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BUFFALO J R Atkinson, Chairman (Hamilton, Ont, Canada) C E Moyer, Vice-Chairman H A Morlock, Secretary CHICAGO H Erler, Chairman (Gary, Ind ) M E Nickel, Vice-Chairman A M Kroner, Secretary-Treasurer CLEVELAND C W Cravens, Chairman (Cleveland) E J Sobey, Vice-Chairman E Kondas, Secretary Leo Svete, Treasurer

Jan 1, 1958

By M. Nicholas, D. M. Poole

The diameters of sessile drops have been found to increase linearly with time in five reacting binary metal systems. The spreading rates of the drops are markedly dependent on temperature and on prior alloying of the solid with the lower melting point metal, hut are independent of the drop volume, wetting atruosphere , solid-surface roughness, and prior alloying of the drop with the substrate metal. A mechanism has been suggested that relates the linear-spreading rate to lateral diffusion of the liquid-metal atoms into the solid at the drop edge. An Arrhenius- type equation has been derived that describes the temperature dependence 0) the spreading rate, and although the agreement between the actual and the predicted pre-exponen-tial terms is poor that between the activation energies is excellent and the variation in the spreading rate of copper on Ni-Cu alloys produced by different extents of alloying can be predicted with considerable accuracy. CHEMICAL interactions frequently change the wetting behavior of solid-liquid systems causing, for example, "secondary spreading1 of sessile drops beyond the size defined by the surface and interfacial tensions of the unreacted components. The kinetics of the contact-angle decreases associated with this spreading are similar for many systems, but few studies have been made with the objective of determining whether the similarities are a reflection of a common mechanism. Some workers2,3 have assumed the secondary spreading is controlled by changes in the liquid surface and liquid-solid interfacial tensions and hence by the composition of the liquid, and contact-angle changes measured by the vertical-plate technique have been used to follow the course of liquid-solid chemical reactions.4 Other processes that have been invoked to explain these time-dependent changes in specific systems include the removal of adsorbed gas from the liquid-solid interface.5 penetration of containment layers on the solid Surface,6 interdiffusion,1,7 reori-entation of the solid surface into a wettable configuration: vapor-phase transport of the liquid onto the solid in advance of the drop,9 and, from vertical-plate studies. capillary flow between oxide layers and the solid surface.10 One of the reasons for the profuseness of these suggestions may be the complexity of the contact-angle change kinetics. However, in an analysis of secondary spreading gold and copper on UC,11 it was found that the diameter of the contact area between the sessile drop and the solid surface showed a simple linear increase with time although contact-angle changes were more complex. To check whether the linearity was merely fortuitous! additional exploratory work was conducted with four reacting metal-metal systems: Au on Ni. Cu on Ni, Cu on Fe, and Ag on Au. Linear spreading was observed in every case even though the kinetics of the contact-angle changes were complex. A further detailed study of the kinetics of linear spreading of five reacting metal-metal systems has been made with the object of determining the mechanism involved. The influence of variables such as temperature, drop volume. and the initial composition of the drop on the linear-spreading rate has been measured and compared with those predicted by a number of possible mechanisms. The systems employed in this study (Cu and Au on Ni and Pt, and Ag on Au) were selected because of the availability of potentially relevant chemical and physical property data. the simplicity of their phase diagrams at the wetting temperatures, and the ease of experimentation. EXPERIMENTAL TECHNIQUES The purities of the metals used in the study were: copper, 99.9 pct; gold. 99.96 pct; nickel, 99.2 pct; platinum 99.99 pct; and silver, 99.999 pct. The wetting tests were performed in a split tantalum tube vacuum resistance furnace of a conventional design. The furnace element was held vertically and was 1 $ in. in diam and 6 in, long. Viewing ports were provided in the water-cooled chamber to enable the specimens to be observed in both the horizontal and vertical planes. The temperature in the hot zone of the furnace could be held at 1500" i 5°C for an indefinite time. The surfaces of the solid-plaque metals were ground flat on Microcut paper and both the sessile drop and substrate metals were ultrasonically cleaned in methyl alcohol prior to their insertion in the furnace. After loading, the furnace was pumped down to a pressure of 2 x 10-5 mm of mercury and degassed for 30 min at 900° to 950°C. The temperature was then increased at more than 100°C per min to that used in the wetting test. The vacuum at the wetting temperature was better than 5 x 10-5 mm of mercury. Dewetting and retraction of the drop on cooling did not occur and the contact-area diameters, therefore, were measured after solidification with a vernier traveling microscope. The diameters quoted later are arithmetic means of ten measurements. The standard error of the mean never exceeded 3 pct and was often less than 1 pct.

