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[Trans. No. Place Date Vol. Page 1, Wilkes-Barre, Pa.* .... May, '71.. 1 3 2. Bethlehem, Pa Aug., '71.. 1 10 3 Troy, N. Y Nov.,'71.. 1 13 4. Philadelphia, Pa Feb., '72.. 1 17 6. New York, N. Y •.... May, '72.. 1 20 6. Pittsburgh, Pa..:.Oct., '72.. 1 25 7. Boston, Mass Feb., '73.. 1 28 8 Philadelphia, Pa.' May, '73.. 2 3 9. Easton, a Oct., '73.. 2 7 10. New York, N. Y Feb., '74.. 2 11 11. St. Louis, Mo.* May, '74.. 3 3 12. Hazleton. Pa Oct.. '74.. 38 13. New Haven, Conn Feb., '75.. 3 15 14. Dover, N. J.' May, '75.. 4 3 16. Cleveland, 0 Oct., '75.. 4 9] [ ]

Jan 1, 1925

By Rztssell H. Bennett

A SURVEY of the Mesabi Range iron-ore industry demonstrates that a satisfactory degree of technical progress has been achieved in the last fifteen years. This advance has not been made over a uniform front, but, by salients and bays, according to the different initial positions, economic and technical, of the component producing companies. The producers endowed with rich ore have in general, because of natural advantages, progressed more slowly than their neighbors with leaner properties. The advance has been made step by step all along the line -blasting, loading, hauling and concentrating-and without the benefit of radical innovation. There have been, for instance, no such parallel discoveries in iron ore as leaching and flotation in copper. The much lower unit price of iron operates, of course, to bar the application of these and other practices developed for the higher-priced metals. There exists, however, a radically new concentration process whose technology is well worked out and which may become economically operative in the not too distant future; this, as so often happens in engineering advance, because of recent developments in an entirely unrelated field. First, however, let me devote a paragraph or two to the more important economies effected in mining.

Jan 1, 1932

By Robert B. Sosman

ONE of the most neglected fields for physicochemical education as well as for research is that of high-temperature phenomena. Few universities or technical schools give instruction in the physical chemistry of substances at high temperatures. On the contrary such instruction is almost entirely confined to the region between the freezing and boiling points of water. This field should be extended to a much wider range of temperatures, both low and high. Such an extension is logical, sound, feasible, and practical.

Jan 1, 1943

By R. J. Evans

The Combined Metals Reduction Co.'s plant is at Bauer, Utah. It was built primarily to treat ore from the Combined Metals mine at Pioche, Nevada. Shortly after its completion, the company acquired the old Honerine mine, and ores from this mine, as well as custom ores from widely scattered districts, are now being treated at the Bauer plant. Pioche Ore The Pioche ore, which comprises about 50 per cent. of the mill feed, occurs as a replacement of an impure thin-bedded limestone. The lime beddings are separated by thin layers of micaceous shale containing appreciable quantities of sericitc and graphite. The ore is an exeeptionally fine-grained, dense mixture of minerals and gangue, assaying approximately 0.03 oz. gold, 7.2 oz. silver, 7 per cent. lead, 15 per cent. zinc, 16 per cent. iron, 29 per cent. insoluble and 1.5 per cent,. lime. Of the total lead 7 per cent. is in the form of sulfate and carbonate. Approximately 10 per cent,. of the ore consists of chert nodules impregnated with barren pyrite; the nodules average 0.8 mm. in size, and ire extrcmely hard, compared with the other constituents of the ore. Microscopic examination of Pioche ore ground to 80 per cent . minus 150 nicsh shows pyrite, sphalerite and galena still attached. Early Attempts at Ore Dressing Metallurgists, both professional and those working for private companies, have been more or less familiar with the Pioche ore sinee. 1913; in fact, a total of 35 commercial and plant laboratories expenmented with the ore between 1913 and 1921. The work during this period was decidedly negative, it being seemingly impossible to effeet a satisfactory separation of the valuable minerals into marketable products. In 1913, it was recognized that fine grinding-—that is, about minus. : 200 mesh—-was required to liberate the minerals from one another, and from the gangue, but such fine grinding was not considertd practicable at this time.

