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By R. K. Buhr, H. Thresh, M. Bergeron, F. Weinberg

The microsegregation of nickel and chromium in directionally solidified AISI 4340 steel castings has been measured using electron probe microanalysis. Minimum concentrations were observed to occur at the center of the dendrite stalks, as reported previously. However, the position of the maximum concentrations could not be determined from the dendrite configuration. An etching technique has been developed which shows the position of maximum concentration. Measurements were made of the distribution of nickel and chromium in the dendritic structure. The ratio of maximum to minimum concentration was determined as a function of primary dendrite arm spacing for both as-cast and partially homogenized materials. The results are compared with observations reported in the literatuve. A S part of an investigation of solute segregation in directionally solidified AISI 4340 steel casting, electron probe microanalysis was used to measure the distribution of nickel and chromium in the dendritically segregated material. This complemented the observations on the segregation of radioactive phosphorus obtained by autoradiographic techniques in the same castings.' Kattamis and I?lemings2 have reported similar measurements, using electron probe microanalysis, on dendritically segregated AISI 4340 steels. They found minimum solute concentrations occurred at the center of dendrites, maximum concentrations occurred in the center of interdendritic regions, for symmetrically oriented dendrites, and a regular variation of concentration within dendrite arms. The ratio of maximum to minimum concentration was found to be essentially independent of position in the castings, except near the chill surface where it was somewhat higher. Assuming complete diffusion in the liquid and no diffusion in the solid during freezing, they considered that isoconcentration curves in the steel were homothetic. As a result, isoconcentration curves of the various elements, contour surfaces of dendrites produced by isothermal-transformation studies, and the contour of the solid-liquid interface would all be similar, and could be superimposed by a uniform expansion or contraction of the contours. Preliminary results of the present investigation suggested that isoconcentration curves were not homothetic. It was also evident that points of maximum concentration could not be predicted from the dendrite configuration. Since the ratio of maximum to minimum concentration appeared to be an important parameter in defining the overall segregation in a casting, other techniques for determining the point of maximum concentration were investigated. In addition the overall solute distribution associated with the dendritic structure was examined for both nickel and chromium, and the consistency of the distribution for neighboring dendrites was determined. METHOD Fifty-pound heats of AISI 4340 steel were cast in a manner similar to that used by Flemings et al3 with a water-cooled copper base plate and exothermic sides and top. The nominal composition of the material was C, 0.41 pct; Mn, 0.66; Si, 0.35; S, 0.012; P, 0.010; Ni, 1.88; Cr, 0.95; Mo, 0.28. The steel solidified directionally from the chill surface, with a dendritic structure which increased in dendrite arm spacing with increased distance from the chill. Results of the general investigation of the cast structure and segregation of radioactive phosphorus in these castings have been reported elsewhere.' For the present measurements, sections were cut from the casting at several distances from the chill surface. The sections were subsequently heat-treated, mounted, and then polished on a plane perpendicular to the general freezing direction of the casting. Electron probe microanalysis was carried out with the JEOL-JXA3 microprobe using a voltage of 25 kev and beam current of 0.15 µa. The take-off angle is 22 deg. Quartz crystals were used in the spectrometers and measurements made for Ka radiation from both nickel and chromium simultaneously. A thin layer of carbon was deposited on all specimen surfaces prior to examination in the microprobe. Early measurements were made on polished surfaces, with indentation marks produced by a hardness tester to indicate the area of interest. It was found desirable to use etched surfaces, as opposed to polished surfaces, to reduce sample preparation time and more readily relate the microprobe scan to the structure. To determine if this could be done, without introducing significant errors, a series of measurements were made on polished and etched surfaces of the same specimen. Both polished and etched surfaces produced similar results within normal scatter as shown in the observations. Subsequent measurements were then made on etched surfaces. Measurements with the microprobe analyzer were made by point counting, for periods of 100 sec, at 10-µ intervals. Ten-second counts were made on pure nickel and chromium standards, incorporated in the specimen mount before and after each set of measurements. The results were adjusted for background, then corrected for dead time using the expression:

Jan 1, 1969

By William Wraith

At the Washoe smelter, Anaconda, Mont., the blister-copper from the converters is transferred, by means of a crane, to a re-fining-furnace, in which it is brought to proper pitch by means of air and poles. From this furnace the refined copper, containing gold and silver, is poured into cast-iron molds placed on a platform-convejor, giving an anode 36.75 in. long, 35 in. wide, and 2 1/16 in. thick. By reason of a disagreement between the smelter and the refinery, in reference to the silver-content of the anodes, it becanle necessary to investigate the methods of sampling used. 11. SMelter Method of SampliNg. At the smelter the sampling is done by " shotting " into water a small portion of the molten stream of copper as it flows from the furnace, by " batting " the stream'with a wooden paddle. The first sample is taken 30 min. after the pouring i.: started, three other samples being taken at 1-hr. interrals, each sample Weighing from 4 to 6 oz. The samples are dried, esamined for particles of burnt wood, screened on a 10-mesh screen of NO. 8 wire to remove the fines, the oversize then screened on a 4-mesh screen of No. 20 wire to remore the coarse, the undersize of this screen being taken as the sample. The four portions thus obtained are thoroughly mixed and split in half by passing over a 16-slot splitting-device, slots being 0.5 in. wide. One-half of the sample is sent to the laboratory for analysis and one-half kept as a duplicate. 111. Refinery Method of Sampling. The method used at the refinery and also used in this in1-estiyation is the one developed by Dr. Edmarcl Keller, of

Jan 1, 1911

By N. F. Mott

Jan 1, 1961

COUNCIL OF SECTION DELEGATES Nicholas A D'Arcy, Jr, Chairman (Southern California Section) Charles Chapman, Vice-Chairman (Florida Section) Ben H Parker, Secretary (Colorado Section) Frontier Refining Co Boston Bldg Denver 2, Colorado

Jan 1, 1956

Jan 1, 1893

Jan 1, 1915

By D. E. Swets, R. C. Frank

It is well known that hydrogen is introduced into iron or steel as a result of many chemical processes (acid pickling, electrolytic cleaning, plating, etc.). One of the reactions that has been of recent interest1 is the reaction between an iron surface and water vapor. It was shown a few years ago2-4 that hydrogen can be introduced into steel at an accelerated rate during abrasion as a result of this reaction. Grun-berg and Scott have also observed that water in mineral oil lubricants increases pitting failure in ball bearings5 and they have suggested that hydrogen from the water is the primary cause of this effect.' In this laboratory, the question was raised as to whether or not hydrogen is also introduced into the metal surface of a bearing as a result of the decomposition of the hydrocarbon lubricant itself, and an experiment was performed to try to find a satisfactory answer. All steel parts contain some residual hydrogen. Therefore, it appeared that the best way to carry out this experiment without the need for highly accurate quantitative analyses was to use deuterium as a tracer. The natural abundance of deuterium in H2 is only 0.015 pct. The tracer was obtained in the form of deuteroparaffin (CD,(CDJ, CD,) and 0.25 g were dissolved in 20 cc of mineral oil to form the lubricant to be used in the tests. The bearings used were New Departure Type QOLOO ball bearings with a ball diam of 0.187 in. Prior to adding the mineral oil-deuteroparaffin lubricant, the bearings were cleaned in warm trichloroethylene to remove the packing grease. After packing with the new deuterated lubricant, the bearings were operated in a bearing fatigue test machine under a radial load of 190 lb and a thrust load of 190 lb at a speed of 3800 rpm. The expected life under these conditions is about 500 hr. Two tests were made; one for a period of 27 hr and the other for a period of 102 hr. The bearings achieved a temperature of 120o F during the tests. When the tests were stopped the balls were mechanically removed from the bearings and were immediately placed in liquid nitrogen to reduce degassing until the analysis for deuterium could be made. Before analyzing, the balls were warmed to room temperature and scrubbed with several degreasing agents to remove all traces of the deuteroparaffin mixture. This cleaning procedure was shown to be satisfactory by running a control test in which one ball bearing was subjected to all parts of the test except running in the fatigue machine. The hydrogen and deuterium were removed from the balls using a hot extraction apparatus attached to a mass spectrometer. Four balls from each bearing were analyzed. Each one was analyzed separately by removing it from a cold storage volume of the hot extraction apparatus and transferring it to the oven tube with a magnet. As the gases were evolved they were analyzed with the mass spectrometer. Since the hydrogen and deuterium pass through steel in the atomic form and since there are many more hydrogen atoms than deuterium atoms in the sample, the probability of forming an HD molecule is greater than forming a D2 molecule. For this reason the evolution of HD and H was followed as each ball was placed in the oven. The results showed that as each ball from the test bearing was dropped into the oven, the mass spectrometer recording of the HD evolution increased by about ten divisions. When balls from the control test bearing were dropped into the oven, the increase was about one division or less. The hydrocarbon background in the mass spectrometer was also monitored to see if hydrocarbons or deuterocarbons were given off when the balls were dropped into the oven, but no change in the hydrocarbon peaks was observed. Since the balls contained a fair amount of residual hydrogen, isotope ratio measurements were made on the gas obtained from each ball. The D/H value found for those balls which had been operated in the fatigue testing machine was consistently about 0.3