Jan 1, 1967

By Jei Y. Choi, Paul G. Shewmon

The surface self-diffusion coefficient of copper (D,) has been measured between 847° and 1069 "C for six different orientations. These were the(111), (110, (100, and three higher index surfaces. The activation energy for Ds (designated Q s) was found to be about 49 kcal per mol for all six surfaces, and Do about 2 x 104 sq cm per sec. At any temperature Ds varied by no more than a factor of three over these orientations. It is shown that, if the free energy of a surface atom is uniquely determined by its number of nearest neighbors, it follows from the Principle of microscopic reversibility that Qs should have the same value for all surface orientations, and Ds should vary little with orientation. This model also suggests that for clean fee metals Qs ~ 2/3 AH, (heat of vaporization). This is true for copper. ALTHOUGH it has been appreciated for several decades that atoms can diffuse more rapidly on a surface than through the bulk of a crystal, it has only been in the last few years that reliable values of the surface self-diffusion coefficient (Ds) have become available. Tracer studies of Ds had been attempted prior to this period, but when a tracer is placed on a surface, an ever increasing fraction of it is drained off into the lattice. The correction for this loss involves a very difficult, and as yet unperformed calculation. Those who have worked with tracers have not corrected for this loss.1, 2 Thus their results indicate that Ds is greater than the self-diffusion coefficient in the lattice (Dl), but it has not been established that they give quantitative data on Ds. A procedure which avoids the problem of tracer loss is to study the rate of mass-transfer under the effect of surface tension. If the surface asperity being studied is very small, the mass transfer occurs entirely by surface diffusion. The kinetics at which a grain boundary groove forms on an initially plane surface is a well-studied case of this type. The smoothing of a slight scratch in an otherwise flat surface is another procedure that has been studied. If these grooves are up to 20 to 30 µ in width, the dominant mechanism for mass transfer is surface diffusion (at least in the case of metals with low vapor pressures), and the widths can easily be measured with an interference microscope. Of these two, mass-transfer techniques only in the case of grain boundary grooving has a rigorous mathematical treatment been given. This was done by Mullins.3,4 His analysis predicted that in the case of copper in an atmosphere of an inert gas, surface diffusion should be the dominant transport mechanism. This analysis gave an equation for the groove profile and predicted that the width of the groove would increase as (time)1/4. Mullins and Shewmon showed that both of these predictions agreed with experiments.5 Thus the validity of the values of Ds given by this procedure seems to be well established. Gjostein has used copper bicrystals and the grain boundary grooving technique to determine Ds and the activation energy for surface selfdiffusion (9,) in the [001] direction on surfaces ranging between the (100) and (110) planes.= He reported that Qs = 41 kcal per mole and Do = 6.5 x 102 sq cm per sec for all orientations studied. Since the results did not change with the dew-point of the dry hydrogen atmosphere or the type of refractory tube used, he concluded that the surfaces were clean, or at least that the results were not influenced by any impurities chemisorbed from the atmosphere. The work reported here reproduces and extends Gjostein's study in that D s and Q s were determined for copper over a wider range of orientations. To study the effects of impurities, two purities of copper were used as well as cathodic etching to remove any possible electropolishing film. Gjostein postulated that the diffusing atoms on a surface near a low index plane are the few atoms which are adsorbed on the smooth region between ledges or steps in the surface. A more rigorous derivation of the equation relating Ds to the concentration and jump frequency of these adsorbed atoms is given here. Using this treatment, our empirical observation that Q s and D s are essentially the same for all surface orientations can be shown to follow from the assumption that the free energy of a surface atom is uniquely determined by its number of nearest neighbors. The studies of D s using the scratch technique have been carried out by Blakely and Mukura on nickel,' and by Geguzin and Oveharenko on copper. The latter study using copper gives values of D s roughly

Jan 1, 1962

By W. C. Winegard, J. E. Gruzleski

The stages in the development of cells in the Sn-Cd eutectic have been studied by unidirectionally solidifying specimens under known conditions of growth rate, temperature gradient, and impurity concentration. By means of a quenching technique, the shape of the solid-liquid interface during solidification could be observed. Cells are shown to develop from defects or depressions which exist on the solid-liquid interface of even a pure eutectic. Th,e container wall, grain boundaries , and fault lines in the micro structure play an important role in cell development. A two-phase eutectic dendrite found at high impurity concentrations is described. L HE cellular or colony structure formed during eutectic solidification caused much confusion among early workers in their attempts to classify eutectic structure, and a major advance in our understanding of eutectic solidification was made when the colony structure was identified with a cellular interface caused by the presence of impurity elements.1'2 To date, however, no detailed investigation of the stages in cell development in eutectics has appeared, and little work has been done on the cell morphology. The present paper presents the results of such an investigation. EXPERIMENTAL The Sn-Cd eutectic was used in this investigation with lead as the impurity element to promote cell formation. Materials of 99.999 pct purity were zone-refined to an approximate purity of 99.9999 pct. Alloys as close as possible to the eutectic composition, 67.75 wt pct Sn, were prepared using zone-refined tin and cadmium. The alloys were then zone-melted to the exact eutectic composition, as described by Yue and Clark,3 using a total of twenty to twenty-five passes on each eutectic bar. Only those portions of the bars which contained no primary phases were used in subsequent experiments. Master ternary alloys were prepared by melting together the required amounts of lead and the Sn-Cd eutectic in a sealed Pyrex tube under argon, and these alloys were then diluted with pure Sn-Cd eutectic as required. Unidirectional solidification was conducted vertically upward using the two-element resistance furnace shown schematically in Fig. 1. With this apparatus, it was possible to obtain a range of growth rates and temperature gradients so that the cell structure could be studied under different growth conditions. Growth rates in the range of 0.4 to 9.1 cm per hr and temperature gradients from 2.25° to 1475°C per cm were used. To ensure steady-state solidification, power to the furnace was stabilized, and the entire apparatus was enclosed in a large box in which the temperature was controlled to within ± 0.2°C. The apparatus was arranged so that the specimen could be quenched in situ during solidification by pouring a large quantity of water down the central vycor tube. Excellent delineation of the solid-liquid interface at the time of the quench was obtained because of the structural changes accompanying the rapid solidification of the remaining liquid. The quenching rate was always extremely rapid as no evidence of a transition in the lamellar spacing at the interface was ever observed. The alloys to be solidified were contained in degassed, high-purity graphite tubes, 1 cm OD and 0.6 cm ID. The specimens were about 18 cm in length. After the alloy had been cast into the tubes, three 0.8-mm holes were drilled in the tube to the center of the specimen. One hole was placed 1 cm from the bottom of the ingot, and the other holes were placed at 8 and 9 cm, respectively, from the base of the ingot. Thirty-four-gage chromel-alumel thermocouples were sealed in the holes. The lower thermocouple was used to position the solid-liquid interface at the start of each experiment,