Jan 1, 1928

By V. C. Allison

Large-scale testing of the explosibility of coal dust as conducted by the Bureau of Mines in its Experimental Mine involves a large initial investment, and a high charge for maintenance and conduct of the test; in addition the work is necessarily slow because of the time required for the preparntion of the tests and the cleaning and repairing of the mine after each test. These tests have been made along practical mining lines that admit of a range of mixtures of dust varying from 5 to 10 per cent. and with gas as low as 0.5 per cent. increments. Because of the time and expense involved, efforts have been made to devise a type of gallery for laboratory use in which the results obtained in the Experimental Mine may be correlated as an aid in a study of dusts, the explosibility of which might be approximately determined quickly and at a minimum of expense. The explosibility of coal dust has been studied by a number of European investors, using small laboratory devices; among these may be mentioned the experiments conducted by Galloway, Vital, Hall and Clark, Abel, Mallard and Chatelier, Thorpe, Bedson and Widdas, Engler, Holwartz and Meyer, and Taffanel, results of whose experiments have becn reviewed by the Bureau of Mines.' The Bureau has conducted many tests with the Frazer-Cle1ncnt5 apparattus, which gives the pressures set up when the dust cloud within is ignited with a platinum coil or tube, heated to different temperatures, but for these tests the sample must be especially prepared as to size (200 mesh) and must be dry. Need for a Dust-testing Apparatus An attempt has been made to design an apparatus that may be used for checking and correlating the expcrimental tests. The first design was a wooden gallery, 8 by 10 in., inside cross section, and 12 ft. long, and having a number of strips along each side for creation of turbulence. The wooden gallery did not get beyond its period of calibration; it mas difficult to make the gallery sufficiently tight, for it was necessary that the top be removable in order that the gallery could be cleaned. In the use of the wooden gallery, however, sufficient operating data were obtained to be a guide in the design of a steel gallery having a circular cross-section. One of the features was a flap valve, at the closed end of the gallery, that would open inwardly thus preventing a reduced pressure within, caused by the cooling of the gases of combustion, and the explosions propagated much better than when the valve was not used; another feature was the determining of the best method for getting a cloud of dust simultaneously in all parts of the gallery, which was accomplished by the use of the concussion wave of a small quantity of powder or by the use of compressed air.

Jan 1, 1927

By O. D. Sherby

In 1938, Kanter' revealed that the steady-state creep rate of low-carbon iron alloys could be correlated by an activation energy expression, where the activation energy for creep, Qc, was found equal to about 90.0 kcal per mole for most of the alloys investigated. He suggested that creep at high temperatures might be controlled by some sort of solid self-diffusion process since the value of Qc was about equal to the known value for self-diffusion, Qd. Correlations were not further attempted along these lines until many years later, when new evidence2-8 was presented suggesting that Qc = Qd for many metals. This equality now appears to be established for ten metals (Al, Pb, Ni, Mg, Cd, In, a Fe, y Fe, Cu, and Au). This experimental fact prompted several investigators to postulate various mechanisms of dislocation motion which would yield an activation energy for creep equal to that for self-diffusion.7-9 Possibly the most accepted theory is that based on dislocation climb7 where a dislocation is envisioned to surmount a barrier by an atom-vacancy exchange process, thereby "climbing" from one slip plane to another. Such a model would suggest that the steady-state creep rate, i, should be directly proportional to the rate of self-diffusion, D, for a given creep stress. In order to more clearly reveal the relationship between creep and diffusion, and to eventually determine the correct model, it would be desirable to obtain data showing correlations between i and D, rather than with a comparison of the temperature coefficients, Q. It has been known for some time that the self-diffusivity of iron atoms is greatly decreased when body-centered-cubic (a) iron transforms to face-centered-cubic (y) iron. This has been ascribed to the more close-packed structure of y iron. The diffusivity ratio at the transition temperature is Da/Dy =350. Correlations of creep data for a and y iron5 reveal that the creep rates under a given stress at the transition temperature differ by about the same ratio (ea/ey 2 200). It would be difficult to reconcile these results on any other basis than that the diffusivity of atoms probably controls creep of iron in some very direct way. No other published data on other allotropic metals appear currently available for further checking such a possible correlation between i and D. Thallium transforms from a hexagonal close-packed (a) structure to a body-centered-cubic (ß) structure at 230°C (503°K) and the self-diffusivities of the two structures have been determined by shirn.10 His results are plotted in Fig. 1 where it will be noted that Dß/Da = 25 at the transition temperature. It would appear desirable, therefore, to determine the creep rates of polycrystalline a and ß thallium at the transition temperature, as well as determine