Jan 1, 1962

By John Wulff, J. H. Hollomon

THE opinion has been widely held that the corrosion of alpha brass occurs by the selective solution of zinc. As late as 1939, Fink1 and Evans2 suggested that in the initial stage of the corrosion the selective solution of zinc produces copper-rich areas, which subsequently act as cathodes that facilitate the deposition of copper. Previously Abrams3 had shown that most of the copper found on corroded brass was redeposited and not residual, although he did not consider the nature of the initiation of the corrosion process. Enough data exist to indicate that any metal surface is sufficiently heterogeneous to provide the anodes and cathodes necessary for the initiation of corrosion.4,5 Thus, for alpha brass we need postulate not an initial selective solution of zinc, but only the existence of local differences in electrochemical potential. The heterogeneity responsible for potential differences may arise from oxide and other films as well as from alloy concentration gradients. Even though selective corrosion may be possible in some alloy systems, previous data on alpha brass as well as the experimental work reported in this paper do not require this supposition. Bengough and May,6 in a discussion of Abrams' paper, first suggested the addition of small amounts of arsenic (0.03 per cent) to alpha brass to prevent the redeposition of copper (dezincification). This suggestion was later substantiated by Nixon.7 In their studies of the inhibiting influence of arsenic, Evans and Fink were led to the selective-solution hypothesis in order to explain the initial corrosion of such alloys. They believed that an arsenic film covered anode areas and prevented the formation of copper-rich spots capable of acting as cathodes for the deposition of copper. They did not consider, however, the mechanism by which the arsenical film was formed. Bengough and May,8 in another publication, suggested that the commonly found gray or black arsenical film may act to: (I) carry oxygen to the brass surface, (2) increase the discharge potential of copper on brass, (3) precipitate cuprous chloride from colloidal suspension in chloride solutions. Masing9 assumed that the film found upon arsenical brass was metallic arsenic. His measurements of hydrogen overvoltage of bulk arsenic led him to believe that the inhibition of dezincification occurs because the overvoltage of a brass surface is lowered by the arsenic film. He reasoned that this film would permit the more rapid reduction of hydrogen at the cathode, which would prevent the redeposition of copper. In a recent paper,10 we have pointed out that the film formed during the corrosion of arsenical brass and copper in stagnant solutions is essentially arsenious oxide (As203),

Jan 1, 1942

By Persifor Frazer

In his " Final Report," Vol. 11, part second, p. 763, Prof. Rogers sums up the metalliferous veins of the mesozoic sandstone by remarking that these are not associated with dykes or trap-rock, but are independent metalliferous injections. But singularly enough, in enumerating the different kinds of ores, no mention is made of