Jan 1, 1969

By E. Posnjak

IT is rather the general belief that acidified, solutions of ferrous salts are readily oxidized when in contact with air, and often elaborate pre-cautions are taken to prevent it. This, however, is not the case and several statements may be found in the literature expressing surprise at the extreme slowness with which oxidation takes place when air or oxygen is bubbled through such a solution. Thus C. Baskerville and R. Stevenson1 "observed with surprise" that no oxidation apparently took place, as shown by titration with 0.5 N KMnO4, when a stream of air was passed for 3 hr. through an acidified solution of ferrous ammonium sulfate or ferrous sulfate. The same authors state that even the presence of salts such as. cobalt, chromium, copper, manganese, etc., which usually act as oxygen carriers, had "no effect upon the oxidation as was observed by passing air for 3 hr.. through solutions of Mohr's salt acidified with sulfuric acid." While this statement will bee proved further on to be at least partly incorrect the slowness of the oxidation of ferrous salts alone has been previously established by McBain.2 His investigation also showed that the rate of oxidation increases markedly with an increase in the concentration of ferrous sulfate as well as that of oxygen; the concentration of free acid had a comparatively small influence, which in the case of sulfuric acid was to retard slightly the rate of reaction. More recently R. Thomas and E. T. Williams3 investigated the catalytic effect of nitric oxide on the oxidation of ferrous salts, which had been earlier patented by McCulloch.4 They found that the probable mechanism of the catalytic action was the oscillation of the catalyst between two stages of oxidation and its interaction alternately with the oxygen and the ferrous iron.

Jan 12, 1926

By John Chipman, Raymond L. Orr

Recently reported high -temperatlnre thermal data have been incorporated in a reuieu' of the therinody-r~ar,zic propesties of iron. The recent data permit mot corlsisterlt and reliuble choices to be made for many of the pvoperties, resnlling in bettev eslablished tabrtlations of the thermodynamic functions. Values of Cp, h°t- - H°298. s°t - S2sa, and (G°T -H298/T are tabulated for -the solid and liquid phases of iron in both stable and melastable regions. Consistency of the tabulations has been maintained to the precision necessr~vg to yield the Gibbs energy change belween the bcc (a, 8) and fcc (y) phases of iron at temperatures pertinenl to alloy studies. THE importance of the metal iron has stimulated many investigations of its thermodynamic properties at elevated temperatures. Reviews and summaries of the data have appeared from time to time. Among these the 1951 paper of Darken and smith' deserves highest recognition for the quality of its criticism and for the precision and thermodynamic consistency of its tabulations. These and the more recent table of Kaufman, Clougherty, and weiss2 reproduce the Gibbs energy of the (a, 6)--Y transformation with sufficient sensitivity for alloy studies. Other recent compilations of equal validity3-' make no attempt to do this. Since this Gibbs energy change is not greater than 22 cal per g-atom over the temperature range 1100° to 1800°K, it is obviously desirable to tabulate values of (G°t - H298)/T to four places of decimals even though the absolute accuracy would not warrant such precision. The necessity for reconsideration of the problem is emphasized by the recent publication of several important researches on the enthalpy and heat capacity of iron. The older work is well-covered in the reviews cited and will be mentioned here only when actually employed in the tabulations. GAMMA IRON Transition temperatures are taken from the selec -tions of Elliott and Gleiser,5 based on the work of Boulanger7 and earlier workers. For the a-y (A3) transition at 1184°K we retain the value 215 cal per g-atom adopted by Darken and smith.' It has received confirmation in the recent work of Dench and Kubaschewski,' and of Braun8 using adiabatic calori-metry, and of Wallace, Sidles, and Danielson10 using a pulse heating technique. The enthalpy data of Olette and ferrier" and of Anderson and Hultgren12 at higher and lower temperatures may be extended to 1184°K to give the following values which are adjusted to the required value of ? 1184 Ha,1184 Ha 298 = 8030 cal per g-atom [11 hr,1184-ha298 = 8245 cal per g-atom [2]

Jan 1, 1968

By Glenn A. Keep

THIS paper is not an announcement of the successful conclusion of the Cerro de Pasco Copper Corporation's pacos-pyrite problems, but merely a description of the commercial-scale, intermittent-roasting operations conducted by the writer, J. H. Lucas and others of the staff. It was prepared by request, for presentation at the February meeting of the Institute. The results obtained in Peru confirm the 1-ton-a-day experiments completed about three years ago at Kearny, N. J. by C. C. Gordon and Mr. Lucas, where it was first demonstrated that a mixture of about 80 per cent. pacos ore with 10 per cent. pyrite ore and 10 per cent. salt could be roasted intermittently in a small 1-ton-a-day Holt-Dern furnace without extraneous fuel, producing porous calcine that could be leached rapidly. Mr. Keep and his staff, by successfully introducing improvements in the construction of the commercial furnace and in their handling of material, have established beyond doubt a low cost for roasting. The other steps in the process of treating pacos and pyrite ores have not as yet been demonstrated as sufficiently conclusive to warrant their acceptance for a permanent plant. Cerro de Pasco Ores The ores of the Cerro de Pasco Copper Corpn. at Cerro de Pasco, Peru, are situated at an altitude of 14,000 ft. The town and mines are served by the Cerro de Pasco Railroad, which operates between Cerro de Pasco and Oroya, the site of the company's copper and lead smelters. Table 1.—Average Analysis of Cerro de Pasco Ores Pacos Ore Pykite Ore Silver, oz............................................... 10.3 12.0 Gold, oz................................................ 0.007 0.01 Lead, per cent........................................... 1.7 1.8 Copper, per cent......................................... 0.19 0.27 Zinc, per. cent........................................... 1.4 1.02 Iron, per cent........................................... 13.4 34.45 Silica, percent.......................................... 61.8 24.5 Alumina, per cent....................................... 2.5 0.62 Lime, per cent........................................... 1.5 0.20 Manganese, per cent..................................... 0.42 0.09 Sulfur, per cent,.......................................... 1.1 34.2