Jan 1, 1959

By C. W. Volek, G. Mandl

Steam-injection tests in the field have shoum that heat transport into the oil/water region, ahead of the steam zone, may have a significant effect on the production process. Earlier theoretical work on reservoir heating by hot-fluid injection can be used to describe the growth of the steam zone, but only if heat transport from steam zone into oil/water region is neglected. It therefore became necessary to re-examine and extend the earlier theory. It was found that this theory ceases to be consistent with the physical model of the process at a certain critical time, tc, which depends on reservoir thickness, temperature, and quality of the steam. The critical time marks an important change in the heat flow across the condensation frovt: the heat flow, which is purely conductive during 0 < t < tc&apos; becomes predominantly convective at t = tc. Accordingly, at t = tc, the equation which governs expansion of the steam zone changes. On the basis of the new equation, an approximate description for the steam-zone growth during t > tc is developed by making use of upper and lower bounds for the exact solution of the problem. The boundary conditions for heat and mass flow inside the oil/water region are established, and a simple method of detennining the saturation at the downstream side of the condensation front is presented. Experimental results show that the theory gives an accurate description of steam-zone expansion before the critical time. At times near critical time, and also after critical time, experimental data show theoretical steam-zone volumes to be high. Even so, the accuracy of the calculated steam-zone volumes is sufficient for practical purposes. THEORY OF STEAM-ZONE GROWTH INTRODUCTION The engineering evaluation of steam-drive processes is based mainly on a mathematical description of reservoir heating by hot fluid injection presented several years ago by Marx and Langenheim.l This theory can be used to determine the growth of the steam zone,2 provided the flow of heat from the steam zone into the liquid zone ahead of the condensation front (Fig. 1) is neglected. Since we must expect, however, that heat transport into and inside the liquid region (the region between condensation front and production wells) will affect both the water/oil flow and the growth of the steam zone, it is necessary to re-examine and to generalize the Marx and Langenheim theory as applied to steam drive, which will hereafter be termed the "old" theory. Observations made in several field tests emphasize the need to study the heat flow across the condensation front (CF). On several occasions it was discovered that heat was transported in the liquid zone far ahead of the advancing CF, resulting in an early breakthrough of warm water. This seems to occur most often when high injection pressures are applied, when "wet" kONINKLIJKE/SHELL EXPLORATIE EN PRODUKTIE LABORATORIUM RIJSWIJK, THE NETHERLANDS SHELL DEVELOPMENT CO. HOUSTON, TEX.

Jan 1, 1970

By T. J. Fabiniak, R. A. Dodd, R. Balow

ALTHOUGH the (111) slip direction in pure bcc metals is well established, the information on operative slip planes is less unambiguously interpreted. So far, (110) {112), and (123) slip planes have been identified, but it is not certain whether glide on (112) and (123) really occurs or if it is composite slip on non-parallel (110) planes. The second of these possibilities is supported by the work of Chen and Maddin on niobium and molybdenum, and a subsequent analysis by these same workers of slip in bcc metals generally.3 The alternative possibility is exemplified by the work of Opinsky and smoluchowsky4 who concluded that slip in Fe-Si crystals can occur on any one of the systems {110}(111), {112}(111), and {123)(111), depending on which system the resolved shear stress is highest. Allen et alS5 also found that glide in ar iron could occur on any of these three systems, the operative system being determined principally by orientation. By an analysis of crystal rotation, slip lines, and X-ray asterism Harris6 concluded that niobium also deforms on these same systems, but if one of these glide planes does not coincide with the plane of maximum resolved shear stress, composite slip on nonparallel (110) planes may occur giving a macroscopic high indices slip plane. Earlier work on iron by Vogel and Brick reached the same conclusion.7 The analysis of slip in bcc metals is made more difficult by the fact that the slip lines may be quite wavy. In fact, the generality of wavy slip lines suggests that screw dislocations slip readily from one plane to another in the (111) zone ("pencil glide") although, as noted, it is not certain whether planes other than (110) really contribute to the slip. If planes of higher indices than {110} do operate, there is a possibility they may do so more readily at higher temperature Argon and Maloof9 observed {100}{211}(111) slip in tungsten single crystals plastically strained at low temperatures, but the results were interpreted in terms of an orientation-dependence rather than temperature-dependence. Therefore, at the present time corroborative evidence for the operation of higher indices slip planes at higher temperatures is lacking. The present results were obtained during the course of an investigation into the effect of cathode and anode surface crystallography on the prebreakdown currents of vacuum insulated devices. In the experiment of particular interest, the 1/8-in.-diam anode and the in.-diam cathode were tungsten crystals (total impurities -230 ppm) with (110) and (100) faces respectively. The faces were electrolytically planed and examined for initial perfection by plastic/carbon replicas and a study of Kikuchi lines in reflection electron diffraction patterns. They were aligned precisely parallel in an insulating holder incorporated into the electron microscope, the measured microscope vacuum being 2 x 10-5 torr, and the electrode spacing 0.01524 cm. The anode structure shown in Fig. 1 was obtained

