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By B. D. Lichter

In a previous paper, Oelsen, Schuermann, and Hey-nertl pointed out the possibility of obtaining complete thermodynamic functions for alloy systems from calorimetric measurements alone. Specifically, if the heat content of a heterogeneous, multicomponent system is known as a function of temperature and composition, then it is possible to derive the heats, entropies, and free energies of formation of liquid phases and of solid intermediate phases of fixed composition. The authors present equations and graphical techniques applicable to eutectic systems and systems with intermediate phases without solid solubility at lower temperatures. eijering has considered possible extension of the treatment to systems with complete solid-state miscibility at lower temperatures; however, experimental difficulties practically restrict the method to systems with very limited miscibility in the solid state. The purpose of this note is to present an alternative derivation of the heats and entropies of formation of liquid phases and of solid intermediate phases from heat-content measurements alone. Fig. 1 shows three types of phase diagram to which the analysis may be applied. If the heat content is determined as a function of composition x, at temperature T, we have quite generally and the heat of mixing of the liquid is obtained directly from heat-content measurements. If the temperature T lies in a two-phase region (solid-liquid) then

Jan 1, 1967

By T. Estelle Gardner

Heat-capacity measurements were made over the range 8° to 350° K on beryllium sulfate dihydrate and beryllium sulfate tetrahydrate using an adiabatic calorimeter. No anomalies were noted in the curve for either compound. Smooth values of heat capacity, entropy, enthalpy function, and free-energy function were calculated from the heat-capacity data at 10° K intervals and at 273.15° and 298.15° K. The entropy values calculated at 298.15° K were 39.01 ± 0.12 entropy units (eu) for the dihydrate and 55.68 ± 0.17 eu for the tetrahydrate.

Jan 1, 1967

By Gordon W. Hines

This paper, dealing with network planning in an industrial complex, discusses the type and size of project that can be handled on a manual basis. After a review of the fundamentals of network planning, and specifically of the Critical Path Method, the author analyses several different types of projects, each with its own characteristics. Some can be handled in conjunction with a computer, but others can be dealt with equally well without one. Among the projects discussed are a blast furnace reline, the installation of a billet mill flying shear, and routine maintenance-type operations.

Jan 1, 1967

By P. G. Shewman, T. L. Wilson

Using published surface-diffusion (D,) data and published sintering equations, it is shouln that surface difusion should dominate the neck-growth stage of intering for all materials in which D, has been measured (six metals and A1as). Also, grain boundary diffusion can be expected to contribute appreciably to shrinkage and possibly to neck growth below some critical temperature of the order of 70 pct 01- the absolute melting temperatuve. In view of the widespread conclusion in previous sintering work that volume diffusion dowzinates neck gvowth, experiments were conducted using spherical copper powders to test this conclusion. Scaling studies on neck growth at 950°and 1020°C clearly demonstrated that suyface diffusion dorninates. Kinetic studies on shrinkage gave more equivocal results that indicated an increasing role of' grain boundary transport at lower temperatures. Five diarszeters from 100 to 300 u were used in the scaling sludy and a temperature range of -650' 10 950 C was covered in the shrinkage studies. All experiments were conducted in dvy hydrogen. In 1949, Kuczynski published his now classic paper on the determination of the transport mechanism in sintering from the time laws of neck growth. In the interim, these laws have been applied to many systems and slightly modified by several authors. Essentially all these authors concluded that, for crystal- line materials, the dominant transport mechanism in neck growth is volume diffusion. This stems from the observation that the neck radius increases about as t"5 and that the activation energy approximates that for lattice diffusion. A related but independent series of studies stems from Mullins' rigorous analysis of the growth of the groove formed where a grain boundary meets a free surface." xperimental work stemming from this analysis has shown that for each crystalline material studied (Au, Ag, Cu, Ni, Fe, Pt, Al2O3) surface diffusion was clearly the dominant transport mechanism for groove widths up to the order 10 to 20 p. The ratio of the quantity of material being carried by lattice diffusion to that carried by surface diffusion increases linearly with the groove width, so surface diffusion is dominant for all widths under 10 to 20 u. The analysis of the relative contributions of surface and volume diffusion to grain boundary grooving, and to neck growth in sintering, shows that they are quite similar. Thus, using the available surface-diffusion data and the approximate equations of Kuczynski, or the more rigorous recent equations of Nichols and Mullins, 3 it can be shown that the small necks between particles must grow almost entirely by surface diffusion. The purpose of this study was to re-examine the basis for the conclusion that the neck-growth stage of sintering proceeds by volume diffusion. Using spherical copper powders, of several different diameters, precise experimental measurements were made of both neck growth and shrinkage. Application of Herring's scaling laws to the neck-growth data clearly indicated that neck growth occurred by surface transport, even though the neck radius increased as or Using the recent analysis of Mullins and Nichols as well as published data on surface diffusion, it is shown that the observed time law, as well as actual rate of neck growth, can be satisfactorily explained by a surface-diffusion mechanism.