Jan 1, 1929

By Mario L. Villa

Another increase in production and the discovery of new pools arc the outstanding developments of the year 1937. Production in 1937 totaled 16,354,706 bbl., compared to 15,457,953 bbl. in the previous year, an increase of 5.8 per cent, of which 5 per cent was due to the Yacimientos Petroliferos Fiscales (Argentine Governnlent Oil Fields) and 0.8 per cent t,o private companies. Table I shows that the most important gain in output was obtained in zone B of Comodoro Rivadavia, partly offset by a 5.7 per cent decrease in the Neuqu6n district. The fields of Salta and Mendoza show an increase of 4.4 and 39.1 per cent, respectively. The determination of bottom-hole pressures was started by Yaci-mientos Petroliferos Fiscales (Y.Y.F.) in Comodoro Rivadavia and

Jan 1, 1938

By R. Simon, L. Yarborough

This paper presents a correlation for predicting the critical pressures of gas-solvent-reservoir oil systems of the type encountered in gas and solvent injection processes. Experimental data from 14 systems were used to develop the correlation which expresses critical pressure as a function of composition, C7+ mol weight, and C7+ characterization factor. Critical pressures predicted by the correlation for the 14 gas-solvent-reservoir oil systems have an average deviation of 2.8 per cent of the experimental values. The correlation war used to study a wide variety of other hydrocarbon mixtures reported in the literature whose critical conditions are in the range of interest in oil recovery work (100 to 280F and 2,000 to 6,000 psia). Critical pressures predicted by the correlation had an average deviation, expressed as per cent of experimental value, of 5 per cent for 20 miscellaneous mixtures from the literature, and 6.4 per cent for I7 methane-butane-decane mixtures reported by Sage and Lucey. INTRODUCTION Predicting critical points of hydrocarbon mixtures is an important part of phase behavior calculations. If the critical point can be predicted for a specific mixture, the separation between the bubble-point and dew-point regions will be defined, and physical properties of the mixture can be calculated by using the principle of corresponding states. Numerous correlations for predicting critical points of hydrocarbon mixtures have been published. Six of these correlationsl-8 were for light hydrocarbons, and two correlations7,8 ere for high boiling-point petroleum distillates. Organick9 And Eilerts" presented correlations which combined the published data from both light and heavy mixtures, and these correlations became the only available methods for predicting critical pressures for wide boiling range mixtures. In the course of the authors' work on secondary recovery by gas and solvent injection, experimental data were obtained for 14 mixtures of dry gas, ethane-propane-butane solvents, and various reservoir oils. The critical pressures and critical temperatures of these gas-solvent-reservoir oil systems were in the range of 1,900 to 4,800 psia and 180 to 265F. The critical pressures predicted for the 14 mixtures by the correlations of Organick and Eilerts had an average deviation from the measured values of about 13 per cent. The authors felt that it was necessary to develop a better correlation for engineering calculations and the resultant correlation, which is presented on Figs. 1 and 2, predicts the critical pressures of the 14 mixtures with an average deviation of 2.8 per cent. The validity of the correlation was tested by applying the correlation to other hydrocarbon mixtures reported in the literature. This subject is discussed later in the paper. The authors feel that there is also a need for an improved critical temperature correlation for gas-solvent-reservoir oil systems. However, developing a critical temperature correlation is a significant study in itself and is not included in this paper. EXPERIMENTAL DATA The compositions and critical points obtained by the authors for 14 gas-solvent-reservoir oil mixtures are shown on Table 1. The methane concentrations in these mixtures varied from 20 to 63 mol per cent. The intermediate hydrocarbon group, consisting of ethane, propane, and butane, varied from 20 to 64 mol per cent, and the concentration of the C,, fraction from 10 to 20 mol per cent. The physical properties of the C,, fraction covered the range from light, paraffinic, nonasphaltic (Mixtures 5, 6, 7, 8, 9 and 10) to heavy, aromatic, and asphaltic (Mixtures 13 and 14).

By P. Barnes

(Read at the Philadelphia Meeting, February, 1878.) IT may be of interest, and perhaps of importance, to the members of the Institute that specific mention should be made in detail of the great value of this method of copying or photographing all kinds of tracings.* Several samples are laid upon the table which may serve as illustrations of the results obtained. Some of these show slight imperfections, depending upon the character of the tracing, and upon the length of the exposure to the light, but it may be clearly seen that even a faint copy would be quite available for actual use. The process is believed to be of French origin, and has been used for many years. Special attention seems to have been directed to it recently, and its great value to engineers appears likely to be fully recognized. The manipulations required are of the simplest possible kind, and are entirely within the skill and comprehension of any office boy who can be trusted to copy a letter in an ordinary press. These particulars may be summarized somewhat thus 1. Provide a flat board as. large as the tracing which is to be copied. 2. Lay on this board two or three thicknesses of common blanket, or its equivalent, to give a slightly yielding backing for the paper. 3. Lay on the blanket the prepared paper with the sensitive side uppermost. 4. Lay on this paper the tracing, smoothing it out as perfectly as possible so as to insure a perfect contact with the paper. 5. Lay on the tracing a plate of clear glass, which should be heavy enough to press the tracing close down upon the paper. Ordinary plate-glass of ill thickness is quite sufficient. 6. Expose the whole to a clear sunlight, by pushing it out on a shelf from an ordinary window, or in any other convenient way, for six to ten minutes. If a clear skylight only can be had, the exposure must be continued for thirty or forty-five minutes, and under a cloudy sky, sixty to ninety minutes may be needed. * The introduction of this process into the United States is due principally to Mr. A. L. Holley, who first drew the attention of American engineers to its simplicity and convenience. Mention was also made of the process at the meeting of the Institute in New York, in February, 1877, by Mr. Ogden Haight.

