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By P. Somasundaran Discussion by Knut L. Sandvik

Knut L. Sandvik (Mining Engineer, Mineral Dressing Laboratory, Technical University of Norway, Trond-heim, Norway) — The discovery that adsorption at solid-liquid interfaces is influenced by adsorption at other interfaces may prove very fruitful in the further development of flotation theory. Having reached the same conclusions as P. Somasundaran in some experiments with amine hydrochlorides, I would like to offer more direct evidence of the interfacial adsorption mechanism based on surface tension measurements and adsorption studies.' This evidence was derived from flotation tests carried out in a Hallimond tube at neutral pH and 60°C. The amount of amine solution and quartz surface were chosen to insure measurable concentration changes during flotation due to adsorption. Adsorption data for

Jan 1, 1969

By K. R. Dorman

To further investigate the potential of precast concrete sets as a support medium for underground mines, the Bureau of Mines designed a five-piece precast concrete drift set for a small opening and tested it to destruction in a straining frame. Twenty-seven tests were made with three sizes of members using three loading conditions. In addition, six tests were made with sets in a distorted configuration, Test results and typical failure patterns are presented. A comparison of results with those previously reported for the three-piece set shows the five-piece set supports considerably larger total loads than does the three-piece set of equivalent cross section designed for the same size of opening. Recommendations are made for improvements in design.

Jan 1, 1969

By M. R. Geer

The Bureau of Mines surveyed the solid wastes that have accumulated from coal mining in Washington, Oregon, and Montana. Location, amount, character, and condition were determined, and both economic and environmental factors were considered. Areas covered by waste comprise 800 acres in Washington, 5 acres in Oregon, and 1,200 acres in Montana. In a few cases waste is being utilized, particularly cinder from burned refuse dumps, as fill in road construction and as a ceramic raw material. It is estimated that wastes deriving from coal mined for electric power generation by 1974 may amount to 3 million tons of washery refuse, 2.7 million tons of fly ash, and 1,000 acres of spoil banks.

Jan 1, 1969

By B. N. Das, H. E. LaBelle, G. A. Wolf

ZnxHg1-xTe and GUPxAS1-x crystals have been grown from solution by a traveling heater method (THM). In a floating zone type fashion a solution zone sandwich of liquidus composition is made to migrate through feed material of solidus composition by a slow-speed movement of <0.25 mm per hr of the total charge through a stationary radiation or rf heater. ZnxHg1-xTe of composition 0 < x < 0.3 and GUPxAS1-x of composition 0.5 < x < 0.7 have thus been grown from their solution in liquid tellurium and gallium, respectively. A simplified analysis of heat and material transport is given. In this method, Proper adjustment of the temperature distribution along the liquid solution zone axis eliminates instability of the crystal growth front and constitutional supercooling. 1) ZnxHg1—xTe: The solid-solution telluride was grown in sealed quartz tubes at a temperature of 500 to 650°C. For first Preparations mechanical mixtures SINGLE crystals of solid solutions of III-V and II-VI compounds have been grown by various techniques from the melt, from the gaseous phase, or from solutions in of ZnTe and HgTe were used. X-ray determinations showed the resulting crystals to be homogeneous throughout their entire length, except for the end sections. The homogeneity is greatly improved by reusing the ingots obtained from first Preparations as feed material in subsequent crystal growth runs. Ingots of up to 4.5 cm have thus been obtained. 2) GaPxAs1-x: Crystals were grown in a EN crucible at a temperature of 1050°C. For first Preparation a mechanical mixture of Gap and GaAs was cemented together by a minimum amount of liquid gallium through "wet" grinding of Gap and GaAs crystals in the liquid metal and subsequent exuding of excess gallium by compacting of the charge in the EN crucible. Electron microprobe measurements using P-Ka and As-Ka radiation showed uniformity over a length of 0.4 cm. Properties of the various Preparations are described. liquid metals.&apos;-&apos; Their growth from the melt by passing a liquid zone of pseudobinary liquidus composition through a solid rod of solidus composition is generally a convenient method of growth of single crystals of solid solutions of homogeneous composition. This method loses much of its usefulness, however, if the melting point or the vapor pressure of the solid solution is high. In the case of a compound having a high melting

