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By Rodney P. Smith

The diffusivity of carbon (0.1 wt pct C) in Fe-Nz alloys (0 to 100 pct Ni) has been determined for the temperature range 860° to 1100°C. As a function of nickel content, the diffusivity has a maximum near 60 pct Ni (the maximum diffusivity being about 1.3 times that in the absence of nickel); the activation energy has a maximum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The difference between the minimum activation energy and that in iron is about 3000 cal pev g-atom; Do has a minimum between 40 and 50 pct Ni and a maximum between 80 and 90 pct Ni. The results cannot be rationalized by an approximate thermodynamic treatment. THE diffusivity of carbon has been determined in a number of iron alloys over a limited concentration range. It seemed desirable to investigate a system which allows an extended range of alloy composition within a single-phase region. The Fe-Ni system is ideal in this respect, in that all alloys from 100 pct Fe to 100 pct Ni are fee in a convenient temperature range.&apos; The carbon diffusivity was determined by a decar-burization method. The experimental procedure was identical with that used to determine the diffusivity of carbon in y Fe-Co alloys.2 The experimental data are given in Table I. A small correction (order of a few percent) has been made to the measured carbon loss to correct for the carbon lost from the ends of the cylinders.&apos; Since the diffusivity of carbon varies with carbon content the measured diffusivity is an average value for a carbon content between zero (surface) and that at the center of the sample at the end of the decarburization periods. In making the correction in D to 0.1 wt pct C it is assumed that the measured D corresponds to the arithmetical mean of the carbon content at the surface and at the center of the sample at the end of the decarburization period.3 Since this correction is small (<4 pct in D) and since for our decarburization times the changes in carbon content at the center of the sample was small the mean carbon content could have been taken as half the initial value. It is further assumed that the change in D with carbon content for the alloys is the same as that for the diffusion of carbon in iron. From the data of Wells, Batz, and Mehl4 and of smith5 the correction of D from the mean carbon content to 0.1 wt pct C is 0.3 (0.1 - mean wt pct C). The results for iron are given in Ref. 2. Within the experimental error log Do.l%C for each alloy is a linear function of 1/T; the constants for the equation determined by the method of least squares are given in Table I. The deviations of the experimental points from the least-squares line are of the order of 2 pct in D. A comparison of our results for the diffusivity of carbon in nickel with those of other investigations is shown in Fig. 1. The lower curve in Fig. 1 is a linear extrapolation of values calculated* from the equation of Diamond6 for the relaxation time (temperature range 100° to 500°C). The results indicate a small increase in the activation energy over the temperature range 100° to 1400°C; however, it is difficult to say whether the change in Q is real or experimental error. Certainly the change in Q is less than the variation of 5 kcal per g-atom in the diffusivity of carbon in a iron.6 The experimental data for all the alloys are plotted in Fig. 2. As a function of nickel content the diffusivity has a maximum near 60 wt pct Ni at all temperatures investigated and possibly a minimum between 80 and 90 wt pct Ni for temperatures below 1000°C. The activation energy, Q, and log Do are plotted as a function of the nickel content in Fig. 3. Due to the limited temperature range of our experiments neither Q nor Do can be determined precisely; the activation energies appear to be consistent to ±0.3 kcal per g-atom; however the deviation from the absolute values may be considerably larger, see Table II. The Do values probably have little significance. The solid line for Do in Fig. 3 represents the values required to reproduce the experimental values for D when Q has values represented by the upper solid line The diffusivity of carbon may be expressed in terms of the mobility B22, the activity coefficient r2,

Jan 1, 1967

By V. B. Kurfman

Grain refinement of Mg-Al melts by carbonaceous additions has been attributed to nucleation by aluminum carbide. The effects of process and alloy variables are interpreted and predicted in terms of the dispersion and chemistry of this phase. The grain coarsening action of Be, Zr, Ti, R.E., chlorination, temperature extremes, and prolonged holding times is described. Measures necessary to insure an adequate dispersion of the catalyst are discussed. CARBON inoculation treatments have become fairly well known and used for grain refinement of magnesium alloys containing Al. Although there is general agreement that a nucleation process occurs, the process is not understood and the inoculants are used in a rather empirical fashion. The treatment is applied to the class of alloys containing 3 to 10 pct Al, i.e., AZ31A to AM100A. Typical methods involve melting, alloying, and adjusting the temperature to 1400° to 1450°F. Then 0.01 to 0.5 pct C as CaC2, C6C16, or lampblack is added by any convenient means, and the melt poured within 10 to 30 min. Investigators generally have been impressed by an assumed similarity of this refinement process to superheat grain refinement, which depends on heating approximately the same alloys to a temperature in the range of 1550" to 1650°F, then pouring promptly after the melt is cooled to the pouring temperature. Various predictions have been made that carbon refinement would replace superheating in commercial practice due to reduced process costs, but this replacement has not fully taken place because of production difficulties and conflicting observations. Davis, Eastwood, and DeHaven1 agree with Nelson2 and wood3 in suggesting that an excess of inoculant may be harmful. Wood however says that overtreat-ment is not a problem in production use of hexa-chlorobenzene inoculation, and Hultgren and Mitchell4 claim no evidence of harm from excess additions. Various grain coarsening reactions are known to occur, including the possibility of overtreatment mentioned above. Trace amounts of Be,2 Zr, and Ti may prevent refinement by either a carbon treatment or a superheat. Occasionally treatment with cl25 may cause coarsening, although the Battelle refinement process&apos; uses a CC14-C12 blend. Grain coarsening also tends to occur on holding at temperatures below 1350°to 1400°F, especially after a superheat treatment, and for this reason Nelson2 stresses the desirability of a refinement method useful at lower temperatures for open pot melting practice. Since a carbon treatment can be made to work at temperatures below 1400°F, it seems desirable to investigate the mechanism of the refinement and the mechanisms of the coarsening reactions in order to establish control conditions for use in commercial production. The identity of the nucleating phase must first be established and then the factors affecting its chemistry and physical dispersion must be determined. THE IDENTITY OF THE NUCLEATING PHASE Davis, Eastwood, and DeHaven suggested that the nucleating phase in this system is Al4c3,1 but Mahoney, Tarr, and LeGrand8 disagree, largely because they found no evidence of the compound in alloys after carbon treatment and because there is no indication that aluminum carbide should be unstable over the temperature range used in the superheat treatment. This latter objection is based on the assumption that both the carbon treatment and the superheat treatment introduce the same nuclei. Electron diffraction studies have been made to identify the nucleating phase. Samples of grain refined A292 have been selectively etched SO that clean surfaces are obtained and so that secondary phases are in relief. Electron diffraction patterns from these surfaces have established that the carbon treatment of A292 introduces into the metal a large number of small, plate-like particles with a structure very similar to Al4C3. In most cases, the plate-like nature of the particles prevented positive identification but in the cases where the identification could be made the particles proved to be AIN A14C3. However, enough variation in lattice constants was observed so that all compositions from pure A14C3 to the 50:50 solid solution A1N.Al4C3 were probably present.14 In A14C3 and especially AlN.Al4C3 the A1 atoms occur in layers within which they have the same hexagonal symmetry and spacing as the Mg atoms in a single basal plane of a magnesium crystal. The solid solution spacing lies between the 3.16 of AIN and the 3.3? for Al4C3, in satisfactory agree-

