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By A. U. Seybolt, J. L. Walter

The effects of the addition of 0.5 pct ThO2 (by volume) on the grain structure and texture of heavily rolled tungsten sheet were studied. Powder metallurgy ingots were rolled to sheet, 0.001 in. thick, and samples were annealed at temperatures from 1200" to 2500°C. The heating rate to the anneal temperature was varied from 3°C per min to 6500°C per min. The orientations of the largest grains were determined by X-ray diffraction. The disposition and loss of the ThO2 particles were determined by electron transmission microscopy and the activation energy for remozlal of the thorium was measured by mass spec-troscopy. Heating rates below about 800 C per min produced large, highly elongated grains. Higher heating rates produced much smaller, less elongated grains. The grain structure and texture of the slowly heated samples were identical to the structures and textures of heavily rolled tungsten foil conventionally doped with aluminum, silicon, and potassium but the recrystallization temperature was about 200°C lower. There was stringer-like dispersion of larger ThO2, particles superimposed on a uniform dispersion of fine particles. The particles increased in size and decreased in number with time at temperature. The loss of particles was accompanied by formation of grain boundary voids and surface pits. The activation energy for removal of the ThO2 was about 40 kcal per mole. THE addition of small amounts of aluminum, silicon, and potassium to tungsten has a profound effect on the grain structure of heavily rolled sheet1 or drawn wire."4 Thus, "doped" tungsten sheet, rolled to 0.001 in. and recrystallized, develops a structure consisting of large, highly elongated grains of a specific preferred orientation.' It has been shown that the elongated grain structure was caused by a dispersion of particles, identified as mullite (Al6si2O13),1,4 in strings parallel to the rolling direction in sheet or to the wire axis. Identical results were obtained for iron which was doped with glass and rolled to 99 pct reduction of thickness and recrystallized.5 Again, the glass particles were disposed in strings parallel to the rolling direction. The strings retarded boundary migration in the lateral direction but grain growth was able to proceed relatively unhindered along the direction parallel to the strings.1,5 In both the doped tungsten and the glass-doped iron, the particles were highly plastic during the high-temperature deformation. Since mullite melts at about 1800°C and the glass employed melts at about 810ºC, the particles were probably molten during the recrystallization anneals (above 1800°C for the doped tungsten and 850°C for the glass-doped iron). There are indications in the literature that particles not plastic at hot-working temperatures (up to about 1550°C for tungsten) may also impart elongated grain structures by primary recrystallization of worked alloys. Examples are dispersions of tantalum carbide in chromium,6 and ThO2 in nickel where elongation ratios of recrystallization grains of up to 20:l were obtained.7 Strings of ThO2 particles in W-ThO2 wire have been seen by Rieck.8 In view of the available evidence, it was of interest to extend the previous studies of doped tungsten and glass-doped iron to include W-ThO2 sheet materials. Of specific interest was the grain structure, preferred orientation, recrystallization temperature, and disposition of the thoria particles. EXPERIMENTAL PROCEDURE A) Material Preparation. About 380 g of blue tungsten oxide (approximate composition WO3) was wet with a sufficient amount of aqueous solution of Th(N03)4 to provide 0.5 vol pct ThO2. The wet mixture was stirred to distribute the doping material uniformly throughout the powder. Stirring was continued while the mixture was heated until it was completely dry. The dried, doped mixture was then reduced to tungsten powder by heating at 850°C for 2 hr in a stream of dry hydrogen. The doped tungsten powder was hydropressed in a rubber sack at pressures of 50,000 psi to produce an ingot approximately 2 cm diam by about 5 cm long. Next, the pressed cylinder was heated in hydrogen for 2 hr at 1350°C to render it strong enough for machining. The cylinder was machined to a square cross section of 1.6 by 1.6 cm with rounded corners. Finally, the bar was heated for 2 hr at 2150°C in hydrogen to provide a sufficiently dense mate rial to withstand the hot-rolling operation. Prior to rolling, the ingot was reduced in thickness by about 20 pct by forging at 1550°C. This served to increase the density of the material and to widen it slightly for better rolling characteristics. The forged ingot was then rolled at 1550°C to a reduction of 45 pct of thickness, following which the rolling temperature was reduced to 1300°C and the slab rolled, with several reheats, to 0.050 in. Further reduction was accomplished at 800°C in tungsten sheet packs to a total reduction of about 99.85 pct. B) Annealing Treatment and Observation of Structure. Small samples of the rolled foil were annealed in one of two ways. Some of the samples were suspended in a covered tungsten can and annealed at temperatures from 1200" to 2200°C for various times in vacuum of l0-7 to 10-6 mm Hg. The can was heated by induction and temperatures were determined by optical pyrometry

Jan 1, 1970

By A. D. Taylor

In recent years there has been an increasing effort to attract students into engineering. Obviously, the effort is necessary because young people find the image of the engineer unattractive. Some of the things they find unattractive are real, some are not, and part of the problem is too little knowledge of the field. First, I would like to comment on some of the ideas which appear to be justified. Engineering is a difficult course of study. True, and nothing can or should be done to change this. The education is continually being improved, but it is unlikely to be made easier.

