears to approach a limiting induction called the saturation value, and does so for values of H of 1000 oersteds. The ratio of the magnetic induction (gauss) to the magnetizing force (oersteds) is called permeability, . Thus u= B/H and if the magnetizing force H (oersteds) is specified as ro or 100 oersteds, the permeability is written as or l00 This is the accepted notation, and will be used in this paper. The values of permeability for H = 10 or I00 are chosen as indices for 106

Jan 1, 1945

Jan 1, 1931

Manganese Resources in Relation to Domestic Consumption Discussion of paper by JOHN V. W. REYNDERS, presented at the Cleveland Meeting and issued, as Pamphlet No. 1656-C, with MINING AND METALLURGY, May, 1927. A. G. BETTS, Kinderhook, N. Y. (written discussion).-When a business concern hires an office boy, it takes on the first bright-appearing young chap to apply and pays him the prevailing rate of wages. One of the chief tasks the .office boy is supposed to be competent to perform, is to clean out the office. The manager of the business is highly competent in many lines, but for some reason lacks the ability to keep the office clean. To the steel man, it would seem that manganese is the office boy, and it is purchased just as found and offered to the purchasing agent. The steel mill is competent to perform many functions on a grand scale and with wonderful efficiency, but it is unable to make real steel. It is the function of the office boy, manganese, to do this. It is open to serious doubt if steel mill operators have ever taken seriously the metallurgy of the preparation of crude manganese. It has merely been found that some usable crude manganese may be obtained by running certain manganese ores through an iron furnace when not busy on anything else, or remote from iron ore, or with a lining that is about gone. It is, however, an entirely unwarranted assumption that the metallurgy of manganese has been worked out, or that the supplies of usable raw ore must be limited to materials of some specified analysis. There was a time when ores of copper, lead and zinc, for example, had to be rich and of specified analysis, to be usable, but the commercial raw materials of today bear little resemblance to such ores of the past. The discussions of manganese that I have seen are based on the assumption that the metallurgy of manganese is fully established and that the only usable manganese raw materials are of the kind used today. These discussions contain another error, not so much of statement, but of implication-that the tonnages of manganese materials in the United States are so much in this state and so much in that. When it requires a period of years and the expenditure of millions of dollars for a competent mining company to explore thoroughly a few acres of mining ground, is it not absurd to say that there are so many hundred tons of manganese ore in a certain state? This fact is not apt to be known fully in 10,000, years. I do not charge the mining engineers. who are on record, of making misstatements, because they merely say that so much

Jan 5, 1927

By AIME AIME

THE CHAIRMAN of the fast growing Petroleum Division is not only a graduate of the University of California, but a third generation native son. After a few years spent in hard-rock geology, his professional efforts were transferred to the sedimentaries and to petroleum investigations, as a consulting geologist. For ten years these investigations covered the Rocky Mountain, Oklahoma, Texas, and eastern districts. After the war he returned to Casper, Wyo., as chief geologist for the Consolidated Royalty Oil and Western Exploration Companies. This employment afforded him the opportunity to study particularly the economic relationship between the lessor-lessee interests in development and production, a somewhat unusual type of petroleum specialization.

Jan 1, 1939

By AIME AIME

NOTWITHSTANDING the metropolitan appearance of M. L. Haider, the present Chairman of the Petroleum Division, he is not a native New Yorker, but was born at Mandan, N. Dak., Oct. 1, 1904. He began his travels at an early stage in life and after attending the University of Southern California for two years he spent two additional years at Stanford University and was graduated in 1927. After a few months as an analytical chemist for the Portland Cement Co. he became research engineer in the natural gasoline department of the Richfield Oil Co. where he remained for approximately two years before taking a position with the Carter Oil Co. in Oklahoma. He was chief engineer for this company for three years before being trans-