Jan 1, 1962

By Robert Baschwitz, John Chipman

The distribution of silicon between liquid silver and Fe-Si-C alloys has been studied at 1420oand 1530°C. The data are consistent with earlier studies. New data of Hager on the liquidus lines of the system Ag-Si and the distribution data are used to obtain the activity coefficient of silicon in both liquid phases. Data on the heat of mixing in iron permit accurate extension to 1600°C. Equilibrium data involving SiO2 and silicon in liquid iron together with revised data on the free energy of SiO2 are used to fix the activity of silicon in the infinitely dilute solution. The binary system exhibits strong negative deviation from ideality. At infinite dilution ? Si at 1600" is 1.25 x 10&apos;3, and at concentrations up to NSi = 0.4 the slope d InySi/dNSi has a constant value of r; = 13. It is found that logysi in the ternary solutzon is approximately but not exactly the same function of Nsi + NC as of NSi in the binary. The results are consistent with currently available data on the free energy of Sic and its solubility in molten iron. LIQUID solutions of the system Fe-Si-C have acquired considerable importance as the laboratory prototypes of blast furnace hot metal. Equilibrium studies involving such solutions and slags approximating those of the blast furnace have yielded useful information concerning the thermodynamic properties of blast furnace slags. In studies of this kind great importance attaches to a knowledge of the thermodynamic activity of silicon in the solution as a function of temperature and composition. An attempt was made by Chipman, Fulton, Gokcen, and askey&apos; to evaluate all of the pertinent data on this system and to deduce the desired relation between activity, composition, and temperature. These authors published data on the solubility of graphite and Sic in molten Fe-C-Si solutions and on the distribution of silicon between liquid iron and liquid silver. They showed further how the activity of silicon in very dilute solutions in liquid iron could be calculated from equilibrium data involving the molten alloy and solid SiO,. These calculations rested on the published thermodynamic properties of SiO, in- cluding its heat of formation which at that time was recorded as -209.8 kcal. This value has been under suspicion for some time and has recently been replaced by the concordant results from two independent laboratories2,3 which place the heat of formation of a-quartz at -217.6 kcal. This revision necessitates a re-evaluation not only of the activity of SiO2 in slag but also of silicon in molten iron. It is the purpose of this paper, therefore, to recalculate the activity of silicon, and in furtherance of this objective to present new data on its distribution between liquid Fe-Si-C alloys and liquid silver. HEAT OF SOLUTION OF SILICON IN IRON In order to determine the effect of temperature upon the activity coefficient it is necessary to know the heat of solution of silicon in iron as a function of composition. This is found in the data of Korber and Oelsen4 shown in Fig. 1. The curve corresponds to the following equation, which is of a form suggested by Wagner:5 Here AH is the heat absorbed in kilocalories in forming one gram atom of molten alloy from its molten elements and the N&apos;s are atom fractions. The relative partial molal enthalpies of the components, each referred to its pureliquid state and defined as zFe = aFe - PFe and zsi = HSi — -psi, are shown graphically. At low concentrations zSi = -28.5 kcal, in agreement with Kijrber and Oelsen&apos;s computation. This is in good agreement with the value of -29.3 kcal obtained by Chipman and Grant6 using an entirely different method. ACTIVITY AT INFINITE DILUTION From the known free energy of SiO, it is possible to obtain the activity of silicon in dilute solution in liquid iron from equilibrium studies. The heat of formation of a-quartz is —217.6 kcal and the heat capacity and entropy data are given by Kelley and ~ing.&apos; The free energy of formation of ß-cristo-balite at temperatures above the melting point of silicon is expressed by the following equation: Si(Z) + O2(g) = SiO2 (crist); AF" =-226,500 + 47.50T [I] The value of the deoxidation product for silicon [%Si] x [%O]2 at 1600°C according to Gokcen and chipmans is 2.8 x 10"5, in agreement with results of Hilty and Crafts.9 More recent works of Matoba,

Jan 1, 1963

By Michael Epstein, Daniel E. Rosner

Fume nucleation sufficiently close to vaporizing suvfaces can augment net vaporization rates into cooler environments. Environmental conditions favoring large vaporization rate enhancements are briefly discussed and a previous theoretical treatment of this nucleation phenomenon is generalized to account for the self-regulating effect of condensalion-heat release within the boundary layer. Despite kinetic limitations on homogeneous nucleation, and latent heat release, non-diffusive condensate removal processes appear to make possible large enhancements in steady-state vaporization rates, provided surface temperatures are well below the boiling point. When condensed phases vaporize (or dissolve) into cooler media, the diffusion-limited mass loss rate can be strongly influenced by the process of nucleation/con-densation (or precipitation) within the thermal boundary layer. This condensation process (which typically leads to mists or fumes in the case of evaporation into cooler gases) has the effect of steepening the vapor pressure profiles near the evaporating surface, since the condensation zone acts as a vapor sink. However. the resulting enhancement in the diffusion-limited evaporation rate can be estimated (as first done by Turkdogan1 for the case of molten iron/nickel alloys evaporating into helium) only if one has independent knowledge of the critical supersaturation, sCrit(T), required to homogeneously nucleate the vapor.* In a recent reformulation and generalization of the theoretical model of Ref. 1 it has been shown that, when log sCrit is approximately linear in reciprocal temperature, rather simple expressions can be derived4 for the ratio of the actual rate of vaporization j" to either the minimum (no condensation) rate j"min, or the maximum (equilibrium condensation) rate j"max In the present communication we wish to briefly report on further developments and implications of the formulation of Ref. 4, with emphasis on i) environmental conditions favoring large enhancements in vaporization rate, and ii) the self-regulatory influence of condensation heat release (neglected in Refs. 1 to 4) on predicted vaporization rates. Additionally, we take this opportunity to correct several misprints appear- ing in Ref. 4, and comment on Elenbaas&apos;s recent criticism5 of Ref. 1. MAXIMUM POSSIBLE VAPORIZATION RATE IN PRESENCE OF CONDENSATION A nonequilibrium theory is of interest because of the very large difference between the minimum (no condensation) and maximum (equilibrium condensation) vaporization rate. The magnitude of this maximum possible enhancement can be shown quite clearly by combining a result of Refs. 3 and 4 with the fact that for most liquids there is a simple relationship between the molar heat of evaporation, A, and its boiling point, i.e., A/(RTBp) = C, where the constant C, often called the Trouton ratio, takes on values not very different from 11.* More generally, for any substance (including The Trouton ratio (which for water is 13, for methane, 10, and so forth) will be recognized as the ratio of the molar entropy change upon vaporization (at TBP or Ttransf) to the unlversal gas constant R. Its near constancy reflects the fact that the change in atomic order upon vaporization depends only weakly on the kinds of molecules involved. those that sublime under ordinary conditions) we can define a characteristic transformation temperature. Ttransf, by a relation of the form Ttransf =A/(CR), and then examine the maximum possible evaporation rates as a function of how far removed from Ttransf are the surface temperature, Tw, and ambient temperature, T. Subject to the assumptions: 1) equilibrium vapor pressure, pv,eq, everywhere small compared to prevailing total pressure, p, and 2) negligible effect of condensation heat on temperature profile, the maximum enhancement ratio was found (Eq. [17], Ref. 4) to be: where, for most vapors, Nu/NuD (the ratio of heat transfer coefficient to mass transfer coefficient for the same configuration) is a number near unity.* Ex- *An alternative derivation of the Nu = NuD special case of this equation. revealing its validity for arbitrary velocity/temperature profiles in a laminar boundary layer, is given in Ref. 3. amining this result for a "Trouton substance", one obtains the results shown in Fig. 1, constructed for C = 11. Since we are concerned with vaporization enhancements (j&apos;max/J"min > 1) at surface temperatures below Ttransf, this area of interest is shown unshaded. One notes that at a fixed ambient temperature (hence, T/TtranSf) there is a unique surface temperature, 2T , at which j"max/j"min attains its peak value; moreover, the peak enhancement ratio, see dashed locus. Fig. 1, is: (NuA/NuD)(C/4)(Ttransf/T,). Hence, if Nu = NuD, when the ambient temperature is less than 1/4 of TtranSf the peak enhancement exceeds the Trouton

Jan 1, 1969

By C. G. Dunn, M. Sharp

IN twinned crystals of the face-centered cubic metals the lattice of one twin is a mirror image of the other in a common twin boundary. When several twins appear within large grain in a sheet specimen, the twin one boundaries form a set of lines at the surface of the specimen which coincide with (111) planes of the large grain. Furthermore, for twins of the same orientation, these lines are parallel. Generally, the presence of identically oriented regions with straight parallel boundaries coinciding with a (111) plane of the surrounding crystal is strong evidence for identifying the island regions as twins of the parent crystal. However, Fig. 1, which shows the macrostructure of a large grain of copper with island regions that satisfy these conditions. is not an illustration of (111) twins. Since the reverse side of the specimen has much the same appearance, it was thought at first that these regions, which appear dark in the macrograph, actually were twins. According to X-ray data, however, these regions are second-order twins of the large crystal. With regard to their formation, these second-order twins formed by secondary recrystallization in a cube texture matrix. Growth occurred in the direction of the arrow (see Fig. 1) as the specimen moved slowly into a gradient temperature furnace as described previously.&apos; Nucleation of the second-order twins occurred, therefore, on the ends facing opposite the arrow. If the origin of the second-order twins were due to repeated twinning, some first-order twin structure should be visible on these ends. This proved to be the case, as very small twins were readily found with the aid of a microscope, and probably could have been seen, in some instances, under ideal lighting conditions without aid of a microscope. Fig. 2 shows a cross-section view taken perpendicular to both the surface and the (111) trace of the parent crystal (visible as a straight boundary in Fig. 1) at the beginning point of growth of a second-order twin and where one first-order twin was relatively thick. In the micrograph, A is the large parent grain; B is the first-order twin of A; and C, which is a first-order twin of B; is a second-order twin of A. Between A and B and between B and C the major straight portions are traces of common (111) twin boundaries. The straight portion of boundary between A and C, however, is not a common crystallographic plane to the two lattices; it is a (111) plane of A and a (115) plane of C. Without considering the mechanism of twinning itself, the origin of the second-order twins may be accounted for in terms of repeated twinning and special growth characteristics. After each nucleation, a selective growth process can be thought of as favoring growth of the first-order twin in local spots only and favoring growth of the second-order twin to an extent comparable with that of the parent grain over relatively large areas in a way similar to that described for twinning in aluminum.&apos; It has already been pointed out that the boundary between the large grain (A) and the second-order twin (C), which is responsible for the straight boundary portions in Fig. 1, involves a (111) plane of A and a (115) plane of C. The same combination of planes is not only possible in first-order twins, but actually appears quite frequently.3 Their prevalence in first-order twins and their presence here in second-order twins, together with the necessary occurrence of a large number of common lattice sites at the boundary, is an indication that this combination produces an "energy cusp"&apos; boundary. (Energy cusp boundaries have been described by Shockley and Read.") The configuration of atoms near a {Ill), (115) boundary in first-order twins is of course different from the configuration near the same type of boundary in second-order twins. References 1 M. Sharp and C. G. Dunn: Secondary Recrystallization Texture in Copper. Journal of Metals (January 1952) Trans. AIME, p. 42. 2W. G. Burgers and W. May: Stimulated Crystals and Twinning in Recrystallized Aluminum. Recueil des travaux chimiques des Pays-Bas (1945) 64, p. 5. aD. Whitwham, M. Mouflard, and P. Lacombe: Discussion of W. C. Ellis and R. G. Treuting, "Atomic Relationships in the Cubic Twinned State." Trans. AIME (1951) 191, p. 1070; Journal of Metals (October 1951). 4 W. Shockley and W. T. Read: Dislocation Models of Crystal Grain Boundaries. Physical Review (1950) 78, p. 275.

