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By Carl Pierce

The writer of this article has not attempted to write a technical paper; on the contrary, he has tried to express in "steel-plant English," for steel men, a viewpoint drawn from his practice and experience. It is not his thought that it shall be taken as the "last word" in the making of this class of steel, or that good rimming steel cannot be made by any other practice. The paper was written to serve as the basis of a discussion from which it is hoped much benefit may be derived. The paper deals only with rimming steel made by the open-hearth process, and with the lower carbon steels, such as sheet and tin bar, rivet stock, skelp, etc., although good rimming steel as high as 40 to 50 carbon can be made by having good open slags and giving proper attention to working and tapping temperatures. Definition of Rimmed Steel Rimmed steel is sometimes called open or effervescing steel to differentiate it from killed or partly killed steel. It is steel made by a process which permits the free escape of gases from the metal in the molds. In passing up through the metal, the gases keep it in a rolling action from the walls of the mold inward. The top of the ingot rims in as the metal chills and the walls of the ingot get thicker, the center part remaining fluid until it reaches a pasty condition when it is covered with a cast-iron cap. The Charge In making up a charge for rimming steel, clean stock of a known composition must be selected, special attention being given to the analysis of the materials. The silicon in good rimming steel must be eliminated to a trace, therefore it is advisable to have a uniform amount going into the charge. Too much silicon gives a raw melting heat from which rimming steel is unlikely to result. For this reason a charge containing not to exceed 40 per cent. pig iron and 60 per cent. scrap, with no iron ore, is preferred to the Monell type of charge in which as high as 65 to 70 per cent. pig iron is used with a proportional amount of iron ore for the removal of the excess silicon and carbon. The silicon content of pig iron varies so much from day to day in the average blast-furnace practice that there is danger of getting too much of this element in the latter mixture when

Jan 1, 1926

By Charles Smeal, Robert J. Schafer, Max Quantinetz

Normally metal powders cannot be ground to sub-micron sizes because of welding and agglomeration phenomena. Through the use of selected grinding aids and grinding fluids, nickel and other metal powders have been ball-milled as fine as 0.1 It was found that certain inorganic salts are more effective grinding aids for metal powders than conventionally used surfactants. METAL and alloy powders are used to produce reagents, pigments, coatings, solders, brazes, and parts for industry by powder metallurgy techniques. They are also combined with refractory compounds to produce cermets and dispersion-hardened products. One of the interests at the Lewis Research Center has been to explore the potentialities of the dispersion strengthening process. Since the work of Ir-mann, many investigators have shown that the strength of dispersion-hardened products may increase with decreasing interparticle spacing.24 One approach to achieving small interparticle spacing is to combine fine refractory compounds and metal powders, preferably below 1 in size. In attempting to obtain fine metal powders, it was found that until very recently the best that could be obtained from commercial suppliers, particularly of ductile metals, was about 1.0 . Interest was therefore developed in providing finer metal powders for dispersion-hardening studies. Information obtained from the literature, from others working in the field, and from prior experimental work performed at NASA, led to a consideration of ball-milling as a technique to produce the desired materials. Some of the variables associated with ball-milling are the size, material, and nature of construction of the grinding container; the nature and amount of the grinding material and material to be ground; and the nature and amount of the grinding liquid and grinding aid, if employed, and the grinding time. In all ball-milling, welding and agglomeration can oc- cur as well as grinding. Because of the tendency of ductile metals to weld together, they are difficult to grind.5 The ultimate particle size obtained on grinding is generally the one at which the rate of grinding becomes equal to the rate of welding. To help delay welding and thus obtain smaller particle sizes, grinding aids are often employed. The principal objective of this investigation was to produce submicron metal powders by ball-milling the powders with selected grinding aids and grinding fluids. A secondary objective has been to attempt to explain the variations observed in grinding behavior by considering possible grinding mechanisms and correlating various parameters with grinding effectiveness. Three groups of ball-milling experiments were run; one in which the grinding aid was varied, a second in which the grinding fluid was varied, and a third in which the material being ground was varied MATERIALS, APPARATUS, AND PROCEDURE In the first group of experiments in which the grinding aid was varied Inco Carbonyl Grade B nickel powder initially 2.5 (all sizes refer to average particle size as measured by Fisher Sub -sieve Sizer) was used as the material being ground and 200-proof ethyl-alcohol as the grinding fluid. Surfactants, representative of typical organic structures, were selected as grinding aids. Inorganic salts used as grinding aids were chosen on the basis of the size and valence of their ions. Water soluble salts were used in order to facilitate their removal from the slurry after grinding. In the second set of experiments, grinding of the 2.5- Ni powder was tried in four different grinding liquids; water, cyclohexane, n -heptane, and methy-lene chloride. In this study seven grinding aids selected from those tried in the first group of experiments were employed. In the third group of experiments 200-proof ethyl alcohol was again used as the grinding fluid to mill Cu, Cr, Fe, Ag, and Ni powders of various initial particle sizes' All mill charges contained 300 ml of grinding liquid and 3000 g of 1/2 in. stainless steel balls. When inorganic salts were used as the grinding aid, 70 g of salt and 210 g of metal powder were employed, and with surfactants 6 g of grinding aid and 300 g of

