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By George F. Comstock

It has been reported recently1 that the hardenability and toughness of forging steels may be improved appreciably by the use of complex deoxidizers containing titanium, aluminum, and vanadium. In the light of these results, an investigation of similar deoxidizers containing various hardening and grain-refining elements was proposed. These deoxidizers included three manganese-silicon-aluminum-titanium al- loys with and without boron and calcium, three titanium-aluminum ferroalloys with vanadium, molybdenum and zirconium, respectively, an aluminum-zirconium ferroalloy, and plain ferroboron. Their approximate compositions are given in Table I, and the results obtained so far in the investigation of their effects on steel are presented in the later parts of this paper. Method of Using Deoxidizers The deoxidizers listed in Table I were used in three series of 0.40 per cent carbon steels, which were melted in a small basic-lined induction furnace and cast in the form of I7-lb. ingots about 2.75 in. square. The basic charge for each heat was 10 lb. Armco iron and 6 lb. of clean low-carbon sheet-steel scrap. When melted, this charge was deoxidized with 15 grams of ferrosilicon, then about 500 grams of pig iron was added to give the desired carbon content. After the pig iron was dissolved, nickel shot and high-carbon ferrochromium were added if required, and additions of 80 per cent high-carbon ferromanganese and 50 per cent ferrosilicon were made to provide the proper amounts of those elements. Aluminum was added to every heat 2 min. after the silicon, for grain-size control and preliminary deoxidation. One minute later the special deoxidizer was added to the clean bare surface of the molten steel, and 2 min. afterward the steel was poured into the ingot mold, using a hot-top and pipe-preventing compound after pouring to decrease the depth of the shrinkage cavity. The special deoxidizers were used mostly in the form of about ½ to¾-in. lumps,

Jan 1, 1942

By George F. Comstock

It has been reported recently1 that the hardenability and toughness of forging steels may be improved appreciably by the use of complex deoxidizers containing titanium, aluminum, and vanadium. In the light of these results, an investigation of similar deoxidizers containing various hardening and grain-refining elements was proposed. These deoxidizers included three manganese-silicon-aluminum-titanium al- loys with and without boron and calcium, three titanium-aluminum ferroalloys with vanadium, molybdenum and zirconium, respectively, an aluminum-zirconium ferroalloy, and plain ferroboron. Their approximate compositions are given in Table I, and the results obtained so far in the investigation of their effects on steel are presented in the later parts of this paper. Method of Using Deoxidizers The deoxidizers listed in Table I were used in three series of 0.40 per cent carbon steels, which were melted in a small basic-lined induction furnace and cast in the form of I7-lb. ingots about 2.75 in. square. The basic charge for each heat was 10 lb. Armco iron and 6 lb. of clean low-carbon sheet-steel scrap. When melted, this charge was deoxidized with 15 grams of ferrosilicon, then about 500 grams of pig iron was added to give the desired carbon content. After the pig iron was dissolved, nickel shot and high-carbon ferrochromium were added if required, and additions of 80 per cent high-carbon ferromanganese and 50 per cent ferrosilicon were made to provide the proper amounts of those elements. Aluminum was added to every heat 2 min. after the silicon, for grain-size control and preliminary deoxidation. One minute later the special deoxidizer was added to the clean bare surface of the molten steel, and 2 min. afterward the steel was poured into the ingot mold, using a hot-top and pipe-preventing compound after pouring to decrease the depth of the shrinkage cavity. The special deoxidizers were used mostly in the form of about ½ to¾-in. lumps,

Jan 1, 1942

By E. T. Turkdogan, P. Grieveson

STAFF: Editor, Gerhard Derge Acting Editor, Paul G. Shewmon Carnegie lnstitute of Technology Sc hen ley Park Pittsburgh 13, Pa. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Karl L. Fetters, President; J.S. Smart, Jr., Past-President; R. C. Cole, Vice President; R. L. Hennebach, Treasurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: W. 0. Phil-brook, Chairman; H. L. Bishop, R. C. Cole, J. N. Hobstetter, W. A. Krivsky, E. R. Morgan, F. C. Langenberg, R. E. Lund, Paul Queneau, L. L. Seigle, R. L. Smith, and T. '4. Wainwright. Review and selection of manuscripts is under the supervision of the following Publications Committes: Extractive Metallurgy Division: R. E. Lund, Chatrmon; M. E. Wodsworth, Vice Chairman; D. H. Baker, Jr., G. M. Bell, R. E. Groce, W. A. Krivsky, R. A. Lewls, Charles O'Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. V. Wainright, Choirman; H. L. Bishop, R. E. Boni, T. E. Dancy, C. W. Murphy, Johonnes M. Uys, J. B. Wagstaff, and R. G. Ward. lnstitute of Metols Division: J. N. Hobstetter, Chairman; P. A. Beck, J. J. Becker, G. F. Bolling, J. O. Brittain, J. 8. Clark, R. S. Davis, A. E. Dwight, R. W. Fountain, L. R. Girifalco, J. C. Gurland, H. S. Kclish, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, H. H. Johnson, Jr., R. R. Nosh, T. N. Rhodin, R. H. Richman, H. C. Rogers, W. Rostoker, C. Sherby, C. W. Spencer, L. Slifkin, J. K. Stanley, R. Steinitz, H. C. Stumpf, and R. Swolin. Published bimonthly by the American Institute of Mining, Metallurgical, and Petroleum Engineers, Inc., 345 East 47th Street, New York 17. N. Y. Telephone PLaza 2-6800. Subscription $30 per year for non-AIME members in United States and North, South, and Central America; $32, foreign; $7.50 for AlME members. Single copies, $6.00, single copies foreign, $6.50. The AlME is not responsible for any statement made or opinion expressed in its publications ... Copyright 1962 by the American lnstitute of Mining, Metollurgical. and Petroleum Engineers. Inc. . . . Registered cable address, AlME New York . . . Indexed in Engineering Index, lndustriol Arts Index, and Chemical Abstracts . . . Second class postage paid at New York, N. Y., and Ann Arbor, Mich. Volume 224, Number 6.