Jan 1, 1969

By J. G. Benford, E. B. Stanley

THERE have been numerous papers in the literature1 on the subjects of secondary and tertiary recrystalli-zation in silicon steels. Secondary re crystallization is believed to occur in silicon steel by either a surface-energy phenomenon such as in the usual development of cube texture or by a second-phase phenomenon such as in the usual production of cube-on-edge texture, (110)[001]. Tertiary recrystallization in silicon steel is thought to be a surface-energy phenomenon in which, for example, grains having a (110) plane parallel to the sheet grow at the expense of other grains in the matrix including those having a (100) plane parallel to the plane of the sheet. In all these instances, the orientations involve either a preferred (100) or (110) plane in the plane of the sheet. Until very recently, there had been no experimental evidence reported of the occurrence of a texture by secondary or tertiary recrystallization that involves a (111) plane in the plane of the sheet, although Kohler reported that grains having the (111) plane parallel to the sheet surface can also grow by a surface energy mechanism. Stickels observed a secondary texture in iron described as "near {554}(225)" about 5 deg from {lll}(211).3 Mee reported that in a vacuum-remelted commercial 3 pct Si steel {lll}(hkl) secondary recrystallization took place in a high vacuum and in pure hydrogen.4 Recently in our Laboratory, large-grained structures such as shown in Fig. 1 having an orientation near (111)[211] or (111)[2ii] have been observed. The arrows point to areas of relatively small matrix grains of the kind that the much larger (111) grains consumed while growing. It is of interest that the matrix grains of samples annealed at 2000°F were essentially the same size as those in samples annealed at 2200°F, a matrix-grain-size stability that is characteristic of secondary recrystallization processes. A torque disc taken from Grain 4 of the sample shown in Fig. 1 revealed a very flat magnetic-torque curve, as expected, with a maximum torque of 7000 dyne-cm per cu cm compared to the typical 180,000 dyne-cm per cu cm observed for conventional (110)[001] textured material. A back-reflection Laue pattern for Grain 4 is shown in Fig. 2 and indicates a near-perfect (111)[211] orientation. The other six numbered grains in the sample of Fig. 1 had a similar orientation. The small circles next to each number were the target areas for the X-ray beam. The starting material was an 0.011-in.-thick oriented silicon steel, (110)[001] texture, containing 3 pct Si. It was lightly pickled, cold-rolled to 0.005 in., and annealed 4 hr at 2200°F within a nickel box (not gas-tight) inside a tube furnace through which dry hydrogen was flowing. The samples were heated to 1500°F in 1 hr and then at 60°F per hr to 2200°F. There were other

Jan 1, 1969

By H. H. Keller, E. J. Couch

Damage to production wells subjected to the high temperatures associated with in-situ combustion projects has been a problem since the advent of this thermal recovery technique. Injection of water down the annulus of hot wells has been successfully utilized for cooling and prolonging the life of such wells. A mathematical model that is suitable for predicting the effectiveness of cooling water in a particular application is developed. Typical results for practical ranges of the various parameters involved are presented. INTRODUCTION In the normal course of in-situ combustion operations, highly damaging conditions develop in the production wells as the combustion zone approaches, and these wells are subjected to high temperatures (up to 1500F). The resulting well damage is recognized as one of the more serious operating problems unique to the in-situ combustion process. Even in operations where well completions have been specifically designed to cope with this problem, the question arises as to how this destructively high temperature can be kept within tolerable limits. A simple and economical approach to this problem is to circulate cooling water down-hole. This method has been used with some success in shallow reservoirs. At greater depths, however, the heat exchange with the overburden surrounding the well and between the fluids in the tubing and the annulus tends to equalize the temperatures of the two fluid streams so that the cooling capacity delivered to the bottom of the hole decreases with well depth. This method would provide no appreciable control over the bottom-hole temperature at great depths. In order to delimit the condition under which cooling by water circulation is effective, the wellbore temperature must be related to the water inlet rate and temperature; to the reservoir depth, production rate, and initial temperature; and to the combustion at at bot tom-hole depth. A model that meets these requirements and that will offer an approach for developing engineering solutions to practical design and operating problems is described in this paper. MATHEMATICAL MODEL Previous studies of temperature distributions include those for flowing wells1p2 and those for hot fluid injection. Adams and Haddenhorst 6 presented solutions for the down-hole circulation of hot oil in the treatment of paraffin-deposition problems. In this paper the thermal model presented by Ramey 4 is adapted to the flow system shown schematically in Fig. 1. Water at temperature Ti is injected at a rate wi and flows down the annulus outside the tubing. It mixes at bottom-hole depth D with the fluids produced at race w from the hot reservoir at temperature T. This mlxtureJ. of injected water and reservoir fluids flows up the tubing and is produced at the surface at TI,. In order to describe the temperature response in this system, we make use of the usual conservation of