Jan 1, 1878

By John Johnston

THIS necessarily brief sketch will attempt to summarize the high lights of perhaps the best meeting so far held by the Iron and Steel Division. All sessions were well attended and the discussion was vigorous and of a high order. The technical sessions opened. on Tuesday morning. "Precipitation Hardening of Copper Steels" was discussed by Cyril S. Smith and Earl W. Palmer, and dealt with steel with a 1 per cent copper content. Discussion brought out that there were no fabricating difficulties, but that the surface might be somewhat checked due to intergranular penetration of copper which could be easily taken care of. Probable advantages of steels of this type for high temperatures were pointed out. "An Improved Nickel-chromium Hardened Chilled Cast Iron," by J. S. Vanick, described a wear-resistant cast iron and evoked a lively discussion.

Jan 1, 1933

By B. C. Wonsiewicz, W. W. Wilkening

Following a procedure proposed by Wheeler and Ireland, Plane stress yield loci were constructed from Knoob hardness numbers. Basically, six differently oriented hardness measurements were made on three orthogml surfaces through pure poly crystalline magnesium sheet, a magnesium single crystal, and sheet of the magnesium alloys: Mg + 0.5 pct Th, Mg + 4 pct Li, AZ31B, and EKOO. Hardness loci were found to be in poor agreement at small strains (E < 0.05) with loci established by a more rigorous technique. At larger strains (E - 0.10) the agreement is fair, but at this stage in deformation the conventional locus has lost much of the asymmetry that characterizes these anisotropic materials. Two effects which will lead to distortions in the Khn locus are discussed with reference to the geometry of plastic flow during a hardness test. DETERMINING a material&apos;s resistance to multiaxial loading is of interest not only from a structural design viewpoint but also from that of deformation processing. Unfortunately, the determination of the yield locus, although simple in principle, involves tedious procedures if the results are to be at all rigorous.&apos; The idea, first proposed by Wheeler and 1reland2 of determining the yield locus by means of six Knoop hardness impressions along the principal directions in a material has obvious appeal. It is simple, quick, and should be applicable to very thin sheets. If such a technique could be demonstrated to produce consistently reliable results, it would be of interest to both researcher and designer. Lee, Jabara, and ackofen have compared the yield locus determined by Knoop hardness measurements (the Khn locus) to a locus determined by more rigorous techniques. They found good agreement for two titanium alloys at a plastic strain of about 1 pct. The purpose of this paper is to investigate if the Khn locus construction is a reasonable approximation to the locus of a highly anisotropic material. Examples of such materials are magnesium and magnesium alloys which have severely distorted yield loci which in turn reflect markedly dfferent yield strength in different directions.&apos; In pure magnesium, for example, the yield stress in tension along the transverse direction may be four times the yield stress in compression in the same direction and twice the tensile yield stress in the rolling direction. Predicting such large differences ought to serve as a severe test of the Khn locus construction. EXPERIMENTAL PROCEDURES Samples of rolled sheet, 0.250 in. (6.35 mm) thick, of pure magnesium and four magnesium alloys (Mg experimental materials. The pure magnesium together with the lithium and thorium alloys were those used in the study of Kelley and Hosford. The grain size was ASTM number 4 for the pure magnesium and number 6 for the alloys. HARDNESS TESTING The materials were sectioned along the rolling and transverse planes, mounted in a quick setting resin, and mechanically polished. Most of the hardness tests were performed on a surface prepared by electro-polishing (30 pct nitric acid in methanol at 0°C and 20 v) with the exception of the AZ31B and EK00 alloys which were made directly on a metallographically polished surface. However, subsequent hardness tests on the same sample after heavily electropolishing, revealed essentially the same hardness as before. At least twenty Knoop hardness impressions under a 100-g load were made in each of the six orientations shown in Fig. 1. The average hardness number and standard deviation were then calculated for each orientation. CONVENTIONAL LOCUS CONSTRUCTION Yield loci were constructed using a technique described in detail by Lee and ackofen,&apos; in which the flow stress (stress at a given plastic strain) fixes the coordinates of a point on the locus and measurements of the strain ratio serve to establish the slope of the locus at that point. The loading paths which correspond to uniaxial tension or compression tests establish the four intercepts of the locus with the coordinate axes plus one point on the balanced biaxial tension line Tensile testing was performed along the rolling and transverse (r, t) directions. Samples had a uniform rectangular gage length 1 by 4 by 4 in. (25.4 by 6.35 by 6.35 mm) and were deformed at a strain rate of 3.33 x 104 sec-&apos;. The tests were interrupted periodically to unload the sample and measure the plastic strains by means of X-Y post yield strain gages. Compression tests in the rolling, transverse, and through-thickness (r, f, z) directions were performed on 1/4 in. (6.35 mm) cubes at an initial strain rate of 8.33 x sec-&apos;. Lubrication was provided by 0.002 in. (51 pm) Teflon sheet which was renewed after unloading for micrometer measurements used to calculate the strains.

