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By B. H. Kear, S. M. Copley

A dynamic theory of precipitation hardening in alloys containing cohevenl, stvess-.free, ordered particles is developed. The yield stvess is predicted from the stress dependence of the plastic strain vale, which is related to a derived dislocation velocity-stress function. The theory is shown to predict the magnilude and temperature dependence of the yield stress of a commercial nickel-base superalloy as well as many details of its slip structure. GLEITER and Hornbogen have developed a theory of the yield stress in alloys hardened by coherent, stress-free ordered ptrticles based on the observation that dislocations (b = a/2 (110)) glide in pairs.' When a dislocation pair shears through an ordered particle, the glide motion of the leading dislocation is impeded since it must create antiphase boundary (APB), whereas the motion of the trailing dislocation is assisted because it annihilates APB produced by the first one. Taking into account the APB energy, the size, and spacing of the particles, G-H predict the observed yielding behavior in Ni/18.8 Cr/6.2 A1 alloys composed of a matrix phase y '(nickel-solid solution) and particles of y' (basically Ni3A1). The G-H theory, as well as all previous theories of hardening by coherent ordered particles, do not include the details of dislocation motion; the present dynamic theory is an attempt to overcome this limitation. In the dynamic theory, the yield stress is predicted from the stress dependence of the plastic strain rate, which is related to a derived dislocation velocity-stress function. This function can be evaluated if the structure of the alloy, the APB energy of the ordered phase, and the characteristic drag or frictional stresses of the matrix and precipitate phases are known. The theory is shown to account for the observed temperature dependence of the yield stress in a commercial nickel-base superalloy. 1) NICKEL-BASE SUPERALLOYS Although their compositions are complex, the nickel-base superalloys have remarkably simple structures. A detailed examination of the commercial superalloy

Jan 1, 1968

By W. W. Lowry, G. C. Eggleston, W. E. Keck

THE potential iron ores of Michigan can be classified from the stand- point of the predominant impurities into siliceous, sulphurous and phosphorous ores. Research on the flotation of each of these classes of ore was carried out in the following manner. The flotative properties of the valuable minerals of iron and of the worthless and deleterious ones were first determined under carefully controlled conditions. This information was then applied to synthetic mixtures of these minerals, which simulated the potential ores. Finally, data obtained during the two foregoing stages of the investigation were used in the flotation beneficiation of samples of the potential ores. Hematite is the most important mineral of iron in each of the above classes of iron ores. This paper deals with a study of that mineral in the very nearly pure state. There are two varieties of the mineral-specular hematite and massive hematite. The latter is the principal variety, but the former is an important mineral of iron in some of the potential ores. Because of this condition, flotation research was performed with both varieties. This research consisted essentially of: (1) a survey of the literature on hematite flotation, (2) the preparation of pure massive hematite, (3) the preparation of pure specular hematite, (4) the development of a laboratory procedure and (5) flotation experimentation. For the purpose of this discussion, the results of previous work on the flotative properties of hematite can be summarized as follows: Specular hematite has been readily floated with terpineol and sodium oleate or heptylic acid1. Further, hematite has been likewise floated with a proprietary frother and oleic acid or other soluble oils2. Finally, lead nitrate, copper sulphate, silver nitrate, chromium nitrate, mercuric chloride, ferric

