Search Documents

By Hsun Hu

The microstructural changes during rolling and at various stages of recrystallization in (111)[112] oriented single crystals of Si-Fe have been studied by transmission electron microscopy. At very low deformation, the dislocation structure consists of jogged dislocation lines, edge dislocation dipoles, and numerous dislocation loops, which may be interpreted by the jog-formation mechanism in moving screw dislocations. Up to 70 pct rolling reduction, no sharply defined cells are formed. Subgrain forma- tion takes place somewhat earlier in the annealing process than in a similarly processed (110)[001] crystal. This may be partly responsible for the reported difference in the rate of recrystallization between (111)[112] and (110)[001] crystals. Evidence indicates that the formation of recrystallization nuclei occurs largely by the coalescence of sub -grains. This is consistent with previous observations on other Si-Fe crystals. AVAILABLE data in the literature indicate that the main features of rolling and annealing textures in (111)[112] and (110)[001] crystals are essentially similar. A (111)[112] or (111)[112] crystal can be rolled 70 pct without changing its initial orienta-

Jan 1, 1964

By Hammett PHJ

Oil Exploration Companies are primarily interested in how much oil or gas is present in the rocks in an area in which an exploratory well is drilled. The solution of this problem requires a combined effort on the part of the petroleum geologists, drilling engineers, logging and drilling contractors. To help in'explaining how the drilling and evaluation is earried out the paper has been divided into two sertions, one titled Drilling which is presented by Mr. P.H.J.-Hammett and the seeond titled Evaluation which is presented by Mr. R.M.L. Elliott. A typical Perth Basin Well has been chosen as art example for this presentation. In Figure 1A is shown the type of sandstone and shale sequence encountered in this area.

Jan 1, 1964

By Jack A. Kanz, Samuel R. Shortes, E. C. Wurst

Zinc diffusion into GaAs from the vapor phase through reactively sputtered SiO, films Izas been inrestigated for various zinc pressures at 1000"C. Diffusions were carried out in evacuated quartz ampules with elemental zinc and with various Zn-Ga alloys. Sputtered films have proved effective in lowering surface concentrations and preventing surface deterioration during diffusion. Approxin.ate complenzentary error-function impurity distributions were found when surface concentrations were reduced to approximately 3 -—4 x 10" atoms cm'3 or less with dilute zinc sources or by diffusion through SiO, films. Zinc difhsions in GaAs tlzrough SiO, films produced more planar diffusion fronts than were observed with uncoated zuafers under identical conditions. A) Surface Deterioration During Diffusion. Device technolorn-- in compound semiconductors has been hampered by several difficult problems not normally encountered with silicon and germanium. 111-V and 11-VI compound semiconductors generally have volatile constituents at temperatures used for diffusion. To achieve specific junction depths in reasonable lengths of time, or to obtain particular impurity distributions and doping levels, it is often necessary to use temperatures which cause surface deterioration and erosion of the wafer. The resultant surfaces are generally unsuitable for devices. The type and extent of surface damage depends to varying degrees on the particular environment of diffusion and on the particular impurity in question. The most common type of deterioration results from simple dissociation of the gallium and the arsenic during diffusin.' The deterioration process is significantly enhanced by thermal gradients in the diffusion zone, usually resulting in vapor transport and condensation at the cooler portion of the system. The resulting damage sometimes appears as a general haziness over the surface or an array of pyramidal etch pits characteristic of the particular orientation. Occasionally, erosion of the surface occurs uniformly over the wafer so that surface loss is not readily apparent. Workers in GaAs usually resort to the sealed-ampule type of diffusion system3"5 rather than the more conventional open system used for silicon and germanium. Another type of deterioration results from direct interaction of the impurity with the surface. The form of deterioration may vary from surface alloying, as in the case of zinc, to direct chemical attack and vapor transport of the reaction products, as in the case of sulfur. Surface alloying with zinc occurs at higher temperatures and source vapor pressures.4 The process is largely controlled by the amount of free gallium on the surface of the wafer in equilibrium with the arsenic lost to the system. The group-VI elements, sulfur, selenium, and tellurium, are commonly used donor impurities for gallium arsenide. These elements are characterized by high vapor pressures and high chemical