Jan 1, 1970

By Donald R. Corson

The effects of adding varying amounts of type I portland cement to hydraulic backfill are described. Six different fill materials, each with three cement contents, were tested to determine which fill properties have the most significant effect on cemented strength. Two strength prediction equations, based on the physical and mineralogical properties of the fills, were formulated, and these accounted for 96 and 99 percent of the variability of the data. Results of both unconfined compression and triaxial tests of cemented fills are given, and the effects of moist curing and fill densification on the 7-day strength are discussed. Permeability test data are given, and the decreased permeability due to cement content and curing time is shown graphically. A discussion of the limited evaluation of other potential stabilization additives (expansive cement, fly ash, sodium silicate, gypsum, and asphalt) is included in an appendix.

Jan 1, 1970

By Herbert Dumont

Since 1947 Preussag AG Metal1 has used a process for fuming zinc- and lead-containing dump slags and residues from vertical retorts in a half-shaft furnace at their Hüttenwerk Harz at Oker. Contrary to the classic shaft furnace, only one side of the half-shaft furnace is fitted with tuyeres. The opposite side is a bricked slope. The upper shaft section is piped. There zinc vapor and combustion gases are burned by sucked-in air. Gases and fume enter a boiler located on the rear length of the furnace via a piped fire bridge. The gases are then cooled in an air preheater prior to dedusting in a bag filter. The furnace is charged with briquettes of metal-bearing materials, coal and pitch. The leaded zinc oxide fume is comparatively rich in both lead and zinc. The copper in the feed is recovered in low-copper matte. The slag can be discarded. The Oker plant comprises 13 furnaces of 2.9 to 4.9 m length in the tuyere area. Two other plants in Italy and Spain are processing zinc leach residues by this technique. Fuming of zinc-lead-oxide ores as well as partially roasted sulfide- zinc-lead-copper bulk concentrates will be possible.

Jan 1, 1970

By J. M. Singer

Approximate equations were used to compute the radiant heating of float coal dust by approaching flames for various combinations of particle size, dust path length (flame travel distance), flame temperature, dust concentration, flame speed, and flame length. The computed values of degree of radiant heating and flame travel distance for preheating the coal dust should be useful for estimating the increased fire hazard of different coal dust-flame parameters. Some findings relating to coal mine disaster control are-- 1. Coal dust clouds cannot be preheated to ignition temperatures by flame radiation alone when deflagration speeds are greater than about 10 m/sec. Thus it appears unlikely that radiation alone will cause flames propagating in dust clouds to accelerate to detonation velocities. 2. Small particles in the radiation flame zone caused by burnout and soot formation increase the degree of preheat significantly. 3. The concentration of float coal dust (radii = 3 to 40 microns) for maximum radiant heating usually peaks in the range 50 to 200 mg/liter of air.

Jan 1, 1970

Copper ores are widespread through the Lachlan Geosyncline in New South Wales, but the size of the orebodies is generally small. The largest deposits occur in the Cobar district where an iron-rich copper ore type has been developed in Silurian sediments. Similar de- . posits to the south in the Nymagee-Mt. Hope-Melrose districts are related to quartz feldspar porphyries of probable Upper Silurian age. Deposits to the east in the Tottenham-Girilambone districts are less complex mineralogically and are possibly related to an ultra-basic source.Copper mineralization in the Highlands further to the east is often developed in Ordovician andesite or MiddleUpper Silurian acid volcanic sequences. The deposits in andesite contain considerably less galena than those in the acid extrusives; a small proportion of the mineralization in the latter has texture, mineralogy, and geologic setting analogous to the Captain's Flat copper-Iead-zinc deposit, for which both syngenetic and epigenetic origins have been proposed. Very little copper mineralization occurs within granitic material, even though rocks of this type ranging from Silurian to Carboniferous in age crop out through much of the geosyncline, and the extent of the metal contribution from plutons to the deposits in volcanics is open to question. Numerous deposits are known in the contact zone around Mid-Devonian and Mid-Carboniferous granites, however, and the formation of these orebodies has undoubtedly been influenced by plutonic activity. Small occurrences of copper with associated minor nickel sulphides are developed in a narrow serpentinite belt of possible Lower-Middle Devonian age in the southern section of the Highlands.

Jan 1, 1970

By Swan. J. D.

Repairing and replacing equipment damaged by corrosion and abrasion is a major cost throughout industry, especially in the coal mining industry. Careful study of corrosion and abrasion, and their causes and effects, often leads to the selection of alternative materials which can provide economies. What, actually, are corrosion and abrasion and how do they contribute to the cost of operating a coal-preparation plant? Furthermore, what can be done to alleviate corrosion and abrasion problems and thereby reduce operating costs? These questions will be answered in the following discussion, which will describe the destructive action of corrosion and abrasion and give several methods for controlling corrosion and abrasion losses, These methods include the substitution of stainless steel for carbon steel, the use of corrosion inhibitors, and the use of design to eliminate corrosion and abrasion. Examples will be given illustrating the benefits that have resulted in plant tests when these methods of controlling corrosion and abrasion were used.