Jan 1, 1937

By H. A. Wriedt

Zinc-vapor pressures in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C were measured by an isopiestic method. Thermody-na?nic properties of zinc in these solutions were derived directly and those of iron with a Gibbs-Duhem integration. Zirzc and iron exhibit large, positive, and moderately temperature-sensitive deviations from ideality. Excess enthalpies and Gibbs energies are positive in the ranges studied. It has been establzshed in relating published phase equilibria to the Gibbs energies of forming solid solutions that positive departures from ideality also exist in the fcc solutions. Tlze stability, as defined by Darken, of the bcc solutions is small but positive at 703.5"C. Its decrease with decreasing temperature indicates that a miscibility gap may exist in the stable or metastable bcc solutions at lower temperatures. The changes of thertnodynanlic properties relatable to changes in magnetic state are minor compared to other changes due to alloying. The accuracy with which the relation between lattice parameter and composition of the bcc solutions is known has been improved. Zinc increases the lattice parameter of a iron by O.ZOZA per unit atom action zinc to at least NZn = 0.25. TO our knowledge, only Ciganl has previously investigated thermodynamic properties of the bcc solutions of the Fe-Zn system. He measured zinc-vapor pressures in the temperature range from about 320" to 360°C by an effusion technique. We have measured the vapor pressures of zinc in equilibrium with bcc solutions of zinc and iron at 703.5", 757", 793", and 900°C by an isopiestic technique. This investigation and the pursuant thermodynamic computations are part of a program for studying several properties of these solid solutions. In the appendix we report a remeasurement of the relation at room temperature between the lattice parameter and zinc content. Related work not reported herein embraces measuring the diffusivity2 of zinc in ferrite at 700" to 900°C and the Curie point temperature3 as functions of composition. EXPERIMENTAL METHOD AND APPARATUS Purified iron at a series of constant temperatures was saturated with zinc at a series of constant zinc-vapor pressures, the range of conditions being so limited that the equilibrated solid solutions were ferri-tic. The equilibration was conducted in long capsules, Fig. 1, that had been evacuated, gettered with titanium, and sealed. The purified iron, part of a vacuum-melted ingot of electrolytic-iron stock (Glidden Co. 1044-grade), had the impurity contents listed in Table I. It was used in the form of millings about 0.001 in. thick. A zinc of 99.999 pct purity (United Mineral and Chemical Corp.) and later one of 99.9999 pct purity (Cominco Products, Inc.) were used, with no observed difference in results. Sufficient zinc was placed in the capsule (separate from the iron and kept at a different temperature) to supply the vapor phase and the iron alloy, while leaving a pool of pure liquid zinc throughout the run. The imposed temperature of the residual zinc pool fixed the vapor pressure of zinc throughout the capsule; condensation was avoided at other locations by making this the lowest temperature in the capsule. Two common complications of nonisothermal systems were, we believe, effectively absent from ours: first, molecular species other than monatomic have no appreciable concentration in zinc vapor at 700" to 900~~: second, the development of zinc-pressure differentials in the capsules was suppressed by use of relatively large-diameter tubing and the absence of diluents in the zinc vapor other than desorbed impurities. The specimens and zinc pool were located at two isothermal zones (each ranging within 1°C over several inches) of a wire-wound, 37-in.-long vertical-tube furnace. The required temperature distribution was achieved by external adjustment of the currents in three electrically isolated windings. The temperatures of the isothermal zones were controlled independently by ther-

Jan 1, 1968

By B. H. Sage, W. N. Lacey

Variations in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydrocarbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs. Theoretical Considerations Muskat1 has discussed the work of earlier authors relating to the equilibrium relationships of multicomponent systems in a gravitational field. He also presented explicit solutions for several cases and discussed the physical significance of gravitational concentration gradients. In engineering work it is customary to consider the pressure, the temperature and the composition of a phase to be the independent variables sufficient to establish its state. This procedure neglects the effect of gravitational or other types of fields upon the energy associated with the system and assumes, among other things, that the pressure is uniform in

Jan 1, 1939

By W. N. Lacey, B. H. Sage

Variations in the composition of the liquid phase of natural reservoirs which are continuous through significant ranges in elevation have been noted by petroleum technologists. In general, there is a greater gas-oil ratio and the gravity of the oil is higher in production from the upper parts of the formation. In the present paper the possible changes in composition with elevation which would result from the attainment of thermodynamic equilibrium in a uniform gravitational field have been evaluated for a naturally occurring hydrocarbon liquid, a binary hydrocarbon liquid phase and a binary hydrocarbon gas. The results indicate a progressive decrease in the mole fraction of the components from methane through the butanes with increasing depth, accompanied by a corresponding increase in the amount of the heavier components making up the system. The magnitude of these variations is perhaps insufficient to explain completely the variations in the properties of the liquid phase that are encountered at various elevations within a particular producing horizon. However, the changes are significant and the treatment presents an example of the application of thermodynamic data to the evaluation of the properties of hydrocarbon fluids under the conditions approaching those encountered in natural reservoirs. Theoretical Considerations Muskat1 has discussed the work of earlier authors relating to the equilibrium relationships of multicomponent systems in a gravitational field. He also presented explicit solutions for several cases and discussed the physical significance of gravitational concentration gradients. In engineering work it is customary to consider the pressure, the temperature and the composition of a phase to be the independent variables sufficient to establish its state. This procedure neglects the effect of gravitational or other types of fields upon the energy associated with the system and assumes, among other things, that the pressure is uniform in

