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By Robert K. Steunenberg, Irving Johnson, James B. Knighton

The activity coefficient of plutonium in liquid magnesium, over the temperature range 650° to 800°C, was obtained from measurements of the distribution of plutoninm between a 50 mole pct MgC12-30 mole pct NaCl-20 mole pct KC1 molten-salt mixture and liquid Zn-Mg alloys. For dilute solutions (0.08 at. pct Pu) the activity coefficient of plutonium was found to vary from 10.1 at 650°C to 12.2 at 800°C. The activity coefficients of plutonium in dilute liquid solutions of plutonium in uranium, silver, lanthanum. cerium, and calcium were estimated to be. The distribution data indicate a value of about 0.1 at 800°C for the activity coefficient of PuCl3 dissolved in the above ternary salt mixture. LIQUID magnesium and several liquid alloys of magnesium with metals such as zinc and cadmium have been shown to be useful solvents in pyrochemical processes for the recovery of uranium and plutonium from discharged nuclear fuels,' and for the separation of transuranium elements.' The present study was undertaken to determine the activity coefficient of plutonium in liquid Pu-Mg alloys in support of process-development work. The activity coefficient of plutonium in liquid magnesium was determined from experimental data on the distribution of plutonium between a liquid ternary MgC12-NaC1-KC1 salt mixture and various liquid Zn-Mg alloys. The distribution data were used to calculate the ratio of the activity coefficients of plutonium in liquid zinc and in liquid magnesium. The activity coefficient of plutonium in liquid magnesium was then computed from the known activity coefficient of plutonium in liquid zinc. It was not necessary to know the thermodynamic properties of the molten-salt system explicitly. The major features of the Pu-Mg system have been reported by Schonfeld.3 At the temperatures of interest in the present study, i.e., above about 600°C, the phase diagram indicates the existence of a wide liquid-miscibility gap, with the plutonium-rich liquid containing about 8 at. pct Mg and the magnesium-rich liquid containing about 10 at. pct Pu at the intersection with the solidus regions. Additional data on the compositions of the two equilibrium liquid phases obtained in this laboratory4 have defined the miscibility gap up to the consolute temperature (at about 1040°C). EXPERIMENTAL PROCEDURE AND RESULTS Materials. The 50 mole pct MgC12-30 mole pct NaC1-20 mole pct KC1 salt mixture was prepared by melting the required proportions of reagent-grade NaCl and KC1 with anhydrous MgC12. The molten salt was then purified by contacting it with liquid Cd-30 wt pct Mg alloy (at 450°C) to reduce oxidizing impurities, followed by filtration through a stainless-steel frit (pore size, 65 µ) to remove solid MgO formed during the reduction. The purity specifications of the zinc, magnesium, and plutonium were 99.999, 99.8, and 99.85 pct, respectively. Apparatus. The liquid salt and metal were contained in a tantalum crucible inside a graphite secondary vessel. The crucible assembly was located inside a resistance-heated stainless-steel furnace tube. The furnace tube was closed by means of a stainless-steel cover, which was attached by bolts, with a neoprene O-ring serving as a gas-tight seal. The top of the furnace tube was water-cooled to protect the O-ring. The furnace-tube cover was provided with a tantalum thermowell, a tantalum stirrer, and a port through which sampling tubes could be inserted and materials could be added to the melt without admitting air to the furnace tube. Vacuum and an argon atmosphere were available through a side-arm on the furnace tube. The furnace temperature was regulated by a proportional controller that was actuated by a chromel-alumel thermocouple between the furnace tube and the heating elements of the furnace. The melt temperature was measured by means of a chromel-alumel thermocouple in the tantalum thermowell. The accuracy of temperature measurement was ±3°C. The salt and metal phases were intermixed by a motor-driven tantalum paddle positioned at the liquid interface. The tantalum crucible was provided with four baffles to increase the turbulence. The sampling tubes consisted of 1/4-in.-OD tantalum tubing that terminated in a tantalum frit (Kawecki Chemical Co.; average pore size, 30 µ). Procedure. The zinc, magnesium, plutonium, and salt were charged to the tantalum crucible; then the system was evacuated and filled with argon. The melt was brought to the desired temperature, and agitated for 1 to 2 hr. After allowing the salt and metal to separate, both phases were sampled. Filtered samples were obtained by immersing the end of the sampling tube in the liquid and increasing the argon pressure sufficiently to force the liquid salt or metal through the frit into the tantalum tube. The sample was then partially withdrawn into the cooler portion of the furnace tube and permitted to solidify before being removed. The temperature sequence for sampling at each magnesium concentration was 800°, 700°, 600°, 650°, and 750°C. The composition of the liquid-metal phase was varied by incremental additions of magnesium in a series of experiments at low magnesium