Jan 1, 1970

By W. D. Forgeng, R. L. Folkman, D. C. Hilty

The solubility of oxygen in molten Fe-Cr alloys has been determined at 1550° , 1600°, and 1650°C for alloys containing up to alloyshasbeenabout 50 pct Cr and found to decrease as chromium increases to 6 pet and then to increase gradually. Phase relations in the Fe-Cr-0 system at steelmaking temperatures have been evaluated and two previously unreported oxides have been identified. OPERATIONS in the melting and refining of chromium steels are dependent to a major degree on the reactions of chromium and iron with oxygen and are primarily directed toward controlling and modifying these reactions to secure maximum advantage in the utilization of chromium. Although fairly effective practices have been developed empirically, understanding of the specific reactions is limited. Moreover, the ability of molten steel to dissolve oxygen that subsequently precipitates as oxide inclusions during solidification is well known, so that clarification of the effect of chromium on the nature and mechanism of formation of these inclusions is desirable. Study of the problem indicated that increased knowledge of the fundamental Fe-Cr-0 system is essential to further technical and economic improvement. Consequently, an investigation of the influence of chromium on the solubility of oxygen in molten iron and of phases and phase relations in the Fe-Cr-0 system was undertaken at the Metals Research Laboratories of the Electro Metallurgical Co. as part of a general program on the effective utilization of chromium in chromium steel production. Experimental Procedure All of the experimental runs made during this investigation were carried out in the rotating crucible induction furnace which has been described in detail in a previous publication.&apos; In review, the principle underlying this furnace is that rotational forces in the crucible cause the molten metal to assume a concave shape in such a manner that the slag is contained in the molten metal cup, thereby minimizing slag/crucible contact and subsequent reaction. Practically all of the heats were melted in commercial-quality magnesia crucibles of the type usually furnished for laboratory induction furnaces. All of the runs were made under an argon atmosphere after the furnace chamber had been degassed. Bath temperatures were controlled by Pt—Pt-10 pct Rh thermocouples. The basic furnace charge consisted of a premelted 12 to 15 lb electrolytic iron slug which had been cast to a shape convenient for fitting into the rotating furnace crucible. A typical analysis of the electrolytic iron slugs is given in Table I. For certain runs, it was desirable to melt down charges containing high initial chromium contents. In these cases the chromium was added to the electrolytic iron during the premelting operations. Chromium was added to the rotating furnace bath in the form of electrolytic chromium of the analysis given in Table 11. In all of the constant temperature runs, the standard procedure was to melt down the electrolytic iron or alloy slug under vacuum, admit argon to slightly greater than atmospheric pressure, and adjust rotational speed to develop a well formed "cup" on the bath surface. The melt was then saturated with oxygen by an addition of ferric oxide and the temperature of the bath adjusted to within +5°C of the desired level. At this point the heat was permitted to come to equilibrium prior to sampling or further addition. This time interval was varied from 15 min to 2 hr but generally was about 20 min. After sampling, the desired chromium addition was made and the bath again equilibrated prior to subsequent sampling. This cycle of addition and sampling continued for the duration of the run which lasted from 4 to 8 hr. At the end of this period, power was shut off and the bath allowed to solidify in the furnace. Quenched metal samples were taken from the equilibrated melts by means of the "Taylor sampler" which has been described by Taylor and Chipman.&apos; Before being submitted to chemical analysis, all samples were carefully examined for surface slag occlusions and cold shuts. Later in the study, each sample was radiographed and examined metal-lographically in cross-section to determine the presence of internal defects. On the basis of these examinations, sound and apparently clean specimens were selected from the Taylor samples for chemical analysis.

Jan 1, 1956

By J. E. Gruzleski, O. Knacke, M. J. Meixner

The evolution of CO from small specimens of solidifying steel was investigated using a thermobalance technique. Gas evolution begins in the temperature range between 1400" to .1450°C. This behavior is independent of the initial carbon content and the cooling rate. At a constant temperature above 1220°C, the rate of gas evolution is temperature independent. Out-gassing of the specimen is thought to proceed through small channels formed by the coalescence of bubbles between dendrites. LIQUID metals have a higher solubility for gas than the solid. During freezing, these gases form bubbles which may either escape or remain trapped in the solid. Recent work1 on the evolution of oxygen from solidifying silver showed that the gas is not liberated until a large fraction of the melt has solidified, and that the gas is evolved in an almost explosive manner. Because of the commercial importance of CO evolution in solidifying steel, a similar investigation was undertaken to study the mechanism of gas liberation in steel. EXPERIMENTAL The thermogravimetric method of Knacke and eixner1 to follow gas evolution by weight changes was employed. Weight differences of 0.1 mg could be reproducibly measured on specimens weighing 2.5 g. These specimens were taken from alloys with varying carbon contents from <0.01 to 0.11 wt pct and <0.01 wt pct of each of silicon, manganese, and aluminum. Specimens contained in 8 mm ID magnesium alumi-nate crucibles were heated to 1550°C under 1 atm of very pure (99.995 pct) CO with a tungsten resistance furnace. The specimen temperature was measured with a Pt-Pt/Rh thermocouple located directly beside the crucible. It is felt that the temperature thus measured was within 5" to 10°C of the specimen temperature since on fusion the weight of the specimen increased due to uptake of CO, and this weight increase was always observed to begin within the temperature range of 1530" to 1540°C. Even after 3 hr there was a small weight increase with time indicating that the molten specimen was not completely saturated with CO. Therefore, complete saturation was not attempted, and all specimens were simply held for 3 hr at 1550°C before cooling. Two types of cooling experiments were performed. One consisted of continuous cooling at linear rates from 5°C to 20°C per min down to 1020°C. The second type of experiment involved continuous cooling at 10°C per min to a predetermined temperature, and then holding the specimen at this temperature for a certain time. During all of these experiments, the sample weight was recorded as a function of time and temperature. OBSERVATIONS Continuous Cooling Experiments. No gas evolution was detected above 1450°C. The initial weight decrease always occurred between 1400" and 1450°C with the average at 1430°C. With further cooling, gas evolution continued to about 1150°C. Between this temperature and 1020°C no further outgassing was observed. This behavior did not seem to depend on the initial carbon content nor on the cooling rate in the range investigated. Typical patterns of gas evolution are shown in Figs. 1 and 2 for different initial carbon levels and cooling rates. The total amount of gas liberated during solidification varied with the rate of cooling. The total weight change on continuous cooling at a rate of 10°C per min