Jan 1, 1939

By Charles L. Mantell, James E. Hoffmann

Mechanical inclusion, electrophoretic deposition, and adsorption were studied as mechanisms for code-position of aluminas present in copper-plating electrolytes as an insoluble disperse phase. Mechanical inclusion was not a significant factor. That codeposi-tzon of aluminas by an electrophoretic mechanism was unlikely was substantiated by measurements of the potential of the aluminas. The alumina content of the deposits was studied as a function of the pH of the bath. These tests in conjunction with sedimentation studies demonstrated the absence of an isoelectric point for the alutninas over the pH range examined. Thiourea in the electrolyte (a substance known to be adsorbed on a copper cathode during electrodeposition) affected the amount of alumina in the electrodeposit. However, no adsorption of thiourea on aluminas in aqueous dispersions was detected. If it were possible to produce a dispersion-hardened alloy of copper and alumina by electrodeposition, an alloy possessing both strength and high conductivity at elevated temperatures might be anticipated. Investigation of the mechanism of codeposition of aluminas with copper was undertaken with the hope that knowledge of the mechanism would aid in the development of such an alloy. The word "codeposit" here does not necessarily imply an electrolytic phenomenon but rather that the materials codepositing, the various aluminas, are transported to and embedded in the electrodeposited copper by some means. Mechanical inclusion in electrodeposition implies a mechanism of codeposition which is wholly mechanical in nature; the only forces acting on a particle are gravity and contact forces. Such a particle is presumed to be electrically inert and incapable of any electrical interaction with electrodes in an electrolytic plating bath. Processes for matrices containing a codeposited phase by electrodeposition from a bath containing a disperse insoluble phase frequently state that code-position is caused by mechanical inclusion.10,2,12 If settling, i.e., gravity, be the controlling mechanism for codeposition of aluminas, then assumptions may be made that 1) the content of alumina in the electrodeposit should be enhanced by increasing the particle size, 2) the geometry of the system, that is, the disposition of the cathode surfaces relative to the di- rection of the falling particles, should affect the alumina content of the electrodeposit, 3) in geometrically identical systems the chemical composition of the electrolyte employed should exercise no effect on the alumina content of the deposit, that is, the alumina content should be the same in all cathode deposits irrespective of bath composition. A bent cathode19 evaluates the clarity of filter effluent in electroplating baths by comparing the roughness of the deposit on the vertical surface with that on the horizontal surface. Two difficulties are inherent in this technique: 1) the current density on the horizontal portion of the cathode would be substantially greater than that on the vertical surface; 2) should the deposit obtained be rough, projections on the vertical face could act as horizontal planes and vitiate the relationship between the vertical and horizontal surfaces. Bath composition should have no substantial effect on the alumina content of the deposit. Two different electrolytic baths were employed. They possessed variant specific conductances and substantially different pH ranges. The experimental tanks were rectangular Pyrex battery jars 6 in. wide by 3 1/4 in. long by 9 3/4 in. deep. The cathodes were stainless steel 316 sheet of 0.030 in. thickness, cut to 7.5 by 1.75 in. and bent at right angles to form an L-shaped cathode whose horizontal surfaces measured 1.75 by 3.0 in. All edges and vertical surfaces were masked with Scotch Elec-troplaters Tape No. 470. The anodes were electrolytic cathode copper 9 in. high by 2.25 in. wide by 0.5 in. thick. To eliminate inordinately high current densities on the projecting edge of the cathode, the anode was masked 1 in. above and below the projected line of intersection of the cathode with the anode. The exposed area of the anode was equal to that of the cathode, providing both with equal average current densities. The agitator in the cell was of Pyrex glass and positioned so its center line was equidistant from cathode and anode, and a plane passed horizontally through the center of the blade would be located equidistant from the bottom of the cathode and the bottom of the deposition tank. The assembled apparatus is depicted in Fig. 1. Hatched areas on anode and cathode represent the area of the electrodes wrapped with electroplaters tape. MATERIALS The chemicals were copper sulfate—CuSO4 • 5H2O— technical powder (Fisher Scientific Co.). Spectro-graphic analysis showed substantial freedom from antimony, arsenic, and iron. Traces of nickel were present.

Jan 1, 1967

By W. B. Heroy

ONLY through the mineral fuels can large amounts of energy be transported to great dlstances and stored for long periods for future use. Coal has the advantages over oil of greater safety of handling and smaller losses in storage. But oil is, in the present stage of technical advancement, the more economical source of liquid fuel for internal-combustion motors. No method for direct use of coal in such motors has been developed that can compete with petroleum products. The automoblle engine and the airplane motor are designed to make the most effective use of gasoline.

Jan 1, 1944

By G. P. Hulst

The Parkes process lead refinery of the International Lead Refining Co., at East Chicago, was built by the International Smelting & Refining CO. to treat the lead bullion produced by its Tooele plant, at Tooele, Utah. The plant was designed and constructed under the direction of the writer. Ground was broken Apr. 16, 1912, and exactly six months later the plant was in operation and lead was being cast. The capacity of the plant, running 25 days per month, is 5,000 tons. The four products of the plant are common lead, corroding lead, antimonial lead, and Dore bullion. The site is an area, 64 acres in extent, lying north of 151st Street, between McCook Avenue and the Canal. The Indiana Harbor Belt Railroad, Baltimore & Ohio Chicago Terminal, and Pennsylvania Railroad enter the yard at the plant. There are five storage tracks and space for storing 100 cars in the yard. the main lead to the storage tracks passes over a 100-ton track scale on entering the yard.