Jan 1, 1945

By Herbert H. Kellogg

C. M. Decroly (University of Brussels, Belgium) — The importance of the fluorides in the process metallurgy of special metals has already been accepted and it will probably increase in the future. Free energy diagrams as such established by Professor Kellogg are therefore very useful. It is interesting to note that the absolute value of the standard free energy of formation of HF increases with temperature, whereas for almost all the other fluorides it decreases; consequently it should be theoretically possible to reduce all the fluorides of the metals which, at low temperature, have a greater affinity for fluorine than hydrogen by this last element, provided a sufficiently high temperature is used in order to have a good efficiency. However, with regard to the reduction of UFe by hydrogen, I doubt that it will be possible to obtain directly the metal at comparatively low temperatures. There are other uranium fluorides which are more stable than UF6 and it is very likely that such fluorides will be obtained first. For example, in considering the reaction: UF6gas + H2gas + UF1so1id + 2 HFgas it is found, using the thermodynamic data of Brewer et al, that ?H298 = —66 kcal and ?G°298, = —65.2 kcal. As a result, the reduction of UF6 to UF4solld should proceed spontaneously even at ordinary temperature. On the other hand, the standard free energy of formation of UF4solid at 298°K is AG°298 = -209 kcal per mol of F2. The reduction of UF4 by hydrogen will be practically difficult and, as it is known, the only practical way of reducing this compound is to use alkaline-earth metals such as calcium or magnesium. I should like to point out, further, that the fluorination of many metal oxides can be carried out very easily by using the ammonium difluoride method of preparation, which renders the use of fluoride gas unnecessary. The first compound formed is generally a double fluoride of the metal and ammonium. This compound can be decomposed by heating either in a vacuum or in an inert atmosphere, ammonium fluoride being volatilized leaving the metal fluoride in a very pure state. H. H. Kellogg (author's reply)—Professor Decroly is quite right in pointing out that the formation of lower halides of uranium may complicate the reduction of UF6 by H2. I was unable to find his reference to the free energy of formation of UF4 in the compilation of Brewer.13 however. The value of AG°298, = —209 kcal for formation of ½ UFa seems rather high, and I hope the source of this value may be made clear.

Jan 1, 1952

By A. Eilers

A number of the copper refineries in this country have lately separated some of the rarer metals from the slimes in the refinery tanks. One of these has furnished me the following table of recoveries from given amounts of blister. I publish this to show the proportions, to gold and silver and to each other, in which these rarer metals may be expected to occur in copper from certain localities. GarFIeld, Utah :—The blister copper comes principally from the Bingham porphyry copper mines. Steptoe, Nev. :—All the blister copper is produced from the Nevada Consolidated mines. (Also porphyry deposits.) Omaha, Neb. :—Blister copper comes principally from concentrated copper-lead mattes shipped from the different lead-silver plants of the Rocky Mountain region to the converters at the Omaha lead refinery. Mountain, Cal. :—Ores occur in connection with diorite (?).

Jan 1, 1914

By AIME AIME

HENRY DAYTON WILDE-"Date," informally- manager- of the technical and research department of the Humble Oil & Refining Co., was born at Aguascalientes, Mexico, Sept. 25, 1900. He is a graduate in chemical engineering: M.S. from the University of Texas and I Sc.D. fro111 the Massachusetts Institute of Technology. t For a year and a half in 1926 and 1927 he was a research : associate in the research laboratory of applied chemistry at M.I.T., under W. K. Lewis. In the latter year Dr. Wilde went with the Humble as head of the laboratory experimental division of its refining development department. In 1929 he was made director of production research. Dr. Wilde is the author of important papers in the TRANSACTIONS of the Institute, wherein are also mans dis-

Jan 1, 1938

By AIME

WE produce Charles Van Ormer "Charlie" Millikan as living proof that man need not make a loud noise to be heard. His quietly affable, analytical, and soft-spoken manner in the face of all problems belies his ability to "get tough" when the situation demands it. As a chief engineer with many responsibilities for the success of a large producing company there must have been many occasions to tempt Charlie to excitement, but there are few, if any, who can say they saw him yield. He has an abiding faith in the benefits of hard and persistent work and will not admit the existence of a problem that cannot be reduced by it.

Jan 1, 1948

By AIME

D R. GILLSON, who was born in Evanston, Ill., in 1895, is another one of those geologists who received his early inspiration and foundation in his science from that great teacher at Northwestern University, the late Professor U. S. Grant, and then went on to give his time and interest to Institute affairs-like those other Northwestern men, Arthur Blair, Gilbert Cady, Charlie Behre, Evan Just, Ian Campbell, Clayton Ball, and many others. After serving in the Navy in the first World War as, of all things for a geologist, a commissary officer on a transport, he went on to MIT and took his doctor's degree under Waldemar Lindgren in 1923. He even assisted in mineralogy at Harvard and thus had training under another great teacher, Charles Palache. He taught mineralogy and petrography at MIT from 1923 to 1928. After several summers of field work as an assistant in the U. S. Geological Survey, Dr. Gillson joined the staff of the du Pont company.

Jan 1, 1947

By AIME AIME

TEXAS not only produces millions of barrels of petroleum daily, but supplies the oil industry with an asset infinitely more valuable than liquld gold. That asset is leadership. The oil industry was built from its humble beginning a few decades ago into a potent force in world economy by human hands and human brains. One of these great leaders in the busy world of oil is Wallace Pratt, of the Humble company, who has been called to a position as director and member of the executive committee of the Standard Oil of New Jersey. So reads the Houston Post of June 3, 1937.

Jan 1, 1944