Jan 1, 1970

By H. E. Exner

This article is a critical review of the influence of surface preparation on crack formation at Vickers indentations in the test used by Palmqvist3-7 to evaluate the toughness of cemented carbides. Experimental results are presented which clearly show that grinding introduces compressive surface stresses into the cobalt phase and thus reduces the crack length. The deformed surface layer is removed by polishing and a stress pattern is approached corresponding to that in the bulk material. Cracks of maximum length are characteristic of this stress state. Deformation stresses can be removed by annealing above 800°C. On the basis of these results , sample preparation for the crack length test can be simplified, the accuracy of measurement is improved, and a simple and significani parameter is found to describe crack resistance of cemented carbides. FOLLOWING suggestions by Ammann and Hinniiber,1&apos;2 Palmqvist3-7 developed a method for testing the toughness of cemented carbides using as a measure the sum of crack lengths at the four corners of a Vickers hardness indentation. This method has several advantages over the bend test commonly used in carbide technology: a) specially formed samples are unnecessary; b) sufficient information can be obtained from one sample; c) the scatter is relatively small; d) the range of actual values for commercial cutting alloys is wide. Thus, this test is both cheaper and more precise than the bend test. Nevertheless, Palmqvist&apos;s method is not widely used, mainly for two reasons: a) The relationship between crack length and the technological properties of the material (wear and shock resistance) is not clear. b) The crack length is strongly dependent on surface treatment. It is necessary, therefore, that surface preparation be very precise and reproducible, conditions usually hard to obtain. While any other simple mechanical test has this first drawback, the second became crucial in the application of the crack length method as a practical test. The reasons that this drawback could not be eliminated are, in our opinion, misleading and inconsistent interpretations of the influence of surface preparation on the crack length given in literature. In the following, after a short review of previous experimental results the interpretations given by different authors,4?&apos;-11 cf. Table I, are discussed critically and a consistent explanation is presented on the basis of which improvements of the method of crack length testing are proposed. 1) PREVIOUS EXPERIMENTAL RESULTS In his first attempt to use the cracks at Vickers impressions as a quantitative measure of the toughness of cemented carbides, palmqvist3 calculated the work necessary to initiate cracks by the formula: Sk =k.Pk. [I] where k = numerical constant = 6.49, Sk = critical work to initiate cracks (gf cm), Pk = critical load (load necessary to initiate cracks) HV = Vickers hardness (kp per sq mm). The difficulties involved in experimental determination of the critical load were overcome by the observation that a linear relation holds between the applied load and the sum of the crack lengths at the four corners of the indentation. This linear function, given by Eq. [2] below, was confirmed by Dawihl and Alt-meyer9and by our experiments, see Fig. 1: I = a1.P +a2 [2] where 1 = sum of the crack lengths at a Vickers indentation, P = applied load, al, a2 = parameters dependent on the toughness of the alloy and the surface preparation. The critical load, Pk, is now given by a2, which can be obtained by extrapolating the load vs crack length line to zero crack length, see Fig. 1. This simple relationship, Eq. [2], led Palmqvist1,7 to a parameter which was more reproducible and easier to obtain experimentally than the critical work: the work, S300, put into the sample to produce an average crack length of 300 µm per indentation. This parameter is calculated using the formula: where the load, P3oo, giving a crack length of 300 µm, can be taken from the load-crack length plot, Fig. 1,

Jan 1, 1970

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By G. P. Pilling

The use of magnetic ore in the blast furnace is a subject of increasing importance. The end of the deposits of lake ore is in sight, although not imminent, and unless some new field is discovered, the use of magnetites will be an increasing factor in the iron production of the country. Enormous deposits of magnetic ore in the country that have been practically untouched contain ore of sufficient richness and purity to prolong materially our ore supply without extensive importation of foreign ores. Magnetic ores can be divided into three general classes: Fine un-sintered, or raw ore; raw lumpy ore; fine ore that has been sintered. Fine Unsintered Ore Typical analysis and screen test of this class of ore from the Adirondack region is as follows: Per Cent. SCREEN TeST pER Cent. Fe.................... 58.00 Remaining on 4 mesh........... 7.50 SiOz.................. 7.50 Through 4 on 8 mesh........ 13.75 Al,O,................. 1.60 8 on 10 meah........ 3.75 Baseg................. 2.77 10 on 20 mesh........ 22.50 P.................... 1.00 20 on 40 mesh........ 27.50 Mn................... 0.13 40 on 60 mesh........ 2.50 S..................... Trace 60 on 80 mesh........ 10.00 80 on 100 mesh........ 2.50 100 mesh........ 10.00 100.00