Jan 1, 1915

By Nelson P. Hulst

To those who have had the happy privilege of friendship with George W. Goetz, the announcement of his death has brought great sadness. He was born in Milwaukee, Wisconsin, February 17, 1855, and died January 15, 1897. In his boyhood days, when I first came to know him, his frank, trustful manner; his eyes brimming with truthfulness; his eagerness, never obtrusive, to gain knowledge from all whom he met; and his equal readiness to give without ostentation of his store, constituted a personality which at once commanded confidence and won friendship. I am told that as a scholar of five years he was conspicuous for brightness, a show-pupil, who was called on to recite when visitors were present at school. Yet this in no way spoiled him. His modesty was too strong a trait in his character to be overcome by any attention which might, be expected to arouse vanity. In his simple-heartedness he was pleased then, as he always was in his maturer years, to give of his knowledge for the gratification of his listeners, with never a thought of himself. So strong was this characteristic that in a brief autobiography, in the form of a letter to his wife and children, found among his papers, he excuses himself to them for recounting what he had accomplished in his life-work. As a preface to this autobiography (which, it seems, was prepared on the eve of a sudden journey to California, taken February, 1895, for his health) he says: " I am writing this rather hastily, and I

Jan 1, 1898

By J. S. Ll. Leach, M. B. Bever

THE system copper-nickel exhibits complete solid and liquid miscibility1 The thermodynamic properties of such a system would not be expected to deviate greatly from ideality. Although the evidence is conflicting, anomalies in the composition dependence of various physical properties of solid copper-nickel alloys suggest that mixing may not be ideal.' From measurements of the Hall coefficient it has been concluded that clustering occurs in these alloys. ' Considerations involving the phase diagram of the ternary system copper-nickel-chromium have led Mei-jering3 to predict a positive heat of formation for solid copper-nickel alloys. An electrochemical investigation of the activity of nickel in copper-nickel alloys showed unexpectedly large positive deviations from ideality.4 wagner5 has proposed that if the entropy can be considered ideal, these measurements would yield the following equation for the heat of mixing at 700°C H" = 3380 x,vl (l-xVi) cal per g atom [I1 The heat of formation at 722°C of solid copper-nickel alloys of the equiatomic composition has been measured in a reaction calorimeter as 540 cal per g atom. This note reports calorimetric measurements of the heat effects on dissolution of some copper-nickel ndon: in tin. These measurements were preliminary to a larger investigation, which was later discontinued. From them the heats of formation of the alloys can be calculated, if certain assumptions are

Jan 1, 1960

By R. L. Bleifuss

Most pellets swell only slightly during reduction, but some swell so enormusly that their increase in size is termed catastrophic. Since catastrophic swelling produces irregularities in blast furnace operation, an understanding of the phenomenon is of practical as well as theoretical interest. Observations have shown that catastrophic swelling is characterized by the growth of a network of fine iron filaments. Evidence is presented to show that the growth of these filaments is promoted by the presence of calcium in the magnetite lattice of the original ore. During reduction, the limited mutual solubility of CaO and FeO produces an unstable condition that inhibits the uniform nucleation of metallic iron. Other elements in the magnetite lattice whose oxides are continuously soluble in FeO in the critical temperature range have no effect. Magmatic segregation or pyrometasomatic replacements are the most likely deposits to contain calciferous magnetite. Over the past few years there has been an increasing concern throughout the iron and steel industry over the tendency of pellets to swell during reduction. Although the tendency for swelling is only one of several attributes that determine the behavior of pellets in the blast furnace, swelling-reduction tests are now part of the normal evaluation procedure of many pellet consumers. During a swelling-reduction test, pellets display either the moderate increase in size known as normal swelling, or the enormous expansion known as catastrophic swelling. This paper is concerned with the origin and control of catastrophic swelling and how it is enhanced or inhibited by the presence of minor elements. Swelling Behavior The swelling behavior of pellets during reduction is indicated in Fig. 1. The lower curve represents normal swelling and the upper curve catastrophic swelling.' During the initial stages of reduction, that is, up to about 20-25% reduction, the two curves are considered to be equivalent. Beyond this point normal pellets undergo a gradual decrease in size with increased reduction. By contrast, pellets which exhibit catastrophic swelling show a second dramatic expansion between 25 and 70% reduction. The initial normal swelling develops as the hematite of the pellet is successively reduced to magnetite, and then to wustite. Work by Edstrom' and others has shown that the reduction of hematite to magnetite is accompanied by a 25% volume increase, whereas the magnetite to wustite stage shows a volume decrease. The volume increase overlaps the wustite field because magnetite is formed simultaneously with the wustite during topochemical reduction of the pellet. The catastrophic expansion is clearly related to the wustite, to

