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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 John E. Caffrey

The Federal Coal Mine Health and Safety Act of 1969, Title III, Interim Mandatory Safety Standards for Underground Coal Mines, is devoted to protection of workmen from hazards of electricity, roof, ribs, fire, and explosions. The Rules and Regulations, promulgated through the Federal Register, provide the criteria by which the law would be administered. Certain aspects of the law involve features that could be summarized under entrapment. These are sections 303 (y)(1), (y)(2) and 317 (f) (4). This paper is intended through the use of the figures to describe how these features of the law affect mine ventilation design, what are the problems, and possible solutions to them.

Jan 1, 1974

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

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 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

By P. M. Blair, D. W. Peaceman

The shape and position of the gas-oil transition zone during downdip displacement of oil by gas has been calculated using flow equations which include the effects of gravity, relative permeability, capillary pressure and compressibility of the fluids. The calculations treat the problem in two space dimensions, and results are compared with data from a laboratory model tilted at 30° and 60° from the horizontal on displacements near and above the maximum rate at which gravity segregation prevents channeling of the gas along the top of the stratum. The good agreement between calculated and experimental results demonstrates the validity of the tecbnique as well as that of the flow equations. INTRODUCTION Knowledge of the fluid distribution and movement in an oil reservoir is important in producing operations and estimation of reserves. The history of the oil industry has included steady progress in improving the accuracy of calculations which provide the required knowledge. The earliest method of calculating reservoir performance consisted of material-balance equations based on the assumption that all properties were uniform throughout a reservoir.l For many reservoirs such a simple formulation is still the most useful. However, when large pressure and saturation gradients exist in a reservoir, the assumption of uniform values throughout may lead to significant error. To reduce these errors, Buckley and Leverett2 introduced a displacement eqation which considers pressure and saturation gradients. Methods available at that time permitted solutions to the Buckley-Leverett equation in one space dimension; these solutions have been very useful in solving many problems related to the production of oil. However, the one-dimensional methods are not adequate for systems in which saturations vary in directions other than the direction of flow. An example of such a system is the case of gas displacing oil down a dipping stratum in which the gas-oil contact becomes significantly tilted. Of course, the Buckley-Leverett displacement method cannot predict the tilt of the gas-oil contact. Recent improvements3,4 of the one-dimensional Buckley-Leverett method achieve some success in predicting the tilt of the gas-oil contact at sufficiently low flow rates. However, at rates high enough that the viscous pressye gradient nearly equals or exceeds the gravity gradient, even these improved one-dimen,sional methods incorrectly predict the shape and velocity of the contact. Further progress in estimating such fluid movements in a reservoir appears to require consideration of the problem in more than one space dimension. The recent two-dimensional method of Douglas, Peaceman and Rachford5 appears adaptable to calculate changes with time of the saturation distribution in a vertical cross-section of a reservoir. The movement of saturation contours should represent the moving fluid contacts and include the effects of crossflow due to gravity, as well as variations in the rock and fluid properties. The nonlinear nature of the equations used in the method has prevented proof of the validity of the solutions. Douglas, Peaceman and Rachford made some comparisons with experiment but did not include cases in which gravity was important nor cases involving displacement by the nonwetting phase.For these reasons, a test of the two-dimensional method for a case in which these factors are included would be very desirable. The test selected was a comparison of calculated results with those from a carefully controlled laboratory experiment on a model with measured physical properties. The model selected was one in which gas displaced oil down a tilted, rectangular sand pack. The model can be thought of as representing a vertical cross-section taken parallel to the dip of a reservoir. The displacement thus simulates gas displacing oil downdip that might result from gas-cap expansion or gas injection. This report outlines the calculation method used