Jan 1, 1962

HUDSON MAXIM, Brooklyn, N. Y.-Immediately after the creation of the Naval Consulting Board, Admiral Strauss, Chief of the Bureau of Ordnance of the Navy, told members of the Board that the most important problem for the scientists to solve was erosion in large guns. The Navy, for years, had been working on the problem with marked suceess, but there was much yet remaining to be accomplished. As Chairman of the Committee on Ordnance and Explosives of the Naval Consulting Board, I communicated with several experts in the manufacture of steel, principal among whom was Prof. Howe. He generously agreed to help in every way possible, and the work that he has done and the time that he has spent upon it can he appreciated only by reading his paper. Prof. Howe asked for some rings. from a, certain 14-in. gun which Admiral Strauss had mentioned in particular, and in which, he had informed us, at each shot the bore of the gun, was enlarged about 0.001 in.,' and that after a relatively small number of rounds it was considerably eroded. It has puzzled scientists for a long time to account for the peculiar erosive effect produced by the powder gases in a gun, arid: what Prof. Howe has done in his paper is worthy of Sherlock Holmes. He is a veritable Sherlock Holmes of science.

Jan 4, 1918

By John W. Cahn

Tile avevage value of the mean curvature of surfaces in a specimen can be precisely delermined by sitrlple measurements performed on random sections or on 1 vojectiotzs of these surfaces. For surjaces enclosing particles, the quanlity is sllown to be velated to the probable tlurrrhev ot particles intevcepted by a random platne and, under certain conditions, to the perimeter of their Projected image and to the increuse in surjace area when the particles grow. Many of the velalionsl~ips are valid for any shape or size of the particles. THE recent growth of the field of stereology or quantitative microscopy is largely the result of the discovery of a limited number of rigorously defined geometrical parameters that can be precisely measured on random sections or projections of a structure without assumption about particle shape.' Such parameters have been the volume fraction and surface area and line length in a unit volume. The present paper introduces the average of the mean curvature of surfaces in a volume, and shows that it can be rigorously measured by counting methods alone. AVERAGE CURVATURE ON A PLANE Consider a curve y = v (x) on the xy plane. The curvature Kp in the plane at any point is given by Kp = (dZy/dx2)/[1 + (dy/dx)2]3/2. The average curvature along the curve may be defined as Kp = (1/L) fKpdl |1] where dl = [(dx)' + {dy)2]1/2 is the length of an element of the curve and .(dl = L is the total length of the curve. The integral on the right-hand side of Eq. [l] will be called the total curvature, It is dimensionless and readily evaluated by substituting d = arctan (dy/dx) to give ah which is the change in direction of the tangents to the ends of the curve, Fig. 1. Hence, Kp = (1/L)(?h) [2] It can also be seen that Eq. [2] is applicable in the limit of sharp corners. Even though the curvature is infinite at a corner, f Kpdl remains integrable and equal to the change of angle. The signs of the quantities Kp and dl are arbitrary and, if the areas adjoining the curve are equivalent, there seems to be no compelling reason to fix the signs. For a closed curve, however, it becomes worthwhile to use the signs to distinguish among different types of areas or phases enclosed. For such a closed curve AO = t2r and As a convention, we shall take the direction of the integration along the curve in such a way that the area or phase under consideration (henceforth called a) is kept to the left side of the curve, Fig. 1. Then Kp is positive where the curve is concave and negative where the curve is convex. For a closed curve Ad - +2n if the curve encloses a, and Ad = —2n if the curve is surrounded by a. PLANAR SECTIONS OF THREE-DIMENSIONAL STRUCTURE OF ISOLATED a PARTICLES Consider next a planar section of a microstructure containing particles of a in a matrix. We place no restriction on shape of connectedness of these particles, and begin by considering the curvature of only the boundary between a particles and matrix' Clumps of contiguous a particles are then treated as a single a particle. The two-dimensional section will show in a unit area na simple closed curves enclosing a particles and nh closed curves of holes, in-