Jan 1, 1967

By H. C. Fiedler

SILICON-IRON strip with a cube-on-edge secondary recrystallization texture is made commercially as thin as 10 mils. With inclusions present to inhibit normal grain growth, a few grains, and these have the (110)[001] orientation, grow very large at the expense of the matrix grains. In the absence of inclusions, only normal grain growth occurs and the texture is not as strong as when it is developed by secondary recrystallization.1 Strip for use at frequencies of 400 cps and higher is made in thicknesses of 1, 2, and 4 mils by a process developed by Littmann.2 Attempts to develop a strong texture in these thin gages by the same methods as were used for the 10 mil and thicker strip were unsuccessful,2 and Littmann's solution to this problem was to cold roll the grain

Jan 1, 1963

By W. S. Owen, T. Bell

The variation ox the M, temperature with nitrogen concentration has been determined experinzentally. The free-energy difference between martensite and the parent y Phase at the M, temperature,is computed for Fe-C and Fe-N alloys using recent solubility data fm the Fe-N system and new data for the variatim of the activity of the interstitial solute in the y phase with concentration. The "geometric model" is considered also, and the importance of Zener ordering is noted. It is shown that, although at any chosen concentration the M, temperature and the activity are significantly different in the two alloy systems, the free-energy duference is the same within the limits of experimental error, thus Providing further evidence of the very close similarity between the martensite transformations in Fe-C and Fe-N alloys. TO estimate the free-energy change accompanying the martensite transformation in binary interstitial alloys it is necessary to know the variation of the Ms temperature with interstitial solute concentration and some thermodynamic data. To date, only the Fe-C system has been discussed because this was the only system for which relevant experimental measurements had been made, but even in this case the data available are insufficient to permit the free-energy change to be calculated without the assumption of a thermodynamic model for the y and a solid solutions. The last comprehensive discussion of the topic was by Kaufman, Radcliffe, and Cohen in 1.960.' Since that time Ellis, Davidson, and Bodsworth2 have redeter mined the activity of carbon in y iron as a function of carbon content and Atkinson3 has measured the activity of nitrogen in Fe-N austenite. The M, temperature of Fe-N is reported in the present paper. Thus, it is now possible to assess the free-energy change accompanying the martensite transformation in Fe-N alloys on the same basis as that used to assess the change in Fe-C alloys. This comparison is of interest because it has been shown recently4 that the structure of the martensite formed in Fe-N alloys changes with nitrogen content in a manner exactly parallel to the changes in structure in the Fe-C series and that the strain associated with the distortion of the iron lattice in either the y or the a phase by a nitrogen atom is the same as that produced by a carbon atom. The work to be described tests whether or not this close similarity between the two systems extends to the thermodynamics of the martensitic transformations. THE Ms TEMPERATURES FOR Fe-N MARTENSITE Bose and Hawkes5 found the M, temperature of a eutectoid Fe-N alloy (2.35 wt pct N) to be 35°C. This single determination appears to be the only reported measurement of the M, temperature of an Fe-N alloy. In the present work a series of more than fifteen different specimens containing between 0 and 2.7 wt pct N were prepared by controlled nitriding of pure iron wire 0.010 in. diam. The iron was supplied by B.I.S.R.A. and was designated ACN2. The nitriding procedure, all aspects of which are critical, has been described in detail elsewhere.' Each specimen was quenched from the austenitizing temperature into brine at 20°C without removing the specimen from the ammonia-hydrogen atmosphere in which it was ni-trided. Alloys containing up to 0.7 wt pct N were fully martensitic. More concentrated alloys contained progressively more retained austenite. At 2.34 wt pct N the specimen was completely austenitic after quenching to 20°C. The M, temperature of specimens with M, temperature above 20°C (those containing less than 2.35 wt pct N) was determined by a thermal arrest technique. For the more concentrated alloys (2.35 to 2.70 wt pct N) the variation of electrical resistance with temperature down to -196°C was used. Unlike Fe-C alloys, Fe-N alloys cannot be reaus-tenitized in vacuum or in an inert atmosphere because excessive loss of nitrogen occurs, even in short times, at high temperatures. Consequently, the alloys were reaustenitized in the ammonia-hydrogen mixture corresponding to nitrogen equilibrium at the temperatures used. The specimens were quenched in a blast of cold hydrogen gas and the temperature, measured by a thermocouple welded to the 2.5-in.-long specimen, was recorded on a high-speed recorder. In the first experiments 0.002-in.-diam chromel-alumel wire thermocouples were used but it was found that these gave erroneous readings due to contamination by nitrogen pickup. Pt-Pt 13 pct Rh wires of 0.002 in. diam were found to be satisfactory. Further details of the experiments are available in the original thesis.7 The cooling rate was controlled between 400° and 4000°C per sec by adjusting the hydrogen pressure. At least three cooling curves were obtained for each composition. Each specimen was analyzed for nitrogen after quenching. To aid in the accurate location of the martensite arrest points a series of cooling curves of 0.010-in.-diam platinum wire were recorded and these, which did not contain an arrest, were used as comparison standards. Four specimens, each in the form of a 3-in. loop, were prepared from each of the four alloys containing more than 2.35 wt pct N. One specimen was used for nitrogen analysis, one for X-ray diffraction, and two for resistance measurements below 20°C. The latter specimens were quenched from 20°C into constant-temperature baths at selected lower temperatures.