Jan 1, 1962

By R. P. Abendroth

The hydrogen-water vapor ratio at which Fe-Cr alloy, chromium oxide, andiron chromite coexist in equilibrium was determined between 900" and 1200°C. A thermogravimetric method was used to determine equilibrium conditions. The results fit a straight-line relationship in the temperature region studied, and are given by Reduction experiments were also performed to confirm the results of the equilibrium investigation. ThE oxygen pressures at which Fe-Cr alloy, chromium oxide, and iron chromite coexist in equilibrium have been previously determined by Boericke and angert,' Morozov and Novokharski,' and Katsura and uan. Only one determination (at 1300°C) was made by Katsura and Muan, but it agrees with the results of orozov and Novokharski. The results of Boericke and Bangert, however, differ appreciably from the results of these investigators. Previous studies have assumed that the equilibrium metallic phase is pure iron, but Dahl and Van vlack have shown that the iron contains from about 1 wt pct Cr at 1000°C to over 2 wt pct above 1300°C. The chromium oxide also contains a small amount of iron in solid solution. In the present study, hydrogen-water vapor mixtures were equilibrated with the condensed phases, using a therrnogravimetric method to determine equilibrium conditions. The reaction can be written EXPERIMENTAL General Procedure. The starting material was a sintered pellet of Fe2O3-Cr2O3 solid solution with a hole in the center, and was placed on a fused silica hook. This assembly was raised into the preheated hot zone of the furnace in a helium atmosphere, hooked onto a fused silica hangdown suspended from one arm of an Ainsworth Model RV-AU-1 recording balance, and the starting weight determined. A flowing hydrogen-water vapor atmosphere was then exchanged for the helium by evacuation, and the sample reduced until the weight loss indicated the sample composition to be in the alloy-Cr2O3-chromite field. The tem- perature was adjusted incrementally until constant sample weight was achieved for several hours, to within 0.02 mg. A hydrogen-water vapor atmosphere of different composition was then admitted, and the same procedure carried out. At the end of a series of determinations, the sample was examined by X-ray diffraction to verify the presence of the desired phases. Microscopic examination of the silica hook showed no interaction with the sample, nor did it lose any weight. Several criteria were used to insure equilibrium besides constancy of weight. For a given hydrogen-water vapor composition, equilibrium was approached from both oxidizing and reducing sides by varying the furnace temperature slightly. The resulting slow weight loss or gain was observed for several hours. Constant weight could be re-established by returning to the original furnace temperature. The last criterion used was varying the relative amounts of the phases by further reduction or oxidation, and observing any changes in temperature required for constant weight for a given hydrogen-water vapor atmosphere. None were observed. This procedure was essentially the same as approaching the equilibrium from oxidizing and reducing sides, but larger weight excursions were carried out. Sample Preparation. Reagent-grade Fe2O3 and Cr83 powders were mixed in the desired proportions and heated in air at 1250°C for 2 hr. The mixture was re-ground and heated in air overnight at 1250°C. X-ray diffraction showed complete solid-solution formation as a result of this procedure. The solid solution was then pressed into l/2-in.-diam pellets using Carbowax 4000 as a binder. The hole was drilled in the center, and the pellets were sintered 24 hr at 1250°C in air on a bed of Fe2O3-Cr2O3 of the same composition, contained in an alundum boat. After cooling, the pellet surfaces were abraded with 310 paper to remove any surface compositional differences, such as loss of Cr2O3. Chemical analysis of the sintered pellets was 67.16 wt pct CrP3 and 33.02 wt pct Fe203. Atmosphere Generation and Control. The hydrogen-water vapor atmospheres were generated by passing Matheson ultrahigh-purity hydrogen, with no further purification, through two water bubblers contained in a constant-temperature water bath. Since the water-vapor dew points required in this study were below room temperature, the bath was insulated, and was cooled by thermoelectric-immersion devices. The bath temperature was controlled to 0.0l0C. Since rather high flow rates of about 900 ml per min were used through the furnace tube, an independent check of the dew point was made to insure saturation of the hydrogen by the water vapor. Although the dew point could only be determined to within 1/2"C, the determined dew points agreed with the water-bath temper-

Jan 1, 1967

By R. H. Schnitzel

Internal-friction peaks have been observed in tungsten single crystals at about 300° and 400°C. The characteristics of these peaks are similar to interstitial peaks observed in other bee metals; therefore, the origin of these peaks appears to he the Snoek mechanism. The interstitial responsible for the peak at about 300°C has not been identified. Carburizing increases the magnitude of the peak at about 400°C; consequently, it appears reasonable to suppose that the specific interstitial associated with this peak is carbon. The activation energies associated with the 300° and 400°Cpeaks are about 35,000 and 45,000 cal per mole, respectively. INTERNAL - friction peaks resulting from the stress-induced diffusion of interstitials (Snoek relaxation peaks) have been frequently observed in bee metals.1-5 Attempts to detect Snoek relaxation peaks in tungsten have, however, not been fruitful.' Failure to find Snoek peaks in sintered tungsten can perhaps be attributed to one or more of the following difficulties: a) the relatively low purity of the sintered tungsten; b) the lack of extensive metallurgical knowledge about tungsten-interstitial alloys, such as suitable interstitial dosing and quenching procedures; and c) the inconsistency of some of the interstitial analyses of tungsten, which reflects itself in one's inability to be sure of the nature of the specimens. This present investigation did not overcome all of these difficulties for successful tungsten internal-friction measurements. Some of these difficulties still persist and new difficulties were encountered during the course of this investigation. Nevertheless, the use of electron-beam tungsten single crystals having somewhat greater purity levels than sintered tungsten combined with appropriate carburizing and quenching procedures permitted a reasonable attempt to be made. As a consequence, internal-friction peaks were observed in these tungsten single crystals at about 300° and 400°C. These peaks were found to be unstable, since they annealed rapidly away during a sequence of internal-friction measurements. Hence, it was necessary to construct an apparatus having a faster heating rate to study some of the details of these peaks. From the behavior of these peaks as well as our knowledge of similar peaks in other bee metals, one can reasonably conclude that these peaks are caused by residual interstitial impurities within these crystals. Further investigation of these peaks after the application of various metallurgical treatments lent credence to this supposition. EXPERIMENTAL TECHNIQUE The internal friction of tungsten single crystals was measured using two different pieces of apparatus both of which are of essentially the same conventional design, namely the KE type of torsion pendulum. The important difference between these two types of apparatus was in the attainable heating rate and method of protection of the specimen from atmospheric contamination. The apparatus designated "number 1" was enclosed in a vacuum chamber which was heated by an externally mounted furnace. It had a slow rate of heating which was estimated to be about 4°C per min from room temperature to about 350°C and then about 1°C per min to 600°C. The internal friction of tantalum was measured with this apparatus and the established Snoek peaks were found.' These tantalum peaks in the temperature range from room temperature to 400° C served as a check for the apparatus. The apparatus designated "number 2" having a faster heating rate than number 1 was not elaborate. It consisted of a mounted nickel tube to which split heating elements were attached. Argon was used as the protective atmosphere. The measured heating rate was about 12° to 15°C per min whereas the cooling rate was somewhat slower at about 10° C per min because of the increased difficulty encountered in stabilizing the temperature. No surface oxidation of the specimen was noted after any test. This apparatus was also checked with the known peaks of tantalum.1 The preparation of the single-crystal specimens for internal-friction measurements consisted of centerless grinding the crystals from an approximate 0.200 in. diameter to 0.030 to 0.040 in. in diameter, and then electropolishing them to about 0.020 in. in diameter. Single crystals processed in this manner are designated as being in the virgin condition. Since the length of crystal varied from 3 to 9 in., the test frequency varied from about 1 to 2 cps. The frequencies of measurement, axial orientations, and chemical analyses for the various crystals are listed in Table I. The controlled addition of carbon into tungsten is a difficult problem. Attempts to find the critical conditions necessary for an equilibrium treatment were not fruitful. Therefore, a simple nonequi-librium method was used. The addition of carbon to these crystals consisted of appropriately combining three treatments—carburizing to achieve a case, annealing to partially dissolve the carbon into the