Jan 1, 1968

By Hugh Steele, Brower Dellinger

U. S. mining trends for 1956 continued steadily U+ S. uphill, technique and equipment advanced with the pull, and exploration and development of once mined districts attracted more attention than new areas. Expansion of the Ambrosia Lake district in New Mexico more than doubled known uranium ore reserves, and production began from several of the large new ore discoveries. In Canada the up trend was more spectacular, especially in exploration and development. To combat increasing problems arising from high labor costs, taxes, low grade orebodies, and dwindling discoveries, manufacturers and mining companies have continued to introduce new techniques and new products-reamer bits for enlarging small holes drilled by jacklegs, whup d'whups for drift mucking, Cryderman machines and over-the-head small crawler-type machines for shaft mucking, the 20-ton TL 220 four-wheeled tractor trailer unit for underground haulage, inertia-type dust collectors, roof bolting in conjunction with chain link fencing for wall support, wooden roof bolting using compression support of ground for wall support, and new one-use carbide bits.

Jan 2, 1957

By T. Johnston, B. Cox

The results of oxidation and corrosion experiments on niobium in oxygen and steam at temperatures of 350° to 650°C, and in dilute sulphate solutions at 300°C are presented. The oxidation of niobium in oxygen can be explained in terms of a pre-transition period, which obeys an approximately parabolic rate law, and a post-transition period in which a more rapid linear rate is partially stifled by restriction of the gas flow due to the gvowth of the porous outer film. Due to changes in the porosity of the outer layers the restriction presented by the porous outel. film attains a limiting value. Subsequent oxidation obeys a linear rate law and shows an almost linear dependence of the rate on gas pressure. liltimately a second failure of the protective film may take place leading to a further acceleration in the oxidation rate. In water vapor the oxidation of niobium follows a parabolic rate law and does not show a transition to linear kinetics. The higher oxide, Nba05, was usually absent from the NbO/NbO2 film which was formed. The addition of a small partial pressure of oxygen to the water vapo3, resulted in accelerated oxidation according to the normal kinetics for oxidation in oxygen. The oxygen reacted preferentially with the niobium, and the protective oxide film was reformed when all the oxygen had been consumed. This behavior supports the theory that nucleation of Nb205 on the surface of the protective NbO/NbO2 film is the cause of the accelerated oxidation. After oxidation in steam at high-pressure Nb2Os was found in the protective film. The mode of formation of Nb2O5 under these conditions did not produce a change in kinetics, but was thought to explain the comparatively large dependence on pressure of the oxidation rate. The kinetics of oxidation in oxygenated aqueous solutions at 300°C were similar to those for oxidation in oxygen. A penetrating attack on niobium sheet may be related to the second breakaway observed by some investigators of oxidation in oxygen.

Jan 1, 1963

By D. E. Hawk, R. F. Burdyn, F. D. Patchen

Earlier work on a mud separator for barite recovery is extended to the design and construct ion of a rugged field unit. Problems associated with scale-up for field use include the me of dilution water and its effect on capacity, power requirements and pressures developed. Equations for these quantities are derived and applied in maximizing the beneficial effects of dilution and minimizing the power required. Tests on the full-size rotor show that its performance can be predicted by theory. The completed unit is compact and lighter than current decanting types. Its capacity is from 10 to 22 gal/min with corresponding barite recovery efficiencies of 92 to 86 per cent. INTRODUC'TION In an earlier publication a new type of centrifugal device was described for solid-liquid separations.l In that paper an operating equation was derived, and its validity demonstrated in laboratory scale experimentation. Some of the features apparent in this new device seem particularly well suited to the conservation of barite in field drilling-mud systems, hence the development was extended to the design and construction of a field unit. In the present paper the design problems associated with scale-up are considered. A full-scale, rugged self-contained field unit is described, and test results discussed which verify that the performance of the large field unit can be described by a simple operating equation. PRINCIPLE OF OPERATION OF SEPARATOR In principle, the new device is simply a perforated cylinder rotating within a body of fluid which is contained within a stationary case, as in Fig. 1. The frictional drag generated by the rotating cylinder causes part of the fluid to rotate. At the surface of the cylinder, assuming no slip occurs, the angular velocity of fluid and of the cylinder are identical. If there are suspended particles present of greater density than the fluid, the centrifugal force acting on these particles causes them to move radially away from the cylinder at some velocity vp . Where the Stokes settling equation holds, this velocity may be expressed as:2 d2 ?p rw2 If the case is provided with openings at both ends, a suspension can be pumped in at one end at a fixed rate. Part of the suspension can then be removed at a fixed rate at the other end of the case as underflow, and the remainder forced through the perforations and hollow shaft of the rotor to appear as effluent, also at a fixed rate. The radial component of the flow velocity of this stream as it reaches the rotor surface, is simply effluent flow rate divided by cylindrical surface area: Because up is a function of particle size, for some particular particle size, the velocities vp and v, will be equal in magnitude. This is defined as the critical particle size and represents the size above which all particles appear in the underflow and below which all particles appear in the effluent. For this equilibrium condition at the rotor surface, Eqs. 1 and 2 combined give