Jan 1, 1969

By James Yancik

The Howe Coal Company located in Leflore County, Oklahoma is mining the Oklahoma Lower Hartshorne Coal bed which ranges in thickness from 38" to 42" and dips approximately 7 degrees to the Northeast. The Lower Hartshorne bed lies within the Hartshorne sandstone in Oklahoma but is as much as 60 feet above this sandstone formation in Arkansas. This coal bed extends throughout the Arkansas Oklahoma coal basin, which is about 50 miles wide and 180 miles long and progresses from a semi anthracite in Arkansas to a low-volatile coal in the eastern part of the Oklahoma to a high-volatile coal in the western area. The Howe Mine #1 in the eastern area is mining a low-volatile bituminous coal which has been used as metallurgical coal since the early 1900&apos;s as evidence of Bee-hive coke ovens still remain near the town Howe, a few miles northwest of the mine site. The Howe Mine is the first mine in the area to use modern mining equipment, however, numerous punch mines have been worked along the outcrop south of the mine site dating from 1900 with the last closing in 1965. The coal characteristics of the Lower Hartshorne rival the Pocahontas seam in chemistry and coking qualities. This paper will be concerned with the preparation of the coal for the Japanese steel market. The three man crew necessary to operate the plant are the operator, the helper, and the equipment operator needed to feed the raw coal hopper. An additional equipment operator is available on the day shift for coal loading and moving the clean coal to the storage pile as the area under the clean coal belt is only large enough for 1 shifts production. We are at present running the plant on a 2 shift per day basis.

Jan 1, 1969

By Carl F. Cline, Richard R. Vandervoort, Willis L. Barmore

THE objective of this investigation was to determine the high-temperature plastic deformation behavior of stoichiometric uranium mononitride as a function of stress and temperature. Interest in the properties of this material stems from its potential use in high-temperature nuclear reactor systems. The creep of other refractory compounds containing uranium (e.g., U02, UC) has been studied by various investigators.1"4 Fassler et al.4 have studied the creep of UN in vacuum from 1100° to 1350°C at stresses of 6000 and 8000 psi. In the present work, the creep of stoichiometric UN was investigated from 1500° to 1800°C at stresses from 2000 to 5000 psi in a partial pressure of 200 mm of nitrogen. The specimens were prepared by hot isostatic pressing of UN powder into cylinders of $ in. diam by about 1 in. high. After pressing, the specimens were heat-treated in nitrogen at 1900°C for 50 hr. The densities of individual specimens were determined by the water displacement method. All specimens were theoretically dense, based on a value of 14.32 g per cu cm.5 Principal metallic impurities in ppm by weight were: Ca, 50; Cu, 5; Fe, 30; Mg, 5; Ni, 10; and Si, 20. Oxygen content was 400 ± 50 pprn and carbon content was 100 i25 ppm. The nitrogen content was 5.56 ±0.05 wt pct. The average grain size for five specimens, as determined by the intercept method, was 0.14 i 0.01 mm. One specimen had a grain size of 2.0 mm. This large grain size is an anomaly, since all specimens had the same chemical and thermal histories. Specimens of 1/4 in. diam by 1/2 in. high were creep-tested in compression in a clam shell furnace heated by W-25 pct Re sheet elements. Temperature was measured to ilODC by an optical pyrometer which had been calibrated by a standard source. The distance between fiducial marks on the specimen was measured before placement into the furnace. The furnace chamber was evacuated to 10-5 Torr and back-filled to 200 mm N2. After heating rapidly to temperature, the load was applied and controlled to ±2 pct by an Instron testing machine. Upon initial loading, the specimen was deformed until a constant crosshead rate was obtained, then quenched to room temperature, remeasured, and replaced in the furnace. Upon subsequent reloading at temperature, the crosshead rate was constant for the selected condition indicating steady-state creep.