Jan 1, 1965

John Chipman (Massachusetts Institute of Technology, Cambridge, Mass.)—After looking over the authors' shoulders for several years and after many discussions on the interesting diagrams of the types shown, it is a pleasure to see a formal paper published on this subject. There can be no doubt of the practical usefulness of the concepts shown. Inclusion formation in steel is such a highly complex matter that any system for understanding the subject is bound to be welcomed by those who must work with steels and who see in their day-to-day experience the good and evil effects of inclusions. A feature of the work with which the discusser has been concerned, and which he would now like to attempt to explain, is the relation between the schematic diagrams which the authors use and the phase diagrams for related systems. Obviously, the authors' diagrams are in no sense complete phase diagrams. However, there is a relation between this type of diagram and the true phase diagram, and the understand- ing of this relation ought to help in understanding the general picture which the authors are presenting. Consider the authors' Fig. 4, which shows the liqui-dus relations in the Fe-Mn-S-0 system. To show the complete relations between temperature and composition in these four ternary systems would require four triangular prisms, the vertical axes of which would represent temperature. The four triangles of Fig. 4 represent basal projections of certain lines from the four prismatic phase diagrams. Readers of the paper are all more or less acquainted with this type of projection and its usefulness and limitations are generally understood. In order to concentrate on the interesting parts and to minimize the less interesting features, the composition scale may be shifted to de-emphasize regions containing gaseous sulphur and oxygen. Such a diagram is shown in Fig. 16, which is a distorted version of the authors' Fig. 4. Here the oxide of iron is wiistite, denoted by W, and it is to be noted that between W and MnO lies the entire MnO-FeO "binary" system. Similarly, between MnS and FeS lies another binary whose

Jan 1, 1956

By John V. Beall

HEAVY-DENSITY separation processes, a commercial application of the sink-float test used in mineralogical laboratories for the separation of mineral particles by their difference in specific gravity, are the biggest development in mineral dressing since flotation, which was at about the same stage of development thirty years ago. The scope of their application has broadened and, though still in the development stage, they are being accepted in a constantly increasing number of commercial installations. This progress in mineral beneficiation is especially satisfying when we realize that our high-grade ore deposits are fast disappearing and a big factor in determining whether a hole in the ground is being sat upon by a liar or an honest citizen is how economically the ore dressers can concentrate comparatively low-grade ores. As early as the middle of the nineteenth century attempts were made to use aqueous salt solutions in a heavy-liquid separation for cleaning coal. But the original and recovery costs of these liquids were high and further, the fact that they were corrosive, unstable, and toxic added to the difficulty in using them.

Jan 1, 1948

By C. H. Mathewson

CHARACTER OF THE WORK IN HAND IN planning the present experiments, we have made a particular effort to secure that adjustment of working conditions which would render the forthcoming tests most serviceable by way of indicating the comparative properties of the three different commercial grades of copper used. More specifically, we have endeavored to obtain certain definite information with respect to the relative behavior under test of ordinary electrolytic copper and furnace-refined lake copper containing (a) a moderate percentage of arsenic and (b) a rather large percentage of arsenic, in addition to the usual content of silver and other impurities. These comparisons were made systematic and comprehensive by testing throughout a series of (eight) reductions running from 0 to 70 per cent. in the case of cold-rolled metal, and throughout a series of (15) temperatures running from 100° C. to 1,000° C. in the case of annealed metal. In other words, a survey of properties similar to that made by Grard,1 in the case of electrolytic copper, was here repeated (with modifications) and extended to two other commercial varieties of copper.

Jan 7, 1916

By R. E. H. Pomeroy

THE statistical data given in this paper are taken from the actual performance of the No. 2 reverberatory furnace of the Nevada Consolidated Copper Co., Me Gill, Nev., for a period of four months, from April to July, 1914. The principal furnace dimensions are: Length, 132 ft. ½ in. at the skim-line level; average width, 18 ft., 10 in. at the skim-line level. The roof is 7 ft. above the skim-line level at the firing end. The average area in the uptake flue is 36 sq. ft., and the area above the skim line under the vulcatory arch is 24.3 sq. ft. Fig. 1 shows a diagrammatic plan and sectional elevation of this furnace. The furnace is equipped with two 400-b.h.p. Stirling waste-heat boilers set in parallel. California crude petroleum is used for fuel and has a specific gravity of 16.5° B., flashing in open test at 199° F. The oil is heated to about 200° F. in a steam heater before going to the burners, requiring about 9 b.h.p. per furnace day to heat it from the line temperature to the burning temperature. Measurement is made by oil meter, checked daily by reservoir readings. The oil is fed by gravity (34 lb. static pressure) to seven low-pressure blast burners of the Steptoe type (Fig. 2). The blast for these burners is supplied at about 40-oz. pressure by a motor-driven Connersville blower of 42 cu. ft. capacity per revolution. The air supplied by the blower through the burners for atomizing the oil amounts to about 10 per cent. of the theoretical air necessary for complete combustion of the oil. The remainder of the necessary air enters the furnace through the burner openings in the firing wall. No checker holes are provided, and the charge holes in the roof are equipped with slide gates and "dog houses? to minimize air leakages. The combustion of the fuel, as shown by gas analysis at the front of the furnace, is practically complete, the carbon monoxide in the gases being less than 0.5 per cent.