Jan 1, 1968

By Charles G. Maier

SCIENCE beginning in rational observation came of age, when its devotees first began to measure and count. It has been said that the most striking aspect, of science today is its growing abstraction, and its preoccupation with mathematical symbolism. Technology with specific and concrete objectives in the satisfaction of human wants, cannot conceivably achieve the abstract unification that science seeks, but .the utility of the' scientist's method has been too well proved to require bolstering. Metallurgy is in its scientific infancy.

Jan 1, 1931

By Julian M. Avery

In its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary purpose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by combustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all ecorlomy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the efficiency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss call be successfully attacked by increasing the over-all pressure; i.e., the "top prcssure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity. In a broad sense, the suggestion of pressure operation of the pig-iron blast furnace is not new, for operation under moderately increased over-all pressure was suggested as early as 1871, by no less an authority than

Jan 1, 1938

By Julian M. Avery

In its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary purpose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by combustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all ecorlomy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the efficiency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss call be successfully attacked by increasing the over-all pressure; i.e., the "top prcssure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity. In a broad sense, the suggestion of pressure operation of the pig-iron blast furnace is not new, for operation under moderately increased over-all pressure was suggested as early as 1871, by no less an authority than

Jan 1, 1938

Weston Portable Electrodynamometer The Weston Electrical Instrument Co. of Newark, N. J., believes that problems hitherto considered impossible of solution in the designing of portable electrodynamometers have been solved in its new models. The voltmeter, Model 341, is an instrument' of precision adapted to use on alterating- or direct-current circuits, guaranteed to an accuracy of 0.25 per cent. full-scale value either on direct or alternating-current circuits of any frequency to 133 cycles per second and commercial frequencies even as high as 500 cycles per second with very slight error. The polyphase electrodynamometer, Model 329, is accurate to 0.5 per cent. under the same conditions.; Double ranges are furnished in all instruments of this model. All current ranges can be used for 100 per cent. overload indefinitely without introducing error in Models 310 and 329.

Jan 12, 1915

By C. W. Merrill

The cyanide process in the United States, notwithstanding numerous failures made under the direction of the owners of the patent-rights, and others, has now passed its experimeiital stage, and can, undoubtedly, be made successful when intelligently applied to suitable material. Much, however, remains to be known as to the exact conditions under which this process is applicable to the treatment of gold-bearing ores. If the owners of the patent-rights in this country have ever scientifically investigated the matter, they have never published any valuable informatioil on the subject. Other parties who are now using the process (often independently of the patentees), have nothing to gain by publishing their experience; and, moreover, many of the chemical reactions described in the text-books refer to the use of solutions of potassium cyanide many times stronger than are used in the metallurgical process.

Jan 1, 1896

By Mahesh C. Jha

Arsenical gold ores occur in many parts of the world, including numerous mines in Canada and the western United States. Free gold is often finely disseminated in the grains of sulfide minerals, arsenopyrite, pyrite, orpiment and realgar. Generally a sulfide concentrate is produced by flotation. Arsenical ores or concentrates are not amenable to direct cyanidation and therefore are considered refractory. A wide variety of roasting equipment and conditions have been used by the mills to remove arsenic and sulfur from these concentrates. The resulting calcine is easy to cyanide and gold is recovered from the cyanide solution by zinc dust cementation. Room-temperature potential-pH diagrams and high-temperature phasestability diagrams are presented to discuss the chemistry of the gold cyanidation, cementation, and roasting steps in the presence of arsenic. The environmental aspects of arsenic discharge are also included.

Jan 1, 1984

By I. Iwasaki, R. H. Heerema

The presence of calcium and magnesium ions in iron ore pulps that are upgraded by selective desliming can result in indiscriminate flocculation of both iron oxide and siliceous gangue slimes. The removal of these alkaline earth cations in pulp solutions by chemical precipitation was ineffective as a means of deflocculation of quartz. It was shown by using various techniques (electron micrographs, abstraction, and streaming potential measurements, and cationic flotation tests) that heterocoagulation between the precipitates [Mg(OH)2, hydroxyapatite, and CaCO3] and quartz particles was the reason behind that observation. In addition, the precipitates adversely affected the recovery of quartz by cationic flotation, due to slime coating, a case of heterocoagulation. Magnesium hydroxide produced a uniform layer of coating across the quartz surface, while hydroxyapatite and calcite produced discrete, localized deposits dotting the surface.

Jan 1, 1981

By William G. Pariseau

Advances in numerical methods of analysis and computer technology during the past decade have brought many formerly intractable ground control problems within easy reach of present day graduate mining engineers. However, the new technology brings with it new problems. The identity of these problems are largely those arising from a lack of familiarity with the capabilities and limitations of the new technology. In this regard, the central problem in ground control planning is the calculation of ground motion associated with mining. The fundamentals of this problem leading to a form suitable for computer programming are therefore reviewed. Solution procedures in the broad sense including the gathering of input data and the interpretation of output are described. Computer program capabilities necessary for ground control analysis are discussed and the steps necessary to implement an analysis are outlined.