By Nicholas J. Grant, Rolf Nordheim, Thomas B. King

Constant-load creep-rupture tests were conducted in an argon atmosphere at temperatures of 1600 to 2200°F on two heats of iron containing about 0.06 and 0.09 pct P in solid solution. The tests were conducted in the as-cast condition. Stresses were selected to give strain rates approaching those encountered in the hot working of steel, and within the limits of the creep-rupture test apparatus, namely. from about 0.001 to 50 pct per sec. FOR generations, rolling and forging practices have been developed largely by empirical methods, based on prior experience. While largely successful, difficulties are frequently encountered when new or different alloy compositions are tried for the first time. There is need to know the relationships which exist among temperature, strain rate, composition, and other variables on the deformation and fracture characteristics of steels. It has been shown for aluminum and several high-temperature alloys that the deformation and fracture characteristics follow rather well-defined laws and patterns which are closely related to the effects of strain rate, temperature, and composition.1"3 As the melting temperature of aluminum or its alloys was approached, it was possible to study the interplay of work-hardening factors and recovery or recrystal-lization, the latter resulting in improved ductility and increased resistance to intercrystalline fracture. In particular, the effects of composition are very poorly known. Within the meaning of "composition" should be included impurity elements, such as sulfur, phosphorous, lead, copper, and many others, as well as those elements which are added for alloying purposes in iron. The role of multiphase structures, in contrast to solid solutions, should also be studied in much greater detail. high strain rate creep-rupture tests would provide information regarding the deformation and fracture characteristics of metals at hot-working temperatures. It was also desired to establish the stresses which are necessary to accomplish the desired deformation, and to relate these to the strain rate and temperature. Secondly, it was the purpose of this particular study to determine the effects of phosphorus, within solid solution limits, on the deformation and fracture characteristics of iron at hot-working temperatures. EXPERIMENTAL PROCEDURE Two phosphorus levels were selected, one corresponding to the upper limit normally found for commercial steels, and one substantially higher than this, but within the region of solid solubility at the test temperatures chosen for this investigation. Twenty-pound heats were prepared by induction melting electrolytic iron in air in a magnesia lined furnace. After deoxidation with about 0.2 pct Al, ferro-phosphorus was added, and the heats were then poured into prefired silica molds. The purpose of using silica molds was to obtain a slow cooling rate during solidification to produce a relatively coarse grain size, producing a structure subject to some segregation and therefore more nearly characteristic of ingot structures. The major part of the casting assembly provided a large shrinkage head in order to produce sound castings and to promote slow cooling of the specimens. The primary austenitic grain size varied from ASTM No. 2 to No. 00. The composition of the heats, including a low phorphorus melt, used for comparison purposes, is shown in Table I. It will be noted that the oxygen content of the phosphorus containing heats is relatively high, in spite of the deoxidation practice, a condition which is difficult to control in small melts. Creep-rupture tests were nevertheless undertaken when it was noted that this quantity of oxygen did not appear to give results any different from those from a heat containing 0.01 pct 0, low phosphorus and comparable carbon Content;4 see Table 11.