Jan 1, 1971

By P. R. Sperry

Aluminum alloy 3S was examined to determine the relationship between the applicable phase diagram and the microstructures produced under conditions tending toward non-equilibrium as well as equilibrium. The only phases present in the alloy were aluminum, (Mn,Fe)A16, aAI(Mn,Fe)Si, and silicon. It was found that the alloy behaved essentially as though it belonged to the Al-Mn-Si system. The effects of various solidification rates and of various homogenization treatments were studied. Particular attention was given to a nonuniform precipitate distribution which reflected the solute distribution in the cast aluminum solid solution. Some possible explanations for the solute distribution based on characteristics of the Al-Mn-Si or AI-Mn systems were discussed. ALUMINUM alloy 3s (aluminum plus 1.25 pct Mn) is one of the oldest and the most widely used of the wrought aluminum alloys. In spite of this fact, there are some aspects of the metallography of 3s which have not been revealed or which have not been brought to the attention of the metallurgist working with the alloy. The purpose of this investigation was to demonstrate in general how some of the fundamentals of equilibrium phase diagrams may be applied to the study of an alloy and to show specifically the origin of certain metal-lographic features of aluminum alloy 3s. It is hoped that this information can serve as a basis for solving specific problems relating microstructure to such things as mechanical properties, recrystallization, grain growth, and surface finish. Literature Survey Considering that alloy 3s contains only one alloying addition, manganese, it seems reasonable that it would have characteristics pertaining to the A1-Mn system. However, those characteristics might well be altered by the impurities in the commercial alloy, especially iron and silicon. Therefore, not only the simple binary but also more complex systems had to be reviewed. One characteristic of the A1-Mn system worthy of mention is its sluggishness, which leads to conflicting solubility data1,'2 and makes it relatively easy to supersaturate the solid solution and shift the eutectic composition during rapid solidification.3'4 Another characteristic is the strong influence which small amounts of impurities, especially iron, exert in lowering the solid solubility of manganese. Undissolved manganese is ordinarily present in an intermetallic phase, MnAl,, having an orthorhombic crystal structure. A metastable precipitating phase designated as "G" has been reported but small amounts of iron and silicon suppress this phase entirely." Raynor has established that MnA1, can dissolve a considerable amount of iron by a substitution of iron for manganese atoms up to 50 atomic pct.'" Consequently, in the Al-Mn-Fe liquidus diagram, the eutectic valley separating the primary aluminum and (Mn,Fe)Al, fields is fairly close to a constant Mn + Fe content." This is an important consideration in regulating the composition of 3s and also other aluminum alloys with high manganese additions."

Jan 1, 1956

By David L. Holt, Walter A. Backofen, Anwar-ul Karirn

ANNEALING the binary alloy, Mg-0.5 wt pct Zr in a hydrogen atmosphere results in extensive precipitation of zirconium hydride. The morphology of these precipitates has already been investigated.lm3 Squires, Weiner, and phillips4 found, following creep testing of the hydrided alloy at 450" and 500°C, that hydride denuded zones formed along grain boundaries that were aligned approximately normal to the tensile axis. Zone formation was attributed to diffusional creep by magnesium transport down the prevailing stress gradients.4'5 Recently, electron microprobe analysis by Karim, Holt, and Backofen6 showed the zones indeed to be zirconium-free and furthermore it was shown that in compression, zones formed along boundaries approximately parallel to the stress axis. Thus it was confirmed that the zones are formed by diffusional creep. Typical zone-formation is shown in Fig. 1. Karim, Holt, and Backofen also measured the con- tribution to the total strain, from diffusional flow, slip creep, and grain boundary shear: results showed that diffusional strain tends to saturate with increasing imposed strain, while grain boundary shear eventually becomes the dominant deformation mode. It was suggested in explanation that the precipitate-denuded zones are soft and easily sheared, such deformation contributing to the grain boundary shear measurement. A point to be emphasized is that the Mg-0.5 Zr alloy was not superplastic for the index of strain rate sensitivity of flow stress, m = a log log 6 was only 0.25. It was recognized that diffusional creep in a poly crystalline aggregate must be accompanied by boundary shearing.' The suggestion was that the non Newtonian-viscous character of diffusional creep in the Mg-0.5 wt pct Zr alloy is due to resistance to sliding of boundaries lying approximately parallel to the tensile axis.= The work described in the present note should be seen against the above background for it represents initial efforts to observe in a similar way diffusional creep in a superplastic alloy. Previous work with the ternary-alloy Mg-6 Zn-0.5 Zr, pellet extruded, showed it to be superplastic however it does not contain resolvable precipitates to act as internal markers for diffusional creep. Also the fine grain size of the alloy (0.5 p) made conventional metallography rather difficult. Solubility relationships in the Mg-Zn-Zr system are not well known, however making reasonable guesses about the probable phase diagram of the ternary, Mg-Zn-Zr, various heat treatments were attempted to produce hydride precipitation. Finally a 16-hr anneal at 495' in hydrogen was found to pro-