Jan 1, 1967

By S. A. LoPilato, J. T. Smith

SEVERAL techniques have been evaluated for cooling the throat area of rocket-nozzle inserts to prevent erosion or fracture of the inserts during exposure to high operating temperatures and pressures. Self-cooled composites, such as infiltrated tungsten, have shown considerable promise for these applications. These composites can be fabricated by infiltrating the refractory matrix with a lower-melting metal or non-metal which is insoluable in tungsten. During firing, the lower-melting substance undergoes a series of continuous endothermic phase changes which absorb sufficient heat to maintain the nozzle matrix material at or below a safe operating temperature. At present, the state-of-the-art has reached a point where the refractory matrix density and microstruc-ture have been established as the critical parameters to be controlled for optimum self-cooled performance.'" Nondestructive testing has been utilized to ensure that porous tungsten billets were of uniform density and free from cracks or other defects prior to fabrication into rocket nozzle inserts. Ultrasonic-velocity techniques have been employed because of their reliability and reproducibility. The purpose of this note is to present and interpret the test data developed for porous tungsten matrices. For evaluation purposes, tungsten powders with Fisher subsieve sizes of approximately 4 and 18 p have been obtained for study from four commercial sources: the General Electric Co., Wah Chang Corp., Fansteel Metallurgical Corp., and Kennametal, Inc. Porous tungsten matrices were fabricated from the powders by hot pressing in induction-heated graphite die assemblies. Typical billets ranged from 3 in. diam, 2 in, high to 5 in. diam, 5 in. high. The ultrasonic-velocity measurement technique employed was through transmission, pulse echo at a frequency of 1.0 mc using matched barium titanate crystal transducers. The testing equipment included a pulsed ultrasonic generator, an amplifier, a specimen holder, and an oscilloscope, as shown in Fig. 1. The porous tungsten thickness was measured to i 0.0005 in, with precision micrometers while the oscilloscope achieved 0.02 psec time measurement accuracy. The time for a sound wave to pass through the billet, the bulk wave velocity, was calculated to 0.5 pct using Eq. [l]: V-} where V = bulk wave velocity, in. per psec, T = specimen thickness, in., and / = time, psec. To develop inspection standards, the bulk density of a porous tungsten billet was determined by the ASTM water-immersion technique.3 The ultrasonic-velocity measurements were completed at seventeen positions for each billet and averaged to develop a characteristic standard velocity for a particular tungsten powder at several density levels. A plot of ultrasonic velocity vs density is presented in Fig. 2 for six different tungsten powders. This graph has been established as

Jan 1, 1967

By Robert E. Barieau

This report describes a method for treating pressure-volume-temperature (PVT) data obtained with a Burnett compressibility apparatus. The method makes use of a general nonlinear least-squares technique developed at the Bureau of Mines Helium Research Center. It is assumed that an adequate functional form is available for the expression of the compressibility factor as a function of either the molal density or the pressure. The functional form of the compressibility factor can be either linear or nonlinear in the parameters to be evaluated. Formulas are given for calculating variances and covariances of all parameters evaluated and for calculating the variance of calculated quantities of interest.