Jan 1, 1961

By I. R. Kramer

In his technical note entitled "Specimen Temperature During Electropolishing of Aluminum Crystals" Dr. Nakada 1 reported that the temperature of his aluminum specimen increased 65°C when it was polished electrolytically; he therefore concluded that the temperature of the specimens used in our work (Nakada's Refs. 4 and 5) similarly increased by this amount. From this he further concluded that the change in plastic-flow characteristics associated with the removal of the surface by electropolishing during deformation were due solely to a temperature effect. We believe that these conclusions are not justified. It is, of course, realized that the amount of the temperature increase is associated with the total heat transfer of the entire system, including the efficiency of the stirring action, heat flow through the grip on the specimen, and so forth. Of great importance is the type of electrolyte used for polishing. For example, in Dr. Nakada's experiment a methanol-perchloric acid solution was used. This solution has a relatively low conductivity and for the current densities of 0.3 amp per sq cm the electrical input appears to be 30 to 40 w. In our research a methanol-nitric acid solution was employed and for the size of specimen employed by Dr. Nakada the power never exceeded 7 w. There are major differences in his test apparatus which also appear to affect the temperature rise. In our case a steel specimen holder was used in order to provide a good heat sink and conduction path. The cathode was a coiled aluminum tube through which a coolant was passed to provide additional cooling capacity near the specimen. The stirrer was placed in a position to obtain maximum cooling efficiency. On the other hand Dr. Nakada used a teflon grip to support the specimen at one end only and a flat copper cathode, thus providing a much less efficient heat sink as compared with the metal grips used in our studies. The relationship between current density and the temperature increase for two sizes of aluminum crystals tested in our tensile apparatus is shown in Fig. 1. The temperature measurements were determined from a thermocouple spot-welded to the surface of the specimen. The thermocouple was protected from the acid by means of a thin film of stop-off lacquer which covered just the outer surface of the thermocouple junction. Whereas Dr. Nakada reported a time delay of 8 min to obtain thermal equilibrium, our temperature change occurred in less than 15 sec. This emphasizes the importance of the heat transfer in the entire system. However, readings were taken over a period in excess of 5 min to assure thermal equilibrium. The data given in Fig. 1 were also confirmed by determining the thermal expansion of the specimen in a sensitive creep apparatus. As may be seen, for the smaller specimen the increase in temperature is 8°C for a current density of 1.5 amp per sq in. The majority of our data on the effects of surface removal on the plastic behavior of aluminum were obtained at current-density values at or below this value. Above 1.5 amp per sq in. the temperature rise is uncertain; for under certain conditions, especially in the vicinity of 2 amp per sq in., the anode can become polarized and the current flow is erratic. This condition is easily recognized because wide fluctuations in the creep and stress-strain data make it virtually impossible to obtain reliable results, a condition which was always avoided in our work. The temperature increase for the larger specimen is less than that of the smaller specimens below a current density of 1.5 amp per sq in. At a current density of 2 amp per sq in. the temperature increased 13°C. The above temperature data are in accord with observations made during creep experiments. Using a transducer capable of detecting strain in the order of 10 -6, temperature changes in excess of 8°C were not detected when the current density was increased to as high a value as 1.5 amp per sq in. Finally we wish to point out that our experimental data cannot be explained solely in terms of a heat effect. For example in Fig. 1 of Ref. 2, the change in slope of Stage II as a function of the rate of re-

Jan 1, 1965

By Irwin Politziner F. M. Townsend, L. S. Reid

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By L. S. Reid, Irwin Politziner F. M. Townsend

Recently published data indicate that the water vapor content of a gas, as determined by dew point measurement, is inaccurate when the gas has been dehydrated with diethylene glycol. Water vapor contents and dew point measurements of gases dehydrated with triethylene glycol have been obtained in this investigation in order to determine the magnitude of a similar error, if one exists. Experimental data show a very low concentration of triethylene glycol vapor in gases dehydrated at atmospheric ternperatures and pressures ranging from 500 to 2,500 psia and that the accuracy of dew point measurements is not impaired by the presence of triethylene glycol vapor. INTRODUCTION Nearly all natural gas transported by pipe line to northern and eastern markets must be dehydrated to a low residual moisture content in order to assure maximum transmission efficiency and continuous delivery under peak load conditions. Without dehydration, water vapor often condenses in pipe lines in quantities sufficient to restrict the flow3 and. under low atmospheric temperature conditions, gas hydrates may form and plug gathering. transmission and distribution facilities. Gas may be dehydrated to pipe line specifications by a number of methods. The most widely used methods are (1) adsorption of water vapor on a solid dessicant such as activated bauxite, alumina or silica gel,' (2) by absorption of water vapor by either diethylene or triethylene glycol-water solutions of high glycol concentration,11,13 and (3) by simultaneous expansion-refrigeration of very high pressure gas in which gas hydrates are purposely formed and then quickly decomposed.'"" Of these three fundamental methods, the adsorption and absorption processes provide the bulk of the dehydrated gas moving to market at the present time. The expansion-refrigeration process. a relatively new development, is gaining in favor because of its simplicity but is sharply limited in its application by available differentials between source and gathering system pressures. Where gas sale or purchase contracts contain a maximum water vapor content specification, the water vapor content is usually determined by measuring the dew point of the gas at system pressure. Knowing he dew point temperature and the system pressure, the water vapor content of the gas is determined from a graphical correlation of saturation, or dew point, temperature us the water vapor content of the gas which is customarily expressed as pounds of water vapor per million cubic feet of gas measured at 14.7 psia and 60°F. Dew points are usually measured with the U. S. Bureau of Mines Dew Point Tester. shown in Fig. 1, which is well suited for use at temperatures lower than 120°F and at pressurei; ranging from atmospheric to 3,000 psi. A number of correlations of dew point temperatures vs water vapor content are available,3,5,15 the most recent of which is that by McCarthy et al.4 Where natural gas is dehydrated by absorhing contact with concentrated diethylene glycol-water solutions. considerable difficulty is experienced in observing water dew points due to condensation of liquid hydrocarbon and glycol films on the mirrored surface of the dew point tester. Riesenfeld and Frazierl2 report that the dew point method for determining the water vapor content of a dietllylene glycol-treated natural gas is in error due to the glycol content of the condensate formed on the tester mirror, and that the water vapor content of the gas tested is actually lower than that indicated by the standard' dew point-water vapor content correlation. Extensive experience in testing gases dehydrated by concentrated triethylene glycol-water solutions lias not revesled difficulties of the nature cited above for diethylene glycol. Water dew points are clear and sharp and condensation of