Jan 2, 1915

By A. D. Zunkel, A. H. Larson

Equilibrium arsenic contents of Pb-As alloys in contact with PbO-As2O3 slags containing less than 30 mol pct As2O3, were determined at 650°, 700: and 750 C in an inert at?rzosphere. In this temperature range, the arsenic content of the alloy increased with increasing temperature in the single-phase liquid slag region and decreased with increasing temperature in the two-phase slag region and the single-phase solid-solution slag region. The PbO-As2O3 phase diagram below 22 mol pct As2O3 was determined by thertrzal analysis and by application of a log ?As2O3/?PbO vS log XAs2o3 /x3pbO plot determined from the equilibrium actiuity data. The resulting phase diagram was not well-defined since the eutectic temperature was not detected in the thermal analysis experiments, although a region of terminal solid solubility of As2O3 was found. Results from the phase diagram determination are compared with an existing diagram in the literature. THIS experimental investigation is an extension of a study by the authors1 on the slag-metal equilibria in the systems concerned with commercial lead refining processes such as softening and dross fuming. The first part of this investigation was a study of the slag-metal equilibria in the Pb-PbO-Sb2O3 system. The only experimental work previously done on the Pb-PbO-As2O3 system was by Pelzel2,3 in which the phase diagram for the PbO-As2O3 system was determined below 50 wt pct As2O3 and the equilibrium constant for the reaction 3Pb + As2O3 + 3PbO + 2As was determined as a function of temperature. No slag-metal equilibrium data have been determined. It is due to the scarcity of information regarding the Pb-PbO-As203 system that this work was undertaken. This paper describes the determination of the slag-metal equilibria in the Pb-PbO-As203 system by equilibrating Pb-As alloys with PbO-As2O3 slags in an inert atmosphere, the effect of 1 wt pct additions of bismuth and copper on the slag-metal equilibria, and the PbO-As2O3 phase diagram both by thermal analysis and the use of the slag-metal equilibria data. EXPERIMENTAL Materials. The materials used in this investigation were analytical reagent-grade and assayed as follows: 1) 99.8 pct PbO (0.014 pct insoluble in CHJCOOH, 0.02 pct not precipitated by H2S, 0.1 pct CaO, and 0.08 pct SiO2); 2) 99.95 pct As2O3; 3) 99.99 pct Pb; 4) 99.0 pct As; 5) 99.99 pct Cu; and 6) 99.97 pct Bi. Room-temperature X-ray patterns revealed no detectable impurities in any of these materials. Apparatus for Equilibrium and Thermal-Analysis Determinations. The resistance-heated crucible furnace used in this investigation employed nichrome elements and was mounted so that it could be raised to surround the reaction tube during each experiment and, subsequently, lowered. A schematic diagram of the apparatus is shown in Fig. 1. Each charge was heated in a 3+-in.-OD by 31/2-in.-high 416 stainless-steel crucible placed in a 41/4-in.-1D by 18-in.-long fused-silica reaction tube which was closed at one end. On a shoulder around the crucible was placed a 3: -in.-OD by 12-in.-long open-end fused-silica condenser tube. The open end of the reaction tube was covered by a water-cooled brass cap with ports for 1) admitting an inert atmosphere to the system through a stopcock, 2) introducing a stainless-steel, motor-driven, paddle stirrer into the crucible, 3) evacuating the system with a mechanical vacuum pump, and 4) sampling the melt with Vycor sampling tubes. The brass cap was fitted to the open end of the reaction tube with a silicone gasket and collar clamp. The furnace temperature was controlled by a Barber-Coleman Capacitrol controller and a chromel-alumel thermocouple. Due to the corrosiveness of the melt, the controlling thermocouple also served as the measuring thermocouple. The temperature of the melt was calibrated against the controller temperature and was checked periodically during each test with a Vycor-enclosed calibrated chromel-alumel thermocouple. The temperature measurement and control can be considered accurate to ±3°C. Procedure. The charge placed in the crucible for each experiment consisted of 1000 g of Pb-As alloy and 300 g of PbO-As2O3 slag. The crucible was then placed in the reaction tube, the condenser tube was placed on the shoulder of the crucible, the silicone gasket and brass cap were fitted on the open end of the reaction tube, and the entire system was evacuated and filled with argon ten times. After the last flushing, a positive argon pressure of 1 psig was impressed on the system. The furnace was then raised to sur-

Jan 1, 1968

By Gustav S. Preller, A. M. Gaudin

Fox the past 20 years it has been generally accepted that the flotation process is made possible as a result of the action of certain chemical substances on the surface of the mineral particles. In fact, it has been suspected, but never demonstrated, that this action produces on the mineral particles a layer of chemosorbed ions that is of the order of magnitude of a monolayer; that is, of a layer one ion deep. It is the purpose of this paper to present certain initial results on the relationship of mineral surface area and collecting-agent requirements. Up to about eight years ago, all considerations involving the surface area of finely divided solids were-limited by the fact that there was not in existence any general method for determining the extent of such surfaces, especially on mixed materials. However, the method invented by Brunauer, Emmett and Teller1 has changed the situation by providing a general procedure (BET method). This procedure has already been applied to mineral dressing problems2 -4 and has now received confirmation as to accuracy by an entirely independent method.5 This confirmatory or "absolute" method uses a very tedious calorimetric procedure and is not suitable for routine determinations; but still another method6 now is available to relate the results obtained by the BET method to those obtained calorimetrically. This Harkins-Jura method has the advantage that it does not require an assumption concerning the parking area per molecule of adsorbate (nitrogen). In the original work by Brunauer, Emmett and Teller the parking area per nitrogen molecule was calculated to be either 13.8Å2. or 16.2Å2. according as the nitrogen was assumed to be closely packed as in crystalline nitrogen or loosely packed as in liquid nitrogen. The initial experimental work from this laboratory2 supported the 13.8Å2. figure; that work was done on glass spheres of measurable geometric area and it was based on the assumption that the glass spheres were truly smooth; any deviation from this assumption would, of course, have made the calculated parking area higher. Harkins and Jura's results suggest that the parking area is not the same for all substrata; furthermore, the average of the 87 measurements cited indicates a "preferred" parking area for the nitrogen molecule of about 15.2Å2., with extreme values at 13.7 and 16.9Å2. The average of 21 determinations made in connection with this study' gave a parking area of 14.3 ± 0.27Å2. In view of this result and of the Harkins and Jura