Jan 1, 1967

By the use of flotation tests it was confirmed that there are two functions of oxygen in sulphide mineral flotation. Sized samples of galena and chalcopyrite were sulphidized, washed free of excess sulphide ion, and then contacted with air-saturated water for certain lengths of time. The mineral was then transferred to a sealed laboratory flotation cell containing water with a known concentration of dissolved oxygen. Xanthate and frother were added and flotation continued for 1 min.Both the extent of mineral oxidation and the concentration of dissolved oxygen markedly affected the flotation of galena and chalcopyrite. The response to a change in either variable is dependent on the level of the other, but generally best flotation occurs with the maximum degree of air saturation of the pulp. Galena flotation is hindered by oxidation of the mineral beyond a small threshold amount but a similar effect for chalcopyrite was not observed...

Jan 1, 1967

By Jr. Hill

Laboratory metallurgical treatments of three high-iron bauxite ores from Arkansas were conducted to determine the relative effectiveness of experimental methods for recovering alumina and a commercially acceptable iron concentrate. The standard for evaluating recoveries from experimental processes was the Al2O3 recovery from Bayer digests of the crude ores; recoveries from digestion of the three ores were 74.1, 87.4, and 88.7 percent. Flotation, magnetic separation, or various combinations of digestion, calcination, and reduction-sintering, leaching, and magnetic separation of leach residues failed to produce Al2O3 recoveries as high as the standard. A high-iron-bearing fraction, containing between 68 and 78 percent of the total iron, was produced in a three-phase treatment involving a caustic, lime reduction-sinter of the crude ore, water extraction of Al2O3 from the sinter, and magnetic separation of the leach residue.

Jan 1, 1967

By Heinz W. Sternberg

A method for the electrochemical reduction of the benzene ring was developed and applied to the electrochemical reduction of coal. Successive electrochemical reductions of a vitrain from low-volatile bituminous coal in ethylenediamine saturated with lithium chloride resulted in the addition of 53 hydrogens per 100 carbon atoms. Ultimate analyses and pyridine solubility of the vitrain recovered after each reduction showed that hydrogen added at the beginning has a much greater effect on solubility than hydrogen added at a later stage. Surprisingly, the removal of sulfur from the vitrain takes place only after the more reactive aromatic rings are reduced. Nuclear magnetic resonance analysis and average molecular weight determination of the extracts of the reduced vitrain samples, representing about 18 percent of the vitrain, showed that these fractions had 95 percent of their hydrogen content on saturated carbon atoms and an average molecular weight of 800 to 900. A study of the effect of operating variables on current efficiency showed that current efficiency is highest with aluminum as cathode material and with lithium chloride as electrolyte. A substantial increase in current efficiency of difficulty reducible olefinic double bonds was achieved by adding a proton donor. This result is significant in connection with the electrochemical reduction of coal which proceeds from readily reducible aromatic double bonds to difficultly reducible isolated double bonds. It is proposed that reduction is achieved by electrolytically generated and subsequently solvated electrons and hence does not require prior adsorption of the substrate at the electrode surface. This offers a distinct advantage for electrolytic reduction of sparingly or insoluble substrates such as coal.

Jan 1, 1967

By J. F. Shultz

The Bureau of Mines investigated the hydrogenation of carbon monoxide and carbon dioxide over Raney nickel catalyst and nitrided fused-iron catalyst using both a single-pass and a recycle system. Activation energy over Raney nickel catalyst is 29 to 32 kcal/mole for synthesis from either CO or CO2, Pressure dependence of the gas conversion is to the 0.3 power for synthesis from CO and to the 0.5 power for synthesis from CO2. Nitrided fused-iron catalysts were tested using high recycle rates and 3H2+lCO, 2H2+lCO, and 1H2+lCO feed gas at 21.4 atmospheres absolute pressure. The relative usage of hydrogen (moles H2 consumed per moles Ha+CO consumed) was larger than in corresponding single-pass tests, and the relative usage of hydrogen approached the feed gas ratio monotonically as conversion increased. Activation energy was found to be 12 or 13 kcal/mole fresh feed gases of 3H2+lCO or 2H2+lCO. For single-pass operation the activation energy under the same conditions was 19 to 21 kcal/mole.