Jan 1, 1964

By Y. Nakada, U. F. Kocks, B. Chalrners

THE orientation dependence of work hardening has previously been studied over the entire range, i.e., including special orientations of high symmetry, in aluminum1-3 and silver.* The differences between various orientations are substantial, and the trend is the same in all fcc crystals. However, there are quantitative differences in behavior between aluminum and silver at room temperature, particularly in the (100) orientation. While many experiments on gold have been reported,5'9 none included the special orientations. We therefore undertook tension tests on gold crystals of the axial orientations (100),(110), (Ill), (211), and, as a representative of single slip, one whose Schmid factor was 0.5 (hereafter referred to as m = 0.5). Single crystals of dimensions 1/4 by .1/4 by 6 in. were grown from the melt1' at a rate of 4 in. per hr, using gold of 99.99 pct purity obtained from Handy and Harman. A growth rate of 1/8 in. per hr, or a purity of 99.999 pct,ll produced no difference in results. The crystals were annealed at 1000°C in air for 24 hr and furnace-cooled down to room temperature, after which they were electro-polished in a solution of potassium cyanide (40 g), potassium ferrocyanide (10 g), soda (20 g), and enough distilled water to make 1 liter of solution, at a current density of 0.02 amp per sq mm. After 2 or 3 hr, a very smooth surface was obtained by this method. Nine m = 0.5, two (loo), one (110), three (Ill), and one (211; crystals were tested at room temperature in a floor-model Instron machine at a tensile strain rate of 0.5 pct per min. The accuracy of the stress measurement was k10 g per sq mm up to 500 g per sq mm, k2 pct for higher stresses. The strain measurement was accurate to t2 pct. The scatter of stress at a given strain among the crystals of the same orientation was small, *5 pct being the largest. The representative stress-strain curves for various orientations are shown in Fig. 1. Table I summarizes the work-hardening parameters as used by seeger.12 Results of other investigators are also included in this table for comparison. There are no previous data for the corner orientations. Values for m = 0.5 crystals agree fairly well with those of Berner. Tm is defined as the stress at which the stress-strain curve begins to deviate from linearity of Stage 11. However, in practice this is a very difficult value to estimate because each investigator has a different idea of linearity. Therefore, the comparison with the values of other investigators may not be valid. In the present experiment, (100) crystals had the highest 111, followed by (111) crystals. The work-hardening rate in Stage I1 was highest for the (111) crystal followed by the (100) crystals. Our value for 0x1 of m = 0.5 orientation agrees very well with those of other investigators. 1) Single-Slip orientation (m = 0.5). These crystals were oriented so that the primary-slip vector was contained in one side face. The dimension perpendicular to this side should then not change if single slip indeed takes place. Within the accuracy of measurement, this dimension did not change during the deformation. Since the accuracy is k0.2 pct, the amount of secondary slip is less than 0.7 pct of the slip on the primary-slip system at 30 pct tensile strain. This is in conformity with the results obtained by Kocks" for aluminum crystals. The tensile axis moved toward (211) during the deformation. Slip bands, Fig. 2(a), were very fine and closely spaced. Some deformation bands were observed. There were no clear-cut cross-slip traces such as the ones observed on aluminum m = 0.5 crystals. 2) (111) Crystals. The orientation of the tensile axis was stable during the deformation. From this observation, one can deduce that at least three slip systems must have operated, and probably all six because the remaining three all have cross-slip relation to one of the first three.' It was very difficult to observe the slip markings. Consequently, we could not confirm by this method that six systems were operative during the deformation. At high strains (above 50 pct shear strain), this orientation had the highest stress-strain curve. At 80