Jan 1, 1970

By Frederick Apgar

(Butte Meeting, August, 1913.) THE valuable results that have followed the application in recent years of microscopic methods of research to problems of ore genesis have been significant, but possibly the recognition of their practical importance is not as general as might be, and while, as a scientific method of investigating ores and rocks, the advantage derived through the use of the microscope is unquestioned, its utility as an aid in solving shining problems arising during actual every-day mine examination and operation may not be fully appreciated. Perhaps the roost logical method of showing some of these practical applications of the microscope will be to consider first the prospect stage of a mining venture, then the uses to which the instrument may be put during the operation of a working and developed mine, and, finally, to discuss some of the problems of a metallurgical nature that ii-my arise during milling and smelting the ore. The valuation of mining property as a preliminary to acquiring ownership or determining the advisability of investing time and money in an enterprise is one of the most important and delicate problems that come before the mining engineer. The many and variable factors that have to be taken into account, as, for example, the geology of the district, availability of supplies, probable mining costs, transportation facilities, and the quality of ore, require a careful balancing of costs against recoverable values.

Jan 6, 1913

By William H. Breeding

The remarks that follow are based substantially on experience covering 45 years, 80% of which has been in placer work, rather than on a review of available literature. Most commercial placers have been deposited by the action of water. The richer and more- difficult-to-mine placers are those in the headwater areas where gradients are steepest. The most lucrative placers are generally in inter- mediate areas where volumes are greater, fewer boulders are present, and gradients are from 3% to 1-1/2%. The higher volume, lower grade placers are in the lower reaches of river systems where gradients are lower. Where gold-bearing rivers have discharged into the sea, wave action can concentrate values on beaches, past and present. Most of the rich, readily accessible placers were mined by our forefathers. Current opportunities exist: (1) in remote areas where infrastructure has been absent in the past, or development has been prohibited by adverse ownership - political or commercial; (2) in deposits that could not be mined by equipment available to our forefathers; (3) in deposits unidentified by our forefathers; (4) where the-price-of-product/cost ratio is substantially better than in earlier years; or (5) a combination of those factors. When I entered the placer business in the late 1930s, and subsequently, a prevailing opinion believed that glacial deposits should be avoided as irregular in mineral content and composition, and unrewarding to explore and develop; yet an operator has been mining a fluvio-glacial deposit profitably for the past 17 years. Rich buried placer channels, of ten called paleo-channels were worked in the last century, generally by hand methods, and under conditions that would be unacceptable today. Exploration and mining equipment now available make some of these channels attractive targets. Well-known examples are in California and Australia. The formation of a commercial placer requires a source of valuable minerals. Above primary deposits, there may be eluvial deposits formed by the erosion of gangue minerals and the concentration "in situ" of valuable minerals. Down slope from these deposits are the hillside or colluvial deposits, and below them are the alluvial deposits of redeposited material. Most of the great placer fields of the world are the result of several generations of erosion and deposition. Well-known examples are in California and Colombia. Gold is a very resistant and malleable material, and gold placers may extend for 64 or 80 km (40 or 50 miles) along a river system. Platinum is less malleable, but is very resistant to disintegration. Diamonds are extremely hard, and (especially gem diamonds) may be found over great lengths of a river system. Cassiterite is less resistant to disintegration, and tin placers seldom extend over two miles without resupply from an additional source or sources of mineralizaton. Tungsten minerals are generally more friable, and within a few hundred yards of the source disintegrate to the point that they are uneconomical to recover. Rutile, ilmenite and zircon placers generally result from the weathering of massive deposits, and may be encountered over extensive areas; most are fine grained and durable. What does a geologist or mining engineer look for in placer exploration? The old adage to look for a mine near an existing mine is still valid. You need a source of valuable mineral. Then you require conditions for concentration, which means a satisfactory gradient and/or other conditions that will permit heavy minerals to settle. Nicely riffled gravel, often called a shingling of the bars, is conducive to placer formation. Coarser gravel is logically associated with coarser gold. Excessive clay and/or high stream velocities in narrow channels can carry gold far downstream and distribute it uncommercially over a large area. When material is extremely fine, in situ weathering and concentration become more important. Placers frequently occur distant from lode mines, and one must remember that in a larger watershed the exceptional floods that occur once in a hundred or a thousand years can move great quantities of material long distances. The carrying power of water is said to vary with the fifth or sixth power of its velocity. I am not ready to disagree with Waldemar Lindgren and accept that many commercial placers are substantially enriched by the chemical deposition of gold from solutions; however, I have seen crystalline gold in clayey material quite distant from known sources of primary gold that is dif-