Jan 1, 1983

By M. E. Straumanis, J. -P. Krumme

In basic ([KOH + KCl] with a total polarity of 2) or acidic (2N H2SO4) electrolytes and at anodic current densities of more thun 2 to 4 ma per sq cnz, n-type GaAs single crystals of lozo resistivity preferentially dissol~je forming etch tunnels with triangular or civc~ilay cross sections and of a width between 0.5 arid 5 p. These etch tunnels are oriented along any one of the four possible (111) directions of GaAs. However, their growth occurs only in one direction of a given (111) whick apparently is determined by the atomic sequence Ga —As (and not the rezlerse) in respect to an individual valence bridge in the crystal. It is concluded from comparison with the cubic lattice structure of GaAs that the etch tunnels represent macroscopic evidence for the tetrahedral bonds and their polar properties. If the anodic current density is increased the tunnel fomation results in the development of a fibrous surface layer consisting of GaAs. The latter separates frorn the substrate (in an anodic s~irface disintegration process) by the growth pressure of an As,0, filnz forming in the interior of the fibrous layer, 100 to 200 µ under the surface, at more than about 50 ma per sq cni. The fibrous GaAs film has the same crystallographic orientation as the substvate and represents a skeleton of the original crystal. Since the etch-tunnel density in a separated GaAs layer is about 108 c?n-', and the etch tunnels develop only along (111) in a given polar direction, it is assurraed tlmt the dislocations have no influence on the growth of these tunnels. ElECTROLYTIC treatment of smooth surfaces of poly- and single-crystalline GaAs at high anodic current densities causes the formation of porous surface layers.' This phenomenon suggests comparison with effects being observed with magnesium,' indium,, gallium,4 and aluminum5 and known as "anodic disintegration". The purpose of the present paper is to explore and to explain the reasons for the formation of such surface layers on GaAs and, in particular, to investigate the influence of the lattice polarity of this III-V compound semiconductor in the (111) direction on the anodic dissolution behavior. GaAs SINGLE CRYSTALS For the experiments described below GaAs single crystals from the Monsanto Co., St. Louis, Mo., were used. Their impurity levels were below 1 ppm and their dopant levels between 1 and 100 ppm. They were grown in (111) using the Czochralski or the gradient-freeze technique. The crystals had n-type conductivity and electric resistivities between 1 and 5 ohm-cm. EXPERIMENTAL The GaAs single-crystal rods were cut perpendicularly to (111) into wafers of about 1 mm thickness using a wire-blade crystal slicer and an aqueous slurry of Sic or a diamond saw. The orientation of the faces of these wafers were checked by Laue back-reflection patterns. If there was a deviation from (111) the faces were abraded under a certain angle using grinding paper and distilled water. The damaged surface layer was removed from each crystal by chemical etching with a mixture of 1HF:1HNO3: 1H20 or 2HF:1HNO3:2HAc (glacial). {110) faces were obtained by mechanical cleavage, producing surfaces which did not require a further treatment. The GaAs wafers were mounted using "alligator" clamps instead of soldered electrical contacts.' Only the bare crystal surfaces were dipped into the electrolyte. The clamps were coated with insulating wax to prevent any contact with the electrolyte. The experiments were carried out in aqueous 2 N H2so4,' or in an aqueous solution of KOH and KCl1 (1 mole KOH + 1 mole KCl in 1000 cu cm solution). Anodic current densities up to several hundred ma per sq cm were applied for periods between 30 sec and 2 hr. For the purpose of investigating the initial steps of disintegration the anodic current density applied never exceeded 20 ma per sq cm. The films which partially separated from the anodic surfaces under high-field conditions were treated with KOH to further their detachment by dissolving the As2O3 formed. The washed and dried films were pasted to strips of filter paper, and Laue pictures were made. The back-reflection patterns obtained were compared with those of the original anode surface before and after anodic dissolution. Furthermore, space reciprocal lattices7 were constructed from asymmetric rotation crystal patternsa which permitted the determination of the crystallographic orientation of the detached films of the corrugated anodic surfaces. The disintegration products were identified from assymmetric powder patterns.8 The polarity of the {111) faces was determined by chemical etching with mixtures of 1HF:1H2O2(30 pct): 2H2O or 1HNO3:2H2O. Different patterns on each of two inverse (111) sides appeared.'-l8 The correlation of these patterns to the Ga{111) or the As(111) side has already been established by the use of light figures,18-20 by X-ray diffraction near the absorption edges of gallium and arsenic,'lmZ4 and by LEED measurements.25 The geometric structure of these surfaces and the interior of the anodically attacked crystals were observed and photographed with a high-power microscope using oil immersion objectives up to magnification of X1720.

Jan 1, 1968

By Albert Sauveur

(New York Meeting, February, 1913.) IT is delightful to read a technical paper like that of J. E. Johnson, The Effect of High Carbon on the Quality of Charcoal-Iron, presented in October, 1912, at the Cleveland meeting of the American Institute of Mining Engineers.1 The clear, simple, and straightforward manner in which he describes his experiments and results makes you feel as if you had been, so to speak, at his elbow during the course of his investigations, while his method of procedure is so rational that you can fairly anticipate each step in the logical sequence of the tests performed. The following notes suggested by Mr. Johnson's paper are presented here in the hope that they may help, if only a mite, towards the final solution of a problem of considerable scientific and industrial importance.