Jan 1, 1969

By Karl C. Dean

The Bureau of Mines stabilized 10 acres of windblown copper mill tailings at McGill, Nev., by a combination chemical-vegetative procedure. Legumes, winter wheat, wheat-grasses, and wild rye were seeded, and the area was subsequently sprayed with a resinous adhesive chemical to stabilize the sands until the vegetation could grow. During the year since treatment, the area has been well stabilized against wind erosion. The established vegetation appears to be capable of self-perpetuation and renewal without irrigation. The cost of stabilizing the area was $135.50 per acre.

Jan 1, 1969

By J. P. Neumann, Y. A. Chang

Lattice parameter measurements of the hcp phase in the system Ag-A1 near the stoichiometric composition Ag2Al were carried out for specimens quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K. The three heat treatments resulted in the same lattice parameters at room temperature. None of the specimens showed any superlattice lines. The lattice parameters of this alloy were also measured at temperature from 77° to 750°K. An anomaly in the temperature variation of the lattice paramete.rs occurs in the region near 400°k, which may be associated with local ordering. FROM measurements of the diffuse scattering of X-rays, it is known that the [ phase in the system Ag-A1 near the stoichiometric composition Ag2A1 ex- hibits a considerable degree of short-range order at room temperature.&apos; Moreover, based on the position of the short-range order peaks a superlattice model had been proposed in the same study and it was suggested that lowering the annealing temperature to 420°K might result in long-range order. In the present study, the diffraction patterns and the lattice parameters of three differently heat-treated specimens, i.e., quenched from 825°K, annealed for 10 days at 453°K, and annealed for 100 days at 413°K, were determined from 77" to 750°K. The purpose of these measurements was to investigate 1) whether long-range order could be established by prolonged annealing and 2) whether the lattice parameters at room temperature depended on the heat treatment, since it had been proposed earlier2 that the lattice parameters in this phase are related to the atomic arrangement. 1) EXPERIMENTAL TECHNIQUES Silver and aluminum, both 99.99 pct purity, were melted in a zirconium oxide crucible under helium in

Jan 1, 1969

By Carl F. Wingquist

In support of Bureau of Mines studies of thermal fragmentation of rock, the elastic moduli of four types of rock were measured at temperatures ranging from room temperature up to 1,500° F (1,089° K). The sonic method was employed to determine the resonant frequencies of the rock specimens and from these frequencies, the elastic moduli were calculated. Data for Young&apos;s modulus, shear modulus, and Poisson&apos;s ratio are given as a function of temperature for Dresser basalt, Reserve taconite, Jasper quartzite, and Charcoal granite. Young&apos;s modulus and the shear modulus decreased with increasing temperature up to about 1,200° F and then became relatively insensitive to temperatures from 1,200° to 1,500° F.

Jan 1, 1969

By J. S. Blakemore, E. O. Hall

SERRATED yielding, commonly called the Portevin-Le Chatelier effect, is known to occur in a wide range of alloys where the moving dislocations are considered to be locked by the diffusion of solute atoms to them. From the work of Cottrell,1 an approximate relationship between strain rate, E, dislocation density, p , and solute diffusion coefficient, D, giving rise to serrated yielding is: e =Dp