Jan 1, 1966

By Albert E. Wiggin, Frederick Laist

Early ill 1914 it was decided to test, on a fairly large scale, the treatment by flotation of Anaconda slime and mill tailing. For this purpose a standard-type Minerals Separation machine was installed at the Washoe Reduction Works during May and June, 1914. This was followed by the installation of a full-size Callow pneumatic machine plant. Experiments were also made, on a smaller scale, with the Froment, the Towne, the Fields, and the Anaconda flotation machines. The last-named machine was developed at this plant. In addition to the tests made in the standard-type Minerals Separation machine some tests were made using a Minerals Separation machine of the sub-aeration type. During the series of experiments a large variety of oils was tested. Experiments were also conducted using both round-table feed and tailing to determine whether it would be better to displace the round tables by flotation for the treatment of the slime, or to supplement the round tables by flotation of the round-table tailing. A series of tests was also made on the treatment of the mill tailing by grinding followed by flotation to determine the relative merits of flotation and leaching for the treatment of this product. In addition, flotation tests were made on mixtures of mill tailing and slime. The round-table feed referred to above is the total slime from the mill. It contains about 35 per cent. colloidal solids and approximately 90 to 95 per cent. of the total solids will pass through 200 mesh (0.067 mm.). It assays from 2.3 to 2.6 per cent. Cu. The mill tailing referred to above is the total discard from the mill, exclusive of the slime. It is all finer than 2 mm. and about 90 to 95 per cent. will remain on 0.25 mm. It assays about 0.60 per cent. Cu. A brief summary of the experimental flotation results follows:

Jan 1, 1917

By H. H. Richardson, E. H. Dix

Of all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations would have been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 525" C. to about 1 per cent. at 300" C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540" C., and that this amount decreases to about 3 per cent. at 20" C. In the same year Ohtani and Hemmi3 reported a solubility of 4.8 per cent. copper at 520" C., 2.6 per cent. at 460" C. and 1.5 per cent. at 420" C.

Jan 1, 1926

By Charles M. Brown, Russell Franks, W. O. Binder

Occasionally in the application of the austenitic chromium-nickel steels to corrosive conditions, failures have occurred by cracking without serious general over-all attack of the metal. As pointed out by Foyt and Scheil(1),2 and by Scheil, et al.(2) as well as by Hodge and Miller(3), the stress-corrosion failures that have occurred have been limited in number, and have taken place only when the steels were exposed to certain corrodents. These investigators have stated that while stress- corrosion cracking can be intergranular in nature and originate at the grain boundaries of the austenitic chromium-nickel steels, it can also take place in trans- granular fashion. They have shown that the cracking may be either initiated at the grain boundaries and may propagate along grain boundaries for some distance and then suddenly extend across grains, or it may begin in a transgranular fashion and suddenly proceed along grain boundaries until the cracking stops. Their data further show that when austenitic stainless steel is subject to intergranular attack, stress will concentrate and cause cracking in service. These investigators have studied the effect of the metals titanium and columbium which are added to the steels to impart immunity to intergranular attack, and molybdenum which is added to improve resistance to general corrosion.