Jan 3, 1913

By G. S. Coe, G. F. Bolling

The columnar-to-equiaxed transition (CET) has often been studied as a function of concentration, C, temperature gradient in the melt, G, and rate of solidification, R. Although it may not be immediately obvious it is sure that the CET, expressed as some ratio G/R necessary to suppress equiaxed nucleation for a given C,' cannot be a single-valued function of C. This restriction which is ignored in theoretical presentations is most trivially illustrated by the following simple reasoning. An ordinary casting is an unconstrained system where the thermal conditions change continuously with progressive solidification, and thus where the ratio G/R decreases from the outset. A CET occurring early in a casting (much equiaxed material) must then mean a higher value of G/R at transition, in comparison with the late CET which implies a more columnar ingot. Therefore, when we choose to experiment under constant superheat for all alloys across the simplest binary, and we find an inversion in the amount of equiaxed material, we shall find two values of C satisfying the G/R condition. However, in addition to this simple instance, the early experiments of ~orthcott' seem to show that the amount of equiaxed material in cast ingots may be a multivalued function of composition in a given binary system. In the present investigation, the CET has been examined in Pb-Sb, Pb-Ag, Pb-Sn, and Sn-Pb under several types of casting conditions. First, we have used the "bidirectional" ingot section Simulation;~ and we have used .'i~z situ" ingot solidification where a hot mold already filled with liquid is chilled so that there is no disturbance provoked by pouring. Differences in method are trivial to our purpose except for the fact that certain variations are more simply observed by one technique than by the other. Second, we have varied the mode of superheating from the simple extreme of casting all alloys from the same temperature regardless of composition to the careful casting at a standard superheat, calculated with respect to the alloy liquidus. Third, we have made provisions for decanting and interface observation, so that some "castings" were not completed. The results obtained with Pb-Sb are exemplary; some of these are shown in Fig. 1 along with explanatory captions. At 9 to 10 at. pct Sb, and thus above the solid-solubility limit Cs = 5.8 at. pct Sb and yet below the eutectic concentration Ceu = 17.5 at. pct Sb, there is a persistent anomaly in all the variations. Measurement was easy enough and standard enough so that we may forgo discussion of either method or possible error, in view of the forceful self-consistency shown by experiment. Solute distributions were measured along the bidirectional ingots in order to determine if a solute buildup had occurred at the CET. No anomalous changes in concentration were observed along the bars at either side of the solute anomaly of 10 at. pct Sb. The microstructures of the ingots were also examined across the range of composition investigated. At concentrations less than 9 at. pct Sb the micro- and macrostructures were typical of the cellular-dendritic growth usually reported for the columnar zone. Above the anomaly, both the columnar grain size and the amount of primary phase decreased. This microstruc-tural observation can be correlated with observations made of decanted interfaces. Below 9 at. pct Sb, the interface reveals the "normal" columnar dendritic structure; however above the anomalous concentration range, preferential growth of certain dendrites appears to form a "super dendrite" pattern. In Fig. 2 a microstructural view of the etched '(super dendrites'' shows their constitution both in terms of relative phase proportion and in terms of the ordinary smaller dendrites.

Jan 1, 1969

By E. I. Salkovitz, F. W. von Batchelder

DURING the last few years several papers1-' have been published in which internal friction measurements have been used to determine the quantity of carbon or nitrogen dissolved in a iron. This method is based on the fact that, in pure Fe-N and Fe-C alloys, nitrogen and carbon cause peaks in the internal friction vs. temperature curve; at a frequency of 1 cycle per sec (cps) these peaks appear at $-200 and +360C, respectively, and if internal friction is expressed as Q-1, which is equal to times the logarithmic decrement, this figure will, by coincidence, give the weight percentage of nitrogen or carbon in solid solution.' In most of the studies published, very pure iron (Puron) was used. In one case the influence of manganese on the behavior of nitrogen in a iron was mentioned.4 It would be of great value, especially for the study of aging and related phenomena, if this method could be applied to commercial mild steel with norrnal percentages of manganese, phosphorus, sulphur, etc. As a rule, in such steels carbon and nitrogen are present together, and the amounts of these elements in solid solution should preferably be determined separately. The fact that their internal friction peaks appear at different temperatures (+36° and + 20°C in pure iron) seems promising for such a selective determination. It is necessary, however, that the peaks are narrow enough not to interfere with one another, and further, that there is no effect from carbon on the behavior of nitrogen in stress induced diffusion, and vice versa. According to Fast,' however, in the presence of manganese the nitrogen peak gets wider and appears at a higher temperature nearer the carbon peak, and thus the prospects for selective determination are reduced. (The carbon peak was not affected by the presence of manganese.) But even if fully quantitative de- terminations of the two elements are not attained, some relative figures on the sum of them and an indication of which one is the predominant one, would be of value. Some results from experiments along these lines will be reported here. An internal friction measuring device was assembled mainly following a description by KG." The measurements were also carried out as reported in that paper. Table I gives the chemical compositions of the four different materials used in this investigation. All materials were drawn to wires with diameter about 0.8 mm, and the analyses refer to these final shapes. Determination of Nitrogen Peak Wires from steels A, B, and C were decarburized in wet hydrogen (about 30 pct H2O) at 700°C until no carbon or nitrogen could be found by chemical analysis. No peak was then found in the internal friction. The wires were further annealed at 580°C for 16 hr in hydrogen bubbled through a solution of 6.8 pct NH3 in distilled water. Chemical analyses gave 0.04 pct N in A and C, and 0.06 pct in B. After annealing at 580°C for 15 min in a lead bath and water quenching, the internal friction was immediately measured. The resulting curves are shown in Fig. 1. At these high values of the internal friction the accuracy is comparatively poor; at Q-1 - 0.030 it is estimated to be 0.002. In order to make possible a calculation of the activation energy for diffusion of nitrogen, measurements were made at two different frequencies. Steel A shows rather broad peaks, and their temperatures can hardly be expected to be very accurate. Steels B and especially C are better in this respect. The finding of Fast' that manganese broadens the nitrogen peak is con-