By K. Stout, E. Van Eeckhout, L. Friel

Previous research at the Montana College of Mineral Science and Technology indicated that it is practical and economically feasible to place stiff back- fill in a cut-and-fill stope. This backfill would reduce wall closure and high stress buildup in pi1llars, thus alleviating rockburst potential. Three ;topes from the Sunshine Mine, of the Coeur d’Alene Mining District, were chosen for a test verification of this concept. Although the first stope was lever mined beyond the initial cut (for economic reasons), some vibrating wire stressmeter results were obtained and found to compare favorably with numerical predictions. Some other instrumentation devices were built and tested, but never installed .

Jan 1, 1984

By A. Keil

TO measure the absolute conductivity of metallic specimens it is generally necessary to have exact geometrical shapes and good electrical contact with the test-piece. To overcome limitations of the standard methods, an electronic conductivity-meter* Trade name, Sigmatest; model Dr. F. Forster; Reutlingen, Ger-many. has been developed, which works on the principle of inducing high frequency eddy-currents in the specimens and measuring the reaction of these curients on a measuring coil.',' To attach the instrument to the test specimen, a flat area of about 10 mm diam is all that is necessary. The reading is taken off a scale calibrated in pet of International Annealed Copper Standard. The induced eddy-currents are propagated in a circular motion parallel to the surface. Thickness of the layer included in a measurement depends on the frequency used. With a frequency of 60 kc per sec, the penetration of the currents was 0.8 mm at the upper limit of the scale, and 2 mm at the lower limit. The method is limited to nonferrous metals and other applications have been described elsewhere." The object of the present investigation was to detect the formation and growth of surface layers of differing conductivity, and to determine the depth to which these changes could be observed. A well known phenomenon which illustrates the problem is the internal oxidation of certain silver alloys containing base metal solutes, such as copper or cadmium, when they are annealed in an oxidizing atmosphere.4, 5 Until now, the only methods available for following these phenomenon have been metallo-graphic examination and hardness tests.0, 7 Changes in mechanical properties of copper alloys by internal oxidation were recently discussed in a more general way by Martin and Smith." When measuring these conductivity changes it must be remembered that the only absolute values of conductivity are those of 1) the nontreated homogeneous specimen, and 2) the final values obtained with a surface layer of depth comparable to the penetration of the eddy-currents. All intermediate values refer to the mixed conductivities of the transformed surface layer and the untransformed alloy, and are thus readings of relative value only. Experimental Results Specimens were annealed for 1/2 hr at 800°C in hydrogen, and the internal oxidation was carried out by thermal treatment in air at 800°C. Fig. 1 shows the results of the first series of experiments. With internal oxidation of a solid solution of 8 pet Cd in silver, the conductivity rises continuously until the surface layer formed has become thick enough to be the deciding factor (about 400µ). Precipitates of CdO are mainly in the form of points, Fig. 2, and, as a result, the electric contact between the silver crystals is not distorted by them. Brine11 tests were run with a 1.25 mm ball and a 7.812 kg load. The specimen annealed in hydrogen and oxidized to a depth of 400µ had a hardness of 40 Bhn,