Jan 1, 1970

By Paul H. Johnson

A field investigation was undertaken to study some of the. chemical and hydrological aspects of leaching an impermeable copper sulfide waste dump. Samples, obtained by means of a Becker pneumatic drill from Kennecott's Chino "J" dump, near Silver City, New Mexico, were analyzed for their moisture and soluble-salt content, Fe +2 , Fe +3, Cu +2 , and H in their interstitial solutions and non-water - soluble Fe, Cu, and S in their rinsed residues. Conclusions were drawn from these data concerning the overall chemistry of impermeable-dump leaching and the hydrological characteristics of the dump.

Jan 1, 1970

By P. Shahinian, H. H. Smith, M. R. Achter

Crack growth rates are measured at elevated temperature in a resonant fatigue machine from vibration frequency decreases calibrated in terms of crack depth. Crack growth rates in Type 316 stainless steel at 500º and 800°C show a sharp increase with oxygen pressure in an intermediate pressure range and little or no change at high and low pressures. At 500°c, I torr of oxygen reduces the fatigue life by almost a factor of 100 in comparison to that in vacuum and raises the growth rate of shallow cracks by the same At At 800°C the effects are smaller. Changes in slope in the crack growth rate curves are discussed in terms of a model in which rates of surface production and of surface coverage by gas are compared. The use of a calculation method in which the surface exposure time is equal to X/v, where x is the interatomic spacing and v is the growth rate, makes it possible to obtain order of magnitude agreement at 500°C between the observed pressure and the predicted pressure at these slope changes. At 800°C oxidation becomes a .factor and the data cannot be treated by simple adsorption theory. THE decrease in the fatigue life of metals as a function of gas pressure usually follows a stepped curve with virtually all of the decrease concentrated in a sharp drop in a transition zone at intermediate pressures and little or no change at low and high ranges. A number of models, differing in the details of the mechanism, have been offered to explain the shape of the curve. Measurements of crack growth in aluminum as a function of gas pressure by Bradshaw and Wheeler' and Hordon2 demonstrated opportunities for quantitative comparison to evaluate the proposed models. Since comparable data were lacking at high temperatures, in the present work rates of crack propagation were measured in Type 316 stainless steel at 500" and 800°C as a function of oxygen pressure. Choice of this material was dictated by two considerations; it is stiff enough at these elevated temperatures to resonate with the regenerative drive on our fatigue machine and it is known to display a large effect of environment. A new method of calculation is described to predict the gas pressure at the critical point. EXPERIMENTAL PROCEDURE Because of the difficulty of measuring crack depths directly at high temperatures, an indirect method was developed based on the decrease in the resonant frequency with the growth of a crack. A reversed bending, constant amplitude fatigue machine, described previously,3 vibrates a specimen at its resonant frequency, automatically records any changes in it and shuts itself off after it has reached a preset value of frequency decrease. The record of frequency change is used to determine the rate of crack growth. Sheet type specimens of Type 316 stainless steel, Fig. 1, incorporated a sharp, shallow notch to localize the formation of a single crack. After machining, they were annealed in a vacuum of l0-6 torr either at 1066" (lot A) or 871°C (lot B) and then electropolished in an acetic-chromic acid solution. Bending strains were measured at 500" and 800°C by an optical technique4 and reported as total strain without correction for the notch. At 500°C, the 0.141 pct strain was 0.085 pct elastic and the remainder plastic. At 800°C the 0.062 pct strain was all elastic. To convert frequency decrease to crack length, calibration curves were obtained by interrupting the vibration at stated intervals of frequency decrease. The crack depth was measured microscopically at a magnification of X400 and reported as the average of the measurement on each edge. Some specimens were sectioned for crack measurement while others were returned to the machine and fatigued further. There was good agreement between the two methods. Before beginning the vibration, the vacuum chamber was first evacuated cold to 1 x 1O-6 torr, then heated to the operating temperature and held there until the pressure was again reduced to 1 x10-6 torr at which time oxygen was introduced to the desired pressure. In this investigation the vibration frequency was nominally 10 cps and a decrease of 0.6 cps was taken as the failure point. The choice of the frequency decrease to represent failure has no appreciable effect on the fatigue life because the crack is growing very fast at this point.