Jan 1, 1945

By R. J. Tailleur, M. Rosenberg

Oil well drilling muds prepared with lubricating aids such as oil, graphite or mica will not produce a sufficiently strong protective lubricant film for the bit bearing surfaces under high load conditions encountered in drilling operations. Consequently, the damage to the bearing surfaces resulting from the absence of such a film frequently results in a shortening of the drill bit life. Several different types of extreme pressure lubricating additives for use in muds have been developed. These arlrlitives are capable of providing a protective lubricating film for bearing surfaces subjected to high load pressures. A modified version of the Timken lubricant tester, an instrument commonly used for testing the extreme pressure lubricating properties of oils, is used for measuring and controlling the lubricating qualities of the mud. Comparison tests made in the laboratory with 55/8-in. tricone bits drilling on steel plates immersed in extreme pressure lubricating muds and conventional muds showed that the bearing life of those bits tested in the lrrbricating mud was three to four times greater than obtained with conventional muds. Drilling tests made with extreme pressure lubricating muds in West Texas increased over-all bit life three to fourfold, reduced drilling torque and wear on drill pipe and drill collars. INTRODUCTION Roller bit cones contain roller, ball and journal-type bearings that are subjected to very heavy loading during drilling operations in which the only lubricant available for these bearings is either water or drilling mud. These bearings must be able to operate satisfac- torily in order for the cutting structures on the surface of the cones to be fully utilized. Frequently, the bearings wear to the point that the cones freeze and the bit must be pulled before the cutting structures on the cones become worn. In some instances the bearings continue to turn with severe wear but the cones, which are held on the bit by the bearings, drop off; and this causes an expensive fishing job. In other instances the bearings wear to the point that the cones pinch in causing an undergauge hole and delays to ream the hole. The advantage of increasing bit bearing life is self-evident. Because of inability to control the internal wear of bits while drilling, it was felt that improvement of the lubricating qualities of the circulating mud would be helpful. However, the often-discussed lubricating property attributed to muds has been a rather vague and intangible one. The literature has implied that the oil-emulsion muds are more effective lubricants than non-emulsion muds. Actually, there has been no direct method of measuring the lubricating property of muds which would indicate that one mud was better than another; there has been no way to determine whether the lubricating property of any mud was adequate. Furthermore, in comparing lubricating properties of muds, two qualities should be considered—the coefficient of friction and the extreme pressure lubricating qualities. For example, graphite can reduce the coefficient of friction, but does not provide a strong enough lubricating film to protect bit bearings subjected to high loads. The primary object of the investigation reported herein was to find a method for prolonging the bearing life of drill bits; and considering the heavy loads used in drilling, it was felt necessary to find both a method of measuring lubricating properties under high load conditions and methods of establishing effective lubrication under these conditions. Extreme pressure lubrication deals with that realm of lubrication where metal surfaces are in rubbing contact with each other under very high pressures. These pressures may be quite high, as for example,

By J. E. JR. Johnson

AT the Cleveland meeting of the Institute in October, 1912, I had the honor to present a paper outlining the conditions surrounding the charcoal iron industry, and giving some of the results of an investigation started about three years ago for the purpose of determining the reason for the poor reputation of the Lake Superior charcoal irons as compared with the Southern and Eastern irons. In that paper I explained the effect of high carbon on quality, and tried to make clear that that paper was a preliminary one, as we felt convinced that we should eventually discover other factors affecting quality. The progress of the investigation has brought out facts that seem to us of the utmost importance practically and theoretically, and the purpose of the present paper is to present these facts with the proofs which seem to us to establish them. The closing year of the nineteenth century saw the publication of the first definite and connected statement of the relationship between the cast irons and the steels.' The metallurgical world was ready to accept the fundamental unity of these two series, acceptance being greatly hastened by Professor Howe's classic paper, The Constitution of Cast Iron, presented at the Richmond meeting of the Institute, February, 1901.

Jan 1, 1914

By A.S. Richardson

AIR conditioning, or air cooling, for the improvement of ventilation in the Butte mines has come into increasing use during the past 10 years. In part, the methods practiced have been described in previous publications of the Institute, but some improvements on earlier methods have been made and a number of new features have been developed. This paper is presented as a record of progress made, and for the sake of completeness describes all general features of the work. The need for air conditioning in the ventilation of mines in the district arises from the fact that the temperature of the ground and mine water has shown a very great increase with increase in mining depth, and has now reached a maximum of slightly over 130°F. The most difficult part of the ventilation problem is the maintenance of temperature and humidity of a satisfactory standard in the working places, especially on the lower levels. Although ordinary ventilation is adequate to maintain good conditions in most of the working places it is subject to a number of limitations at great depth. Most important among these limitations is that with increase in depth the air becomes heated before it reaches the working places, both by compression from increase in atmospheric Pressure and by heat transferred to it from rock at high temPerature, so that its capacity for lowering temperatures is greatly reduced before it reaches the operating zone. Increasing depth of mining also increases the distance traveled by the air in its passage through the mine, and this causes a corresponding increase in resistance to air flow, so that there is greater difficulty in maintaining even the same volume in circulation. Thus, in the face of a demand that the ventilating system have a very much greater capacity to remove heat from the mine, the tendency is for that capacity to diminish. The only evident alternatives were (I) the opening of additional air shafts to increase the volume of air in circulation, (2) an extension of the existing system that would be subject to the same limitations, or (3) the adoption of an entirely different method such as air cooling. Fortunately for an economic solution of the problem, the mean annual temperature of the surface atmosphere at Butte is about 40°F., with very low relative humidity in summer, so that there is unlimited natural cooling power at a temperature range adaptable to air-conditioning methods. Methods Two similar methods of air conditioning are used, as necessitated by service requirements and dependent upon the equipment available. In one, which is the more important and has the greater cooling capacity, water is circulated in a closed circuit, and, alternately, first absorbs heat from warm mine air and then dissipates it in the surface atmosphere by cooling at a cooling tower. The second