Jan 1, 1970

By H. S. Cannon, F. N. Rhines

The application of a static load to a copper powder compact during sintering at an elevated temperature accelerates the rate of sintering in such a way that a given load induces the same proportional increase in rate for all times of sintering. It is shown that sintering under a load is like creep under a fixed load in that the stress required to accomplish a given degree of densification is proportional to the logarithm of the sintering time. VIRTUALLY all of the theories of sintering that have been put forward within recent years have contained the assumption that the chief driving force of the process is the surface tension resident in the exposed surfaces and internal pores of the compact, or powder mass. An externally applied load might be expected to provide a somewhat equivalent driving force for sintering. It is known that the application of a compressive load, during sintering, hastens densification, but it is by no means clear whether sintering under the influence of surface tension alone and sintering under an applied load are fundamentally similar processes. The present study was undertaken in an effort to obtain an answer to this question and with the hope that the answer may contribute to an understanding of the mechanism of sintering. It has been found that there is a close relationship between sintering and creep processes. Copper powder compacts were sintered in hydrogen at 1000 °C under dead loads of 0 to 165 psi and the progress of sintering was observed by means of density measurements. Using a commercial reduced oxide copper powder, see Table I, cylindrical compacts Yz in. x x in. high were made at a pressure of 12,500 psi. For sintering, these were placed in a cylindrical graphite container into which they fitted snugly. A compressive axial load was applied to the compact through a graphite rod of similar diameter, which rested upon the upper end face of the compact; iron weights, in suitable amount, were placed upon the graphite rod to provide the load. This assembly was encased in a vertical silica tube within a resistance-type furnace capable of maintaining a substantially constant temperature within the working zone. After various predetermined times at temperature, the samples were removed from the furnace and their density was measured by conventional means. The heating-up and cooling-down times have been included in the computed sintering time, using the assumption that the sintering rate doubles for each increase of 10 °C in temperature. The experimental results are presented in Table 11. Upon metallographic examination of the specimens, it was found that there was no apparent change in the shape of the pores as a result of loading, i.e, no flattening, Fig. 1. Substantial contraction away from the container walls was observed in all samples sintered with loads of 10.5 psi and less.

Jan 1, 1952

By J. W. Marx

A method is given for predicting the complete gravity drainage characteristics of arbitrarily long columns from centrifuge drainage measurements on reconstituted core samples. Oil residuals corresponding to hundreds of years of normal gravity depletion can be obtained in a few hours on the centrifuge. The gravity flow rate at any stage of the depletion process may be determined from the time correlation derived, and experimentally checked, in this study. INTRODUCTION Apart from the original observations of Muskat et al1, research publications2,3,4 on the subject of gravity drainage have been largely concerned with establishing in detail the saturation, S as a function of the height, z, in a draining column at any given time, t. Some form of numerical integration must be employed to obtain production rates and cumulative production even when S(z, t) is known. Furthermore, the relevant experimental work has been concentrated on drainage of a single wetting liquid from unconsolidated media. Since oil production usually concerns the drainage of a partially wetting liquid from consolidated media, in the presence of connate water, and since it is unlikely that sufficient information exists to establish S(z, t) in detail for any natural reservoir, the published research work appears to be, at best, only qualitatively applicable to production problems. With this in mind, the present study was undertaken by the writer. Experiments were planned whose results would have two advantages over existing measurements: 1. Observations were to be made on specific reservoir rock, reconstituted with formation water and formation oil. This would reduce their generality, from the research viewpoint, but increase their utility for production purposes. 2. The measurements were to be self-integrating, i.e., the phenomena were to be described and interpreted in terms of cumulative results. THEORETICAL DEVELOPMENT It was commonly known that centrifuging a liquid bearing porous medium increases the drainage rates and minimizes capillary end effects. The specific problem lay in selecting an acceleration, a, such that the mean residual saturation of a model cylinder was equal to the residual saturation of an arbitrarily long prototype column when the latter was drained by earth gravity alone. The physical conditions required to permit a valid scaling of model drainage time, tm with prototype drainage time, t, may be stated as follows: (a) At t = tm = O, So = Smo; (b) At t = tm? 8 Sr. = Smr.; (c) For all intermediate values of t and dS/dt=dsm/dtm whenever S = Sm; (d) S(z) = Sm(z) = a constant when t = tm = 0. 1 Here S = T I S(z)dz, where h is the length of the « Jo cylindrical column being drained and the subscripts S,Sm, and refer to model, initial, and residual systems, respectively. The first three conditions mean, simply, that an 3 vs t plot will be numerically identical with an S, vs t, plot,