Jan 1, 1970

By Pradeep K. Rohatgi, David N. French, Surendar M. Jain, Clyde M. Adams

The effect of solute concentration and diffussivity on dendritic solidification of dilute binary aqueous solutions has been investigated; chlorides of sodium, potassium, lithiurn, and hydrogen were used as solutes. Dendrite spacings were measured in spherical droplets and in unidirectionally solidified specimens. In the droplets, the freezing rate is uniform over the entire specimen and remains constant from the beginning to the end of solidification. In the unidirec-tionally frozen specimens the freezing rate varies within a given volume of liquid during the solidification cycle; in addition, it varies with location uithin the specimen. Mass transport analysis has been used to calculate the supersaturation, AC, supercooling, AT, and transcerse growth velocity, V , of ice dendrites during solidijication from the dendrite spacings measured in the droplels. The ice dendrite spacing in a given solute increases lineary with the solule concentralion at a fixed freezing rate. The ualues of AC, AT, and V increase with an increase in solule concentration. The value of AT in the aqueous solution is of the same order of magnitude as in Al-Cu alloys of the same concentration; the dendrite spacings in Al-Cu alloys also increase with an increase in solute concentralion. For the jamily of aqueozrs solulions incestigaled, the dendrite spacing increases linearly with solute diffusivity at fixed values of concertralion and freezing ,rate. The values of ?C and ?T decrease, whereas the value of V increases with an increase in solule diffusicity. The measured dendrite spacings , L, can be expressed by the relatiun: L = K;(dfa/db) 4 K2C +K3D - K4 where dfs/d? is-change in fraction solid with time (freezing rate), C is solute concentration, D is solute diffusivit K1 = (14 * 4)pmin1'2, K2 = (70 ± 10) pl (moles)- K3 = (24 r 3) . l05 psec (cm)-~. K. = -132 ± 10) 1. FREEZING of solutions is almost always an ehunmix-ing" process because the composition of crystallizing solid generally differs from that of the parent liquid. " Solute concentration and transport are therefore in]portant considerations in solidification of solutions. The influence of these factors on the dendritic solutions produced from metallic solutions is of practical significance since the properties of the solid aggre-gate are often strongly influenced by dendrite spacing.''' Alexander and Fthines3 found that dendrite spac- ings generally increase with solute concentration in several metallic systems. Michael and Bever1 have observed an increase in a aluminum dendrite spacings in dilute A1-Cu alloys. Rohatgi and AdamsJ have reported a linear increase in a aluminum dendrite spacings with increasing copper contents up to 28 pct in A1-Cu alloys. Bolling and Tiller"' have theoretically examined the effects of solute concentration and diffusivity on the growth of cells and dendrites. Their analysis of dendritic growth assumes a steady-state growth and the maximum possible velocity for dendrite propagation. In addition, the quantitative analysis is restricted to dendrites of rotational symmetry and is therefore not directly applicable to the plate-shaped dendrites of ice obtained in the present study. There are practically no experimental observations of the effect of solute diffusivity on dendrite spacings in metallic systems. The reason appears to be the lack of experimental data on solute diffusion coefficients in liquid metallic solutions. The present work is concerned with the effect of solute concentration and diffusivity on dendritic solidification of dilute aqueous solutions: the solutes examined are potassium chloride. sodium chloride, lithium chloride. and hydrogen chloride. There were several reasons for selecting these solutes. The variation of dendrite spacing with freezing rate in these solutiolls is similar to that observed in A1-Cu alloys.8 These aqueous solutions have almost identical phase diagrams at dilute concentrations. Fig. 1. and the diffusion coefficients show very little variation with solute Concentration.9,10 Dendrite spacings were measured as a function of freezing rate. solute concentration. and solute diffusivity. Dendrite spacings were measured in two different types of freezing systems. droplet and unidirectional, respectively. In the droplet freezing system