Jan 1, 1953

By E. Teghtsoonian, E. M. Schulson

The tensile behavior of bcc ordered P&apos; AuZn single crystals (CsCl structure) has been investigated under varying conditions of temperature, composition, and orientation. Between -0.2 and 0.4 T, multi-stage hardening occurs fm stoichiometric and nonstoichio-metric crystals oriented near the middle of the primary stereographic triangle. At higher and lower temperatures, parabolic type hardening occurs, followed by work - softening at the higher temperatwes. Deviations from stoichiometry give rise to increased flow stresses. Multi-stage hardening was observed for most orientations, except along the [loll-[lll] boundary and near the [001] corner of the stereo -graphic triangle, where parabolic type hardening occurs. Along two slip systems, (hk0)[001] and (, operate simultaneously while in the [001] comer, slip occurs mainly on the system. Electron microscopy of deformed crystals revealed bundles of edge dislocations forming walls approximately Perpendicular to the glide plane. In general the plasticity of 4&apos; AuZn closely resembles the plasticity of bcc crystals. In recent years, considerable interest has arisen concerning the mechanical properties of the CsCl type intermetallic compounds Ag Mg,&apos;- Fe co,&apos; and Ni Al.&apos;-&apos; The compound P&apos;AuZn is structurally similar. It has a low and congruent melting point of 725"~,&apos;" remains ordered up to the melting point,16 and pos-esses a range of solid solubility from 47.5 to 52.0 at. pct Au at room temperature.15 The present paper reports the results of an investigation on the general tensile behavior of material in single crystal form. Some dislocation configurations characteristic of the deformed state are also reported. The results of a detailed study of the slip geometry in AuZn are presented in a separate paper.17 PROCEDURE Alloy preparation, crystal growing techniques, and the procedure followed in selecting specimens of minimum composition variation are reported elsewhere.17 Dumb-bell shaped tensile specimens were prepared by carefully machining single crystals in a jewellers&apos; lathe to a gage length of 0.80 in. and diam of 0.090 in. Back-reflection Laue X-ray patterns and room temperature tensile tests revealed that machining damage could be eliminated by electrochemically polishing 0.005 in. from the machined surface followed by annealing at 300°C for 1 hr. Specimens were polished in fresh 5 pct KCN solution (40°C, 12 v). Experiments were performed by gripping specimens in a self-aligning pin-chuck and threaded collet system, then straining in a floor model Instron tensile machine. All tests were performed in duplicate. Experimental variables included temperature, composition, and orientation. Unless otherwise stated the strain rate was 2.5 x 10"3 per sec. Liquid testing environments included nitrogen (WOK), nitrogen cooled petroleum ether (133" to 293"K), and silicone oil (293" to 488°K). Resolved shear stress-shear strain curves were electronically computed from autographically recorded load-elongation curves. Stress and strain were resolved on the macroscopic noncrystallographic (hkO) [001] system operative under the specific test conditions of temperature, strain rate, and orientation reported earlier.17 RESULTS The temperature dependence of the work-hardening curves is shown in Fig. 1 for gold-rich crystals of 51.0 at. pct Au oriented near the center of the stereo-graphic triangle. Over the range of intermediate temperatures from -200" to 400°K, they are very similar to those classically observed for fcc metals (reviewed by Nabarro et al.).&apos;&apos; The beginning of deformation is characterized by a region of decreasing hardening rate, stage 0, which is followed by a region of low linear hardening, stage I, and then a region of higher linear hardening, stage 11. At the higher temperatures, stage 111 is observed, a region of decreasing hardening rate. Over the intermediate temperature range, the extent of stage 0 and of the slow transition between stages I and I1 decreases with increasing temperature. Total ductility is large, often greater than 300 pct shear. As the temperature is either increased or decreased, the extent of stage I is decreased, giving rise to parabolic type flow and reduced ductility. Similar temperature effects have been reported for bcc ~r~stals.~~-~~ Below -14O°K, hardening is terminated in brittle fracture while above -400°K. initial hardening is followed first by work-softening and then by chisel-edge type ductile fracture. Stoichiometric (50.0 at. pct Au) and Zn-rich (51.0 at. pct Zn) crystals were also tested from 77" to -500°K. The effect of composition on the flow behavior is illus-

Jan 1, 1970

By David W. James, Howard Jones, George M. Leak

Conditions are described for producing, by primary recrystallization, a matrix suitable for the growth of large grains near (110)[001] orientation in silicon iron strip by secondary recrystallizaliun in a steep temperature gradient. The orientation distribution of these large grains is expressed in terms of rotational deviations about the cross-rolling direction, the rolling direction, and the normal to the sheet, the deviational spread increasing in that order. With the aid of cowplenientary published data on the orientation dependence of growth rate, it is shown that this observation is consistent with the oriented-growth theory of recrystallization lextures. It is conclutled that growth-rate and orientation-distribution data obtained in a steep thermal gradient should be used with caution to account for isothermally Produced recrystallization textures. SEVERAL authors have reported methods of growing large grains by re crystallization of a small-grained matrix in silicon iron 1- B and pure a cr The present study was a preliminary in the growth of single crystals and bicrystals for surface relaxation," grain boundary mobility, and grain boundary diffusion studies. The method was to control the growth of a seed crystal into a suitable primary re crystallized matrix by feeding through a steep temperature gradient. The driving energy for growth derived from the grain boundary energy released as the seed crystals grew into the matrix. Thus, stability of the matrix against normal grain growth was considered to be essential for success. It was known that the manganese sulfide dispersion present in commercial silicon iron performs this function during secondary recrystallization to the (110)[001.] texture.12 Hence commercial, rather than high-purity, material was used throughout. The paper describes the growth conditions for grains large enough to be used as seed crystals for further growth into single crystals. The orientation distribution of the seed crystals is analyzed and its significance for the theory of recrystallization textures is discussed. EXPERIMENTAL PROCEDURE Strip material was supplied by the Steel Co. of Wales, Ltd. The chemical analysis in weight percent was Si, 2.90; C, 0.015; Mn, 0.059; P, 0.011; S, 0.027; Ni, 0.032; 0, 0.009; Fe, balance. A gradient furnace of similar design to one described previously4 was loaned from B.I.S.R.A. It consisted essentially of a vertical water-cooled copper slot projecting downwards into the hot zone of a molybdenum furnace. Hydrogen was passed through the furnace to protect both heating element and specimen from oxidation. Strip specimens up to 8 cm wide and 0.2 cm thick were sealed into the furnace at the mouth of the copper slot. A coating of light oil on the strip surface maintained the seal during translation of a specimen. The maximum temperature gradient in the region just below the copper slot was 500°C per cm over 1 cm, with the hottest point controlled at 1175°C. Several large grains would usually grow by secondary recrystallization from the primary matrix when a specimen was immersed in the hot zone for about 30 min. A back-reflection X-ray camera was constructed to facilitate rapid and accurate orientation determinations of the large grains produced. It was possible to reproduce a standard geometry, with regard to strip and camera, without the tedium of careful alignment on each occasion. Specimens, typically 4 cm wide and 75 cm long, were cut with the longitudinal axis parallel to the rolling direction of the original strip. The surfaces were cleaned by immersion alternately in a hot aqueous solution containing 2 pct hydrofluoric acid plus 10 pct sulfuric acid and in cold 10 pct nitric acid. The nitric acid etch was just sufficient to reveal the grain structure. Rolling and annealing treatments to prepare the matrix (discussed below) were followed by growth of seed crystals in the gradient furnace. The matrix was transformed to a single crystal by growth of a selected seed crystal connected to the matrix by a thin neck. 4,5 Growth was promoted by controlled feeding into the gradient furnace. Several single crystals of controlled orientation were grown successfully from seed crystals by twisting the interconnecting neck in a reorien-tation jig.4 EXPERIMENTAL RESULTS AND DISCUSSION Growth Conditions. A suitable matrix for growth of large grains was prepared starting from primary re-crystallized strip 1.9 mm thick. This was cold-rolled in two stages each being followed by a recrystallization anneal at 800°C for a few minutes. Such treatment gave the required growth matrix only if the two cold-reduction stages were each performed in several passes and in the following ranges: the first, 30 to 70 pct; the second, 10 to 50 pct. Immersion in the temperature gradient otherwise resulted in an equiaxed