Jan 1, 1946

By C. G. Dunn, W. W. Martin

Various X ray diffraction techniques have been developed for determining orientations of crystals. Transmission and back-reflection Laue methods1,2,3 in particular have been found to be very useful. In many applications, however, a need still exists for a simplification of the details of analysis so that orientations can be determined more rapidly, and operators with little or no training in crystallography can be easily instructed in the necessary procedures. Filling this need in part is a system of analysis that has been in use for several years in the Metals Section of the Laboratory, General Electric Co., Pittsfield, Mass. This method is an extension of the one of Majima and Togino,4 which uses fifty-five indexed standard transmission Lauemams to cover the entire range of crystal orientations. Greater rapidity in determining the orientation of a crystal is achieved by using a slightly larger set of standard Lauegrams and by systematizing the steps followed. This system of analysis in its present form constitutes the subject matter of the present paper. Although the method uses transmission X ray Laue patterns, many of the operations are applicable to the analysis of back-reflection Lauegrams. Very briefly the method is based on the fact that Bragg and azimuthal angles for two or more identified Laue diffraction spots completely determine the orientation of a crystal, and standard Laue photographs of the Majima and Togino type provide a ready means for identifying Laue spots. After a preliminary analysis, which consists of identifying the pattern in terms of one of the standard patterns, a correctly marked Lauegram is selected to carry out the final analysis. From measured Bragg and azimuthal angles, the normals (poles) of the reflecting planes for the selected Laue spots are located on a stereographic projection and the orient.at.ion of the crystal determined (in terms of the positions of cube poles for example) by a few additional operations on a \I1ulff net. The actual procedure followed will be illustrated in detail after a brief treatment or X ray problems connected with orientation determinations and a discussion of useful principles and techniques. X Ray and Plotting Problems RELATIVE ADVANTAGES OF BACK-REFLECTION AND TRANSMISSION LAUE DIFFRACTION METHODS In the back-reflection Laue method it is easy to make a direct measurement of the tilt of a zone of Laue spots. Specimen thickness also is generally no problem. In the case of thin specimens, however, the time of exposure is less for the transmission Laue method. For example, with silicon ferrite this advantage holds up to a thickness of 0.6 mm if tungsten radiation at 40 kv peak voltage is used. Furthermore, the transmission photograph represents the entire thickness of the crystal whereas the back-reflection picture represents only a surface layer (a thickness of less than 0.05 mm for silicon ferrite), the deeper layers supplying a negligible amount to the diffraction pattern. If a crystal is distorted, the transmission Laue pattern gives more information particularly with regard to the orientation of the crystal and the overall amount of spread in orientation. Finally a 3 1/4 X 4 in. film suffices for transmission photograms; a 4 X 5 in. or 5 X 7 in. film with a central hole is needed for back-reflection patterns Not only is the manipulation of film easier because of the size of film, but

Jan 1, 1950

By Kenneth A. Gutschick, Robert S. Boynton

Lime has become a very general loosely used term that includes virtually all finely divided types of limestone as well as burned forms of lime. However, actually (and according to Webster) lime is only calcined limestone (known as quicklime, calcium oxide, or calcia). It also embraces the secondary product of quicklime-namely hydrated lime or slaked lime (calcium hydroxide). Fundamentally there are two basic types of limestone-high calcium and high magnesium (dolomitic). The dolomitic quicklimes and hydrated limes correspond to their "high calcium" counterparts in terminology. The only difference is that the dolomitic types are a combination of the elements, calcium and magnesium, whereas high calcium limes contain only 0.5 to 2 pct of magnesium. Both types, which are made through calcination at high temperatures, are shown chemically as follows: [ ] In the above reactions either type of limestone is burned (calcined) in furnaces known as lime kilns so that the carbon dioxide content of the stone is expelled as a gas. With high calcium limestone 44 pct of the weight of the stone is lost; with dolomitic limestone the loss is 48 pct. Also, both reactions are chemically reversible since quicklime absorbs carbon dioxide readily and in so doing transforms itself back to the original carbonate form. Most quicklimes correspond in size to the original rock, which varies from one to eight inches, depending upon the type of kiln employed. Slight shrinkage occurs during calcination. A few limestones when calcined will decrepitate (break down) into a fine powdery form; however, chemically it is the same as the pebble or lump-sized material. For some uses the lumps of quicklime are pulverized and packaged. Since quicklime has great affinity for moisture and carbon dioxide, it is perishable. When it absorbs moisture and CO2 slowly from the atmosphere, the resulting product is "airslaked." Consequently, it must be stored in dry, moisture-proof areas that are free from CO2. Because of its fugitive nature, it is usually consumed within a few weeks after manufacture. A more stable form of lime is hydrated lime-commercially made by adding water to the quicklime until the lumps break down into a fine, white powder. This product, which is usually packaged, can be stored more safely; and many of its uses are interchangeable with quicklime. The irreversible chemical reactions of hydrated lime for both high calcium and dolomitic types are: [ ]