Jan 1, 1943

By Shun-ichi Satoh

The electric arc welding of cast iron has been studied by Braune Lamberton, Schimpke, Kenyon, Gale Manufacturing Co., Wedemeyer Candy, Neese, Miller, Carter, American Welding Society, Namack Lebrun, Achenbach, Jansson, Xochendorffer and others.' The write of this paper has been able to obtain a series of cast irons, from gray tc white, without using cast-iron electrodes but by coating on wrought-iron bars mixtures of carborundum (Sic) and graphite (C). In this work, he found the curious phenomenon of barium carbonate.

Jan 1, 1929

By C. M. Sellars, F. Maak

Electvomotie -force measurements hazle been made on ten Au-Ni alloys at temperatures 7754 825O, 900O, and 935°C using galvanic cells with solid electrolyte. Partial and ivtegral thermodynamic functions are derived from the determined activities. which show la9,ge positive deviations jvom Raoult's law. The enthalpies of mixing- are in close accord with calorinletric data and are of comparable accuracy. The results are used to determine the miscibility gap and the spinoidal curL1e, and are qlalitaticely interpreted in terms of the large size difference and electvonic interactions between gold and nickel. Tabulated nalues of the actielities and partial and inteqal free energies, entropies , and enthalpies of mixing are given in the appendix. The Au-Ni binary alloys are of particular interest thermodynamically as despite the large size difference between gold and nickel atoms they have a simple phase diagram.' This shows complete solid solubility above a miscibility gap with a maximum at about 71 at. pct Ni and 810°C. Activity measurements (over a range of temperature) have been made previously on this system using an electrolytic-cell method with a liquid chloride eletrolyte. The accuracy of this data has, however, been queried3'4 as it leads to values for the enthalpy of mixing which are too high when compared with calorimetric measurements.46 Also, the entropy of mixing is too high when compared with the values derived from specific-heat measrements. It was therefore considered worthwhile redetermining the activity data using a galvanic cell with a solid electrolyte (0.85 ZrO, 0.15 CaO). This method is based on a technique introduced by Kiukkola and aner'' and has been used to determine the thermodynamic data for Cu-Ni alloys.' THE ELECTROLYTIC CELL The cell used to determine the activity of nickel in Au-Ni alloys was: The cell reaction, which is discussed for a similar cell by Rapp and Maak, gives a direct measurement of the activity of nickel in the alloys as where aNi(alloy) is the activity of nickel in the alloy, 3 is Faraday's constant, E is the measured electromotive force, R is the gas constant, and T is absolute temperature. For the valid application of this type of cell the arrangement must be ther modynamic ally stable, which means that: 1) The free energies of formation of the oxides fulfill the relation 2) The vapor pressures or dissociation pressures of each component must be so small that during the time of the experiment the amount of any material transported by the gas is negligible. 3) Side reactions which change the alloy composition must be negligible. These reactions are possible both with the surrounding gas atmosphere and with neighboring solid material. The first two conditions are fulfilled by the above cell.' The third condition is approached by care in the experimental technique. The factors which control the attainment of equilibrium in this type of cell have been considered by Rapp and aak, who conclude that metallic diffusion in the alloy is the rate-control ling step. A lower temperature limit for the practical application of this cell is therefore set by the condition that equilibrium must be attained in reasonable times. EXPERIMENTAL MATERIALS AND TECHNIQUE The starting materials were mint gold (99.99 pct Au) and Mond nickel (99.9 pct Ni). Alloys, nominally 5 at. pct Ni and then each 10 at. pct across the system, were produced by vacuum-levitation melting compacts of mixed drillings of the pure metals. The nickel used for the reference tablets in the cells was melted in a similar manner. The alloy ingots, cast in boron nitride molds, were cold-forged and