Jan 1, 1967

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy&apos; has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as &apos;idea1 gases,&apos; and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called &apos;ideal&apos; behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

By Paul F. Kerr, Raymond F. Robinson

Uranium mineralization occurs in the footwall of the Sunshine vein from the 2900 to the 3700 level. Veinlets of uraninite associated with pyrite and jasper have been so extensively divided and recemented that units more than a few feet in length are seldom observed. The wall rock is St. Regis quartzite of the Belt series. The age of the uraninite, on the basis of isotopic analyses, is 750 * 50, which agrees with geological data suggesting that phases of the Sunshine mineralization are pre Cambrian. THE Sunshine mine in the Coeur d&apos;Alene district, Idaho, is well known for its silver-bearing veins but prior to the summer of 1949 had not been recognized as a possible source of uranium. At that time, during a geiger counter reconnaissance by T. E. Gillingham, R. F. Robinson, and E. E. Thurlow, high radioactivity was noted and radioactive specimens were collected from the footwall of the Sunshine vein.&apos; The detection led to the identification of uraninite-bearing veins, since explored jointly by the Atomic Energy Commission and the Sunshine Mining Co. After the occurrence was noted, the geology of the uranium deposit was studied by the Sunshine staff, and a laboratory examination of the ores was conducted at Columbia University. Several types of laboratory work were undertaken. Differential thermal curves were made of selected siderite samples and results from many more were secured through the work of Mitcham.2 X-ray diffraction and X-ray fluorescence analyses were employed on uraninite, jasper, and siderite. Chemical analyses were made through the cooperation of the Division of Raw Materials of the Atomic Energy Commission. General Geological Features Several silver-bearing veins cut the overturned north limb of the Big Creek anticline as mapped by Shenon and McConne1,³ while the Osburn fault, a long-recognized regional feature about a mile away, marks the north boundary of the Silver Belt. The Sunshine vein, Fig. 1, has a south dip more or less parallel to the 60" axial plane of the fold and cuts rocks of the Belt. Series, starting with the Wallace formation near the surface, continuing downward through the St. Regis formation, and probably extending into the Revett quartzite which lies below the bottom or 3700-ft level. The limb of the anticline is locally modified by secondary folds, one being prominently exposed in the uranian area along the Jewel1 crosscut near the Sunshine vein. Crumpling of the limb resulted from compression which formed the anticline and probably preceded the faults in which the vein deposits accumulated. Evidence of drag along these faults points to reverse movement in the uranium-bearing area and elsewhere. This is true of major faults in the mine workings, and the majority of faults which can be mapped, as pointed out by Robinson.&apos; The St. Regis formation, as measured in the mine, appears to have an initial thickness of some 2000 ft, but the apparent thickness due to thickening during folding is some 3400 ft. Along the Sunshine vein the purple and green rocks characteristic of the Wallace formation in the nearby Military Gulch section p. 37 of ref. 5) have been completely bleached because of introduced sericite. Hydrothermal solutions acting on the wall rock have substituted for the original color a pale greenish cast, although no pronounced mineralogical change has resulted, as Mitcham has observed.&apos; The silver and the uranium depositions appear to belong to distinct epochs resulting from several periods of emplacement. Likewise, multiple periods of deformation account for the faulting. Uraninite is generally associated with silicification, while silver . mineralization accompanies carbonate veins. Rarely, uraninite may be found in a matrix of siderite. Ordinarily uraninite formed prior to ar-gentian tetrahedrite. Where clusters of veins form a stockwork, uraninite-jasper veins often favor one trend while tetrahedrite-siderite veins favor another. During deformation, brecciation of the St. Regis quartzite provided openings between broken rock fragments for precipitation from vein-forming solutions. Fractures due to major breaks were filled during the first stages of vein formation, while later deformation displaced the first veins and provided new channels along which further mineralizing solutions proceeded. The uraninite veins, as the first formed, have suffered fracturing, displacement, and segmentation. Uranian vein segments uncut by faults and more than a few feet in length are rare or nonexistent. Siderite veins are more massive and often extend without a break for tens and even hundreds of feet. In general they show much less segmentation. While the siderite is usually later, there is an overlap in the periods of deposition, some earlier siderite veins being extensively segmented in much the same way uraninite veins have been broken. Vein silica is more extensively distributed than the uranium and iron mineralization it carries. Along the vein course concentrations of uraninite frequently fade away and barren white quartz continues, the transition often occurring within a few feet along strike or down dip. An example appears on the 3700-ft level where a uraninite vein, see Fig. 2a,

Jan 1, 1954

By C. A. Stickels

A heat of electrolytic iron, to whzch alunzinutn and nitrogen had been added, was hot-rolled, cold-rolled 90 pct, and recrystallized at temperatures from 500" to 700°C. Primary recrystallization textures appear to arise from competitive growth of two types of nuclei: 1) those having orientations belonging to the "usual" primary recrystallization texture found in riming steel, and 2) those with the {111} (110) ovientation. Development of a (111}(1 10) component in the primary recrystallization texture occurs only over a certain interval of isothermal recrystallizatzon temperatures when the material is supersaturated with respect to the precipitation of AlN. Lowering the degree of supersaturation depresses the temperature interval in which a (111)(110) component occurs. An elongated, &apos;pancake-shaped" recrystallized pain structure and a marked delay in the start of recrystallization were found in all specimens which were supersaturated with respect to A1N precipitation after cold work, regardless of their recrystallization texture. ONE of the consequences of killing low-carbon steel with aluminum is a significant change in recrystallization behavior. About 15 years ago, Solter and eatttiel showed that this behavior was largely controlled by aluminum and nitrogen in the steel. If complete precipitation of A1N was prevented before cold rolling, an increased "recrystallization temperature" was observed in subsequent. annealing, and the recrystal-lized grains were not equiaxed. Leslie et a1.2 studied this phenomenon in some detail and clearly demonstrated the relationship between A1N precipitation, recrystallization kinetics, and the development of "pancake-shaped" grains. It has also been known for some time that aluminum-killed steels, processed to produce elongated "pancake" grains, develop a (11 I}( 110) primary recrystallization texture. This texture has not been found in iron or low-carbon rimming steel as a primary texture4j5 but has been observed following grain growth in electrolytic iron.5 The present work was undertaken to study in more detail the effect of A1N supersaturation on recrystallization textures in iron. LITERATURE REVIEW The deformation texture in heavily rolled iron has been studied in detail by Bennewitz.~ The texture consists primarily of a partial fiber texture about a (110) axis in the rolling direction, designated here as fiber texture A. It includes the range of orienta- tions (111)[110] - (001)[ 110] - (11l)[110]. A weak secondary texture also is present.6 This is a duplex partial fiber texture about two (110) fiber axes located 60 deg from the rolling direction and 30 deg from the sheet normal. The range of this texture, designated here as fiber texture B, about the [101} fiber axis is (112)[110] - near (545)[252] - (211:1[011] *The range given here follows Bennewit~.~ A few pole figures from re-crystallized material indicate a broader range than this.&apos; However, the components which are strongest in the recrystallization texture are in this range.&apos;________________________________________________________ Primary recrystallization textures in unkilled steels can be accounted for by growth of members of fiber texture B present in the deformed metal.5 However, while members of fiber texture B dominate the primary texture, other orientations survive primary recrystallization as well. In particular, some {111}(110) members of fiber texture A must also grow during primary recrystallization, because a well-defined {1ll)( 110) texture develops during subsequent grain growth at 700°C.5 The unusual recrystallization behavior of deformed supersaturated solid solutions has been attributed to: 1) retention of the solute in solution,&apos; 2) formation of coherent, preprecipitation solute clusters prior to and during re~r~stallization,~ and 3) formation of a precipitate prior to and concurrent with recrystallization.&apos;~-&apos;~ When aluminum is supersaturated with iron, the difference in grain boundary mobility between general high-angle boundaries and certain special coincidence site boundaries is apparently eliminated.&apos; In aluminum-killed steels, precipitation of A1N can take place at ordinary subcritical recrystallization temperatures. The rate of precipitation increases with increasing aluminum or nitrogen contents.2&apos;13 There is some doubt, however, as to whether true precipitates form during the time at temperature needed to complete recrystallization. Leslie ef a1.2 found that precipitation in one steel was complete after about 100 min at 700GC, or after about 1000 min at 650GC, as measured by chemical analysis for AlN. Aoki et a1.,13 using internal friction for dissolved nitrogen, showed that a large fraction of the dissolved nitrogen was removed from solution within a few minutes annealing time at temperatures from 400" to 800°C. However , the rate of formation of AlN, as detected bv chemical analvsis. was much slower than the apparent rate of nitrogen removal. Hasebe,&apos;~~ using carbon extraction replicas, has identified A1N precipitates by electron diffraction in a 0.2 C steel, solution-treated at 1300°C and annealed 2 hr at 700°C. Borchers and kim,I6 also using a replication technique, observed precipitates after annealing treatments as short as 2 min at 640°C. However, Leslie et a1.&apos; state that no A1N precipitate can be seen while recrystallization is being inhibited in aluminum-killed steel.