Jan 1, 1964

By H. R. Ogden, E. S. Bartlett, A. G. Imgram

THE tensile and notch tensile ductile-to-brittle transition characteristics of several refractory metals and alloys have been well documented.1-3 Electron-beam melted tantalum and columbium have been shown to retain excellent ductility at very low temperatures. Some indications of brittle behavior (low ductility and cleavage fracture) were observed with columbium tested at -253oC, but no similar effects were noticed with tantalum. Increasing the interstitial oxygen content in these two materials resulted in the detection of indications of brittle behavior at higher temperatures, although good ductility was retained in both bases at -196°C when they contained about 1 at. pet 0. Detailed descriptions of the impact transition behavior of these two materials at various purity levels have not been available. This technical note describes the effect of interstitial oxygen on the impact properties of wrought, fibered tantalum and columbium and compares the transition behavior to the previously determined tensile transition characteristics. Tantalum and columbium impact specimens with three different interstitial oxygen levels indicated in Table I were tested at temperatures ranging from -196o to 300°C. Oxygen additions were made to 1/2-in.-diam bars of electron-beam melted material in a Seiverts Apparatus. The oxygenated bars were then homogenization-annealed to obtain uniform cross-section hardnesses and swaged to

Jan 1, 1964

By D. R. Bomberger, M. Deul

An automatic microscope has been developed to measure the size and populations of macerals and minerals in fine coal particles. Differentiations are made on the basis of reflectance. This study is concerned with the size distribution of pyrite inclusions. Most fine coal cleaning processes do not remove pyrite as completely as a straight density separation. Consideration of the pyrite size distribution is suggested as a more accurate method of predicting sulfur reduction by a cleaning process. Analyses of float-sink results and Deister Table operation in terms of pyrite particle sizes are made. Other potential applications of automatic microscopy are also discussed. In the study of coal cleaning by pseudo-gravity methods (tables, cyclones, hydrotators, etc.), it is customary to express the deficiency of the process relative to float-sink measurements in some form of "percent efficiency". These have been calculated in many different ways in order to provide a means of extrapolation of test data to untested coal feeds. This works quite well with coarse coal (here defined as larger than one-eighth in.). Large, heavy pieces of refuse are rejected rather thoroughly by many cleaning processes, and the efficiencies relative to float-sink results approach 100%. In coarse coals, the difference in the sizes of fine pyrite is masked by the averaging effect of the large coal envelopes. The existence and fate of fine pyrite is often hidden in the larger numbers representing coarse (and easily removed) pyrite. There are cases where it is desirable to subject fine coal (here defined as smaller than one-eighth in.) to cleaning processes. This is true of naturally occurring fie coal streams and in cases where comminution followed by cleaning is necessary to provide the quality desired. It is in this area that the use of process efficiency relative to float sink fails. Percent efficiencies decline to very low figures, and equivalent separation densities become a matter for conjecture. The net result is that an attempt to estimate product quality from float-sink data and a process efficiency figure often results in large errors. This work represents a new approach to the problem by observing the fate of pyrite particles, grouped by sizes, in a cleaning process. Examples are given which relate pyrite size measurements to float-sink washability and to a Deister Table operation. EXPERIMENTAL WORK The automatic microscope used here has been previously described.' Briefly, it is an instrument which measures the diam of particles (as defined by a range of reflectance) exposed on a polished specimen. The instrument scans a sample briquet, measures diam of exposed pyrite inclusions and records the data by size intervals. Preparation of the briquet is critical, due to the automatic nature of the process. The principal requirement is for an optically flat surface, so that focus will be maintained as the motorized stage moves the specimen under the lens. The various substances present must be polished to the same level in spite of the wide difference in hardness between coal substance and minerals. The polishing method must not pluck out small grains, which might be rather loosely held by surrounding coal. The procedure below was successful in producing all of these results. The coal sample (8 mesh or finer) was riffled (a micro vibrating riffle is essential) to obtain 15 g. One volume of Lucite powder (thermosetting plastic mounting medium) was mixed with three volumes of coal and mixed thoroughly. A briquet was formed using a cylindrical die (1 1/4 in. diam) at 3000 lb per in.* pressure and 150°C. Preparation of the optical surface was accomplished on automatic polishing equipment, according to the following schedule: 1) Grinding: 3 stages, using successively fine Carborundum grits of 180, 320 and 600 mesh. 2) Rough polishing: 2 stages, using 3µ alumina on cast iron, followed by 1µ alumina on lead. 3) Fine polishing: 2 stages, using 0.5µ alumina on napless broadcloth over bronze, followed by 0.1µ alumina on silk filament cloth over bronze. Raw data were corrected for the fact that the chords