Jan 1, 1967

"Far from being eclipsed by petroleum and natural gas, Canadian coal continues to command wide (and apparently growing) interest.Major R & D investigations are currently heavily oriented toward coal beneficiation (e.g., cleaning and utilization of fines) and toward a broad range of studies on metallurgical coals and cokes. However, active work is also being carried out in the areas of coal geology, mining, transportation and combustion; and, in some laboratories, increasing stress has been laid on developing a number of new, essentially non-fuel uses for coal and coal products.This review summarizes the work of Canadian coal research agencies during 1966 and indicates some of the more important advances made by them."

Jan 1, 1967

By S. J. Aresco

The Bureau of Mines has been active in promoting the purchase of coal for Government use under specifications that define the requirements in terms of heating value of the coal, expressed in British thermal units, and the composition as shown by proximate analyses. To these, when required, are added the ash-softening temperature, the free-swelling index, and the Hardgrove grindablity index. Under most of these specification contracts the bidders guarantee the quality of the coal, and that guaranteed by the successful bidder becomes the standard of his contract. The deliveries are sampled in accordance with instructions3 issued by the Bureau of Mines; the samples are analyzed in the Bureau laboratory to determine whether the coal is of the quality guaranteed by the contractor; if it is not, a price adjustment is made. Analyses of the delivered coal and tipple samples (samples collected at mine tipples as coal is being loaded into railroad cars or trucks) provide valuable data for use in evaluating future bids. In addition, the continuous of coal as delivered is a check on the practical results obtained in the coal.

Jan 1, 1967

By D. A. Elkins

This report is the second of a series of three that will evaluate, in order, the metallothermic, carbothermic, and electrolytic methods of magnesium production. The historical development of the carbothermic process is outlined. Production costs varying from 38.9 to 21.8 cents per pound of magnesium are estimated for different versions of the process. Additional suggested process modifications are listed. The technical and economic potential of the different versions are compared. Areas deemed most promising for future research on the process are delineated.

Jan 1, 1967

By H. G. Iverson

Solid state reactions of manganese with silica were investigated in high-temperature tests. Reactions of 0.5 to 4.0 moles manganese (Mn) with 1 mole silica (SiO2) at 1,100° C and of 2.0 Mn:SiO2 mole-ratio mixtures at 1,000° to 1,150° C yielded products consisting of a slag phase and a metallic phase. At 1,100° C, the slag phase from reactions of the low Mn:SiO2 mole-ratio mixtures was composed of SiO2 and rhodonite (MnSiO3), and the slag phase from the high Mn:SiO2 mixtures was composed of MnSiOs and tephroite (Mn2SiO4). The metallic phase from the corresponding low Mn:SiO2 mole-ratio reactants consisted of two manganese silicides, Mn5Si3 and Mn3Si; from the high Mn:SiOg mixtures, it was Mn and the manganese silicide (Mn5Si). For the higher mole ratios of MnSiO2 the manganese content in the metallic phase increased, while the manganese and silica contents of the slag phase remained nearly constant. The slags did not contain free or uncombined manganese oxide (MuO). For the 2.5 to 4.0 Mn:SiO2 mole-ratio mixtures reacted at 1,100° C, the maximum quantities of silica reduced and of the manganese in the slag appeared to become asymptotical at about 41 and 48 percent, respectively. A brominating procedure was developed that was highly selective in removing the metallic constituents from the reaction product, leaving the slag phase as residue. X-ray diffraction patterns were obtained on prepared silicides Mn5Si, Mn3Si, and MnSi.