Jan 1, 1967

By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.&apos; More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.&apos; This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.&apos; These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer&apos;s6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By M. V. Nevitt

In the systems Ti-Mn-O, Ti-Fe-O, Ti-Co-O, and Ti-Ni-O the bounda.r-ies of the Ti2Ni-type phases were determined at one or more temperatures and the variation of the lattice parameter with oxygen content was determined. Densities were calculated from the lattice parameters and compared with measured density values. The: results indicate that the occurrence of the phase in these systesms can be correlated qualitatively with valency electron concentration, and that the role of oxygen is that of an electron acceptor. The lower limit of oxygen solubility appears to be determined by the valencies of Mn, Fe, Co, and Ni, while the maximum oxygen concentration coincides with the filling of the 16 (c) positions of the O 7h - Fd 3m space group. THE suggestion has been made by several investigators&apos;" that the phases having the cubic E9,-type structure, and known as 17-carbide-type, double-carbide-type and Ti,Ni-type, are members of a family of electron compounds. This concept has been given additional support by recent work8 in which new isostructural phases involving second and third long period combinations were found, and which provided further evidence of the regularity of occurrence of the phase in terms of periodic table relationships. In this laboratory attention has been focused on the isomorphs containing titanium, zirconium, or hafnium, and the role that oxygen plays in their occurrence. In some binary systems Ti,Nitype* phases occur having the formula A,B where A is the titanium group element. Based on previous workq and the present investigation, oxygen is known to be soluble in two of these binary phases, Ti,Co and Ti2Ni. It is probable that oxygen is also soluble in the other phases of this kind. In other binary systems the Ti,Ni-type phase does not occur, but does occur in the corresponding ternary systems with oxygen .3-5 The experiments described here were performed to determine whether the occurrence and composition of certain of the Ti,Ni-type phases could be related to an electronic effect and whether oxygen&apos;s stabilizing role is exerted through an influence on the electron: atom ratio. The ternary systems Ti-Mn-O, Ti-Fe-O, n-Co-O, and Ti-Ni-O were selected for study for two reasons: First, several schemes have been proposed for first long period elements which, although not in quantitative agreement, show a generally consistent trend for the variation of valency with atomic number. Although for a transition metal the term valency is difficult to define and is generally not a constant number which can be applied to all alloys, it is usually assumed to be an index of the number of electrons per atom involved in metallic cohesion. Second, the determination of the Ti2Ni-type phase boundaries was facilitated by the fact that the phase relations in several of these ternary systems have been investigated by other workers."&apos; EXPERIMENTAL PROCEDURE___________________ The alloys were prepared by arc melting crystal-bar titanium, reagent grade TiO, and electrolytic manganese, iron, cobalt, and nickel. Each button was remelted at least three times. The metals had a minimum purity of 99.9 pct except the nickel whose purity was 99.4 pct, the major impurity in this instance being cobalt. The preparation of the manganese alloys was attended by the customary difficulties associated with the vaporization of manganese. The technique used in this case was to add approximately 10 pct extra manganese to the original charge and to continue remelting the button until the final weight was in agreement with its intended weight. At least three alloys in each system were analyzed chemically and the results, even for the manganese alloys, were in good agreement with the intended compositions. A few additional alloys in the Ti-Mn-O system were prepared by the sintering of mixed powders in evacuated quartz tubes followed in some cases by arc melting. For annealing, the alloys were wrapped in molybdenum foil and placed in fused silica tubes containing zirconium chips. The fused silica tubes were evacuated at room temperature to a pressure of 1 x l0-6 mm of Hg and sealed. These capsules were then annealed for 72 hr at an external pressure of 5 x 10-5 mm of Hg in a vacuum furnace whose temperature could be controlled to + 1°C. The success of this procedure in avoiding significant oxygen or nitrogen pickup was indicated by the bright, ductile condition of the molybdenum foil and by the complete absence of a microscopic reaction layer on the specimens. This method did not permit rapid quenching of the specimens but in no case did metal-lographic examination indicate that a solid-state transformation had occurred on cooling. Metallo-

Jan 1, 1961

By P. L. De Bruyn, R. J. Charles

THE transfer of kinetic energy of translation into other forms of energy by impact is a fundamental process in most crushing and grinding operations. During and after the impact process the original source energy may be accounted for in any of the following possible forms: 1) Kinetic energy of translation of both the impacted and impacting objects. 2) Kinetic energy of vibration of the components of the impact system. 3) Potential energy as strain energy of the components of the system or in the form of residual stresses. 4) Heat generated by internal friction during plastic deformation or during damping of elastic waves. 5) New surface energy of fractured materials. At any instant during the impact process only the strain energy of the components of the system can contribute directly to the brittle fracture process. If fracture is the desired result, as in comminution, it would seem advantageous to choose or arrange the conditions of impact so that a maximum amount of the original kinetic energy could be converted to strain energy at some moment during a single impact. The present work deals with determination of these desirable conditions for a simple case of impact and application of the principles involved to general cases of impact. Experimental Method: Longitudinal impact of a rod with a fixed end was chosen as the impact system for investigation. The rod was mounted horizontally and the fixed end was formed by butting one end of the rod against a rigidly mounted steel anvil. The rod, of pyrex glass, was 10 in. long by 1 in. diam with both ends rounded to a 6 in. radius. The rounded ends permitted reproducible impacts on the free end of the rod and assured a symmetrical fixed end. Pyrex was selected as the rod material because of the marked elastic properties of such glass and the similarity of fracture between pyrex and many materials encountered in crushing and grinding operations. The frequency of natural longitudinal oscillation of the rod was 10 kc, and thus simple electronic equipment could be used for observation of strain changes occurring in the rod at this frequency. As shown in Fig. 1, impacts on the free end of the rod were obtained either by a pendulum device or by a spring-loaded gun. Relatively heavy hammers (100 to 600 g) of mild steel were used in the pendu- lum impacts, while fairly light projectiles (20 to 80 g) were fired from the spring-loaded gun. One of the main objects of the experimental work was to obtain the strain-time history of the rod as a function of the mass and kinetic energy of the impacting hammers. For this purpose a technique involving wire resistance strain gages and a recording oscilloscope was employed. Five gages were applied at equidistant sections along the rod, and by means of a switching arrangement the strain-time history at any section, and for any impact, could be obtained in the form of an oscillograph with a time base. The equation relating strain and voltage change across a strain gage through which a constant current is flowing is as follows: e = ?v/iRF [1] ? = strain, ?v = voltage change, i = gage current, R = gage resistance, and F = gage factor (from manufacturer&apos;s data — SRA type, Baldwin Lima Corp.). With the above equation an oscillograph depicting voltage change vs time on a single trace can be converted directly to a strain-time diagram if a calibration of the vertical response on the oscilloscope screen for specific voltage inputs is available. In the present case the calibration was obtained by photographing precisely known audio frequency voltages on the same oscillograph as that on which a voltage-time trace from a strain gage had been made. Synchronization of the beginning of the single trace with the beginning of the impact was accomplished by permitting contact of the impacting objects to close an electrical circuit from which a voltage pulse, sufficient to initiate the trace, was obtained. The struck end of the rod was lightly silvered for purposes of electrical conduction so that it would form one of the electrical contacts. Markers every 100 micro-seconds on the traces served for a time base calibration. Determinations of the kinetic energies of translation prior to impact were made in the case of the pendulum hammers by measuring the height of fall of the hammer and in the case of the projectiles by measuring the exit velocity from the gun barrel by means of an electrical circuit employing light sources, slits, and phototubes.&apos; During the experimental work it became evident that the time of contact between the impacting object and the rod was an important variable in the impact process. Measurements of the times of contact were made, therefore, for every impact for which a strain-time record was obtained. The time of contact was determined by permitting the impacting components, when in contact, to act as a closed switch and discharge a condenser at relatively constant voltage. The discharge was observed and photographed with a time base on the oscilloscope screen.