Jan 1, 1957

By W. C. Ellis, E. S. Greiner

WHEN metallic materials are deformed plastically, the process may be considered as one in which hardening and recovery occur simultaneously. The net hardening is that produced by deformation in the absence of recovery lessened by recovery during and immediately following deformation. Strain hardening takes place through movements of large groups of atoms acting to a degree as an entity. A complex microstress system is developed. Recovery is a diffusive-type process involving single atoms or, at most, only a few atoms in concerted action. This is accompanied by elastic strain relaxation. Recovery is strongly temperature-dependent. The driving energy for the process resides in thermal fluctuations of the atoms augmented by the energy of the stress field producing the deformation, and by that produced by the deformation. At very low temperatures recovery is essentially absent, or very small. At high temperatures in the hot working range, recovery is so rapid that deformation results in no appreciable net hardening. The interplay of strain-hardening and recovery results in differing end structures depending on the temperature and the strain rate of the process. For example, there is a prominent difference in the spacing of the slip markings and in the detail of X-ray diffraction patterns. High temperatures and slow strain rates favor a wide spacing of slip markings and sharp reflections.&apos;,&apos; This suggests that change in rate of the recovery concurrent with deformation modifies to a degree the manner of the deformation. Different slip systems may operate. For very slow rates, the mechanism may, as has been suggested, differ from that of "classical slip." In the experimental work that follows the findings will be interpreted from the point of view developed in this section. Recovery and Electrical Conductivity Electrical conductivity is a sensitive indicator of the state of strain in a material3&apos; * and was used in this investigation. The materials studied in wire form were: OFHC copper, a high purity (99.99 pct) and 2s grade aluminum, and grade A nickel. Wire annealed and initially 0.050 in. in diam was drawn through diamond dies in a simple holder maintained at 25", —75°, or — 195°C. Precautions were taken that for each material all conditions of drawing were the same except the temperature. Electrical resistivity was measured for each condition at 20°C. This was done as soon as practical after drawing to minimize possible room temperature recovery. The data for the four materials are plotted in Fig. 1 in terms of the change in resistivity for drawing at the several temperatures. The effect of temperature of drawing on the increase in resistivity is most pronounced for copper. Drawing at 25°C to 80 pct reduction in area increases the resistivity approximately 2 pct; drawing at —195°C to the same reduction increases the resistivity about 6 pct. The increase in resistivity" & in this metal is due to extra scattering of conduction electrons originating in the lack of orderly arrangement of the atoms induced by the deformation process. It has been suggested

Jan 1, 1953

By Strathmore R. B. Cooke, Emert W. Lindroos, Norman F. Schulz

DURING the course of an investigation of the effects of various starch products on hematite and quartz in regard to their separation by&apos; flotation, it was found that whereas most starches flocculated suspensions of hematite in water, they did not flocculate similar suspensions of quartz. However, a derivative of whole corn starch containing approximately one tenth aminoethyl group (--CH2CH2NH2) per glucose unit proved to be an exception. This aminoethyl starch was a very good flocculant for both hematite and quartz, and also possessed the property of depressing both minerals in cationic flotation tests. In view of the widespread use of starch as a flocculating agent of solids in tailing water, pulps, and for coal slimes, ore and various other purposes in sulphide and nonsulphide flotation, attention is called to the effective surface activity of aminoethyl starch in flocculating suspensions of the two minerals investigated. Test Materials The starch products employed included Globe Pearl starch No. 144 and fresh aminoethyl starch, both supplied by the Corn Products Refining Co. Dr. A. L. Elder[4] has kindly furnished a description The minerals used in the various tests are listed in Table I. Their specific surfaces were determined by the air permeability method, which gave results reproducible to within plus or minus 3 pct. Surface areas obtained by krypton adsorption were greater than the air permeability values by a factor of 2.0 for quartz and 62.4 for hematite. Starch Adsorption on Mineral Surfaces Starch adsorption data were obtained by agitating for 1 hr measured volumes of neutral starch solutions of known concentrations with weighed quantities of finely divided mineral of measured specific surface. The mineral then was separated from the pulp liquor by centrifugation and the residual starch content determined by chemical analysis. The analytical procedure consisted of oxidizing the starch with an excess of dichromate in acid medium at elevated temperature and titrating the excess dichromate by the ferrous ammonium sulphate-potassium permanganate method. Analytical results were reproducible to within less than 1 pct. Adsorption data obtained in unbuffered solutions near the neutral point are plotted in Fig. 1. The adsorption on either mineral was far greater for the aminoethyl starch than for the Pearl starch. Flocculation The degree of flocculation was determined for a given pulp by measuring the time required for the supernatant liquid to reach a certain degree of clarity. This was accomplished by passing a standard light beam through the pulp, contained in a glass settling tube, and measuring the time required after agitation ceased for the intensity of the transmitted beam to reach a predetermined value. Starch reagent was added to each pulp in small uniform increments, and the settling time was determined after each such addition. Increase in pulp liquor volume due to the added starch reagent was ignored in these tests. Pulps were maintained at or near neutrality.