Jan 1, 1923

By G. Nabi, W-K. Lu

Cylindrical specimens of natural dense hematite were reduced to magnetite at atmospheric pressure in H2-H2O mixtures of known composition over the temperature range 1084° to 1284°K. The rate of reduction was measured by the rate of movement of the interface between hematite and magnetite. The diffusion of gases through the gaseous boundary layer, the magnetite layer, and the interfacial chemical reaction were all considered in the interpretation of experimental data. The mass transfer coefficient through the boundary layer was calculated using accepted correlations. Values of the chemical reaction rate constant and the diffusivity of hydrogen in the magnetite phase were determined. THE present investigation is concerned with the reduction kinetics of natural hematite to magnetite by H2-H2O mixtures in the temperature range 1084" to 1284°K at atmospheric pressure. This reaction is the first step in the series of topochemical reactions in the process of reducing hematite to iron. Kinetic information of the simple steps such as hematite-magnetite transformation is necessary in order to have a better understanding of the complex processes of hematite reduction in iron-making. It also has direct industrial significance because magnetic roasting is one of the most important methods in benefication of lean ore.&apos; Although many technical papers have been published on the process of magnetic roasting and iron oxide reduction, very little information is available in the literature concerning the fundamental nature of hematite reduction to magnetite by reducing gases. Hansen et al.2 reduced the dense synthetic pellets of high-purity oxide in CO-CO2 mixtures and determined the reaction rate by weight-loss method. They were able to interpret most of their results by applying the interfacial area control theory developed by Mckewan.3 In contrast, Wilhelm and St. Pierre,4 who studied reduction of hematite to magnetite in H2-H2O mixtures by weight-loss method, stressed that the resistance of the porous magnetite layer to the diffusion of gases cannot be neglected in consideration of the overall reaction rate. In the present study the contributions of interfacial chemical reaction, diffusion of gases through the magnetite phase, and the gaseous boundary layer to the overall reaction rate will be considered. APPARATUS AND PROCEDURE Hematite Specimens Preparation. Natural hematite ore from Vermillon range of Northern Minnesota was selected for the present investigation because of its high purity and thermal stability. Chemical analysis of five samples gave the following average values: 67.52 pct total iron (96.62 pct Fe2O3, 0.28 pct FeO, 0.03 pct metallic iron), 2.53 pct SiO2, <0.07 pct MgO, 0.03 pct CaO, 0.05 pct combined mixture, 0.07 pct loss on ignition, and 0.34 pct other. Cylindrical specimens of 0.93 cm in diam and 2.7 cm in length were drilled from slabs of ore with a water-cooled diamond core drill. These specimens were heated to 1000°C and furnace-cooled. Specimens with silica pockets developed large cracks. The uncracked specimens were heated a second time, and their surfaces were carefully examined with a microscope. Those with hairline cracks or surface inhomoaenitv-- were rejected. Preparation of H2-H2O Mixtures. H2-H2O mixtures were prepared by the combustion of H2-O2, mixtures in a pyrex glass chamber in the presence of a catalyst. Alumina pellets coated with palladium, supplied by Englehard Industries, were used as the catalyst. Purified grades of hydrogen and oxygen were used which were repurified by usual techniques. Hydrogen before entering the combustion chamber was passed through an activated alumina H2O absorption bulb, with copper turning at the top. The cover of this bulb was not made pressure-tight so that any pressure development in the hydrogen line would cause the cover to blow off and also the copper turnings would act as a flame arrester in the case of a flashback from the combustion flame. Oxygen flow rates were measured with a bubble flow meter after purification with 1 pct accuracy. Hydrogen flow rates were measured by "precision wet test meter" and the amount of unburnt hydrogen was accurately measured by a bubble flow meter, after condensing water vapor in the gaseous stream. The Pyrex glass bulb contained concentric Vycor glass tubes as shown in Fig. 1. Oxygen was prevented from diffusing into the hydrogen line by threading platinum wire through pores at the combustion end of gas inlet tube. The glass bulb was heated with a Kanthal heating wire pasted in asbestos paper. The surface temperature of the bulb was measured with a thermocouple and adjusted to remain at approximately 350°C. The gaseous reaction chamber also served as a preheater for gases to avoid thermal segregation. The following sequence of operation was adopted. 1) Nitrogen was passed through the outer concentric tube to purge the catalyst bulb of oxygen. 2) Hydrogen was introduced through the inner tube until a steady flow was obtained. 3) Oxygen was then introduced into the nitrogen stream passing through the outer tube. 4) When combustion had commenced and a flame was visible over the platinum wire, the N2 was turned off.

Jan 1, 1969

By A. M. Nicholas

WheN attempting to lift mill pulp containing a considerable percentage of wolframite, in an ordinary bucket elevator, difficulty was encountered from the tendency of the tungsten minerals to settle, on account of their high specific gravity. Lifts not exceeding 20 ft. (6 m.) could be accomplished without particular difficulty, because there was insufficient time for consolidation of the heavy minerals in the bottom of the bucket; but with higher lifts, the heavy tungsten minerals would settle so solidly that when the bucket turned over at the top of the elevator the contents could be only partially dumped. In this case it was necessary to lift the material a distance of 34 ft. (10m.); hence some means had to be adopted to prevent settling, at least to such an extent that the material could be dumped from the buckets. To reduce the carrying time to a sufficient extent would have required a belt speed of 475 ft. (144.7 m.) per minute, which was not feasible. It was decided to try, by vibrating the belt about midway of its span, to keep the material sufficiently agitated during elevation to prevent settling. Underneath the rising side of the belt was placed a 12-in. (30.48-cm.) idler pulley, 18 ft. (5.5 m.) up in the total lift of 34 ft. The idler pulley was set eccentric by % in. (19 mm.) and it was hoped that the vibration thus imparted to the belt, running at a speed of 280 ft. (85 m.) per minute, would prevent settling in the buckets. It was found that the pressure of the belt on the idler, due to the small inclination of the elevator, was not sufficient to overcome sliding on the idler, and the agitation was insufficient to accomplish the desired purpose. The idler was then connected to the drive shaft of the elevator through an intermediate pulley, gearing down to a speed of 20 r.p.m., so that a positive vibration was imparted to the belt; this imparted enough motion to the belt to prevent settling and the contents of buckets dumped satisfactorily. Protecting Elevator Belts When elevating, from the crusher, a rock which was very sharp and abrasive, considerable difficulty arose from cutting of the belt under-

Jan 1, 1918

By Daniel L. Murphy

The iron ore province of Quebec and Baffin Island trends from the southern shore of Baffin Island northeasterly through the Labrador Trough to Matonipi Lake, approximately 185 miles northwest of Seven Islands, but future geologic field studies will very likely extend the limits of the province to include the ferruginous and associated rocks of the Lake Mistassini area. Recent improvements in the beneficiation of low-grade iron ore have stimulated widespread exploration for deposits amenable to concentration, particularly along the southwest extension of the Trough. GENERAL LITHOLOGY Pleistocene and recent deposits of clay, sand, gravel and erratic boulders cover roughly 60% of the land surface. All of the bedrock is of Precambrian age (Table I). Paragneisses and paraschists together with metasedimentary iron-formation, marble and quartzite are abundant and, for the most part, appear to be metamorphic equivalents of the relatively unmetamorphosed rocks of the Labrador Trough to the north beyond the "Grenville Front." Bodies of amphibolite are widely scattered. A large portion of the metamorphic rock shows some degree of permeation by granite material as well as alteration by hydrothermal solutions. The youngest bedrock consists of a complex containing slightly altered ultramafic to monozonitic intrusives.

Jan 9, 1962