Jan 1, 1951

By P. T. Carter, A. B. Murad, H. B. Bell

The distribution of manganese and oxygen between molten iron and FeO-MnO-SiO2 slags not saturated with SiO2 has been determined and used to calculate activities of MnO and SiO2 in MnO-SiO2 slags. These were found to be intermediate between the corresponding activities in FeO-SiO2 and CaO-SiO2 slags. THE equilibrium constant for the reaction between molten iron containing manganese and slags containing FeO and MnO, namely: FeO(slag) + Mn = MnO (slag) + Fe(1iquid) is most conveniently represented by: (MnO) Kmn== (FeOHMn] [Fe] is omitted, since for dilute solutions of manganese in iron, afe is approximately constant. When activities are used for (MnO), (FeO) and [Mn], Kmn is a true equilibrium constant and will apply to all types of slags, but when weight percentages are used, the values obtained for Kmn for different slags vary considerably. The equilibrium between iron containing manganese and relatively pure FeO-MnO slags has been investigated by several workers;1-4 the most recent investigation reported is that of Chipman, Gero, and Winkler.4 Their results, corresponding to slags containing up to 4 pct SiO2, were represented by the equation: 6440 log KMn = +2.95 In this case both slag and metal may be assumed to be ideal solutions, therefore the values of Kmn so derived represent the true constant for the manganese reaction. As the molecular weights of MnO and FeO are almost equal, weight concentration of these oxides may also be used in the above expression. Acidic oxides such as SiO2 and P2O5 affect the activities of FeO and MnO differently, so that when total concentrations by weight of FeO and MnO are used in the above expression for Kmn the values obtained are no longer constant. These will be denoted by K'mn. Körber and Oelsen5 investigated the manganese reaction using silica-saturated iron-manganese-silicate slags and found: 7940 logK'mn =3.172 This corresponds to Kmn values much higher than those obtained for pure oxide slags. The results of Körber and Oelsen, and Chipman, Gero, and Winkler are summarized in Table I. In the present investigation it was decided to study the manganese reaction using iron-manganese-silicate slags not saturated with silica, and which fell mainly between the orthosilicate join 2FeO . SiO2 - 2MnO.SiO2 and the FeO-MnO side of the ternary system FeO-MnO-SiO2. It has been shown" that the phases present in solidified slags of this part of the diagram are (FeO, MnO) and (2Fe0.Si02, 2Mn0-SiO,) solid solutions. Such an investigation would be of interest in deoxidation and also gives information on activities in liquid slags. This equilibrium has not as yet been investigated successfully. Hilty and Crafts7 attempted to examine this reaction in a rotating crucible furnace, but were unable to obtain suitable slag samples. In the present investigation one series of experiments was carried out in a rotating crucible furnace, because the success of Taylor and Chipman8 with such a furnace in their study of oxygen distribution between molten iron and (CaO, MgO) — FeO-Si0, slags suggested that it would minimize contamination of the slag by the crucible material. A second series was carried out using a wire-wound resistance furnace. Rotating Crucible Furnace Experiments In all cases the metallic charge consisted of 800 to 1000 g Armco iron containing 0.02 pct C, 0.03 pct Mn, and traces of Si. Manganese and silicon additions consisted of electrolytic manganese (99.9 pct)