Jan 1, 1952

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

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

Jan 1, 1967

By Rex B. McLellan, M. L. Rudee, T. Ishibachi

A modelfor dilute quasi-regular interstitial solid solutions is proposed in which the solute atoms can occupy both the octahedral and tetrahedral interstices in the bee solvent lattice. The distribution function, according to which the solute atoms are apportioned between the two kinds of sites, is calculated. The partial thermodynamic functions of the solution are calculated from the distribution function. It is shown that such a solution model can explain the deviation from linearity of the Arrhenius plot of the temperature variation of the diffusivity of carbon through a iron. The published difiusivity data is analyzed to obtain numerical values for the distribution function. Finally it is shown from the numerical values of the distribution function that the possibility of dual-site occupancy will have a negligible effect on the solution thermodynamics for this system. DeSPITE the large amount of experimental data available on the thermodynamics and diffusion kinetics of dilute solid solutions of carbon in a iron, many of the elementary properties of these solutions are not understood due to real or apparent discrepancies in the experimental data. Basically there is a lack of agreement between the solubility and diffusion data obtained by anelastic damping techniques and by bulk chemical thermodynamic methods. SPecifically the heat of solution of cementite in ferrite estimated from thermodynamic measurement1, 2 is about twice as high as that determined from anelastic damping measurements.3 Furthermore the diffusion coefficient D of carbon in a iron in the range -40" to about 150°C (covering about ten orders of magnitude) determined from anelastic damping techniques is such that an Arrhenius plot of In D vs 1/T is linear. However in the range of about 300o to 850°C where mass flow measurements of D have been made (covering about four orders of magnitude), although the data merges with the low-temperature data, the Arrhenius plot departs from linearity. The object of this paper is to present a more refined model of dilute ferrite solutions in which the solute atoms can occupy two kinds of interstitial sites. The experimental data is analyzed in the light of this model and it is believed that thereby some of the anomalies can be resolved. snoek4 explained the room-temperature internal-friction peak (usually referred to as the Snoek peak) in iron as the stress-induced ordering of interstitial carbon and nitrogen atoms occupying the octahedral (0, 0, 1/2) interstices in the bee lattice. From the consideration of a hard-sphere lattice model the (0, 1/4, 1/4) tetrahedral interstices are larger than the octahedrons but their symmetry would not produce the strain dipole necessary to give rise to the Snoek peak. Thus the presence of the Snoek peak is direct evidence that the octahedrons are occupied. Since the publication of Snoek&apos;s explanation, most workers have assumed that all of the carbon and nitrogen in the a solid solution was located in the octahedral sites. This assumption of universal octahedral occupancy has been implicit in the theory of wert5 for interstitial

Jan 1, 1965

By H. T. Bowman

For more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the I860&apos;s it was recognized that the process would benefit by some type of instrumental contro1.l IIowever, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower&apos;s eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham,3 A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient menoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. Carbon-FeO Relationship In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by Mccutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per. cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a . different method than were those

Jan 1, 1942

By H. T. Bowman

For more than 80 years the Bessemer process has depended upon the ability, skill, and judgment of the blower, although as early as the I860&apos;s it was recognized that the process would benefit by some type of instrumental contro1.l IIowever, instruments with sufficient recording speeds did not exist, so the end-point determination was always dependent upon the blower&apos;s eye. This placed an obstacle in the way of precise experimental work, because of the absence of the necessary records and reference points as reported by Work.2 The use of the photocell provided the instantaneous record of the blow that made this experimental work possible and provided more scientific control for the process as discussed by Graham,3 A brief description of the progress of the blow will illustrate the recording function of the instrument. The silicon in the iron is being oxidized during the first minutes of the blow, as pointed out by Henning4 in a table showing the order of metalloid elimination. The product of this oxidation is a solid that remains in the converter, so there is virtually no flame during this part of the blow. This low flame luminosity is illustrated by the flame recording shown in Fig. I, where the silicon blow is plainly marked. The dull flame of the silicon blow gradually gives way to the brilliant carbon flame as the increasing quantities of carbon monoxide formed inside the converter burn to dioxide upon contact with the atmosphere above the vessel. When the carbon reaches some low value under 0.20 per cent, there is insufficient menoxide formed to maintain the dioxide flame, so its intensity drops. Throughout the flame drop carbon continues to burn, until at some value around 0.05 per cent an arrest occurs in the recorded drop. This point has been designated as the end point. The period of time from this end point until the vessel is turned upon its side and blowing has stopped has been called the afterblow. This afterblow is used as a measure of the degree of metal oxidation, and uniformity demands that it be controlled within narrow limits. Iron and blowing conditions are likely to change several times during a turn, necessitating corresponding changes in end-point control. It is the purpose of this paper to discuss these changes, the factors that make them necessary, and their bearing upon the quality of steel. Carbon-FeO Relationship In the Bessemer process oxidation relationships are precise. Fig. 2 shows a graph of the carbon-FeO relationship. The familiar "bomb-test" method, described by Mccutcheon and Rautio,5 was used for obtaining these and all other dissolved FeO values herein reported, all tests being taken from the converter before deoxidation unless otherwise noted. All tests of 0.10 per. cent carbon and above were obtained from metal blown for duplexing. McGinley and Woodworth6 reported iron oxide values for blown metal, but their tests were obtained by a . different method than were those