Jan 1, 1970

By F. I. Grace, L. E. Murr

The mechanical responses and residual defect structures in 70/30 brass and type 304 stainless steel following explosive shock loading and cold reduction by rolling have been studied. A distinct relationship was observed to exist between the residual mechanical properties and micro structures observed by transmission electron microscopy. Shock-loaded brass deformed primarily by the formation of coplanar arrays of dislocations and stacking faults at lower pressures, and twin-faults (deformation twins and €-martensite bundles) at higher pressures (> 200 kbar). The micro -structures of cold-rolled brass were characterized by dense dislocation fields elongated in the rolling direction. Stainless steel was observed to deform by the formation of dense arrays of stacking faults at lower shock pressures and twin-faults at high shock pressures (>200 kbar). Lightly cold-rolled stainless steel deformed similar to low Pressure shock-loaded stainless steel, but transformed to a' martensite in heavily cold-rolled stainless steel. Discontinuous yielding was observed for the heavily cold-rolled stainless steel, and stress reluxution in the weyield region for cold-rolled and shock -loaded stainless steel was interpreted as an indication of the ability of twin-faults and stacking faults to act as effective barriers to dislocation motion. A simple model for the formation of the planar defects and a' martetnsite is presented based on the propagating of Shochley partial and half-partial dislocations. A considerable effort has been expended over the past decade in an attempt to elucidate the response of metallic-crystalline solids to the passage of a high velocity shock wave (e.g., smith,' Dieter,2 and zukas3). While it has been possible to obtain relevant information pertaining to the residual defect structures and mechanical properties, there have been few rigorous attempts to draw a direct comparison between these structures and properties. In addition, numerous investigators have recently observed the occurrence of deformation twinning in shock deformed fcc metals (e.g., Nolder and Thomas,4 and Johari and Thomas5), but little attempt has been made to elucidate the mechanisms of formation of these defects. Comparative data for metals deformed by shock-loading and the same metals deformed by more conventional modes of deformation such as cold-reduction by rolling is also generally lacking. The present investigation therefore has the following objectives: 1) to examine the mechanical properties of some explosively shock loaded and cold-rolled fcc metals of low stacking-fault energy as a function of their residual substructures; 2) to present a simple model for the formation twin-faults and related defect structures in the low stack-ing-fault energy materials of interest (70/30 brass, ySFg= 14 ergs per sq cm; and 304 stainless steel, ySF = 21 ergs per sq cm); 3) to make some deductions with regard to the residual characteristics of dislocation and planar defect substructures in cold rolled and shock loaded 70/30 brass and type 304 stainless steel. In particular, it was desirable to characterize the residual hardening effects of particular deformation substructures. I) EXPERIMENTAL PROCEDURE Sheet samples of 70/30 brass (0.005 and 0.15 in. thick; annealed at 659°C for 2 hr) and type 304 stainless steel (0.007 in. thick; annealed 0.25 hr at 1060°C) of nominal compositions shown in Table I were cold-rolled in one direction only to produce reductions in thickness of 15, 30, 45, 60, and 75 pct in the brass; and 5, 15, 25, 35, and 45 pct in the stainless steel. Identical sheet samples in the annealed (unrolled) state were subjected to plane compressive shock waves to various peak pressures ranging from 0 to 400 kbar in the brass and 0 to 425 kbar in the stainless steel; and with a constant peak pressure duration of approximately 2 microseconds. A detailed description of the shock loading technique has been given previously.6 Tensile specimens 1.0 in. in length and 0.125 in. in width were cut from the cold-rolled sheets (tensile axis parallel to the rolling direction), and the shock-loaded sheet specimens. Stress (load)-strain (elongation) measurements on the tensile specimens were made on a Tinius-Olsen load-compensating tensile tester using a strain rate of 2.7 x 10-3 sec-1. Tensile tests were repeated at least twice, giving essentially the same results. Stress relaxation measurements in the preyield region were also made using an initial strain rate of 5.4 x 10-4 sec-1. In addition to tensile and stress relaxation measurements, Vickers microhardness measurements were made on all samples. A total of 100 microhard-ness readings were obtained for each specimen following a light electropolish to ensure uniform surface conditions for all tests. The hardness averages ob-

Jan 1, 1970

By John Campbell

An approximate theoretical model is proposed to quantitatively predict freezing ranges Tf and hydrostatic tensions P developed within solidifying binary alloys, allowing for a certain amount of diffusion of solute in the solid during solidification. The maxima in ATf and AP as functions of composition are shorn to occur at smaller solute concentrations than would be expected from the equilibrium diagram, and are found to correspond closely to experimentally observed maxima in microporosity. THE freezing range of simple binary alloys appears to have been little studied, except for certain indirect observations on the defects, particularly microporosity and hot tearing, arising in long freezing range materials. Two theories relating to the freezing range of alloys and its effect upon porosity are reasonably well established, and appear to have been held in isolation from each other: a) From purely equilibrium considerations early researchers expected that an increase in solute content of an alloy should increase the freezing range (defined here as the equilibrium freezing range ?Tf = Tl-Ts where TL and Ts are the liquidus and solidus temperatures, respectively) and thereby increase the width of the pasty zone for a given set of conditions. This in turn should increase the difficulty of feeding the residual liquid through the dendrite mesh to compensate for the contraction on solidification, and consequently tend to increase the observed amount of porosity. From qualitative observations on steels Czikel1 reports an increase in porosity with increasing carbon content up to 0.46 pct C. More careful measurements by Whittenberger and Rhines2 on fourteen different alloy systems showed an approximately linear relation between ?Tf and pct porosity (although unfortunately the precise experimental data is not given). b) Conversely however, other authors3"5 propose that porosity is reduced by the presence of increased amounts of eutectic present at the final solidification temperature. Lees7 and Bochvar6 claim that the hot tearing of alloys is similarly reduced. Scheuer8 has put forward a theory to explain this effect, Fig. 1. The argument is basically that solidification progresses on a plane front through a relatively open dendrite network and is thus (the argument is not developed more explicitly) easier to feed. One would expect effect a) to operate at low solute contents, and b) to be important at higher solute contents, so that at some critical composition a max-

Jan 1, 1970

By George S. Koch

The distribution of gold in part of the Getchell mine, Humboldt County, Nev., is presented through the statistical analysis of 956 assays of rock cuttings from wagon-drill holes. Two methods to predict grade in undeveloped parts of the ore body are evaluated, and the possibility of sampling bias is tested. The distribution of gold is compared with that in three other Nevada gold deposits of the same type characterized by gold particles mostly of submicron size associated with carbonaceous rocks, and also with that in deposits with coarse-grained gold. Usually, fewer samples of a given type are required to make a satisfactory grade estimate for submicron deposits than for coarse-grained deposits. The economic consequence is that submicron gold deposits are likely to be less expensive to sample and evaluate than coarse-grained deposits.