Jan 1, 1967

By U. C. Tainton

The paper reviews the evolution of electrolytic zinc, describing some of the major obstacles that have been encountered and overcome. The chief remaining limitations of present-day standard practice are: Difficulty of obtaining high extractions, especially from low-grade and complex ores; filtration troubles, if ores contain much soluble silica; and irregularities in electrolysis, if more than certain limited amounts of antimony, arsenic, cobalt; etc., are present in the ores. These factors dictate a relatively high-grade plant feed, thus subjecting the electroytic-zinc process to the same kind of limitations as the zinc smelter. The "high acid process," in which both acid strength and current density are raised to about four times the usual figures, is described. This system concentrates both plant and operations, allows a simple type of flow sheet, and. minimizes some of the difficulties above mentioned. The large-scale operation of the process is described. SOME time ago, at a meeting of the Institute Prof. J. W. Richards1 said, "I take exception to the statement that all the factors in the production of electrolytic zinc were known long ago. There is possible in my opinion an improvement of perhaps 50 per cent. in the new electrolytic processes." An examination of the literature of the subject will show the justness of Professor Richards' contention. The work of the earlier investigators was carried on in the shadow of difficulties that, today, are hardly more than memories. We seldom hear now of zinc sponge, that bête noir of the electrolytic-zinc pioneers. Zinc sponge, was the name given to a peculiar, soft, black, non-adherent form of zinc deposit that was utterly useless for melting into ingot form. At the big plant at Cockle Creek, New South Wales, in 1897, Edgar Ashcroft2 said that the solution in the plant would suddenly, and without ascertainable cause, go "bad" and begin to deposit spongy zinc. The most delicate, even spectroscopic, methods of analysis were unable to detect any difference between "good solution and "bad" solution; either form might change to the other on being kept for a while. When it is added that an outbreak of this insidious disease (which. appeared to

Jan 2, 1924

By J. B. Cohen, O. F. Kimball

Aging of specimens of Au-20 at. pct Ni and Au-40 at. pct Ni has been followed with electron microscopy, resistance, magnetic measurements, and X-ray diffraction. The periodic structures observed by electron microscopy in Au-Ni alloys by Fisher and Embury are shown to be due to nickel-rich prepre-cipitates. Assuming this alloy system undergoes spinodal decomposition, our observations and available data on thermodynamic properties and elastic constants indicate that the gradient energy coefficient in this system is of the order of 10-5 ergs cm-1 . Shifts of X-ray peaks in this system have been found to be due primarily to residual stresses, not faulting. A large effect of applied stress during aging was detected by X-rays and electron microscopy for the Au-20 at. pct Ni alloy. The presence of a preprecipitation stage during aging of gold-rich Au-Ni alloys for short times below 300°C has been indicated by several previous investigations. Changes in electrical resistivity,1"3 elastic modulus,4 superparamagnetisrn,5 positions of X-ray diffraction peaks,6 and hardness7 have been studied. Electron diffraction and microscopic studies by Fukano8 and Fisher and Embury9 respectively showed that the precipitation process resulted in the formation of periodic composition fluctuations—perhaps spinodal decomposition. MOSS10 detected a satellite with X-rays in quenched specimens, but the wavelength was much smallerthan that found by Fukano. Recently Woodilla and Averbac11 detected a modulation similar to that found by Moss, but with electron diffraction. They suggested that the microstructures observed by Fisher and Embury may be simply due to a Moir'e effect from a back deposit of gold during electropolishing. Satellites in electron diffraction can be enhanced by small bends or tilts of a foil. Even if this were not the case, asymmetric satellites, as are found in Au-Ni are difficult to analyze. They are principally influenced by the large differences in atomic size in this system, and obtaining information on the associated composition fluctuations depends on assumptions as to whether or not there are isolated clusters or composition "waves", and in the latter case whether or not the entire specimen has decomposed. Assuming that decomposition was complete in alloys aged at low temperatures, Woodilla and Averbach suggested that the satellites indicated a composition which varied about the average value by only± 5 pct, much less than that predicted from the phase limits, Fig. 1; they attributed this small variation to a cessation of the reaction caused by the loss of mobile vacancies. In Ref. 12 it was shown that vacancies are trapped by the preprecipitate in this system. Furthermore, after reversion, aging proceeds at a much slower rate than immediately after a quench from the solution temperature,5'11,13 indicating the importance of vacancies in the kinetics. In some senses Au-Ni is a favorable system for studying preprecipitation and reversion mechanisms because of the simplicity of the equilibrium diagram14 and the availability of good thermodynamic15 and diffusion data.16,l7 The calculations necessary to relate the decomposition process to classical nucleation and growth or to spinodal decomposition, as well as those necessary for understanding reversion mechanisms, can, therefore, be made. As an example, the position of the chemical spinodal, calculated from the thermo-dynamic data of Sellars and Maak15 with the method described by Rundman and Hilliard,18 is included in Fig. 1. It is compared to the chemical spinodal calculated from the equilibrium miscibility gap by Cook and Hilliard's method.l9 Included is the coherent spinodal suggested by Golding and MOSS," using measured elastic constants for their calculations and the same ther-modynamic data. The spinodal estimated by Woodilla and Averbach,11 by determining the temperature limits for the observation of the satellites discussed above, is also given. Actually this last curve is open to question on the following grounds: As a phase boundary is approached the spacing of particles or the wavelength