Jan 1, 1969

By S. Dinda

A series of as -quenched 4340 bars were drawn through a carbide die to various reductions. The X-ray diffraction technique of Lopata and Kula was employed to detect preferred orientation in drawn martensitic steel bars with low amounts of deformation, as lord as 0.8 pct The specimen face of each bar examined was cut at a 45-deg angle to the bar axis. The reflecting planes in the 45-deg face were varied by appropriate rotation of the sample using a spectrogonionzeter. TIE X-ray bean of a diffractometer was reflected from the center of the bar and the diffracted intensity was delected with a proportional counter and recorded. Intensity peaks were developed by cold working for 110 planes oriented at 0 and 60 deg to the bar axis. The intensity peaks increased with increasing defortnalion us a preferred orientation with a 110 texture developed parallel to the drawing direction. The intensity peaks for deformed as-quenched specimens remain unchanged after tempering at temperatures as high as 1000°F. The same amount of preferred orienlalion was observed both inferritic (hot-rolled) and martensitic (as-quenched) structures after an equivalent amount of deformation. THE deformation of martensite with medium carbon content. less than 0.5 pct, has been studied by Breyer et a1.1,2 It was reported that changes in properties such as resistivity, carbide precipitation, and the introduction of a yield point phenomenon were produced after cold reduction of as-quenched AISI 4340 steel bars. Later, Breyer and Nachtman3 studied the effect of cold reduction upon X-ray line intensity. They showed that the integrated 110 line intensity increased with increasing deformation when the planes examined were perpendicular to the die drawing direction. The integrated 110 line intensity for planes oriented at 45 deg to the die drawing direction, in contrast, were found to slightly decrease. These changes were proposed to be consistent with the previously proposed model of a stress-induced ordering of carbon atoms in the vicinity of dislocations.1,2 Objections can be raised to the above interpretation of the X-ray results on two grounds: a) Rough structure factor calculations indicate that the intensity changes are too large (50 pct observed vs 2 pct calculated4,5) to be the result of changes in the location of iron atoms produced by the stress-induced ordering of the carbon atoms. b) The results might be explained in terms of preferred orientations, although X-ray evidence of the development of texture has not been reported in the literature for deformations as slight as 1 or 2 pct. The aim of the present work was to determine if preferred orientation was present in such cold-drawn martensitic steel bars. In drawn rod or wire there is generally a certain crystallographic direction which is aligned in the direction of the wire axis, and the crystallographic planes are distributed symmetrically around this "fiber axis".6-8 This type of cylindrical specimen, with the fiber axis located at the center, will show rotational symmetry. Lopata and Kula9 proposed an experimental method utilizing a specimen cut at 45 deg, see Fig. 1. The X-ray beam is diffracted from the center of this bar cross section. The specimen is rotated around an axis perpendicular to the bar axis and lying in the 45-deg cut face. This permits the angle between the normals to the reflecting planes and the bar axis to be varied from 0 to 90 deg.9 With this arrangement the errors due to absorption and irradiated volume compensate each other.&apos; This greatly simplifies analysis of the data and is of considerable advantage for quantitative measurements. If there is preferred orientation in the specimen, more planes are oriented in a particular direction in the bar. When the bar is rotated to the favorable Bragg condition for that particular orientation, the intensity will be higher than that for some other angle. This technique was adopted for the present investigation.

Jan 1, 1969

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The existence of a surface charge on the alkali halide salts is shown, and a flotation mechanism involving surface charge and collector solubility is developed. Data suggest that KC1 is positively charged and that NaCl is negatively charged in saturated brines, and that the neutral molecule RNH,Cl is the collector in the amine-KC1 system, RSO, is the collector in the sulfonate-KC1 system, and RCOONa) is the collector in the fatty acid-NaCl system. A number of hypotheses have been advanced to explain the mechanism of soluble salt flotation; one of these involves exchange between collector ions and surface cations. With this mechanism Gaudin1 suggested that the differences in flotability of halite and sylvite with primary amines are due to the ionic size of the RNH;, Kt, and Na t ions. Fuerstenau and Fuerstenau expanded this hypothesis to include many other alkali halide salts. Several exceptions to this hypothesis are known. That is, this model does not explain why salts containing the same cation, or why salts of different degrees of hydration, respond differently to flotation. For example, why NaI is floated with an amine whereas NaI .2H,O is not. Further, no correlation between ionic size and flotation response can be made with sulfonate or car-boxylate as collectors. In addition, this hypothesis does not explain the effect of magnesium or lead activation, nor does it offer any explanation of the role of temperature in salt flotation. Rogers and Schulman3 realized some of the inadequacies of the ion exchange mechanism and proposed another mechanism based on the heat of solution of the salts. They concluded that weakly hydrated salts can be floated with alkyl amines and sulfonates, that strongly hydrated salts can be floated with fatty acids, and that excessively hydrated salts cannot be floated at all. Their work was not limited to the al-

Jan 1, 1969

By N. G. W. Cook

The conventional cyclic system of deep-level mining by drilling and blasting gives rise to an inadequate degree of stope sorting when mining thin reefs. This results in poor utilization of the capital facilities of a mine in the form of shafts, haulages, airways and associated equipment. Continuous and controlled removal of the thin gold-bearing portion of the reefs would permit better stope sorting and hence greater utilization of capital facilities. Results of experiments to develop hard rock cutting machines for mining are reported and the benefits which could be derived from their use are discussed.