Jan 1, 1967

By E. R. Dean

A wire-feed mechanism has been employed to fabricute metal alloy film resistors to various sheet resistivities on oxidized silicon substrates. The effect of several thousand hours storage in air at elevated temperatures on the resistance and temperature coefficient of resistance is presented. Unprotected films of- sheet resistivity between 100 and 500 ohms per sq fabricated at 300°C substrate tenzperatures were unstable when stored at 150°Cfor extended periods. The higher sheet resistivity films exhibited the greatest instability; however, even the 100 ohms per sq films drijted excessively for device application. When stored at still higher temperatures, the normalized resistance increases to maximum, then decreases until a minimum value is obtained, then finally increases in resistance until open. The use of a protective overcoating of SiO has had considerable benejicial effects on the film stability, so that 250 ohms per sq films deposited on 300°C substrates are now stable after 1000 hr storage at 250°C and possess a temperature coefficient of resistance less than 200 ppm per C. The use of a low substrate temperature during depositon (100°C) enables the preparation oj resistors with very low tenperature coefficients of resistance (10 to 20 ppnl per 'C). However, these films are less stable than their higher substrate temperatuve counterparts. During extended storage, the resistance of the protected films always decreases with lower substrate films exhibiting larger normalized resistance decreases. This resistance decrease is accompanied by a linearly related increase in the temperature coefficient of resistance. The electrical behavior of these films may be explained by postulating That the structure of the films is in the transition region between thick continuous films and ultrathin island structure films so that the conductivity is the restlt of both electron scattering and tunneling-activated charge carrier creation between neighboring grains. The annealing behavior when thermally aged is the result of defect anneal, grain growth, and selective oxidation. TheRE is a considerable interest in thin metallic films for use as resistor elements in microelectronic circuits.1,2 These resistor films must be stable when exposed to elevated-temperature storage or operating ambient, possess low temperature coefficients of resistance (hereafter referred to as T.C.R.), and be of a high enough sheet resistivity to be useful. The resistivity and T.C.R. of a thin metallic film are determined by the structure and thickness of the film. Hence the stability of the film when exposed to stress would depend on the stability of the structure. The resistivity of a thin film is the result of the electrons' interaction with the lattice vibrations (electron-phonon scattering), scattering of electrons due to impurities, defects, and grain boundaries and specula reflection from the film surfaces.3' All of these effects serve to reduce the electron mean free path and result in a resistivity higher than the ideal bulk. In ultrathin films possessing essentially an island structure consisting of a planar array of aggregates separated by a few to a few tens of angstroms, conduction is dominated by a combination of tunneling and activated charge carrier reation. Thin films would be characterized by relatively low resistivity, positive T.C.R., and reasonable structure stability whereas ultrathin films possess unstable structures, negative T.C.R., and exhibit high resistivity. Feldman6 has investigated films intermediate between the two regions and postulates that the resistivity of a film in the transition region is composed of two linearly additive parts: that due to the resistance of the grains and that due to the gaps. The grain resistivity would represent the scattering of the conduction electrons by defects, surfaces, and phonon interaction while the gap term represents the tunneling contribution. For gold and platinum films, he found as the film structure becomes progressively less continuous, corresponding to thinner films, the absolute value of the T.C.R. becomes progressively smaller until negative values are observed with respective zero T.C.R.'s at about 35 and 150 ohm per sq, respectively. Recently the author7 investigated the behavior of a multicomponent alloy of nickel, chromium, and iron and found the T.C.R.'s of these films decrease with decreasing substrate temperature during deposition. The lower T.C.A. associated with lower substrate temperatures was attributed to an increased contribution to the total resistivity from the negatively temperature-dependent gap tunneling since it is well-known that thin films deposited on low-temperature substrates consist of a higher density of smaller grains than the same sheet resistivity films deposited on higher-temperature substrates. Under conditions of thermal anneal, the author found that, when various sheet resistivity films fabricated at 300°C substrate temperature are exposed to extended storage in air at 300°C, the thinner films increase in resistance until open, while the thicker films

Jan 1, 1967

By Robert E. Barieau

General expressions for evaluating practically all the thermodynamic properties of a fluid from a single equation of state are derived. Most of the formulas are expressed in terms of the compressibility factor, with this factor being an explicit function of the temperature and the molal density. Similar expressions are given using reduced variables.

Jan 1, 1967

By L. C. George

The Bureau of Mines measured vapor pressures of selected mixtures in the binary system SnCla-ZnC12 by the static pressure method. Equations expressing the vapor pressure) and the heat and free energy of vaporization) as functions of temperature were developed by numerical analysis based on the sigma-plot method. It was found that the vapor pressure of any SnCl2-ZnCl2 mixture) at any temperature within the range of this investigation) could be accurately calculated from the derived values for the heat and free energy of vaporization for the mixture, with a probable error of 0.01 cm Hg or less.