Jan 1, 1964

This paper generalizes open stopes into elliptical cross sections and applies the results of calculations based on the mathematical theory of elasticity to indicate stress distribution on the boundaries of such stopes. These show both compressive and tensile stresses and provide an ex-planation for the development of excessive dilution in shrinkage toping. Introduction T HE stress pattern around shrinkage stopes is identical with that around other stopes under the same physical conditions. However, a shrinkage stope ends as an unsupported open stope, and the method i limited to the stress range within which the rock is generally self-supporting. If it is acceptable to generalize the outline of a shrinkage stope into an elliptical cross section, then the graphs of Geldart & Udd (1) (see also Panek (2) and Denkhaus (3)) provide a good base for approximating the stress distribution as mining progresses. However, with failure conditions in the walls, the axis ratio, as cut

Jan 1, 1964

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

The iron ore deposits of the Port Hedland district of North Western Australia are associated with band'ed sedimentary iron formations that form part of the local succession of folded and faulted Archaean volcanic and sedimentary rocks. The iron formations are regarded as the protore beds or sources of the iron which became concentrated by supergene processes to form commercial grade iron ore deposits.Iron oxide deposits occurring in situ within the protore beds are considered to be of residual-replacement origin, due to supergene leaching of gangue minerals and' deposition of secondary iron oxides in their place, Two types of deposit have been recognized. Lode deposits are deep lenses of massive hematite located adjacent to major faults. These deposits are thought to be very old and to have originated by supergene processes during the long period of erosion represented by the major unconformity between the Archaean rocks and the overlying Proterozoic beds. The other type, known as crust ore deposits, are shallow cappings of hematite and goethite on hills formed by the outcrops of steeply dipping protore beds. These deposits could have originated as far back as the early Mesozoic and it is possible that the ore-forming process is continuing at a slow rate at the present day.Deposits formed by erosion and re-deposition of material derived from pre-existing residual-type deposits are known as derived deposits. These include conglomerates and scree accumulations of various types and ages and pisolitic deposits formed by supergene leaching of transported detritus. Derived deposits range in age from early Proterozoic to Recent. The presence of pebble accumulatio,ns of lode-type hematite in the Proterozoic basal conglomerate provides good evidence that lode hematite deposits existed in pre-Proterozoic times.INTRODUCTIONThe existence of iron ore deposits in the Port Hedland district of Western Australia has been known since the beginning of the century, but little attention was paid to them untIl the 1930's, when the Commonwealth Aerial, Geological and Geophysical Survey of Northern Australia carried out investigations of most of the then known mining fields of the Northwest Division. The only iron...