Jan 1, 1953

By U. Andres

U. Andres (The Technion, Haifa, Israel)-The authors are to be congratulated on their research, new and interesting, in a field which, however, the present writer and his assistants have been trying since 1962 to bring to the attention of the scientific and technical world, by means of publications covering several different aspects of this many-sided problem. We announced, in these publications, the results of magneto-hydrostatic (MHD) separation of magnetic and nonmagnetic minerals which we made in magnetic fluids (in paramagnetic solutions and suspensions of magnetic particles) which interact with permanent" and impermanent" inhomogeneous magnetic fields. There is no doubt that the authors have succeeded in creating ferrimagnetic colloids made by dispergation of 10-30 wt % of magnetite in kerosene in the presence of 7-10 vl % oleic acid. It may be judged by [Figs. 3 and 4] that the suspensions represent great stability systems and also "hysteresisless" fluids [(Fig. 5)] which bear witness to the existence of superparamagnetic suspensions. If the viscosity of these colloids is not so high, and the cost of preparing them can be covered, the fluids which have here been received can possibly be of interest to the technology of mineral separation. The potential possibility and technological perspective of similar media is demonstrated in our joint work with G. Bunin18 in 1965. The research carried out on the pushing out of cylinders and spheres from magnetic fluid is impressive; it would, however, have been interesting if the authors had compared their results with those on the pushing out of bodies from magnetic fluids adduced from our work." In my books" there happens to be described an experiment on the pushing out of a sphere in magnetic wedge field, in which the pushing out force of suspension with 5 vl % of magnetite reached 125 g per cc. This testifies to interesting possibilities of these media. Our works' shows also, on the basis of Laplace's equation the receiving of an interesting distribution of pushing out forces by selection of corresponding configurations of magnetic poles. Objection must be made to the authors' introduction of the term "antigravity force." The direction of this force does not depend on the direction of the gravity force and their opposition, i.e., antigravity is only one particular case. I am in full agreement with the authors' statement that magnetic pushing out forces "can be utilized to separate nonmagnetic objects according to variations in their densities." It is, however, necessary to make only one important addition, which can be found in our research on MHS at the Technion in Haifa, namely, that magnetic fluids in magnetic fields can be utilized in the separation of minerals according to variations in their magnetic susceptibility. The authors' conclusion is especially important considering the fact that in our publications" (including one in English") some designs of MHS separators and some technological results received on MHS-separators have already been described. S. E. Khalafalla and G. W. Reimers (Authors' Reply)We were aware (mostly through Chemical Abstracts of the American Chemical Society) of the use of solutions of paramagnetic salts such as manganous sulfate in agnetohydrodynamic separations by the Russian school headed by G. Bunin."n Professor Andres' contributions to this school are also evident in his application of the ponderomotive forces in an electrolyte placed in electric and magnetic cross-fields to separate coal and other useful minerals." It must be realized, however, that the foregoing research by Bunin et al." involved the use of magnetic fields and field gradients of very large magnitudes, i.e., such that H • grad H - 101 Oe2 per cm. The magnetization of paramagnetic salt solutions range from 0.1 to 0.5 gauss (at fields of a few thousand Oersteds) and never reach saturation. The magnetization of our superparamagnetic ferrofluids ranges from 100 to 500 gauss and reach saturation at fields of a few hundred Oersteds. Hence, to effect the same separation, the quantity "H

Jan 1, 1974

By Julian M. Avery

IN its dual role of pig-lion smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary purpose During the past 10 years or more, improvements in blast-furnace technique and economy have, n fact, been directed primarily to increasing efficiency n the use of the reducing power of the gases produced by combustion of coke at the tuyeres, to reduce iron ore within the furnace The net over-all result is a decrease n the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently amore than offset n value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements The purpose of the present paper is to suggest that, while progress has been made n this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all economy of a different order of magnitude than results thus far obtained by the use of other expedients The present argument is based in large part upon the hypothesis that the efficiency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss can be successfully attacked by increasing the over-all pressure, i e , the "top pressure" under which the furnace is operated It is indicated that pressure operation may also be expected to result n concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity In a broad sense, the suggestion of pressure operation of the pig-iron blast furnace is not new, for operation under moderately increased over-all pressure was suggested as early as 1871, by no less an authority than