Jan 1, 1942

By M. G. Benz, J. F. Elliott

A new type of solution calorimeter has been constructed to measure heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction at temperatures above 1000°C. With it, measurements hove been made of the partial molar heats of mixing joy tin in the Cu-Sn system from 0 to 13 at. pet Sn at 1127°C and fir nickel in the Cu-Ni system from 0 to 9 at, pet Ni at 1200°C. The integral molar heat of mixing for the Cu-Sn system is strongly negative with a calculated minimum value corresponding to the composition Cu3Sn. The integrnl molar heat of mixing for the Czi-Ni system is slightly positive at these temperatures. These integral molar values have been measured with a probable error less than 30 cal per g-atom at an atom fraction of nickel or tin equal to 0.1. The estimated probable error for the Cu-Sn system is approximately 450 cal for a measured heat of solution of approximately 9000 cal. For the Cu-Ni system it is approximately 700 cal for a measured heat of&apos; solution of approximately 60 cal. A new type of heat of solution calorimeter was designed and constructed to provide a more accurate experimental method for determining heat effects at high temperatures, (T > 1000°C). With it, partial molar heats of mixing, enthalpy increments, heats of fusion, and heats of formation and reaction for metal systems can be measured directly. Previously it has been necessary to rely upon the use of the dropping calorimeter or the van&apos;t Hoff equation applied to equilibrium data for this information. For the most part equilibrium data are scarce and difficult to obtain in many cases, and it has been necessary to rely upon the "method of mixtures" for the desired enthalpy measurements. An earlier study1 provides a prototype for this work. The "method of mixtures" as outlined by K. K. kelley,2 "consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a calorimeter operating at or near room temperature.&apos;&apos; In this manner the change in the total heat content (enthalpy) of the substance between the temperature of the furnace and that of the calorimeter is determined. In order to determine high-temperature heats of mixing, enthalpy increments, and heats of fusion, formation, and reaction, it is necessary to take the difference between two such measurements, one before and one after the occurrence of the enthalpy change being studied. The desired enthalpy change is then the small difference between two large numbers. Small errors in the large numbers are included as large errors in this small difference. It is this difficulty that must be avoided for accurate measurement of the desired functions. The procedure with the new solution calorimeter consists of dropping the substance under investigation from a furnace, with controlled and measured temperature, into a solution calorimeter operating in the temperature range of 1000o to 1200°C. Measurements in the range of 1200" to 1600°C are planned for the future. By selection of the composition and

Jan 1, 1964

By H. T. Clark

Within the last twenty years at least three sets of lattice constants for the room temperature (alpha, hexagonal close packed) phase of titanium have been reported in the literature. These values, summarized in Table 1, differ one from another by amounts far greater than can be explained on the basis of inaccuracies in parameter measurements. This paper presents new values determined for high purity titanium. It also details the effect of two elements, oxygen and nitrogen, on these parameters and shows that two of the previously reported values are probably in error because of the presence of one or both of these elements in the material used for examination. Preparation of Samples The titanium+ used for this study was prepared by the thermal decomposition of titanium tetraiodide7 on a hot titanium filament. This titanium rod was prepared for X ray examination by melting about 10 g in purified argon in an electric arc furnace on a cold hearth. This cast button was cold rolled to 0.040 in. thick sheet, cleaned, annealed in vacuum at 1000°C and cold rolled to 0.020 in. thickness. About 0.003 in. of surface material was then removed by hand grinding on papers to remove any contamination caused by the rolls and the sample was bent to the radius of the focusing camera. The sample was then vacuum annealed at 600°C, a temperature just high enough to cause recrystallization, producing a fine grained structure. Such a structure is essential in sheet specimens prepared for focusing cameras in order to have a sufficient quantity of grains to develop continuous diffraction lines. The use of sheet specimens rather than powder samples appears to be essential for the X ray examination of titanium. This is because of titanium&apos;s exceptionally high gettering power and its rapid absorption of adsorbed gases, water -vapor, and the like at annealing temperatures. While the effect of this contamination may be neglected for sheet specimens, its effect on 200-300 mesh powder is appreciable. Titanium alloys of oxygen and nitrogen were prepared by a technique simi- lar to that described above except that the required amount of the highest purity titanium oxide or nitride available was added prior to melting in the arc furnace. These materials were added by placing them in holes drilled in the titanium. A small weight loss invariably occurs during the melting of these oxygen and nitrogen alloys. This is believed to be due entirely to the loss of some of the powdered compound in the blast of the electric arc, an assumption which is justified on the basis that there is no weight loss during the melting of titanium metal and that wet analyses for nitrogen on representative samples have checked with the calculated analyses when it was assumed that the entire loss during melting was due to the loss of titanium nitride powder. These alloy buttons were reduced to sheet in the same manner as used for the unalloyed titanium. Experimental Procedure A North American Phillips 12 cm diam symmetrical precision focusing vacuum camera and copper radiation