Jan 1, 1953

By D. I. Bardos, A. M. Bardos, Paul A. Beck

The approximate effective silicon radii in ternary Laves phase alloys with transition elements and silicon were found to range between 1.16 and 1.21A, i.e., considerably smaller than the atomic radius calculated for elemental silicon. The atomic radii were found to increase with the size of the transition element atoms in the structure. It has been noted by Aronsson1 that silicon in solid solution in iron, cobalt, and nickel has an effective CN 12 atomic radius of approximately 1.20Å, a value very much smaller than the CN 12 radius of 1.34Å derived from the interatomic distances in elemental silicon.7 The unusually short metal-silicon interatomic distances in transition element monosilicides and disilicides have been also pointed out by various investigators.1 A similar tendency was observed by Nevitt in Cr3O type silicides.2 Recent work on Laves phases in ternary systems of silicon with transition elements4"8 suggested that extensive Laves phase fields may occur in such systems.8 It has been pointed out by Laves7 that the MgCu2 and MgZn2 type structures lend themselves particularly well for the determination of the effective radii of the component atoms. In these AB2 phases the B atoms are arranged in close packed straight lines, and their distances are related in a simple manner to the lattice parameters.8 The present work was undertaken in order to find out whether or not the B transition element in such AB2 Laves phases can be replaced to an appreciable extent by silicon. In cases where extensive substitution proves to be possible, the "average atomic radius for the B site" at various silicon contents was to be determined, and the effective atomic radius of silicon calculated by extrapolation to complete replacement of the B component by silicon. The following ternary systems were studied: Ti-Mn-Si, Ti-Fe-Si, V-Co-Si, V-Ni-Si, Nb-Fe-Si, Nb-Co-Si, Ta-Fe-Si, Ta-Co-Si, and Mo-Fe-Si. In all of these alloy systems, the Laves phase solid solutions were found to extend over a considerable range of silicon content. As previously reported,4"8 in the V-Co-Si, V-Ni-Si, and Mo-Fe-Si ternary systems Laves phases do occur, even though there are no corresponding binary Laves phases. In stabilizing the Laves phase, silicon acts as if it were decreasing the effective electron concentration of the alloy.8 A more detailed study of the boundaries of the Laves phases in the V-Co-Si and V-Ni-Si systems has been made and will be published elsewhere. In both cases, the elongated Laves phase fields extend parallel to the B-Si side of the composition triangle, clearly showing that silicon is substituting for cobalt, respectively, nickel over a wide range of compositions. The binary Laves phases NbCo2 and TaCo2 have the cubic MgCu2-type structure. It was found that, in both ternary systems with silicon, again the MgZn2-type hexagonal Laves phase is stabilized and that this phase extends to high-silicon contents. In each ternary system at least three Laves phase alloys of the composition A(B1_xSix)2 were used, x here denoting the fractional substitution of the B-transition element atoms by silicon. The alloys, listed in Table I, were prepared by arc melting in argon. Each specimen was water quenched after a homogenizing anneal of 3 days at 110(FC, except for the Mo-Fe-Si alloys, which were annealed at 1200°C. Metallographic examination showed that most of the homogenized alloys consisted of a single phase, although some had minor amounts of a second phase, as shown in Table I. X-ray diffraction patterns were prepared using an asymmetrical focusing camera of large resolution and Fe Ka radiation. The patterns were indexed, and the lattice parameters of the hexagonal Laves phases were determined from the available diffraction lines of highest indices: (213), (205), and (313). The lat-

Jan 1, 1963