Jan 1, 1970

By W. O. Philbrook, K. Natesan

A mathematical model was derived for the temperature change in a particle undergoing heterogeneous chemical reaction and heal exchange with a stream of fluid. The model has been applied specifically to the exothermic oxidation of spherical particles of zinc sulfide. Very good agreement was obtained between the theoretical prediclion and experimental observation. It was found that at no stage of the reaction was the particle subjected to a state of thermal instability. In studies of gas-solid reactions, it is generally assumed that the gaseous and the solid phases are at the same temperature throughout the reaction period. This is not strictly true since most of the reactions are either exothermic or endothermic in nature. This paper deals only with heterogeneous gas-solid reactions of noncatalytic type. In the case of exothermic reactions (e.g., roasting of sulfides), there may result an increase in temperature of the particle due to the release of the heat of reaction, and this increase in temperature may enhance the reaction rate and thus cause further release of heat. Such a "spiralling" effect may lead to a thermally unstable situation within the particle. On the other hand, in the case of endothermic reactions (e.g., calcination of limestone), there may occur a decrease in temperature of the particle as the reaction proceeds, leading to a virtual "quenching" of the reaction front. A general discussion of autothermic processes with emphasis on properties and reactor design is given by Van Heerden. 1 Levesque and cubicciotti 2 observed self heating of the sample in the oxidation of thorium. Anous et al. 3 observed self cooling of the sample in their dehydration studies on chrome alum. Cannon and Denbigh, 4 and Ong et al.5 reported self heating of the sample in their studies of the kinetics of oxidation of zinc sulfide. A typical plot of heat generation and heat loss rates with reaction temperature is shown in Fig. 1.'14 The Sigmoid curve represents the heat generation rate while the straight lines represent the heat loss rate. The main objectives of this analysis are to estimate the temperature increase of a single particle undergoing an exothermic reaction and to study the possibility of a thermally unstable situation within the particle. Also, a study of the dependence of the tempera- ture increase on different process variables has been attempted. A "she ll-by-shell" method has been proposed to analyze the problem. The shells may be made as small as necessary, and equations may be set up for heat transfer by various mechanisms. Such equations will have to be solved for each shell, with the boundary conditions for ith shell being obtained from the (i - 1)th shell, using a high speed digital computer. The oxidation of spherical particles of zinc sulfide is considered for this analysis, but the treatment is general enough to be applicable to other reactions and particle shapes. The oxidation reaction can be written as AH =« -115 kcal/mole ZnS [1] Such a reaction has been found to proceed in a topo-chemical manner; i.e., as the reaction proceeds, a progressively thicker outer shell of zinc oxide is formed, while the inner core of unreacted sulfide decreases. It has been found experimentally, both in the present work and in the previous investigations,4-6 that the particle retains its original dimensions. Therefore, at any given time, the particle may be

Jan 1, 1970

By R. D. Nelson, F. E. Bowman

Assumptions are made of ideal mixing and that the density of silver can be obtained by extrapolating reported liquid density-temperature data through the freezing point back to the temperature range of interest. The results of this procedure using liquid silver density data of Kirshenbaum et al.5 are presented in Table I1 where it is observed that agreement is everywhere within <0.1 pct and generally is within 0.05 pct. Because the Sn-Ag alloys are dilute, the assumption of ideal behavior is, therefore, probably justified. In conclusion, the densities of dilute liquid solutions of silver in tin have been determined. Even for concentrations as low as 0.1 pct, the effect of silver on the density of liquid tin is clearly measurable. This work also suggests that for dilute alloys at temperatures far below the freezing point of the solute metal, densities may be accurately calculated by extrapolation of the pure metal data without having recourse to physical measurement on the alloy itself. plutonium having a grain size of about 100 µ. This paper presents data showing that large elongations of fine-grained a Pu can be obtained by using slow deformation rates. Large plasticity, however, of a Pu in compression has been observed.4 Reductions in thickness of 90 pct have been observed with no edge cracking. These large reductions are accompanied by concurrent re-crystallization. The deformation modes, which are quite complex, have been studied extensively by observing the deformation microstructures of polished surfaces that had been deformed in compression.5-7 Although slip apparently is a predominant mode of deformation at room temperature, grain boundary sliding and concurrent recrystallization become more predominant at high a temperatures.4&apos;7 Although recovery occurs,8,9 no grain growth has been reported in a Pu even at temperatures near the a =ß equilibrium temperature (-115oC), which is 0.7 of the calculated melting temperature of a Pu.10 From studies on other materials, it appears that high elongations can be obtained in alloys when the THE purpose of this technical note is to present briefly some data revealing high ductility of a Pu, which is normally considered brittle. The very low ductility of a Pu in tension has been reported by many investigators.&apos;-3 Gardner,1 for example, reported that the total elongation of a Pu at a testing speed of 0.015 ipm is less than 0.1 pct at room temperature and only about 1 pct at 100°C. The only tensile creep studies that have been reported&apos; indicate no large ductility, but they were performed on relatively low purity