Jan 1, 1950

By H. C. Gatos, J. T. A. Pollock, V. Sadagopan

PREVIOUS investigations on the effect of neutron irradiation on the superconducting properties of bulk transition metals indicated that little or no change occurred in poly crystalline disordered materials, particularly if cold-worked prior to irradiation. Only the superconducting properties of ordered intermetal-lic A15 compounds were found to be sensitive to irradiation, and the observed reduction in Tc and increased magnetic hysteresis or critical current densities were attributed to the introduction of flux pinning vacancy clusters and disorder in the lattice. Since the former would also be expected to be present after irradiation in disordered alloys, the general conclusion was that the disordering effect of the irradiation was the primary reason for the changes observed. The present note reports some unusual effects of neutron irradiation on cold worked Nb(Cb)-Ti-V alloys. Specimens with nominal composition as given in Table I were prepared by repeated arc melting, taking the usual precautions, and homogenized at 1000°C for 24 hr prior to a reduction of 15:l by cold rolling. Samples of size 1 by 1 by 25 mm were sliced from the rolled strips. The sarmples chosen for irradiating were sealed in a cadmium tube (wall thickness 1 mm) prior to exposure in a fast neutron flux of 3.7 x 1019 neutrons per sq cm in the swimming pool reactor of Union Carbide Corporation&apos;s Sterling Forest Reactor. During irradiation the temperature of the samples was maintained below 70°C. The irradiated samples were stored at room temperature for approximately 1 year allowing the radiation levels to reach a safe handling value. Tc measurements were made employing a self-inductance coil technique. Jc data at 4.2"Kwere obtained using a four lead resistivity method. The latter measurements were made at the Francis Bitter National Magnet Laboratory by setting the perpendicularly applied field and increasing the direct current through the sample until a potential of about 10-6 v was detected. Tc values for the nonirradiated samples are listed in Table I together with the change in Tc after irradiation. A decrease in Tc of 0.25 or 0.3"K was measured for three of the four samples, the exception being the Nb-30 at. pct V-20 at. pct Ti alloy which showed a decrease of 0.5K. Jc vs applied field data are plotted in Fig. 1 for the Nb-20 at. pct V-30 at. pct Ti alloy. These curves are typical of the four alloys and surprisingly indicate that a degradation occurred in all the samples after irradiation. Hc2 values, obtained by extrapolation to zero current, are 8 to 15 pct lower than those measured for the nonirradiated specimens. The reasons for the degradation of Tc and jc ob-served in the alloys on exposure to neutron irradiation are not immediately apparent. The temperature at which the samples were maintained during bombardment (<70°C) and stored (20°C) make it highly unlikely that any significant change in the dislocation density of the materials through thermally activated migration and annihilation would occur. The explanation must lie in the type of damage produced by the bombardment. McEvoy et a1. reported no change in superconduct-

Jan 1, 1970

By J. S. Billheimer, B. H. Sage, W. N. Lacey, C. G. Yundt

As a part of a general investigation of the separation of bitumen from hydrocarbon mixtures a study was made of a restricted quaternary system composed of methane, decane, tetralin, and bitumen. The work was limited to a pressure of 8000 psi, a temperature of 220 °F, and to a fixed relative proportion of decane, tetralin, and bitumen. The measurements permitted the determination of the distribution of these components in each of the fluid phases. It was not possible to distinguish a second liquid phase in the course of these measurements. Gas-liquid equilibrium "constants" of each of the components were found to vary markedly with the composition of the system while temperature and pressure remained fixed. INTRODUCTION The separation of bitumen frorn naturally occurring hydrocarbon mixtures has been of importance for a number of years in the production of petroleum, especially in the California area. The deposition of this material from crude oils was noted in earlier studies of the solubility of natural gas in crude oil.¹,²,3 Studies of the separation of bitumen from crude oils from the Greeley and Santa Fe Springs fields were carried out."." The behavior of these systems appeared complex and studies of two restricted ternary systems involving mixtures of n-pentane, tetralin, and bitumen,&apos; and of decane, tetralin; and hitumen, confirmed this belief. Reviews of the literature pertaining to the separation of bitumen from naturally occuring and refined hydrocarbons are available." The important effect of methane in the separation of bitu- men from naturally occurring hydrocarbon mixtures was apparent from the earlier studies and for that reason it appeared desirable to investigate a restricted quarternary system involving mixtures of methane. decane, tetralin, and bitumen; data concerning the behavior of mixtures of decane. tetralin. and bitumen having already been obtained.V his study was restricted to a pressure of 8000 psi," a temperatue of 220° F, and fixed relative proportions of bitumen, decane. and tetralin. This composite constituent, hereinafter designated as the less volatile constituent, was made up of 0.0455 weight fraction bitumen. 0.0909 weight fraction decane, and 0.8636 weight fraction tetralin. The experimental method involved bringing together mixtures of methane and the less volatile constituent in varying proportions in a constant volume container at the pressure and temperature indicated above. The composition of each of the phases was determined and from this the extent of the separation of bitumen was established. MATERIALS The bitumen used in this investigation was obtained from the same stocks employed in earlier studies. The crude material from the North Coles Levee field was stored in the laboratory] in a closed drum for a period of five years. Several samples from this stock were subjected to refining operations which were described earlier,&apos; and every effort was made to follow the same procedure in all cases. It was necessary to prepare supplies of bitumen for this investigation at two rather widely different times. These materials have been identified as samples 1 and 2. The composition of the crude bitumen after it was washed with n-pentane at room temperature

Jan 1, 1949