Jan 1, 1938

By D. J. DeLazaro, W. Rostoker, R. E. Riley, M. Hansen

At very low concentrations, carbon dissolves interstitially in molybdenum resulting in a linear expansion of lattice parameter with increase of carbon in solid solution. Geometrical consideration of the relative size of carbon atom to size of interstice approximately predicts the observed volume expansion. THE element carbon, occurring in molybdenum, either as an unavoidable impurity, or purposely added, markedly affects the mechanical properties of molybdenum. Several investigators1-" have noted the occurrence of molybdenum carbide at the grain boundaries of cast molybdenum, and Fischer and Rengstorff' have shown that this intergranular constituent can induce intergranular brittleness. The appreciable change, with temperature, of the solid solubility of carbon in molybdenum, found by Few and Manning," suggests other important effects upon mechanical properties. Finally the relative atom diameters of carbon and molybdenum (the ratio of atom diameters is 0.59) are indicative, by analogy with iron (ratio of carbon atom diameter to iron atom diameter is 0.65), of a possible interstitial solid solution. If carbon dissolves intersti-tially in molybdenum, anelastic effects and age-hardening effects, similar to those observed in other body-centered cubic metals, could be expected. However, from the work of Sykes, Van Horn, and Tucker," it might be inferred that carbon forms only a substitutional solid solution with molybdenum. These considerations made it desirable to study the effect of carbon on the lattice parameter of molybdenum in greater detail than heretofore. All heat treating was done in a high temperature furnace7 built specifically for heat treatment of molybdenum. The temperatures and times of heat treatment were determined from the a solubility limit for the Mo-C system." These heat treatments were carried out in argon which was purified with respect to N, and H.!0." Purification of the argon was accomplished by passing the argon over hot (750°C) titanium and then through a magnesium perchlorate drying tower. As many as six samples were run concurrently and quenched at different times without interrupting the furnace cycle. Both the purity of the furnace atmosphere and ability to quench samples from any temperature up to 4000 °F were of prime importance in the successful heat treatment of samples for the lattice parameter investigation. Carbon Analysis The Leco Combustion apparatus was used for carbon analysis. This apparatus is capable of an accuracy of & 0.003 pct for a 1 g sample in the range below 0.10 pct. However, it is felt the degree of accuracy is somewhat better than this limit in view of the consistency evident by cross checking a number of determinations. The Battelle Analytical Laboratory consistently reported check results to within k 0.001 pct C. X-ray Measurements The molybdenum wire specimens (20 mils) were carefully filed down to about 12 mils and then etched with nitric acid to 8 mils. Carbon analyses were made on specimens before reduction in size; however, since there was no evidence of surface carburization, it is probable that the carbon was uniformly distributed throughout the sample. The resultant specimens were strain free and small enough to minimize the error in the lattice parameter determinations due to X-ray absorption. Diffraction patterns were obtained with a Debye-Scherrer powder camera 114.59 mm in diam utilizing the Straumanis type asymmetrical film mounting. Nickel-filtered copper. Ka radiation and zirconium-filtered molybdenum Ka radiation were used. Line positions on the film were measured with a traveling microscope equipped with a vernier scale permitting measurement to 0.001 cm. The average of five readings was used to determine the position of each line. The lattice parameter for each specimen was determined from the data by the extrapolation method of Bradley and Jay, Y.e., the intercept at 90" of the straight line obtained by plotting the apparent lat-