Jan 1, 1957

By R. R. Judd, H. W. Paxton

The rate of dissolution of cementite was studied in three low-carbon materials: a zone-refined Fe-C alloy, an Fe-0.5pct Mn-C alloy, and a commercial low-carbon steel. The materials were spheroidized, ad then held isothermally at temperatures above the Al. The isothermal anneal was interrupted periodically by a water quench and the specimens were analyzed by quantitative metallography for the amount of aus-tenite formed during the anneal. The results of this study were compared with an analytical model for the process, which assumes that carbon diffusion in aus-tenite is the rate-controlling step for the cementite dissolution process. The correlation between the model and the experimental data is excellent for the zone-refined Fe-C alloys; however, the Fe-0.5 pct Mn-C alloys and the commercial steel deviate from the calculated model. This deviation is thought to be a result of manganese segregation between the carbide and the matrix. The rate of nucleation of austenite at carbide interfaces was reduced by the manganese addition and enhanced by the presence of ferrite-ferrite grain boundaries. PREVIOUS investigations of the nucleation and growth of austenite from ferrite-carbide aggregates are not entirely satisfying for at least one of several reasons. The most prevalent of these is a lack of quantitative data. Engineering studies have been run on many steels with little control over important parameters such as composition and initial aggregate structure. The data obtained are valid only for material with identical chemistry and thermal history. A more informative approach to the problem of aus-tenitization would be to determine the mechanism that controls the rate of solution of carbide in austenite and how it is modified by alloying elements. This information could then be used to calculate an austeniti-zation rate for any material, provided its composition and structure are known. The object of the present work is to establish the rate-controlling step for cementite dissolution in Fe-C austenite and to investigate the modification of this rate by small manganese additions. The composition and structure of the material used were carefully controlled and all measurements were designed to allow a quantitative analysis of the kinetic process that controls the austenitization rate. A MODEL FOR DISSOLUTION OF CEMENTITE Cementite dissolution has been analyzed mathematically by a model that approximates the material used in the experiments. This model postulates a regular ar-array of identical cementite spheroids with 4 C( diam, embedded in a grain boundary- free ferrite matrix. The analysis provides a detailed description of the dissolution of one carbide spheroid and a generalization of the solution by summation over all the carbides in the material. The carbides may be isolated by defining identical, space-filling cells of ferrite around them. If the cell dimensions are greater than the diameter of the austenite sphere resulting from complete dissolution of the carbide, and no interaction (through diffusion in ferrite) takes place between cells during the dissolution process, the model need concern only one cell, since the solution in each cell is identical. In the experimental material, the dimensions of the cell, the carbide, and the final austenite sphere are approximately 24, 4, and 8 p, respectively; use of the single cell is therefore justified. The experimental observations are made on the austenite nodules that form around each carbide during the dissolution process. The model concerns the growth of these austenite nodules. The attendant shrinking of the carbide can be obtained from the same analysis by an extension of the calculations. Several a priori assumptions are necessary to make the analysis of the growth problem tractable. They are: 1) carbon diffusion through the austenite nodule is the rate-controlling process; 2) local equilibrium exists at all interfaces, 3) the austenite nucleus that forms on each carbide instantaneously envelops the carbide; 4) during the austenite growth process, the diffusion flux of carbon in ferrite is insignificant; 5) a quasi-steady state exists in the austenite concentration field; that is, at any instant during the dissolution process, the austenite carbon concentration gradient closely approximates that for a steady-state solution; and 6) the effects of capillarity on the dissolution rate of the carbides can be neglected. Referring to Fig. 1, a mass balance at the y-a interface for an infinitesimal boundary movement gives: Where rb is the outer radius of the austenite shell, C1 and C are carbon concentrations at the interface in austenite and ferrite, respectively, see Fig. 2, is the diffusion coefficient of carbon in austenite for the concentration of carbon at the interface, and t is time. The fifth assumption permits the austenite carbon concentration to be approximated by the Laplace solution for the spherical case. Therefore, where C(Y) is the carbon concentration at r, and A and B are constants. Local interfacial equilibrium fixes the boundary conditions for the diffusion problem. They are:

Jan 1, 1969

By M. E. Fine, A. A. Henderson

Investigation of the tensile properties of silver based aluminum alloy crystals was undertaken because it appeared attractive for studying strengthening effects due to Suzuki locking with minimum complication. Yield drops were observed in all alloy crystals (1, 2. 3. 4, and 6 at. pct Al) after strain aging at room temperature. No yield drops were found in similarly grown and tested silver crystals. The yield effects are attributed to Suzuki locking but the major portion of the solid solution strengthening to other mechanisms. INVESTIGATION of the tensile properties of single crystds of silver alloyed with aluminum was undertaken because it appeared to be a system in which segregation at stacking faults associated with partial dislocations1 would be the dominant factor in anchoring dislocations. First, silver and aluminum have closely similar atomic sizes and thus solute atom locking of a dislocation due to elastic interactions should be unimportant. Second, while both X-ray2 and thermodynamic3 investigations show short-range ordering in silver-based aluminum alloys, the degree of local order is quite small (X-ray measurements give v = EAB - 1/2(EAA + EBB) = - 0.025 ev and thermodynamic measurements give v r -0.007 ev) and should not be important in strengthening dilute alloys. Third, the stacking fault energy of silver is probably low (as indicated by the profusity of annealing twins) and is very likely diminished further and quite rapidly by aluminum additions since the A1-Ag phase diagram shows a stable hexagonal phase at only 25 at. pct Al. Also, a careful investigation in this laboratory4 has shown that the ratio of twin to normal grain boundaries in recrystallized alloys increases with aluminum content. Thus, with minimum complication from other factors, Ag-A1 alloys seem attractive for studying strengthening effects due to segregation at stacking faults of extended dislocations. EXPERIMENTAL METHOD Single crystals measuring 250 by 5 by 1.5 mm of pure Ag (99.99 pct) and Ag-A1 alloys (A1 of 99.999 pct purity) of nominal compositions* 1, 2, 3, 4, and 6 at. pct were grown in high-purity graphite molds from the melt under a dynamic vacuum (1 x l0-5 mm Hg). The technique consisted of moving a furnace having a hot zone (which melted about 0.5 cm of alloy) over a horizontal, evacuated quartz tube con- taining the mold and alloy at a rate of 3/8 in. per hr. Chemical analysis showed roughly the first inch of the crystal to be solute poor, the last inch solute rich; and the center section uniform in composition within the sensitivity of the analytical method (± 0.2 at. pct Al). The center section of the crystal was cut into five specimens. Gage lengths of reduced cross section, measuring from 1.5 to 2 cm in length, were mechanically introduced by means of jeweler&apos;s files and fine abrasive cloth with the crystal firmly held in polished steel guides. One-third of the cross section was then removed by etching and electro-polishing, the crystals were all subsequently annealed for several days at 850°C in a dynamic vacuum (<1 x 10-5 mm Hg) and furnace cooled to 200°C. The crystal orientations were determined using the usual back-reflection Laue technique. The Laue spots were sharp and of the same size as the incident beam. However, microscopic examination showed the crystals to contain substructures with subgrains of the order of a micron in diameter. The details of this substructure are presently under investigation. Tensile testing was done with a table model Instron using a cross-head speed of 0.002 in. per min. For testing at various temperatures the following media were used: 1) 415oK, hot ethylene glycol; 2) 296ºK, air, acetone, water; 3) 273ºK, ice water; 4) 258ºK, ethylene glycol "ice" in ethylene glycol; 5) 200°K, dry ice in acetone; 6) 77ºK, liquid nitrogen. EXPERIMENTAL RESULTS A) Yield Behavior—A portion of an interrupted stress-strain curve for a 6 at. pct A1 crystal of the indicated orientation tested at room temperature is shown in Fig. 1. Initially, at (a), there is a small, gradual yield drop of about 10 mg per sq mm2. However, on stopping the test, and aging for a few minutes at (b), a sharp yield drop is found. Aging for longer times at (c) and (dl results in larger yield drops (and larger AT&apos;S). At, defined in Fig. 1, is usually larger than the yield drop by about 20 pct; however, this increase in the lower yield is transient since extrapolations of the flow stress curves join as may be seen from Fig. 1. (Both Laue and low-angle scattering photographs revealed no evidence of precipitation in a strain-aged 6 at. pct A1 crystal.)