Jan 1, 1967

By N. F. Schulz, H. A. Lex, J. D. Zetterstrom

A green ball of iron ore faces many perils from the time it is formed until it finally emerges from the pelletizing furnace as a hardened pellet. For instance, if the rate of heat transfer into a ball is sufficient to produce vapor from either the free or combined water more rapidly than it can escape at a tolerable pressure, the ball may split, spall, or even explode, a failure commonly known as decrepitation. To avoid such failures, one must either limit the rate of heat transfer during the drying and preheating stages, at the expense of production rates, or improve the decrepitation resistance of the green balls. The latter remedy may often be accomplished through changes in ore preparation, balling procedures, or the judicious use of binders or other additives. INTRODUCTION Pelletization has become established as an especially desirable method for the agglomeration of fine taconite concentrates and it promises to be equally satisfactory for improving the physical structures of certain natural ores. A high-quality pelletized iron ore consists of uniformly sized spheres, usually about 1/2-in. diam, which are strong enough to resist abrasion and breakage during handling and which reduce well without disintegration in the blast furnace. The unfired agglomerates, "green balls", are subject to several destructive effects that must be avoided or minimized if a high-quality product is to be obtained by pelletization. Among these are abrasion and impact deformation or breakage during handling of the wet green balls, deformation and breakage by compressive forces in the bed of ore in the pel-letizing furnace, decrepitation during drying and preheating, wind erosion, and radial cracking at firing temperatures. Moisture condensation from the warm saturated gases downstream from the drying zone on wet, cool balls may cause bed collapse if it becomes excessive. Decrepitation is defined as the sudden disintegration of green balls, usually with an audible pop, that occurs when they are heated too rapidly during the drying or preheating stages of the pelletization process. The extent of ball disintegration may vary from merely splitting off a small fragment to almost total disintegration into the original ore particles making up the ball. Such ball destruction results in a decreased yield of pellets, and the fragments, which also tend to interfere by obstructing the gas flow through the bed, must eventually be screened from the fired product and recycled. The closely related type of ball failure that sometimes occurs during the high temperature firing stage, resulting in radial cracks without fragmentation, was not considered to be decrepitation for the purpose of this investigation. Failure by decrepitation is not usually a serious problem in the pelletization of taconite concentrates. The problem is significant, however, in the pelletization of some natural ores, especially those containing hydrous iron oxides. In some instances, economicd production rates cannot be maintained if the drying and preheating rates are slowed down enough to avoid decrepitation. OBJECTIVES This investigation was undertaken to: (1) Develop a practical laboratory means for quantitatively measuring the tendency for green balls to decrepitate in iron ore pelletizing furnaces, and (2) Investigate the causes and cures of ball decrepitation. MATERIALS Two iron ores were used in the work reported here: a taconite concentrate at 90% minus 325 mesh, containing 65.0% Fe, 8.4% SiO2, and no loss-on-ignition; and a crude oxidized ore at 54% minus 325 mesh, containing 59.1% Fe, 3.6% SiO2, 1.1% A12O3, and 9.5% loss-on-ignition. For a special test of effect of particle size distribution on decrepitation, two other