Jan 1, 1959

By John F. Elliott

STAFF: Editor, Gerhard Derge Acting Editor, Poul G. Shewmon Carnegie lnstitute of Technology Schenley Pork Pittsburgh 13, PO. Editorial Assistant, M. A. Redmerski Production Editor, Otto T. Johnson THE METALLURGICAL SOCIETY: Rich-ard C. Cole, President; Karl L. Fetters, Past-President; J. H. Scoff, Vice President; R. L. Henneboch, Treasurer, R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: R. E. Lund, Chairmon; T. E. Dancy, P. R. Gouwens, W. A. Krivsky, F. C. Longenberg, E. R. Morgan, R.R. Nosh, Poul Queneou, W.O. Philbrook, J. H. Scoff, L. L. Seigle, and M. E. Wadsworth. Review and selection of manuscripts is under the supervision of the following Publications Committees: Extractive Metallurgy Division: M. E. Wadsworth, Chairmon; R. E. Grace, Vice Chairman; D. H. Baker, Jr., G. M. Bell, D. H. Bridges, J. M. Cigon, G. W. Healy, R. A. Lewis, C. E. O'Neill, A. W. Schlechten, R. E. Shinkoskey, and W. W. Stephens. Iron and Steel Division: T. E. Dancy, Chairman; A. Muan, D.W. Murphy, R. D. Pehlke, J. M. Uys, J. 5. Wagstoff, and R. G. Word. lnstitute of Metals Division: R. R. Nash, Chairman, H. H. Johnson, Jr., Vice Chairman; M. R. Achter, P. A. Beck, J. J. Becker, G. F. Bolling, J. 0. Brittain, J. 8. Clark, R. 5. Davis, A. E. Dwight, R. W. Fountain, L. A. Girifalco, E. L. Harmon, J. J. Heger, A. A. Hendrickson, L. Himmel, J. P. Hirth, R. H. Richmao, H.C.Rogers, W. Rostoker, 0. D. Sherby. E. A. Steigawald, R. Steinitz, H. C. Stumpf, R. A. Swalin, W. A. Tiller, W. R. Upthegrove, D. Walton, H.W. Weart, and D. Wilsdorf. Published bimonthly by the American lnstitute 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;$30per $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 1963 by the American lnstitute of Mining, Metallurgical, and Petroleum Engineers, Inc....Registered cable address, AlME New York . .. Indexed in Engineering Index, Industrial Arts Index, and Chemical Abstracts . . Second class postage paid ot New York, N. Y., and Ann Arbor, Mich. Volume 227, Number 4.

Jan 1, 1963

By R. Stratton-Crawley

Flotation-related processes utilizing an oil phase for processing fine mineral particles have been described and various applications discussed. The problems associated with the techniques are varied, but may be summarized by the following areas; (1) applicability to fine particle beneficiation, e.g. collector extender and emulsion flotation. (2) major 'mechanical' problems, e.g. emulsion breakage and oil recovery in oil flotation. (3) complex interfacial chemistry, e.g. empirical nature of pigment flushing .

Jan 1, 1979

By Thys B. Johnson

Traditional mine planning concepts are discussed and suggestions for improvement through use of the developed model are proposed. The approach developed in this paper allows optimal planning of the complete mining-concentrating-refining system over the entire planning horizon and permits the system to dictate how and when to process a block of material, i. e., a dynamic cutoff.