Jan 1, 1985

By A. U. Seybolt

A. U. Seybolt (General Electric Research Laboratory)— As pointed out in an earlier paper,41 it appears to be very difficult to nucleate Si3N4 in Si-Fe of silicon content up to around 5 pet. Therefore, one observes, as did Pearce, that equilibrations with nitrogen gas yield only nitrogen in solid solution at temperatures above about 700°C, or, as Pearce found, 770°C. Evidently, the free energy of formation of Si3N4 only becomes high enough at -770°C to overcome the reluctance of Si3N4 to nucleate. However, as mentioned in Ref. 41, if some Si3N4 is first formed by a mixture of ammonia and hydrogen, one can then replace this gas mixture by nitrogen gas, and either increase or decrease the amount of Si3N4 present at any temperature by suitable adjustment of nitrogen pressure: that is, to equilibrate with Si3N4. In the equilibration experiments cited in Ref. 41, equilibrium was approached from both sides, and it was found that samples up to 944oC, at least, were in equilibrium with Si3N4. Higher temperatures were not employed, as this would have necessitated a redesign of the apparatus for using nitrogen pressures in excess of 1 atm. To summarize, the results of Pearce's experiments and those of Ref. 41 cannot be directly compared because two quite different equilibria were studied. Therefore, the statement by Pearce on p. 1398 indicating apparent error in Ref. 41 is unjustified. M. L. Pearce (author's reply)— There was limited evidence obtained in the current investigation which would indicate that excessive "supercooling" did not occur. A small piece of the same resulting from heat treatment No. 5 in Table III was subsequently held at 800°C for 16 hr in 95 pet N-5 pet H. Isotope-

Jan 1, 1964

By Bernt Ellingsaeter, Terkel Rosenqvist

IN the silicothermic reduction of magnesia, burned dolomite is treated with high grade ferrosilicon in an evacuated steel retort at temperatures between 1150° and 1200°C. The following reaction is assumed to occur MgO + CaO + 1/2 Si (Fe) - Mg(g) +- & Ca,SiO, + Fe with the equilibrium constant on the basis of thermodynamic data for the substances involved and assuming unit activity for all solid constituents, Kubaschewski and Evans' calculated the magnesium pressure as a function of temperature logp,, (mmHg) = 15.06-1.61 T- log T- 13,16O/T. Pidgeon and King," who measured the magnesium pressure by means of a flow method, found values about three times the calculated ones. This may be caused by uncertainties in the thermodynamic data, but may also be caused by the formation of other reaction products, such as Ca,SiO,, which is known to be the stable silicate in equilibrium with lime. Whatever the exact reaction may be, it is evident that as long as all other factors are maintained constant the magnesium pressure will vary with the silicon activity, viz: p,, = &,. (p,,) ", where (p,,)" is the magnesium pressure by the reduction with silicon of unit activity. In the present investigation, p,,, was therefore measured for various grades of ferrosilicon and their silicon activities were calculated. The experimental method was similar to that used by Pidgeon and King. Briquettes of burned dolomite and Fe-Si alloys were placed in a 1 in. heat resistant steel tube and were heated to 1200°C. By means of a flow of purified hydrogen, the magnesium vapor was swept into a condenser filled with steel wool. From the amounts of hydrogen used and magnesium condensed the magnesium partial pressure was calculated. First a tube of 28 pct Cr steel, and later a tube of Kanthal D (a ferrous alloy with 22.6 pct Cr, 2 pct Co, and 4.5 pct Al), was used as a heat resistant tube. The latter tube showed the best heat resistance. The dolomite used had the following composition: 43.6 pct MgO, 55.5 pct CaO, 0.2 pct K,O + NalO, 0.2 pct Fe,O,, and 0.3 pct insoluble. The ferrosilicons were prepared from 98 pct Si of technical grade (0.7 pct Al, 0.3 pct Ca, and 1 pct Fe) by melting with various amounts of electrolytic iron of high purity. The alloys thus obtained were analyzed on their iron and silicon contents, which added up to between 99 and 100 pct. The amounts of reactants were chosen so that there would always be an excess of the oxides, and the average decrease in silicon content during the experiments would be about 1 pct. Most of the reaction occurred in the part of the reaction mixture facing the gas flow. The change in the silicon concentration in the part facing the condenser was, therefore, negligible. To facilitate the reaction, about 1 pct fluorspar was added to the briquette mixture. Fluorspar does not enter the reaction, but is known to act as a