Jan 1, 1960

By H. H. Kaveler, W. R. Evans, Jack Tarner

The geological features, development history and engineering detail of the Shuler Field and the results of approximately two years of unitized operation of the Shuler Jones Sand Pool, were discussed in a prior publication.' The purpose of this paper is to present the results of pressure maintenance in the Shuler Jones Sand Pool after nine years of unit operation. GENERAL INFORMATION The Shuler Jones Sand Pool is located in and about Section 18, Township 18 South, Range 17 West, Union County, Ark. The pool was discovered .in September, 1937, unitized in February, 1941, and subjected to gas injection operations in July, 1941. Water was first returned to the reservoir in July, 1944. The reservoir is an anticlinal trap covering about 4,000 acres. The 154,000 acre-ft of sandstone initially consisted of approximately 150,000 acre-ft of productive oil zone and 4,000 acre-ft of gas-cap. The average depth of production is 7,400 ft. Maximum closure of the reservoir is 135 ft and the oil column lies between a gas-oil contact at -7,270 ft and a water-oil contact at -7,370 to -7,380 ft. The field is approximately four miles long. east and .west, and one and one-half miles wide. The sand grains are angular and vary from fine to medium size. The porosity of the sandstone averages 20.2 per cent. The specific permeability averages 400 md. Some zones have as high as 30 per cent porosity and specific permeability of 4,000 md. The reservoir rock is not uniform in character but consists of sandstone zones interspersed with shale. The variation in rock characteristics is evident in the electric log and core analyses presented in the original publication. Asphalt present in the pore space of the sandstone limited the reservoir to the southeast and apparently blocked any encroachment of water from that direction. The initial reservoir pressure at a subsea depth of 7,300 ft was 3,520 psi. The reservoir temperature was 198ºF. Initially, the solution gas volume was 765 cu ft per bbl and the reservoir volume factor was 1.45. The gas solubility and formation-volume-factors of the reservoir liquid are related with reservoir pressures above 300 psi as follows: Solution gas, cu ft per cu ft, S = 0.0334 P + 18.65 Formation volume factor of reservoir oil, FVF = 8.0 x 10 -5 P + 1.168 Gas volume factor, standard cu ft of gas equivalent to one cu ft of gas at reservoir conditions of temperature and pressure, F = .062 P - 4 Pressure (P) measured in psia. The equation for the gas volume factor presented above is based on a direct measurement of a sample of the gas and is a correction of that used in the original paper. The gravity of the oil produced is from 32 to 34" API. CALCULATION OF INITIAL OIL IN PLACE The Jones Sand production history is interesting because it lends itself to analysis by material balance. Production statistics from discovery of the Jones Sand through 1949 and material balance calculations of the initial stock tank oil in place are shown in Table I. The usual procedure in testing the application of material balance calculations is to compute the apparent initial volume of oil in place, using production and pressure information obtained at different time periods. If the apparent oil in place volumes computed increase with successive time periods, water encroachment is indicated and approximations must be mads to correct for its influence. The first requirement in utilizing such calculations is reliable reservoir pressure, accumulated gas, oil and water production, and PVT data. Calculations of apparent oil in place in the Jones Pool, based on field data

Jan 1, 1951

By W. R. Evans, H. H. Kaveler, Jack Tarner

The geological features, development history and engineering detail of the Shuler Field and the results of approximately two years of unitized operation of the Shuler Jones Sand Pool, were discussed in a prior publication.' The purpose of this paper is to present the results of pressure maintenance in the Shuler Jones Sand Pool after nine years of unit operation. GENERAL INFORMATION The Shuler Jones Sand Pool is located in and about Section 18, Township 18 South, Range 17 West, Union County, Ark. The pool was discovered .in September, 1937, unitized in February, 1941, and subjected to gas injection operations in July, 1941. Water was first returned to the reservoir in July, 1944. The reservoir is an anticlinal trap covering about 4,000 acres. The 154,000 acre-ft of sandstone initially consisted of approximately 150,000 acre-ft of productive oil zone and 4,000 acre-ft of gas-cap. The average depth of production is 7,400 ft. Maximum closure of the reservoir is 135 ft and the oil column lies between a gas-oil contact at -7,270 ft and a water-oil contact at -7,370 to -7,380 ft. The field is approximately four miles long. east and .west, and one and one-half miles wide. The sand grains are angular and vary from fine to medium size. The porosity of the sandstone averages 20.2 per cent. The specific permeability averages 400 md. Some zones have as high as 30 per cent porosity and specific permeability of 4,000 md. The reservoir rock is not uniform in character but consists of sandstone zones interspersed with shale. The variation in rock characteristics is evident in the electric log and core analyses presented in the original publication. Asphalt present in the pore space of the sandstone limited the reservoir to the southeast and apparently blocked any encroachment of water from that direction. The initial reservoir pressure at a subsea depth of 7,300 ft was 3,520 psi. The reservoir temperature was 198ºF. Initially, the solution gas volume was 765 cu ft per bbl and the reservoir volume factor was 1.45. The gas solubility and formation-volume-factors of the reservoir liquid are related with reservoir pressures above 300 psi as follows: Solution gas, cu ft per cu ft, S = 0.0334 P + 18.65 Formation volume factor of reservoir oil, FVF = 8.0 x 10 -5 P + 1.168 Gas volume factor, standard cu ft of gas equivalent to one cu ft of gas at reservoir conditions of temperature and pressure, F = .062 P - 4 Pressure (P) measured in psia. The equation for the gas volume factor presented above is based on a direct measurement of a sample of the gas and is a correction of that used in the original paper. The gravity of the oil produced is from 32 to 34" API. CALCULATION OF INITIAL OIL IN PLACE The Jones Sand production history is interesting because it lends itself to analysis by material balance. Production statistics from discovery of the Jones Sand through 1949 and material balance calculations of the initial stock tank oil in place are shown in Table I. The usual procedure in testing the application of material balance calculations is to compute the apparent initial volume of oil in place, using production and pressure information obtained at different time periods. If the apparent oil in place volumes computed increase with successive time periods, water encroachment is indicated and approximations must be mads to correct for its influence. The first requirement in utilizing such calculations is reliable reservoir pressure, accumulated gas, oil and water production, and PVT data. Calculations of apparent oil in place in the Jones Pool, based on field data