Jan 1, 1969

By B. C. Allen

The solubility of chromium in liquid silver and that of molybdenum and tungsten in liquid tin have been determined by equilibrating Ike Liquid in a crucible of the solule metal. Generally the weight of solute in solulion was delermined both chemically and from crucible weight losses. The resulting weight percent solubilily of chromium in silver as a function of absolule temperature T is given by log w = -6660/T + 4.02 in the range 960° to 1445°C, and that of molybdenlttrl in tin by log w = —5050/T + 1. 79 in the range 1200° to 2200°C. The values appear unaffected by minor changes in solute composition. Calculations aye made of the parlial molar heal and excess entropy of mixing. The estimated solubility of tungsten in tin is 0.001 pct at 2000°C. Evidence is presented that molybdenwm dissolves in tin without compound for mation and that tungsten and tin form W10Sn. RECENT developments in coatings, heat transfer, and brazing require a knowledge of equilibrium solubilities in a variety of systems at elevated temperatures. Of particular interest are solid-liquid interactions in metal systems involving dilute solutions. This investigation was undertaken since little is known about the phase relations or solubility of chromium in liquid silver or of molybdenum and tungsten in liquid tin.1,2 EXPERIMENTAL WORK As indicated in Table I, high-purity metals or those of known impurity levels were used. Crucibles were machined from chromium, molybdenum, and tungsten bar stock 1.3 cm diam and 2.2 cm long. Chromium rod was prepared by arc melting and extruding iodide process crystals.3 The five chromium impurity alloys were in the form of 0.6-cm-diam swaged rod. A Cr-0.06N* alloy was prepared by exposure to NH3 at 1150°C in a closed quartz capsule for 24 hr. Because significant nitrogen was lost during annealing in argon at 1600°C,4 the estimated level was 0.01 pct N. Chromium and Mo,W crucibles were outgassed at 1200" and 1600°C, respectively, at 3 X 10-5 mm. The solvent was placed In crucibles of the solute metal- 6 g Ag in chromium, 0.4 g Ag in the five chromium impurity alloys, and 4 g Sn in Mo,W crucibles. The silver and tin series were outgassed at 900" and 110O°C, respectively, and held at the desired solution temperature in a tantalum resistance furnace under 1.05 atm 99.995 pct Ar. An equilibration time of 0.5 to 1 hr was chosen since 0.3-, I-, and 4-hr anneals at 1235°C for Cr-Ag yielded similar results. Temperatures were measured optically to +10°C under essentially black body conditions which were checked against the melting point of silver. The Cr-Ag and Mo-Sn,W-Sn series were respectively equilibrated at 990° to 1400°C and 1200" to 2000°C. Vaporization losses were generally held to <1 pct by the argon. In the 1800" and 2000°C anneals for 0.5 hr, the crucibles were placed in tightly sealed tantalum cans which kept tin losses to <5 pct. After the anneals, the specimens were furnace-cooled. One anneal was made on small Mo-0.02 C, Mo-0.5Ti-0.lZr, and tungsten crucibles containing tin at 2200°C. The metals were sealed in an electron-beam-welded tantalum can of minimum volume. After the anneal, tin was still present in each crucible, none of which was severely attacked. After equilibration, the saturated solvent metal was selectively removed from the crucible by acid leaching. Weight losses sustained by the crucibles were determined from the initial weight minus the final blank-corrected weight after acid leaching. Chemical analyses were performed on some of the samples. Hot 1:l HNO3-H2O removed silver from chromium with the blank running <0.1 mg or <0.002 pct on measured solubility. Tin was removed from molybdenum and tungsten by hot concentrated HC1 with the respective blanks amounting to -0.004 and -0.0004 pct in the presence of tin. The insoluble residues were weighed and checked for composition. The leaching solutions contained traces of the solute metals which were analyzed by colorimetric methods, Diphenyl Carbazide for chromium, Thiocyanate for molybdenum, and Dithiol for tungsten. The total of the two percentages found from the residue and leaching solution minus the blank gave the desired solubility values. On the basis of annealing empty molybdenum and tungsten crucibles, weight losses due to MoO3 or WO3 volatilization were found to be generally 10.4 mg and affect measured solubilities by <0.01pct. RESULTS AND DISCUSSION Chromium-Silver . Since no intermediate compounds are reported to form in the Cr-An system,&apos; crucible weight losses and chemical analysis of the entire melt should provide reliable measures of the chromium in solution. Values obtained by the two methods are in agreement as shown by the results for unalloyed chromium in Table II and plotted in Fig. 1. Furthermore, the results are consistent with those previously determined by melting equilibrated silver out of the crucible and analyzing calorimetrically for chromium.&apos; On the basis of limited thermal analysis data, the solubility of chromium in silver has been quoted as 8 pct at the monotectic temperature of -1445°C.1 This investigation indicates an extrapolated solubility of 1.38 pct which is believed to be more reliable. At the eu-

Jan 1, 1968

By S. K. Nicol, A. R. Swanson, J. C. Day

Addition of oil to a suspension of hydrophobic coal particles can influence its dewatering characteristics. An agglomeration process occurs in which coal particles are held together by negative capillary pressure at particle/oil/water contacts. Consequently, the units round which flow can occur are enlarged and this improves dewatering parameters such as drainage rate, solids recovery, and equilibrium moisture content. This paper discusses processes which attempt to use this principle, in terms of metallurgical and economic efficiency. The discussion is augmented by results of recent experiments on the effect of oil addition to centrifuges and vacuum filters.