Jan 1, 1957

A little more than a year and a half ago construction started on Canada's largest initial milling plant. Today the zinc concentrating plant 7 miles north of Barraute sits on ground that once was forest and clay flats. The plant is part of Barvue Mines Ltd. zinc-silver operation. Employees of the plant live in the model community of Barvue, built like the plant in record time. About 5000 tons of ore are handled by the plant daily, with an output of 200 tons of zinc concentrate. Management hopes to raise capacity of the $8 million plant to 6000 tons.

Jan 8, 1953

By MARIUS R. CIMPBELL, Edward W. Parker

DESCRIPTION. ACCORDING to the estimates prepared by the U. S. Geological Survey, the area underlain by workable coal-beds in the United States is 496,776 sq. miles. Of this total area, 480 sq. miles contain the entire anthracite coal-fields of Pennsylvania. The bituminous coal-fields are estimated to be contained in areas aggregating 250,051 sq. miles. The grade of coal between bituminous and lignite, and which is designated by the Geological Survey as " sub-bituminous," is estimated to be contained within areas aggregating 97,636 sq. miles, while the areas containing lignite aggregate 148,609 sq. miles. The coal-fields are divided, for the sake of convenience in classification, into six main provinces, as follows: 1. The Eastern. Province, containing the anthracite coal-fields of Pennsylvania and the bituminous coal-fields of the Appalachian region-namely, those of western Pennsylvania, Ohio, Virginia, West Virginia, Kentucky, Tennessee, Georgia, Alabama, and small outlying areas in North Carolina. 2. The Interior .Province, containing the bituminous coal-producing regions of Michigan, Illinois, Indiana, western Kentucky, Iowa, Kansas, Missouri, Oklahoma, Arkansas, and Texas. 3. The Gulf Province, containing the lignite-areas of Alabama, Mississippi, Louisiana, Arkansas, and Texas. 4. The Northern or Great Plains Province, containing the lignite and sub-bituminous areas of North and South Dakota, eastern Montana, and northeastern Wyoming. 5. The Rocky Mountain Province, containing the bituminous and sub-bituminous areas of western Montana and western Wyoming, Colorado, Utah, and New Mexico. 6. The Pacific Coast Province, containing-the areas of Washington, Oregon, and California.

Apr 1, 1909

By A. K. Jena, M. O. Bever

The thermodynamic behavior of dilute solutions of copper, silver, and gold in liquid tin is not explained by current solution theories.1-3 The relative partial gram-atomic enthalpies, or heats of solution, of silver, gold, and platinum in liquid lead at 623°K have been measured in the investigation reported here. Their interpretation requires a modification of the regular-solution theory although lead-rich solutions may be expected to be simpler than tin-rich solutions. The liquid metal solution calorimeter used has been described.4 At the start of a run the bath consisted of 621 g of reagent-grade lead. Several calibrating additions of lead were made during a run; a value of 3.48 kcal per g-atom5 was taken for H623°K - H273°K Two runs were made with each of the solutes silver, gold, and platinum. Annealed wire samples of 99.999+ pct purity were used. Four to six samples each weighing 0.5 to 1,0 g were added from 273°K to the bath at 623°K and the associated heat effects were measured. The samples dissolved in approximately 3 min. No serious experimental difficulties were encountered. The heat effects of the additions in a run plotted against the average atom fraction of solute before and after each addition314 were linear functions of the concentration in lead of silver, gold, and platinum, respectively. By subtracting the difference between the heat contents of a solute element at 623° and. 273°K5 from the measuredheat effects, the partial gram-atomic enthalpy relative to the solid solute was obtained. The relativ: partial gram-atomic enthalpy at infinite dilution and the concentration dependence of the partial gram-atomic enthalpies obtained from the plots of vs atomic fraction x are listed in Table I. The relative partial gram-atomic enthalpy at infinite dilution of silver in lead of 5.46 kcal per g-atom at 623°K compares with values at 723°K of 5.74' and 5.765 kcal per g-atom. These data yield a temperature coefficient of 3.0 cal per g-atom-OK. The partial gram-atomic enthalpy at infinite dilution of gold in lead at 623°K is 0.89 kcal per g-atom compared with 0.85 kcal per g-atoms (obtained by extrapolation) and 0.95 kcal per g-atom.5 By combining these values for 623°K with those for several other temperatures5" the temperature coefficient of was found to be 3.2 cal per g-atom-OK. No thermodynamic data are

Jan 1, 1968