Jan 1, 1951

By A. R. Rosenfield, G. T. Hahn

The effects of adding 0.025 volume fraction of uniformly dispersed Tho2, particles (particle size -380A) to iron have been examined. The two-phase alloy is shown to have a lower transition temperature and higher cleavage stress than either the base metal or a solid-solution alloy (Fe-3Si). Enhanced cleavage resistance is thought to be a consequence of particles limiting the effective slip distance of dislocations and thus the ability of Pile-ups to act as stress concentrations. Further calculations predict that the highest cleavage strengths are attained with uniform dispersions, where the particle size is kept small (-250A) and the volume fraction is relatively large (-2 to 3 pct). ALTHOUGH a fine dispersion of second-phase particles is known to impart strength to an alloy, the possibility that it might also impart ductility has only recently been explored. Outstanding progress has been made in the production of ductile tungsten alloys containing Tho21,2or (Hf, Zr)C,= but the contribution of the dispersion to ductility has neither been optimized nor fully analyzed. The basis for such an analysis has now been developed1,5 and is discussed briefly below. Experiments on iron are also described that attempt to isolate one of the possible ductilizing mechanisms and test its effectiveness. In analyzing these experiments, it is important to remember that cleavage obeys a stress criterion, and that either a lower ductile-to-brittle transition temperature or a higher cleavage stress is evidence of enhanced resistance to cleavage. DUCTILIZING MECHANISMS Slip Blockage. Cleavage fracture of polycrystals may be initiated at the intersection of a slip band (or twin) and a neighboring grain or a large (-1 to 5 µ) particle. The slip band generates a stress concentration at its head, and either the grain boundary fractures, the particle fractures, or cleavage is initiated in a neighboring grain. Experimental evidence for this viewpoint is found in metallographic studies8-8 and from the observation that cleavage is usually preceded by yielding.8-11 The potency of a slip band as a stress concentrator

Jan 1, 1968

By E. W. Cawthorne, R. I. Jaffee, C. M. Craighead

SOLUTION of a solid metal or alloy in a molten metal bath is used daily in melting operations, extractive metallurgical processes, and in brazing. It is generally recognized that temperature, time, agitation, and the composition of the solute metal and the solvent bath all affect solution rate. However, there is little information available in the literature on the kinetics of the process or the relative effect that these variables have on solution rate. In connection with an aluminum brazing study, data on the solution of aluminum in an A1-Si* bath to promote rapid solidification. The chemical analyses were made on drillings taken from the cast plates. The results of this work are listed in Table I. The thermal-analysis data were obtained on 200 gram samples cooled at approximately 1.5" per min. A calibrated chromel-alumel couple was used. The thermal arrests were recorded autographically on a General Electric photoelectric potentiometer recorder. The instrument was calibrated to 22.5 pct. The thermal emf was bucked with a Leeds and Northrup semiprecision potentiometer so that 1 mv represented the full scale of the GE recorder. Referring to Table I, it will be noted that the analytical results tend to be lower than the intended compositions by about 0.3 pct Si in the higher ranges. In view of the known difficulties in obtaining accurate silicon determinations by wet analysis when the silicon content is high and in view of the care that was employed in weighing and preparing the alloys, the intended compositions are believed to be more accurate than the analyses. Furthermore, when the thermal-arrest data are plotted against the intended compositions, a smooth curve is obtained, as shown in Fig. 1. This is not the case when the data are plotted against the analytical results. It will be noted from Table I that the 12.5 pct Si alloy (melt 4) showed a primary arrest at 577.6"C and the eutectic at 576.l°C. The metallographic examination of this chill-cast plate sample showed a small amount of primary silicon. These results, Fig. 1, place the eutectic at slightly less than 12.5 pct Si and are in rather good agreement with the unpublished Hanford data. In all of the subsequent work, the composition of the A1-Si dipping baths was determined by thermal analysis (spread between the primary arrest and the eutectic temperature) employing 12.5 pct Si and 577.2 °C as the composition and temperature of the eutectic. Material Preparation and Selection of the Techniques: At the beginning of this work, it was anticipated that, owing to oxide film present on the surface of the aluminum, difficulty would be encountered in obtaining rapid uniform wetting of aluminum specimens dipped in the A1-Si bath. The following etchants were investigated as possible methods of providing a thin uniform oxide film on the specimen surface: 1—phosphoric acid (H³O4), 2—fluoboric acid (HBFI), 3—sodium hydroxide (NaOH), and 4—hydrofluoric acid (HF). Tests with sheet .specimens (2x½x0.06 in.) of 2s aluminum prepared with these etchants indicated that the fast uniform wetting required for this work could not be obtained if any oxide film existed on the specimen surface. Tests were then conducted by dipping similar specimens etched in 5 pct NaOH and given a thin

Jan 1, 1956

By R. F. Hehemann, Darrell W. Smith

The kinetics of alloying- in W-5 rot pct Re powder compacts were investigated at temperature about the upper limit for the formation of the x phase, such that a single intermediate phase was involved in the process. The rates and directions of motion of the a-o and o-b interface were assessed as functions of tinze at the sintering teri7peraticve by quantitative izetallog-ralhic techtziques. The iiotion 01 these interjuces could be specified approxitnate1.y by u Parabolic )-ate law and deviations from this ,rate law were attribuled to a complex interaction between surface dif'fusion and volume diffusion during the initial stages of sintering. WHEN binary or more complex alloys are produced by sintering compacted blends of elemental powders, a complication is encountered which does not arise in the sintering of pure metals. In addition to concern for grain size and densification, the rate of inter diffusion of the component elements must be considered. The general problem of alloying during sintering has been treated by numerous investigators.'-7 These investigations have been concerned only with systems that form continuous series of solid solutions and a concentric-sphere diffusion model4 provides a useful description of homogenization in these stems.' Some controversy remains, however, over the contribution of surface and grain boundary diffusion to the homogenization process. Heckel% ePorts that homogenization can be described by volume diffusion at all temperatures, whereas other invetiators'' recognize the importance of surface and grain boundary diffusion, particularly at lower temperatures. Analysis of the homogenization process in partially miscible systems is complicated by the motion of the interfaces separating the individual phases. A simple analytical solution does not exist for such finite systems with spherical symmetry. It was the purpose of this work to examine the kinetics of the formation and dissolution of an intermediate phase in a binary system through an assessment of the motion of the interfaces separating this phase from the terminal solid solutions. PROCEDURE The W-Re system is an example of a partially miscible binary system and was selected for study because of its current importance in refractory-metal technology. The equilibrium phase diagram, Fig. 1, shows that the o phase will be formed by interdiffu-sion between tungsten and rhenium. At temperatures between approximately 2125" and 282O°C, the o phase will appear as the only intermediate phase in the diffusion system. In this work, a mixture of elemental powders containing 5 pct Re was employed. In such a mixture, the rhenium particles will be distributed randomly in a tungsten matrix. During sintering, a o-phase layer will form at the W-Re interface. The development and subsequent disappearance of the o phase are controlled by the relative rates and directions of motion of the 0-0 and a-p interfaces. The motion of these interfaces can be inferred from quantitative metallographic measurements of the average radii of the o shells surrounding rhenium particles. Elemental tungsten and rhenium powders of commercial purity were employed in these investigations. The rhenium powder was spheroidized from +200 mesh agglomerates by plasma-arc spraying and was then classified to yield a powder composed of essentially