Jan 1, 1980

By R. A. Meussner, C. T. Fujii

Chromium solution in wustite depresses the oxygen activity in a nonideal manner and expands the lattice slightly. Gravimetric measurements of the equilibrium compositions of wustite containing 0.00 to 1.38 wt pct Cr define the oxygen potential (CO2-CO atm) and the limits of the phase field at 1000°C. These data extrapolate to a maximum solubility of 2 wt pct Cr. The lattice parameter data, room-temperature measurements of quenched samples, differ significantly from those in the literature. Both pure and chromium wus-tites contract at uniform and equal rates as the oxygen content (metal deficit) increases. The a. US metal deficit relationships are straight lines showing none of the curvature previously reported. At constant metal deficit, the a. expands by 0.002? on alloying with 0.4 to 0.5 wt pct Cr but is insensitive to further chromium additions: a small expansion rather than a marked contraction. These results require a modification of the accepted alloying mechanism. IN the high-temperature oxidation of Fe-Cr alloys in Ha-H,and CO2-CO atmospheres the vapor transfer of oxygen from the continuous wustite outer scale to the porous inner scale/alloy interface sustains the high oxidation rates.1"3 The driving force for this transport is the difference in the oxygen activity of the outer wustite and that at the inner scale/alloy interface. In pure CO2, as well as in CO2-CO atmospheres, carburization of the alloy accompanies this oxidation. Current efforts to evaluate the parameters controlling this carburization have shown that the process is not simple; i.e., the carbon concentration in the alloy initially increases rapidly, reaches a maximum, and then decreases slowly as the oxidation time is extended. This is the same pattern reported by McCoy for the more complex oxidation-carburization of stainless steels and an Fe-Cr alloy in CO2 at lower temperatures.4 These changes in the carburization process occur while the overall oxidation rate and the lattice parameters of the scale layers remain constant. If this invariance of the lattice parameter is assumed to indicate a constant scale composition and thus a constant oxygen potential, the carburization results are not easily explained. Electron microprobe traces across the thickness of these outer scales, however, have revealed distinct chromium gradients penetrating 10 to 50 µ from the inner surface where the chromium concentrations were estimated at a few tenths percent. The variation of the chromium cmcentration on the inner surface of the scale, and the resulting change of the oxygen activity, during the oxidation process is considered to be important in defining the carburization process. Thus, to gain an understanding of the complex oxidation-carburization proc- ess, it was necessary to measure the properties of wustite containing known amounts of chromium (chromium wustite). Although the general features of the Fe-Cr-0 equilibrium diagram between 900° and 1300°C have been fairly well established by Richards and white: Wood-house and White,6 Seybolt,7 and Katsura and Muan,8 there have been no detailed studies of the limits of the chromium wustite phase field or the properties of these alloyed wustites. The recent results of a limited study of chromium wustite by Levin and wagner9 indicate that more than 0.67 wt pct Cr is soluble in wustite above 850°C and that this alloying is accompanied by a substantial lattice contraction. This change in the lattice parameter was not evident in the X-ray diffraction patterns of wustite layers from the oxidation experiments;1,3 the lines were sharp even though a chromium gradient existed in the scale. The present paper describes gravimetric equilibrium experiments which delineate the boundaries of the chromium wustite single-phase field at 1000°C and define the changes in the oxygen activity and the lattice parameter of wustite as functions of chromium and oxygen contents. The lattice parameter data of chromium wustite obtained from these equilibrium and special quenching experiments differ considerably from those reported.9 Those for pure wustite show significant differences from the widely accepted data of Jette and Foote.10 Since the causes of these differences are not easily assignable, and since the literature contains many sets of data on wustite which if not in conflict are at best not in harmony, the experimental procedures are discussed in the present paper. EXPERIMENTAL Oxide Preparation. The specimens used in these studies were porous pellets compacted from high-purity (Fe,Cr)2O3 or Fe2O3 powders. These powders were prepared from electrolytic chromium (99.8 pct purity) and electrolytic iron purified by consumable-electrode, vacuum arc-melting processing (299.9 pct purity).11 The oxides were produced by standard analytical procedures: solution of the metals in acids (HC1, then HNO3 added), coprecipitation of the hydroxides (NHaOH), and filtering and washing these precipitates. Initial dehydration of the coprecipitated hydroxides was done in a porcelain evaporating dish heated by a Meker-type burner, final dehydration by firing in a recrystallized alumina crucible at 1000" to 1050°C for 20 hr in an electrically heated furnace. Spectrographic analysis detected the following impurities: silicon, 0.01 pct or less; aluminum, 0.001 pct to trace; manganese and copper, 0.0001 pct to none. Each of these levels is at least one order of magnitude lower than in commercially available CP grade ferric and chromic oxides. Fluorescence analy-