Jan 1, 1970

By A. Moskowitz, L. S. Redmerski

The corrosion resistance of stainless steels can be strongly affected by surface treatments. Changes in corrosion resistance can relate to surface composition, integrity and stability of the passive film, and to surface profile (roughness). Operations producing oxidation at the surface, such as annealing, heat treating, and welding, can result in a chromium-rich scale and a chromium-depleted metal surface. In order to restore full corrosion resistance, chemical or mechanical clean-up techniques must remove not only the oxide, but also a very thin layer of metal. Laboratory and field test studies show that these factors are particularly significant in less highly alloyed steels. Annealing stainless in a reducing atmosphere (bright annealing) avoids chromium depletion, but as-bright-annealed material does not display optimum corrosion resistance in certain environments. Electro passiva-tion can be applied to improve pitting resistance without significantly changing bright surface appearance. Potentiometric studies show that electropassivated material also displays significantly greater resistance to breakdown of passivity in acid solutions. The application of special surface finishes for appearance purposes can affect corrosion resistance. Roughness is a key factor. Samples of related appearance but with different surface profiles can show significant differences in corrosion resistance. Thus nonreflec-tive stainless with a relatively smooth surface produced by a special rolling process is much superior to material chemically etched to a similar low reflectivity. THE corrosion resistance of a stainless steel is affected by other factors in addition to its bulk composition and metallurgical structure. These other factors include those relating to the specific chemical and physical condition of the steel&apos;s surface. This paper will consider certain aspects of surface condition in relation to corrosion resistance. In particular, studies will be described on the effects of oxidation encountered in heat treating or welding operations, of passivation after bright annealing, and of different surface finishes. EFFECTS DUE TO OXIDATION When stainless steels are exposed to high temperature in an oxidizing environment, as in annealing or welding, the oxides formed are relatively rich in chromium. As a consequence of oxidation, the metallic layer directly beneath the scale may be low in chromium to some very thin but finite depth.1"8 Such a change in chromium content could lower the corrosion resistance at the surface, whether or not the oxide layer is removed. Studies were performed relating to the effect of oxidation and chromium depletion produced during annealing and welding on the corrosion resistance of stainless steels. The nominal compositions of steels used in this study and others are given in Table I. A) Annealing Studies on 17 pet Cr Steels. 1) Effects of Pickling Treatments. Studies were performed to investigate the corrosion resistance of air annealed type 430 stainless as a function of the amount of electrolytic pickling after annealing. The material used in this study had been air annealed and electrolytically pickled in the mill. All scale had been removed, and yet the material showed unusually poor corrosion resistance. Laboratory electrolytic pickling studies were performed to determine whether additional metal removal from the surface would improve corrosion resistance. Electrolytic pickling was performed in a sulfuric acid bath using various conditions of bath acidity, temperature, time, and current density. The samples were then rated for corrosion resistance in a ferric chloride spot test. For this spot test, a solution was prepared by dissolving 10 g of FeCl3 . 6H2O, 5 g of NaCl, and 2.5 ml of concentrated HC1 in 200 ml of water. An area on a specimen was cleaned and a drop of test solution was placed on the prepared area. After 5 min, the drop was rinsed off and the area wiped dry. The spot was then rated between 1 and 5 by visual comparison with standard spots. The numerical rating of the standard spots can be described as follows: 1—No clouding of surface; 2—very slight clouding of surface; 3—slight clouding of surface; 4—moderate clouding of surface; 5—strong clouding of surface. A rating of 1 or 2 was considered to have passed the test, a rating of 4 or 5 represented failure, and a rating of 3 was considered borderline. The severity of etching in this test has been related to the actual chromium content at the surface.4 Etching (clouding) occurs on type 430 stainless (rating of 4 to 5) when the surface chromium content is 14 pct or less. The effects of current density and retention time when electrolytically repickling this material in 6 pct sulfuric acid are shown in Fig. 1. Increasing the cur-rent density or retention time improved corrosion resistance as measured by the spot test. Similarly, increasing acid concentration of the bath or bath tem-perature was found to improve corrosion resistance. The conditions making for improved spot ratings resulted in increased metal removal, regardless of specific pickling conditions used, Fig. 2.

Jan 1, 1970

Wabush Mines is the largest single supplier of iron ore to the Canadian steel industry, with 42% of its 6 million tpy of iron ore production going to the company&apos;s two Canadian owners-The Steel Co. of Canada and Dominion Foundries and Steel Ltd. Six other companies hold interests in Wabush Iron Co. Ltd. These are Lykes-Youngstown, Inland Steel Co., Intrerlake Steel Corp., Wheeling-Pittsburgh Steel Co., Finsider of Italy and Pickands Mather & Co. Field work on Wabush began in mid-1957 when a long-range program of economic, geologic, and metallurgical investigations started. This work was followed in 1959 by the construction of a temporary camp and a 700-tpd pilot plant. At the same time, work was also started on a 38-mi railway connection to Ross Bay, Newfoundland.