Jan 1, 1967

By A. R. Troiano, R. F. Hehemann

The influence of partial decomposition to high temperature bainite on reaction kinetics at a lower temperature has been studied in two alloy steels. Reaction at the lower temperature is retarded by the prior treatment, and the extent of decomposition may be reduced. Interpretation of these results is based on a mechanism involving a limitation in the nucleation and growth of bainite plates. OF the major transformations in steel, the characteristics and general behavior of the bainite reaction are probably the least understood and appreciated. Limitations of space preclude a critical evaluation of the present status of the bainite transformation in this presentation; however, such a treatment will shortly appear elsewhere. Only the salient features pertinent to the present investigation will be introduced briefly here. Although the reaction curve for the formation of bainite is similar to that for a nucleation and growth process, other kinetic features are more in keeping with the martensitic mode of transformation. A definite temperature exists above which austenite will not transform to bainite.1-5 his temperature, which has been designated B., is determined by the composition of the austenite. Unlike other nucleation and growth processes, the amount of austenite transformed to .bainite is a function of reaction temperature. The extent of decomposition increases from 0 at H. to 100 pct at some lower temperature.' , This lower temperature will be designated B1 and appears to be relatively insensitive to austenite composition.% 5 The similarity in the effect of reaction temperature on the bainite and martensite transformations serves to emphasize the close connection between these two decomposition processes. Austenite decomposition in the bainite range proceeds without partition of the alloying elements.8-11 Partition of carbon has been proposed" primarily on the basis that partial transformation to bainite lowers M, and increases the amount of austenite retained at room temperature. Carbon enrichment resuslting from such partition has been employed to explain the influence of reaction temperature on the extent of decomposition.'" It should be noted, however, that no enrichment has been detected experimentally in high carbon steels.1,14,15 Lattice-parameter measurements of retained austenite in steels containing 0.3 to 0.4 pct C have indicated carbon enrichment, 3,10-18 although the split indicative of a high carbon martensite has not been reported. Carbon enrichment, if it does occur, must be highly localized around the bainite plates. Therefore, carbon enrichment does not account for the influence of temperature on the progress of the bainite reaction."' Thermal history is known to influence the martensite transformation through stabilization.20,21 No similar phenomenon in the bainite transformation has been reported. Materials and Procedure Two triple-alloy steels were chosen for this investigation. Their compositions were as given in Table I. These steels were chosen because the pearlite reaction did not interfere with the bainite reaction. Steel K was received in the cast condition and forged from 2 in. square bars to 1/2 x1 3/4 in. plates. The 4340 was received as 11/4 in. hot-rolled rounds. Both steels were homogenized in vacuum for one week at 2300°F in order to minimize segregation. A quenching dilatometer similar to that described by Flinn, Cook, and Fellows" was employed for the kinetic measurements. Dimensional changes were detected by a differential transformer coupled with a high speed recorder. The dilatometer was mounted so that it could be transferred to any one of three furnaces: a nitrogen-atmosphere austenitiz-ing furnace and two salt-bath furnaces for isothermal transformation. Dilatometer specimens were 1/32 x 1/4x 1/2 in. with a gage length of 1.4 in. All specimens were nickel plated in order to minimize decarburization during austenitizing. The austenitiz-ing conditions consisted of 10 min at the temperatures given above. Austenitizing temperatures were controlled to 210°F and transformation temperatures to ±3ºF. The precision of the dimensional measurements was estimated to be ± 5 x105 in. per in. Results and Discussion Isothermal Transformation: The characteristics of the isothermal bainite reaction will be described

Jan 1, 1955

By R. L. Rickett, W. C. Leslie, W. D. Lafferty

Notch toughness of 0.10'pct C steels, rimmed or killed, is improved by holding the steel at a temperature just above the Ae,, followed by air cooling. The improvement can be gained without apparent change in gross microstructure or hardness. The limits of the process have been determined and some possible reasons for the observed effects are discussed. The results appear to indicate that the current theories of transition temperature are inadequate. THE effects of gross microstructural variables (ferrite grain size, austenite grain size, type and distribution of carbides) on the notch toughness of mild steels have been the subject of many investigations.'-' The results indicate that increasing ferrite grain size raises the notch-impact transition temperature. The transition temperature also rises with increasing size of pearlite colonies and with increasing prior austenite grain size, but these factors are not independent of ferrite grain size. The effects of gross composition of steels have also received considerable attention. As a result, manganese, nickel, aluminum, and silicon are known to improve the notch toughness of mild steels. The other elements that have been investigated—carbon, nitrogen, boron, copper, chromium, molybdenum, phosphorus, sulfur, titanium, and vanadium—reportedly are either deleterious or have little effect on notch toughness. Despite this large volume of work, it is still not possible to predict the notch toughness of a mild steel from its microstructure and composition, even when these are supplemented by hardness and tensile tests. Steels with equivalent microstructures, but different thermal and/or mechanical histories, can differ in notch toughness. Such factors as type and distribution of precipitates, substructure, local variations in composition, or unrecognized variables, may be important in determining the notch toughness of mild steels. However, quantitative knowledge of the effects produced by these factors is almost completely lacking. In an effort to improve this situation, an investigation was begun to determine the effect of a very fine precipitate on the notch toughness of low-carbon steels. Aluminum nitride was chosen as the precipitate because of its presence in aluminum-killed steels, the ease of control of precipitation, and past

Jan 1, 1961