Jan 1, 1953

By E. E. Thurlow

The Geology Div. of Northern Pacific Railway Co. has adapted to its exploration efforts field procedures for geochemical sampling and semi-quantitative analysis which have been developed through research by the U. S. Geological Survey. The sampling is done in conjunction with reconnaissance geologic mapping on aerial photographs or during field checking of maps which have been prepared largely by photo-geologic interpretation. Stream sediment or soil samples are taken and readily soluble combined heavy metals are extracted with ammonium citrate followed by colorimetric titration with dithizone at the sample site. The effectiveness of this approach has been demonstrated both in positive and negative results, thereby assisting in the elimination of large areas of land from further immediate attention and in providing targets for followup exploration. An occa sional sample is submitted for spectrographic analysis as a check on the possible presence of other elements of economic significance. Field laboratory procedures are also being implemented for determining molybdenum, mercury, and other metals which may be valuable in themselves or useful as pathfinder elements in outlining mineralized areas. A lead-zinc occurrence in Oregon and a copper deposit in Montana were readily detected and outlined by stream sediment and soil sampling and a heavy metal anomaly that lacks obvious interpretation has been found in northwestern Montana. Detailed mapping and additional sampling are followed by other exploration techniques if warranted. Northern Pacific's program of reconnaissance mineral evaluation of company-owned lands and adjoining areas was outlined in a paper presented at the American Mining Congress meeting in Las Vegas four years ago. That report included policies and procedures with respect to mineral development on Railway Co. lands and may be referred to for information on these matters.1 In a sense this paper is a progress report on the use of geochemical prospecting in Northern Pacific's continuing mineral evaluation program. At this time there are positive results but as yet there is no real success story in the form of a minable ore body. GEOCHEMICAL PROSPECTING PROCEDURES The decision to use geochemistry as a reconnaissance exploration tool must be followed by research into sampling and analytical methods and into the interpretation of results. Various analytical methods were tried and evaluated by the Geology Div., including hot and cold acid extraction with and without fusion of the sample, panning and magnetic separation followed by dithizone testing of the magnetite, and cold aqueous extraction of metallic ions followed by indicator tests. Samples were first sent to the laboratory for analysis; later field laboratories were established and now virtually all testing is done at the sample site. It was concluded that, where applicable, the quickest dependable methods for reconnaissance use are the dithizone field tests for readily extractable heavy metals. This involves the simultaneous treatment of a sample, usually of soil or stream sediment, with two immiscible liquids; one a cold aqueous extractant (ammonium citrate) and the other a solution of dithizone in toluene or xylene.2 Dithizone is a colorimetric indicator that reacts quantitatively with copper, lead, zinc, and several other metals to form colored complexes in organic solvents. Results may be expressed in ml of 0.001 pct dithizone that are required to reach the blue end point, or calibration of the test results can be carried out with standard solutions of zinc; conversion factors would then be expressed in ppm, zinc equivalent. Calibration of dithizone solution with zinc standards indicates that 1 ml of 0.001 pct dithizone is equivalent to approximately 0.25 ppm of zinc. An authoritative report on dithizone field tests authored by H. E. Hawkes in the June-July 1963 issue of Economic Geology* states "The appeal of these techniques has been the simplicity and speed of the determinations as compared with more tedious laboratory determinations of trace metals in weathered rocks, soils, or plant materials. This obvious appeal, however, has often been more than matched by misuse of the method in such a manner that the results are

Jan 1, 1964

By J. J. Scott

This investigation utilizes three dimensional photo-elastic techniques to determine the stress distributions in the pillars and the roof of a room and pillar mine model. Castolite plastic was used for the construction of the model in which a stress pattern was developed by the stress freezing process. Analysis of the stress pattern was accomplished by observation of points in slices from the model with a polariscope and solving the data thus obtained by the shear-difference method. Slices through the centerline, edge of pillar and centerline of span were investigated. The results of this work provide information on the overall stress distribution in points of stress concentration in compression, shear and tension, show relative magnitude of stress throughout the model and indicate directions of the most important stress values. A generalized roof bolt pattern is developed for room and pillar mines based on the stress distribution. A digital computer was used in the reduction of data and proved to be extremely useful for investigation of this type. Underground excavations disturb the equilibrium of the earth's crust and a core of fracture, or altered stress distributions exists around the openings. This fact is well known by mining operators and investigators in the rock mechanics field. Analysis of the stress distribution in the areas around mine workings is a most difficult problem and one which has no simple and direct solution. Some of the approaches used by investigators in attempts to study stress distribution around mine openings involve mathematical analysis, photoelastic techniques, statistical analysis, model studies on brittle materials and observation of fracture patterns. Models involving imbedded strain gauges, gelatin models using imbedded strings to show internal movement, and many other unique laboratory techniques are employed. Work is also being done in mining operations where load cells, strain gauges, photostress material, convergence plugs, dynamic plugs, etc., are used to measure strain which can in turn be used to obtain stress. Some of these devices measure strain from which stress may be derived. All approaches to the solution of stress distribution are hampered by the fact that the earth is not a homogeneous, isotropic and elastic media. Geologic faults, fractures, bedding planes, vugs, variations in material composition, variations in grain size and structure, etc., make it extremely difficult to obtain results which can be universally applied to mining operations. The purpose of this investigation will be to demonstrate the use of three-dimensional photoelastic techniques to obtain the stress distribution in the pillars and roof of a room and pillar mining operation. This method utilizes full analysis of interior points, and thus it may be that small tensile or shear stresses found in the investigation will prove to be of greater significance than the more obvious points of stress concentration found by two-dimensional techniques. A digital computer was employed to simplify and to shorten the time necessary to obtain final results. Application of the computer to problems of this type may enable future investigators to attempt more elaborate analyses than have been previously considered feasible. THEORY Three Dimensional Stress Analysis-Shear Difference Solution:' Photoelastic studies are based on the fact that an optically isotropic transparent solid becomes optically anisotropic when subjected to forced deformation; the degree of optical anisotropy being proportional to the deformation of the material. There are two fundamental laws which govern photoelasticity: 1) Light is polarized in the directions of the principal stress axes, and is transmitted only on planes of principal stress. 2) The difference in principal stresses is proportional to the difference in the indices of refraction along the planes of principal stress. One method used in three-dimensional photoelastic work is to examine a slice of the object by normal incidence and oblique incidence. In normal incidence,

Jan 1, 1964