Jan 1, 1962

By E. P. Dahlberg, R. E. Reed-Hill

On the assumption that stress or strain relaxation occurs as the result of a thermally activated process, equations are derived relating to tensile experiments that give the strain as a function of the time under the condition of constant stress, and the stress as a function of the time for constant strain. It is demonstrated that if the strain-rate equation i = previously proPosed by Kuhlmann., is used as a starting point, then the relaxation of strain at constant stress may be expressed by the equation c = (-RT/(Y) 1tz tanh (t + is the strain capable of being relaxed at any given instant. Similarly, it is shown that the relaxation of stress at constant strain may be given by a = (-RT/B) In tanh (t + t0)/27, where a is the instantaneois value of the relaxable stress. The fact that these relationships reduce to well-known empirical equations at both large and small values of the stress Or strain is also shozcn. The present theory is shown to agree well with experimental data obtained from tensile elastic aftereffect experiments on a zirconium specimen prestrained at 77 k as to make it strongly anelastic. It is also demonstrated that elastic aftereffect data obtained using torsional specimens ?,Lay agree reasonably well with the equation derived for the case of tension. RELAXATION experiments are often employed as a means of studying metallic deformation mechanisms.&apos; The simplest and most commonly employed techniques involve stress relaxation at constant strain and strain relaxation at constant stress. In general, however, investigations of this nature have been seriously handicapped in the past by a lack of suitable equations giving the time dependence of the relaxing variable over an interval that extends from small strains up into the region where internal-friction experiments become strain-amplitude dependent. This paper presents a derivation of such a set of equations for the case where the time-dependent part of the strain is anelastic or recoverable and the specimens are loaded in simple tension. The relaxation of strain under the condition of constant stress will be considered first. Let us assume that strain relaxation occurs as the result of a reversible thermally activated process that occurs at a number of relaxation centers lying in an elastic matrix. Then, following Kuhlmann,2 we may express the rate of strain relaxation as follows: where C is the strain rate, AFx the free energy of activation of the process controlling strain relaxation, a, the effective or average resolved stress at the relaxation centers, u an activation volume, R the universal gas constant, T the absolute temperature, > a factor with dimensions of a volume that accounts for the strain contribution of a successful operation of a unit process, N the number of relaxation centers per unit volume, and v the Debye frequency. The first term on the right of Eq. [I] represents a strain rate in the direction favored by the stress, while the second term represents the rate in the opposite direction. It is implied in Eq. [I.] that both F and v are symmetrical with respect to the two basic directions of operation of a relaxation process. Eq. [I] may also be written where and S and Q are the activation entropy and activation energy, respectively, of the relaxation process. In the following, A will be considered a constant. This is compatible with a set of experimental conditions where the relaxation rate is controlled by a single basic reversible process in which it may be assumed that the temperature dependence of the product ?Nv is negligible in comparison with the temperature variation of the exponential term. It is also implied that v, 7, and N do not depend strongly on a, . In deriving a relationship for the strain as a function of the time from her equation, equivalent to Eq. [2], Kuhlmann2 chose to consider only the limiting cases where the time was either very small or very large. It will now be shown that it is possible to integrate Eq. [2] to obtain a single equation valid over a wide range of strains if the concept of relaxable strain is introduced. The use of this quantity, which is the difference between the instantaneous value of the strain and the value of the strain at complete relaxation, represents the primary point of departure of the present theory from that of earlier workers. Let us express the effective stress at the relaxation centers in terms of strain. For this purpose we may use the following equation derived by zener3 for the case of strain relaxation at slip bands: where M? and M are the relaxed and unrelaxed moduli respectively, go the applied constant tensile stress, and m an average orientation factor that takes account of the fact that a,, the effective stress at the relaxation center, may not be a tensile stress (i.e., a

Jan 1, 1967

By D. J. Carney, R. L. Stephenson

A sampling technique has been developed for procuring a sample of sinter representative of the entire depth of the sintering bed. The sampling method involves the use of an open-bottom metal basket that rides on the grate of the sintering machine and when removed contains a sample of the sintered product. Additional data have been obtained to indicate that the tumbler test is a suitable means of measuring sinter strength. IN the last few years additional sintering facilities have been installed in both the Pittsburgh and the Chicago district of the United States Steel Co. Since the construction of these sintering plants made possible the use of higher percentages of flue-dust sinter in our blast-furnace burdens, it became important to study means of controlling the quality of sinter to obtain optimum results in the blast furnace. For controlling an operating process, it is necessary first to establish standards by which the quality of the product can be judged. For sinter, it appeared that an important property was its strength or its resistance to degradation during transportation and charging into the furnace. Consequently work was undertaken to establish a standard for sinter strength that could be used both for controlling sintering-plant operations and for correlating sinter quality with blast-furnace performance. The first problem in setting up a standard was that of procuring a sample that would be representative of the sinter made under any particular set of conditions at the sintering plant. Since the United States Steel Co. sintering plants discharge the finished sinter either into a large pit or onto a rotary cooler, the sinter becomes inseparably mixed with material sintered 2 hr before or 2 hr afterwards. For this reason the exact identity of the sinter is lost. A sample selected as the cooler is discharged, or as the sinter is removed from the pit, cannot be said to be truly representative of the sinter made at any specific time. Sampling The first attempt to procure a sample that would be representative of a specific sinter mix and of specific operating conditions was made by stopping the Dwight Lloyd sintering machine and removing an entire pallet full of sinter. This method, however, proved very difficult to perform and interfered considerably with the operation of the plant. To overcome this difficulty, a sampling method was devised by technologists at South Works enabling them to secure, without interrupting the sintering operation, a sample of about 1 cu ft of sinter, representative of sinter for the full depth of the sintering bed. The South Works method involves the use of a steel-frame-work basket. A typical basket is shown in Fig. 1. The basket has been used both with and without crossbars along the bottom. As long as the crossbars are in the same direction as the grate bars on the sintering machine they do not interfere with the sintering process. The basket is set on an empty grate of the Dwight Lloyd sintering machine before it passes under the swinging feed spout, see Fig. 2. When the basket is removed after it has travelled the length of the sintering machine, it contains the sample. Just before the basket is removed, the sinter is scored and chipped to facilitate removal of the sample from the sinter bed. A view of the basket after its removal is shown in Fig. 3. Although the sampling method was originally designed for use on a Dwight Lloyd sintering machine, it can also be used on the Greenawalt type of machine. When used on the Greenawalt-type machine, the basket is placed on the sintering grate before the charging car passes over it, and finally it is removed just before the pan is dumped. Testing After a method of obtaining a representative sample of sinter had been developed, the next step was to select a method of measuring its strength. The irregular shape and size of the sinter pieces precluded the use of a simple compression test for determining strength; consequently, the shatter test and tumbler test were investigated. To perform the shatter test, a sample of sinter, approximately 5 lb, is dropped from a hinged-bottom box at a height of 3 ft onto a steel plate. The broken sinter is sieve-analyzed after a specified number of drops. The tumbler test is performed with the use of a standard ASTM coke-tumbling drum. The drum is 3 ft in diam and is equipped with two lifter bars diametrically opposite one another on the inner periphery of the drum. The drum is rotated at a speed of 24 rpm for 200 revolutions, and after tumbling the sample is sieve-analyzed. To express as single numbers the results of sieve analyses after shattering or tumbling, the method suggested by R. E. Powers1 was employed. This method involved plotting the size of the sieve openings on a logarithmic scale and the cumulative per cent larger than each sieve on a probability scale as described by J. B. Austin.&apos; By interpolating from the plotted data, which in most cases approximated

Jan 1, 1954

By L. F. Bryant, J. P. Hirth, R. Speiser

The surface, gain boundary, and twin boundary energies, as well as the surface diffusion coefficient, of cobalt were determined from tests at 1354°C in pure hydrogen. A value of 1970 ergs per sq cm was calculated for the surface energy, using the zero creep method. It was possible to measure the creep strains at room temperature because the phase transformation was accompanied by negligible irreversible strain and no kinking. Established techniques based on interference microscopy were used to obtain values for the other three properties. The gain boundary and twin boundary energies were 650 ad 12.7 ergs per sq cm, respectively, while a value of 2.75 x l0 sq cm per sec was determined for the surface dufusion coefficient. In the course of a general study of cobalt and cobalt-base alloys, information was required about the surface energy of cobalt. Hence, the present program was undertaken to measure the interfacial free energy, or, briefly, the surface energy, of the solid-vapor interface of cobalt. The microcreep method was selected for this measurement because other surface properties could also be determined from the accompanying thermal grooving at grain boundaries and twin boundaries. A brief summary of the methods for determining the various surface properties follows. At very high temperatures and under applied stresses too small to initiate slip, small-diameter wires will change in length by the process of diffu-sional creep described by Herring.1 The wires acquire the familiar bamboo structure and increase or decrease in length in direct proportion to the net force on the specimen. For a specimen experiencing a zero creep rate, the applied load, wo, necessary to offset the effects of the surface energy, y,, and grain boundary energy, y b, is given by the relation: where r is the wire radius and n is the number of grains per unit length of wire. The first results obtained from wire specimens were reported by Udin, Shaler, and Wulff.&apos; udin3 later corrected these results for the effect of grain boundary energy. The grain boundary energy is determined from measurements of the dihedral angle 8 of the groove which develops by thermal etching at the grain boundary-free surface junction. For an equilibrium configuration: Measurements of the angle 8 can be made on the creep specimens4&apos;5 or on sheet material, as was done in this investigation by a method employing interference microscopy.= If the vapor pressure is low, the rate at which grain boundary grooves widen is determined primarily by surface diffusion and, to a lesser extent, by bulk diffusion. The surface diffusion coefficient, D,, is obtained from interferometric measurements of the groove width as a function of the annealing time, t. As predicted by Mullins~ and verified by experiment, the distance, w,, between the maxima of the humps formed on either side of the grain boundary increases in proportion to if grooving proceeds by surface diffusion alone. For this case: where fl is the atomic volume and n is the number of atoms per square centimeter of surface. When volume diffusion also contributes to the widening, the surface diffusion contribution can be extracted from the data by the method described by Mullins and shewmon.8 Where a pair of twin boundaries intersects a free surface, a groove with an included angle of A + B (using the groove figure and notations of Robertson and shewmong) forms by thermal etching at one twin boundary-free surface junction. If the "torque terms", i.e., the terms in the Herring10 equations describing the orientation dependence of the surface energy, are sufficiently large, an "inverted groove" with an included angle of 360 deg-A&apos;-B&apos; develops at the other intersection. The angles A + B and A&apos; + B&apos; are measured interferometrically. When the angle, , between the twinning plane and the macroscopic surface plane is near 90 deg, the twin boundary energy is calculated from the relation: 1) EXPERIMENTAL TECHNIQUES Five-mil-diam wire containing 56 parts per million impurities was used for making ten creep specimens. These specimens had about 15 mm gage lengths with appended loops of wire and carried loads (the specimen weight below the midpoint of the gage length) ranging from 3.7 to 149.8 mg. The wires were hung inside a can made from 99.6 pct pure cobalt sheet. Beneath the wires were placed small specimens of 20-mil-thick, 99.9982 pct pure cobalt sheet from which the relative twin boundary and grain boundary energies and the surface diffusion coefficient were measured. All the specimens were annealed at a temperature of 1354" i 3°C which is 92 pct of the absolute melting point of cobalt. The furnace atmosphere was 99.9 pct pure hydrogen that was purified further by a Deoxo catalytic unit, magnesium perchlorate, and a liquid-nitrogen cold trap. As a precautionary measure the gas was then passed through titanium alloy turnings which were heated to 280" to 420°C and replaced after every test period. The hydrogen was maintained at a