Jan 1, 1969

Executive.. CHARLES F. RAND, Chairman. JAMES F. KEMP, JOSEPH W. RICHARDS. ALBERT R. LEDOUX, BENJAMIN B. THAYER. Membership. BENJAMIN B. THAYER, Chairman. WALTER R. INGALLS, JOHN H. JANEWAY, Jr., JOHN D. IRVING, HERMAN A. PROSSER. Finance. EDWARD L, YOUNG, Chairman. KARL EILERS, JAMES GAYLEY. Library. JAMES F. KEMP, Chairman. JOHN HAYS HAMMOND,3 E. GYBBON SPILSBURY,2 ALES. C. HUMPHREYS 4 BRADLEY STOUGHTON.

Jan 7, 1913

By Mungo Park, C. Baring Horwood

This paper is intended, in the light of recent investigations, to call attention to some of the essential features of good practice in sampling and mine-valuation. Mine-sampling may be divided broadly into two classes: (1) development-sampling and cornputatioll of ore-reserves; and, (2) stope-sampling and estimation of stope-values. Development-Sampling. It is with development-sampling only that this paper deals— the term development being taken to mean the opening-up of a mine by cross-cuts, drives, connections, etc., preparatory to actual extraction of the ore for milling. In development-sampling the work of the sampler and the consequent estima-

Jan 1, 1909

By L. G. Jones, A. S. Odeh

A theoretical developtment is presented which provides a straightforward method of handling the drawdown analysis for both oil and gas wells flowing at variable rates. In the past our inability to analyze variable-rate drawdowns has been a major obstacle in using them for formation evaluation. This method should permit wider use of these tests in the future. INTRODUCTION Pressure build-up analyses are widely used to obtain reservoir data such as the effective flow capacity of the formation. On the other hand. although pressure drawdowns have been run for a long time, they have not been used extensively to evaluate reservoirs because they are difficult to analyze. One of the difficulties in analyzing pressure drawdowns has been that the theory developed until now has required the test to be run at a constant rate. For both oil and gas wells this is a difficult requirement to satisfy. especially during the early period of a well&apos;s life when drawdown tests are usually run. In spite of this limitation, drawdown tests are often run with build-ups as a check. In this paper a theory, which handles the drawdown analysis for variable rates, is presented for both oil and gas wells. Thus, one of the biggest deterrents to running drawdowns is removed, and they should become a much more useful engineering tool in the future. THEORETICAL CONSIDERATIONS 011, RESERVOIRS The general equation used for describing the unsteady-state radial flow of slightly compressible fluids in homogeneous porous media can be written in cylindrical coordinates as where r is the radial distance in cm, t is the time in seconds, p is the pressure at r and t in atmospheres, + is the fractional porosity, p is the viscosity in cp, c is the compressibility in vol/vol/atm, and k is the permeability in darcies. There are a number of solutions of Eq. 1 for various boundary conditions. One of these is the so-called "point-source" solution, which approximates the case of an infinite oil reservoir with a well located at r = 0 and produced at a constant rate. The point-source solution of Eq. 1 is

Jan 1, 1966