Jan 1, 1970

Jan 1, 1902

By Arnulf Muan, Klaus Schwerdtfeger, L. S. Darken

The equilibrium ratios CO/CO, of. a gas pharse coexislitrg with selected oxide phase assemblages of the system "FeO"-MnO-SiO2 and metallic iron have been determined at 1150°C. The data obtained are combined wilh the thermodynamic data on fayalite (Fe2SiOi) and "FeO"-MnO solid solutions to derive the actiuity-coiHpQsiUon relations for the various oxide components of the olivine (Fe2SiO4-,lIn2Si04) and pyroxenoid (standard free energies of formation of ferrosilile (FeSiO,), tephroite , and rhodonite from their oxides have been evaluated. In the Appendicc~s by Darken and Schivcerdtjeger the ideal solution law for solid deri oed. THE quaternary system Fe-Mn-Si-0 is of interest in many important phases of iron- and steelmaking. For instance, reduction in the blast furnace of ores containing Fe-Mn silicates, deoxidation of liquid steel with Mn-Si alloys, formation and subsequent alterations of oxide inclusions in steels, and the oxidation of manganese- and silicon-containing steels during processing are all governed largely by the thermodynamic relations existing in the system Fe-Mn-Si-O. Although the equilibria between liquid iron and Fe-Mn silicates have been studied in detail previously,' experimental data are lacking for equilibria among the solid phases. The present paper provides such data for a selected temperature, 1150°C. I) PREVIOUS WORK The general feature of subsolidus phase relations in the system iron oxide-manganese oxide-silica under strongly reducing conditions is known.' Fig. 1 represents an isothermal section at 1150°C. The phases present, in addition to silica, are three solid-solution series, viz.. the oxide solid-solution series "Fe0"-MnO (manganowiistite), the orthosilicate solid-solution series Fe2SiO4-Mn2SiO4 (olivine), and the metasilicate solid-solution series FeSi03-MnSi03 (pyroxenoid). The "FeO"-MnO solid solution is continuous between the two end members wustite and manganositeV3 as is the orthosilicate series between the two end members Fe2SiO4 and Mn2 SiO4. 4 The metasilicate solid solution, on the other hand, extends only part way from the MnSi0.l end member toward FeSiO because the latter end member is unstable relative to the phase assemblage fayalite + silica. The letters a through m in Fig. 1 identify end members of the individual solid phases dealt with [for instance, c designates fayalite (FeZSiO4) in equilibrium with wustite, e designates fayalite in equilibrium with silica, and so forth]. In addition to the phase relations there are some thermodynamic data available for the end members of the silicate solid solutions and for the "FeO" -MnO solid solution. The free energy of formation of fayalite (Fe2Si04) from its oxide components has been studied by several investigators. Unfortunately, the data obtained show considerable discrepancies. According to recent tabulations by Kelley, the change in standard free energy Affn for the reaction

Jan 1, 1967

By George F. Becker

A Nere record of Emmons's professional career would very inadequately represent the man. That he was eminent mc know, and our successors will realize in due time; but they must depend upon us for knowledge of a singularly ~vholesome, modest, unselfish personality, and of a character that did honor to a profession in which trustworthiness is indispensable. Those members of the Institute who met Emmons are his friends, and I never knew .one of these who was not the better for that friendship. Emmons was born in Boston, Mar. 29, 1841, the son of Xathaniel H. and Elizabeth (Wales) Emmons, and was named Samuel Frankliri after an ancestor who was of the sarne family as Benjamin Franklin. He took the degrcc of Bachelor of Arts at Harvard in 1861, and soon afterwards went abroad to complete his education. From 1862 to 1864 he attended the courses at the fieole Impkriale des Mines at Paris, Elie de Beaumont arid Daubrke being among his professors. The year 1864-1865 he spent at Freiberg under Cotta and other famous teachers; after which he spent another year in traveling through Europe. Like many other renowned geologists, he approached his ultimate profession from its economic side, and was thus from the first imbued with a sense of high responsibility in the promulgation of scientific opinions or conclusions. With hypotheses which were interesting merely because they were ingenious or even plausible, he would have nothing to do. In 1867 he joined the Geological Exploration of the Fortieth Parallel at its organization under Clarence King, serving at first as a volunteer, but soon receiving a regular appointment. This expedition was the first one of purely geological character sent out by the United States government. As Emmons has shown in his admirable presidential address on " The Geology of Government Explorations," its work was founded on a com-

Jan 1, 1912