Jan 1, 1969

By D. D. Dunlop, J. R. Welker

The growing interest in the use of CO, in crude oil recovery increases the need for data on the effect of CO, on hydrocarbon physical properties. Data are presented on the solubility of CO, in various dead oils, the swelling changes in CO2-oil solutions and the effect of CO, on dead oil viscosity. This latter property shows the most pronounced effect, with viscosity reductions up to 98 per cent of the uncarbonated viscosities. An empirical method of estimating the viscosity of carbonated oils is presented. The apparatus and procedures used are described in sufficient detail to allow others to make similar studies. INTRODUCTION The effect of dissolved carbon dioxide on the swelling and viscosity reduction of specific hydrocarbon oils has been observed and recorded by a number of investigators.&apos;- me object of this paper is to offer a means of predicting these effects for crude oils free from natural gas, using the dead state viscosity and gravity of the crude oils. The CO, solubility and swelling of numerous crude oils were determined in a visual cell at various pressure levels. The viscosity of the oils carbonated to various pressure levels was then determined by measuring the pressure drop across a capillary tube. From these data, the physical properties were correlated empirically. The resulting correlations allow the prediction of CO, solubility, swelling and viscosity reduction if the dead state gravity and viscosity of the oils are known. SOLUBILITY AND SWELLING MEASUREMENT EQUIPMENT AND PROCEDURE A high pressure visual cell was installed in a constant temperature cabinet. A test gauge was attached at the top of the cell for pressure measurement, and a line was run through the cabinet wall to a wet test meter which was used for volumetric measurement of the gas. The first step in making a test run was to put the oil in the cell up to a level about half to two-thirds of the total volume. This required about 50 to 65 ml of oil. carbon dioxide was then bubbled up through the oil for a time during which the pressure of CO2 in the cell was kept above 800 psia. Saturation of the oil with CO2 at this pressure and ambient temperature was confirmed by slowly bleeding CO2 through a valve to the atmosphere. If the oil was completely saturated with CO2, bubbles of gas would form in the oil at the first small decrease in pressure. If the oil was under-saturated, no bubbles formed until the pressure was decreased to the saturation pressure existing in the oil. If this saturation pressure was lower than that desired, more CO2 was bubbled through the oil until the desired level was reached. After saturation at ambient temperature was completed, the cabinet temperature was adjusted to the desired level and the cell was allowed to reach temperature equilibrium. After temperature equilibrium was reached, the pressure was again decreased slightly, and the oil again checked for full CO2 saturation at the cell pressure. The pressure now had changed because of the difference in solubility of the CO, in the oil at higher temperatures and the expansion of CO2 as the temperature increased. The outlet tube from the cell was then connected to the wet test meter and the CO2 was allowed to flow slowly out of the cell and through the wet test meter at ambient temperature and pressure. The water in the wet test meter had previously been saturated with CO2 at ambient temperature and pressure by allowing CO2 to flow continuously through it lor a period of several hours. The gas flow was stopped at several pressures during the run and the cell was allowed to come to equilibrium; this made possible the measurement of solubility and swelling data at the intermediate pressures. The volume of the oil in the cell was recorded at each of the equilibrium pressures in order to obtain swelling data. DATA AND RESULTS The solubility of CO2 in the oil was calculated by the relationship V — V, where R. = solubility of CO, in crude oil, cubic feet of CO, measured at 60F and 1.0 atm/ bbl of dead state oil at the temperature under which solubility was measured, V, = volume of gas released from the cell between the saturation pressure and zero pressure, corrected to 60F and 1.0 atm, cu ft, V, = volume of CO: contained in the gas space above the oil, corrected to 60F and 1.0 atm, cu ft, and V, = volume of the dead oil in the cell in bbl at the temperature of the run. The volumetric data of Sage and Lacey&apos; were used to calculate V., from the volume of CO2 at high pressures. The swelling factor was calculated as where V, is the volume of the C0,-

By Vard H. Johnson

IN 1943 the U. S. Bureau of Mines undertook drilling in an effort to develop new reserves of coking coal in an area near Paonia, Colo., as a part of an attempt to alleviate the shortage of known coking coal of good quality in the western United States. Geologic mapping of the area was undertaken by the U. S. Geological Survey with the purpose of first furnishing guidance in location of drillholes and later aiding in interpreting the results of the drilling. The drilling program was under the general supervision of A. L. Toenges of the U. S. Bureau of Mines. J. J. Dowd and R. G. Travis were in charge of the work in the field. Geologic mapping was started by D. A. Andrews of the Geological Survey in the summer of 1943 and was continued from the spring of 1944 to 1949 by the writer. The first few holes drilled failed to locate coking coal, but in the summer of 1944 coking coal was discovered by drilling 6 miles east of Somerset, Colo., the site of present mining. In the succeeding years, 1945 to 1948, 100 to 150 million tons of coal suitable for coking were blocked out by drilling. The ensuing discussion of the geologic controls on the distribution of coking coal in the area is based on the geologic mapping as well as the drilling done in the Paonia area, more complete descriptions of which have appeared or are in process of publication."&apos; In order that the possible geologic controls affecting the present distribution of coking coal may be considered, it is necessary to discuss briefly the indicators of coking quality coals. Coking Coal Coal that cokes has the property of softening to form a pastelike mass at high temperatures under reducing conditions in the coke oven. This softening is accompanied by the release of the volatile constituents as bubbles of gas. After release of the contained gases and upon cooling, a hard gray coherent but spongelike mass remains that is referred to as coke. This substance varies greatly in physical properties and, to be suitable for industrial use, must be sufficiently dense and strong to withstand the crushing pressure of heavy furnace loads. Western coals have a generally high volatile content and therefore form a satisfactory coke only when they attain a rather high fluidity during the process of heating arid distillation in the coke oven. When this high degree of fluidity is developed, the volatile constituents escape and leave a finely porous coke. On the other hand, when the degree of fluidity is low the product is an excessively porous and therefore physically weak mass that is called char." Small quantities of oxygen present in coal are believed to decrease the fluidity of the material during the coking process and to favor the development of char rather than coke. In consequence, coal chemists have for some time considered the possibility of developing an index to coking qualities by inspection of chemical analyses of coals.&apos; A formula has now been developed that does permit a rough preliminary estimate of the cokability of coal on the basis of the analysis on an ash and moisture-free basis. Coals may be eliminated as possible coking fuels if the oxygen content is greater than 11 pct. Similarly the ratio of hydrogen to oxygen must be greater than 0.5 and the ratio of fixed carbon to volatile constituents must be greater than 1.3. If the coal, on the basis of these limiting factors, appears to have possible coking qualities, the following formula permits determination of the coking index: a+b+c+d Coking index = -------- 5 a equals 22/oxygen content on ash and moisture-free basis, b equals two times the hydrogen content divided by oxygen content on moisture and ash-free basis, c equals fixed carbon/l.3 x volatile matter, and d equals the heating value on moist, ash-free basis/13,600. Coking indices higher than 1.0 suggest that the coal will coke, and indices above&apos; 1.1 indicate good coking tendencies. Although generally usable, this formula &apos;is not completely satisfactory because the percentage of oxygen shown in ultimate analyses is derived only by difference; i.e., by subtracting the sum of the percentages of the constituents determined analytically from 100 pct. Although the coking index indicates the coking tendencies of coal, it is necessary to make physical tests of coke before its industrial value can be determined. The U. S. Bureau of Mines has developed a standard procedure for determining the approximate strength of coke that would be formed from a given coal. In this test one part of ground coal, mixed with 15 parts of carborundum, is baked to form a standard briquette. The weight, in kilograms, necessary to crush the briquette is termed the agglutinating index. This test determines the relative fluidity attained in the coking process by measuring the cementing strength of the coal in the briquette. A

Jan 1, 1953