Jan 1, 1969

By Norman F. Schulz

The technical excellence of separation achieved in a mineral concentration process, or any other process where two constituents of any kind are physically separated from each other, is expressed uniquely and quantitatively by the Separation Efficiency: ES = (R ? Rg) where R is the percentage of the valuable constituent and Rg the percentage of the waste appearing in the concentrate. The Separation Efficiency meets all the usual requirements of a true efficiency and is independent of the nature of the process used. It can be visualized as the percentage of the feed material that, in effect, actually undergoes complete separation while the rest of the feed is distributed randomly and unchanged into the two separation products.

Jan 1, 1969

The Bulli and Wongawilli Seams, the two principal sources of coking coal for the Port Kembla steelworks of Australian Iron &amp; Steel Pty. Ltd., vary in rank and in type over the Southern and South Western Coalfields.The Bulli Seam, ranging widely in type, produces coke varying from weak to strong. The Wongawilli Seam, more consistent in type, produces coke of more consistent strength, but considerably less strong than that from the best Bulli Seam coal.Plans of seam variation show the regional trends in rank and type for each seam.The strongest coke is derived from coal containing between 45 and 55 per cent vitrinite, m.m.f. This is obtainable from the Bulli Seam in a zone embracing Bulli and Appin collieries.A satisfactory correlation is achieved between vitrinite content and coke stability and hardness, enabling prediction of coke strength for Southern Coalfield coals.The use of vitrinite reflectance, as an indicator of rank, in addition to type to predict coke strengths is at present hampered by lack of data, particularly in the South Western Coalfield. Nevertheless, data available at present allow the use of both variables and give better correlations with coke strengths than type alone.A spread of comprehensive data across both coalfields will enable advance assessment of cokes produced from coals having known rank and type. Blending to a ranktype specification for optimum coke strengths would allow the best use of the coal reserves of the coalfields.

Jan 1, 1969

By E. T. Turkdogan, W. L. Worrell

The rate of reaction of hydrogen sulfide with ferrous sulfide was studied by measuring the initial rates of sulfidation of iron strips in hydrogen sulfide-hydrogen-argon mixtures at 670°, 800°, and 900" C. The time-dependent surface sulfur activity is derived from the instantaneous rate of sulfidation with the assumption that diffusion in the sulfide layer is in a pseudo-steady state with the gas-sulfide chemical reaction. The rate of sulfur transfer from hydrogen sulfide to the surface of iron sulfide is proportional to the partial pressure of hydrogen sulfide and inversely proportional to the activity of sulfur at the surface of the sulfide layer. The derived rate equation is based on the assumption that most of the surface sites on the chemisorbed layer of iron sulfide are occupied by sulfur atoms and that the slow rate-controlling reaction is the dissociation of hydrogen sulfide on the chemisorbed layer. The experimental results are in reasonable accord with this reaction model. 1 HE slow approach to parabolic growth rate in the sulfidation of iron in hydrogen sulfide-hydrogen mixtures is a manifestation of slow approach to surface equilibrium between the gas and the surface of the sulfide layer. For example, at 800°C and Fig. 7 in Part I, the parabolic growth rate begins after approximately 1 day of sulfidation time. With decreasing temperature and decreasing partial pressure of hydrogen sulfide, the time necessary to reach gas-sulfide surface equilibrium is much longer. These observations are similar to those reported previously by Turkdogan et al.&apos; on the oxidation of iron to wustite in hydrogen-water vapor mixtures. The slow approach to gas-sulfide equilibrium is well-demonstrated by the results in Fig. 1 where the square of the weight gain per unit area, ( g S per sq cmI2, is plotted against time for gas mixtures having PH g//>H = 1.0 with 0, 25, 50, and 67 pct Ar at 800°C. The value of 1.5 X lo-&apos; (g S per sq cm)&apos; corresponds to almost complete sulfidation of the iron strip (- 0.05 cm thick) to iron sulfide. The points fall on S-shaped curves. If the inflection parts of the curves are considered to be linear, thus indicating parabolic growth rate and the establishment of gas-sulfide equilibrium, their slopes would have to be the same for a fixed ratio in the gas mixture. Such is not the case, and the slopes for the "linear" parts of the S-shaped curves are lower than the value when gas-sulfide surface equilibrium is established. The subject matter of this paper is the kinetics of the surface reaction of hydrogen sulfide with iron sulfide during the early stages of sulfidation of an iron strip. EXPERIMENTAL RESULTS The apparatus and materials used were the same as those discussed in Part I. In the present experiments of relatively short duration, a purified iron strip, 5 by 2 by 0.05 cm, which was suspended in the uniform hot zone of a vertical zircon tube, reacted with a flowing gas mixture of hydrogen sulfide-hydrogen-argon. The sample was suspended from a gold chain attached to a calibrated silica spring. The amount of sulfur picked up by the iron, which formed a layer of iron sulfide, was determined by measuring the displacement of a reference point on the silica spring, using a cathetom-eter. In all cases, the degreased sample was first annealed in a stream of oxygen-free dry hydrogen for several hours to remove any impurities such as oxygen, nitrogen, or carbon which might have been present on the surface of the sample.&apos; The rate measurements were carried out at 670°, 800°, and 900° C in hydrogen sulfide-hydrogen-argon mixtures with pH2 s/Ph2 ratios from 4 to 0.1. In a few experiments of short duration no sulfur deposition was observed in gas mixtures with (comments concerning sulfur deposition at high pH s/ph ratios were made in Part I.) Typical examples of the results obtained are shown in Fig. 2 for two temperatures and two gas compositions. With the present experimental technique, reproducible rate data could be obtained only after a uniform