Jan 1, 1970

By Michael A. Arkoosh, E. A. Peretti

ANALYTICAL results have previously been presented for the diffusion-controlled solution of a second phase in a finite medium for planar, cylindrical, and spherical geometries.&apos; These results were obtained by numerical methods using digital computer techniques and are applicable not only to the stage of the problem where the unstable phase shrinks to zero size, but also the subsequent stage where the concentration gradients in the matrix phase become negligible (essentially complete homogenization). It is anticipated that the results of such an analysis may be of use to those workers who are interested in the processes

Jan 1, 1970

By John D. Rockaway

This report and accompanying engineering geologic map describe the generalized engineering geology of St. Louis County, Missouri for use in determining the most efficient, economical, and environmentally sound program for land development and urban growth. It includes an evaluation of such factors as the physical and engineering properties of soil and bedrock, surface stability, and subsurface geologic structure. The map and text are designed primarily for property owners, engineers, architects, real estate developers, and city planners involved in land-use planning. The geologic information and engineering interpretation must be considered as a general guide and not as a substitute for a complete on site investigation prior to initiation of any land-use project. The map scale, 1:63,360 (1 inch to a mile) is too small to include the detailed information normally provided on the 7 1/2-minute quadrangle series (1:24,000). The smaller scale is most useful at regional planning levels and was chosen to present information on the more significant engineering factors of the geologic environment for county-wide planning and development. A conventional geologic map deals primarily with the distribution and variation of bedrock formations, and a pedologic map presents information on the soil or natural medium for plant growth. Basic geologic maps and pedological maps are valuable tools that can be of assistance in studying the geologic environment, however, these maps do not provide all the information required for land-use planning. The engineering geologic maps are designed to provide this data. The engineering geologic map is related to both of these basic maps but emphasizes the engineering properties of the rock formations and soils rather than their age or origin. Some of the unit boundaries shown on the county map will closely follow some geologic formation and/or pedologic boundaries; others will transgress these conventional boundaries. Earth materials, bedrock and soil, that have similar engineering characteristics have been mapped as one unit without regard to their geologic or pedologic classifications. This is to assure that geological factors are recognized, adequately interpreted, and presented for use in engineering practice.

Jan 1, 1970

By G. A. Colligan, G. L. F. Powell

A new experimental technique has been developed to study nucleation behavior in eutectic alloys. It is somewhat similar to that applied by Sundquist and Mondolfo1 but with the advantages that: 1) bulk samples are undercooled instead of small droplets thus allowing the thermal behavior to be monitored by a thermocouple immersed in the sample, and 2) nucleation behavior is investigated in the same sample on either side of the eutectic composition by adding additional component to the sample under controlled conditions which preclude the addition of nu-cleation contaminants. Sundquist and Mondolfo carried out ]nucleation ex-periments on a large number of eutectic alloy sys-tems and concluded that nonreciprocal nucleation operated. If one phase a was a good nucleant for the other phase 0, then B was a poor nucleant for a. This was determined experinlentally by comparing the nucleation temperatures of 100 to 300 u diameter droplets of hypereutectic and hypoeutectic composition cooled from above the liquidus and from a temperature between the liquidus and the eutectic temperature. Primary phase a was concluded to be an efficient nucleant for the other phase B, if the following experimental result was obtained. Referring to Fig. 1, the temperature TI at which a drop of hypereutectic alloy of composition B froze when cooled from above the B liquidus was noted. This was the nucleation temperature for B in the absence of a. A drop of hypoeutectic alloy of composition A was then frozen from temperature T2 between the a liquidus and the eutectic temperature. The temperature T3 at which the eutectic nucleated in the presence of the primary or proeutec-tic a was noted. If this temperature T3 was higher than the temperature TI at which the B nucleated in a hypereutectic alloy, it was concluded that the primary a had nucleated the 6. This temperature T3, representing a certain undercooling below the equilibrium eutectic temperature Te , was designated ?TB by a> the undercooling below T, for nucleation of 13 by a. If there was no substantial difference in nucleation temperature between the hypereutectic drop cooled from above the /3 liquidus and the hypo-eutectic drop cooled from a temperature between the a liquidus and the eutectic temperature, it was considered that the a nucleated B at an undercooling equal to or greater than that at which P nucleated from a hypereutectic alloy. Sundquist and Mondolfo1 found that faceted primary crystals were good nucle-ants for metals that grow as orthogonal dendrites when present as the primary phase. Jackson2 has questioned Sundquist and Mondolfo&apos;s technique and proposed that in Sundquist and Mon-dolfo&apos;s samples, such as composition A, primary a retained B in reentrant grooves at their surfaces when heated to a temperature above the eutectic but below the a liquidus. This objection was suggested by experiments with organic eutectics where reten-

Jan 1, 1970