Jan 1, 1967

By Ursula E. Wolff

The precipitation of carbides from an alloy containing 33 pct Ni, 21 pct Cr, balance iron, was investigated electron microscopically by means of extraction replicas and thinned metal foils. Annealing temperatures ranged from 565°to 870°C and up to several thousand hours. M23C6 precipitated in pain boundaries, incoherent and coherent twin boundaries in that sequence. The orientation relationship between carbides and austenite matrix was determined and correlated with the morphology of the carbides and with the type of boundary in which precipitation occurred. In large-angle grain boundaries, as well as in coherent twin boundaries, the carbides had the same orientation as one of the adjacent pains. These carbides formed sheets of individual flakes with shapes related to the orientation of the boundary. In incoherent twin boundaries carbides precipitated in ribbons composed of pavallel rods. An unidentified subcarbide was found to precede precipitation of M23C6 in these boundaries. The M 23 C6 rods had a kind of fiber texture with (110) parallel to the long dimension of the rods and ribbon, and with orientations of both of the adjacent twin-related austenite crystals Predominant in the texture of the carbide. A hard sphere crystal model has been used to discuss orientation and morphology of the carbides in terms of free volume and vacancies available in the boundaries. A number of papers have dealt with the morphology of chromium carbide (M23 C6) precipitated in austenitic stainless steels.1"7 In all these investigations, the carbides were examined in the electron microscope by means of extraction replicas. With this technique, the carbides retain the spatial distribution they had in the bulk sample. However, since the matrix is dissolved in the process, the particles can turn in an unpredictable way; and the orientation relationship between matrix and carbides cannot be established. In this paper the results of studies on extraction replicas and on thinned metal foils are reported. These studies were undertaken to determine the matrix-to-car bide orientation relationship, and to correlate the orientation of the carbides with their morphology. PROCEDURE The material used was an austenitic alloy with 33 pct Ni, 21 pct Cr, balance iron, containing approximately 0.05 pct C. Coupons of 1.25-mm sheet were first solution-annealed at 1050°C for 15 min and air-cooled. Then, to precipitate the carbides, samples were isothermally annealed in the range from 565" to 870°C for times up to several thousand hours. All further specimen-preparation procedures were carried out after the final anneal. Carbon extraction replicas from polished and etched surfaces were made with 10 pct bromine in methyl alcohol.' Thin foils were prepared from punched-out 3-mm-diam disksg which fit into the electron-microscope holder. The disks were prethinned by grinding to approximately 0.5 mm thickness, and then electro-polished in a polytetrafluoroethylene holder1' with a solution containing 5 pct perchloric acid in acetic acid to which 10 g per 1 Cro3 and 5 g per 1 nickel chloride were added (etchant modified from that of Briers et al."). This solution dissolves neither the carbides nor the austenite around the carbides preferentially. By using extraction replicas, electron micrographs and selected-area electron-diffraction patterns were taken from the same carbide arrays. By using thin foils, electron micrographs were made from a grain boundary area containing carbides. Electron-diffraction patterns were then taken from the same area and from each of the adjacent grains separately. In this manner, the orientation of each grain could be determined without interference by the carbide pattern. A peculiarity of extraction replicas should be pointed out. After the matrix is etched away, the carbide arrays float freely in the etching and washing solutions, and are held in place only at the anchoring points in the carbon replica. When the replica is picked up with a screen the carbide arrays tend to flip to one side. Thus, while the surface features are preserved, the original arrangement of the carbides may severely and unpredictably be disturbed whenever the specimen contains large amounts of interconnected carbides. Nevertheless, it is possible to correlate the different morphologies of the carbides with the type of boundary in which they have precipitated. RESULTS 1) Extraction Replicas. Fig. 1 shows that the grain boundaries usually are curved, multicornered surfaces of random orientation. The coherent twin boundaries (which are (111) planes) cut a grain into parallel slices. Incoherent twin boundaries occur at the ends and on the steps of twins and are often narrow, parallel-sided strips which are much longer than they are wide. Different morphologies can clearly be distinguished for the M23Ce carbides precipitated in each of these types of boundaries, and agree well with those observed by kinzel.2 The kinetics of this precipitation has been investigated." The first carbides precipitate in junctions of three grain boundaries and fan out from there into the adjoining boundary surfaces, Fig. 2(a). These carbides are oriented randomly, Fig. 2(b), and become coarser and thicker as annealing time increases. The large-angle grain boundaries are next to fill

Jan 1, 1967

By E. G. King

The Bureau of Mines made experimental determinations of the heats of formation of forsterite and chrysotile at 298.15° K. The heat capacities of two polymorphs of serpentine, chrysotile and antigorite, were measured over the temperature range from 50° to 298° K and the entropies at 298.15° K were evaluated. The heat content of antigorite above 298.15° K was measured to 850° K. These thermochemical data were combined with other pertinent data to give heat and free energy of formation values at high temperatures. Free energy values are given for the reaction, forsterite + water = brucite + serpentine at different temperatures and pressures.

Jan 1, 1967