Jan 1, 1969

By C. Y. Cheng

THE purpose of this note is to show that the dislocation mechanism controlling the creep of Fe-4 pet Si alloy1 may equally account for the behavior of a-Fe2 over the same temperature range. A recent study of the creep behavior of a-Fe has been made by Ishida et al.2 Their results were in agreement with the mechanism of nonconservative motion of jogged screw dislocations over the entire range of temperatures investigated, from 480° to 1045°K. However, the observed creep rate was much higher than that which could be accounted for by the above model unless the authors assumed that pipe diffusion became significant below 775°K. More recently, Cheng et al.1 inves-gated the creep of Fe-4 pet Si alloy over about the same temperature range and found that the results could be correlated fairly well with a dislocation climb mechanism as represented by Eq. [l]. Proceeding as shown previously,1 if creep is controlled by a single climb mechanism, at intermediate stresses, the shear creep rate, y, can be represented by where n and K are material constants {K is independent of the temperature but dependent on the structure, that is, K decreases during the primary stage and reaches a steady-state value over the secondary stage of creep), t is the applied shear stress, G is the shear modulus, gc is the free energy of activation for creep (usually equal to that for self-diffusion, gd), and RT has the usual meaning. By solving for y, the apparent activation energy for creep, Q which can be determined experimentally, is given by where hc is the enthalpy of activation for creep which usually is also equal to that for self-diffusion, h^. By using Eq. [2], the data in Fig. 2 of Ref. 2 can be re-plotted as shown in Fig. 1. By comparing the two figures, it is seen that the slight increase in the apparent activation for creep over Region II, as noted in Fig. 2 of Ref. 2, is due to the influence of temperature on the shear modulus rather than of the stress on the

Jan 1, 1969

By J. K. Abraham

In recent years there has been interest displayed in the precipitation phenomena occurring in austenitic alloys based on the binary Fe-Ni system.1&apos;2 Previous communications have been extended covering the kinetics of clustering in the Fe-Ni-Ti system and the effect of cluster size on subsequent mechanical properties.3&apos;4 To a great extent the question of coherency, which has a dominant role in determining the mechanical properties, is dictated by the degree of misfit between the precipitate and matrix. Thus, the change in lattice parameter of the matrix with composition is an important variable that should be examined. The lattice parameter, ao, of austenite was determined for Fe-29.75 Ni-1 to 6 Ti and Fe-27 Ni-1 to 10 Ti alloys in this study. The alloys used in this investigation were melted in a vacuum induction furnace from a starting stock of plast iron (99.95), electrolytic nickel (99.9), and ti- tanium sheet (99.5) in a MgO crucible. The alloy compositions in atomic percent are given in Table I and their relative position in the Fe-Ni-Ti ternary is indicated in Fig. 1. The chemical analyses were taken from the homogenized bulk materials treated in a manner related earlier.3 A diamond file was used to obtain powder from the bulk. To remove the stresses induced by filing, the powders were austenitized at 1875°F for

Jan 1, 1969