Jan 1, 1964

By M. Shelef, A. W. Fletcher

The effect of alkali sulfates in promoting the sul-fation of nickel and copper in a bulk sulfide flota -tion concentrate by fluidized bed roasting has been studied in the laboratory, and it was shown that the various alkali sulfates promote sulfation to approximately the same extent. The sulfation of a mixture of synthetically prepared iron and nickel oxide and of nickel ferrite has also been studied. Nickel sulfation was promoted by high ratios of Fe:Ni and by the presence of sodium sulfate. THE work described in this paper was a continuation of earlier studies into the role of alkali sulfates in promoting the sulfation roasting of nickel sulfides1,2 in an endeavor to determine how the system was affected by the presence of compounds of iron and copper. The earlier work1 showed that, in the sulfation of NiO at 680°C, the reaction was limited by the formation of an impermeable film of nickel sulfate on the oxide surface. The relative effect of the various alkali sulfates in promoting nickel sulfation varied in the order: Li > Na >Cs > Rb > K A study of alkali sulfate/ nickel sulfate interactions at high temperatures showed that the promoting action was due to the fact that the nickel sulfate product layer sintered and agglomerated only when the more active additives were present. This resulted in the formation of discontinuities in the nickel sulfate layer so that diffusion of the sulfating gases to the NiO surface was no longer impeded and the reaction could proceed to completion. A similar explanation was used for the observation that sodium and lithium sulfates promote the oxidation of NiS to NiO at temperatures below 750°C since small amounts of nickel sulfate were formed during oxidation.2 It was of interest to study the effect of alkali sulfates on the sulfate roasting of a sulfide flotation concentrate which is typical of material treated commercially. In order to control temperature it is essential to roast sulfides in a fluidized bed and this technique was therefore used, although the batchwise operation of a small-scale laboratory reactor does not reproduce all conditions which prevail in full-scale continuous plant. The results obtained are therefore only comparative, and cannot be used for predicting the optimum conditions for metal extraction. The sulfation of synthetically prepared mixed oxides of nickel + copper and nickel + iron and of nickel ferrite was also studied to evaluate the relative effects of alkali sulfates with more complex systems. SULFATION ROASTING OF A SULFIDE FLOTATION CONCENTRATE The bulk sulfide flotation concentrate used in this work contained 7.92 pct Ni, 1.74 pct Cu, 35.66 pct Fe, and 31.28 pct S. The sulfide minerals present in order of abundance were pyrrhotite FeS, pyrite FeS2, pentlandite (FeNi)S, and chalcopyrite CuFeS2. Two samples described as coarse and fine were used. The coarse sample, which was a flotation concentrate (58 pct plus 300 mesh), was ground to 100 pct minus 350 mesh to produce the fine sample. Before roasting, the sample of sulfide concentrate was agglomerated by wetting witli a solution of the alkali sulfate (or water), thoroughly mixing, and drying at 110°C. This gave a cake which was gently crushed and screened, the -18 +100 mesh fraction being used for fluidized bed roasting. A similar-size fraction had been used by the authors in pilot plant work with a 4-in.-diam fluidized bed reactor.' In this work it was found that the molar ratio of additive to the total iron + nickel + copper content of the sulfide sample should be adjusted to a value of approximately 0.06, as this was the optimum amount necessary for nickel sulfation. Experimental. The fluidized bed reactor consisted of a quartz tube approximately 60 cm long and 30 mm in diameter resting in a vertical tube furnace. The sulfide bed (30 g) was supported on a bed of -4 +12 mesh quartz particles 3 cm high, which rested on a sintered quartz disc welded to the tube. The temperature of the furnace was controlled with a variable transformer to give a final bed temperature of 680°C. The bed was fluidized with air or mixtures of air + 10 pct v/v SO2, at a total apparent gas velocity of 60 to 65 cm per sec at 680°C. The SO2 was introduced into the fluidizing air stream only when the oxidation of the sulfides was completed. At the end of the roasting period the calcine was leached with boiling water and the

Jan 1, 1964

By R. Maurice King

In the operation of today's large scale ore-processing mills, it is extremely important to have some way of making an objective evalu¬ation of the performance of the available flotation reagents. Attempts to do this may often result in inconclusive findings since the magnitude of the difference in the mill results for any two reagents is apt to be quite small compared to the variability introduced by the process and 'the analytical procedures used to measure them. In cases where two reagents give vastly; different mill results, evaluation becomes a simple matter and as such deserves no further attention here. A question of primary concern, however, is how a mill can go about evaluating the performance of two reagents which may, for example, give a difference of only 0.001% copper in the-tailings or of 0.2% in copper recovery. The casual observer may feel that such small differences may be of little importance, but in a mill-whose daily tonnage is between 30 and 40 thousand, these differences could mean a substantial savings. Before the presentation of an actual example of a reagent testing scheme designed for just this-purpose, perhaps a few minutes should be devoted to a review of some statistical methodology to be used later in the discussion.

Jan 1, 1964

By P. A. Tucker, T. B. Rhinehammer, D. E. Etter, J. E. Selle

The Ce-Cu phase diagram was investigated by differential thermal analysis and rnetallography. Two congruent melting compounds, CeCu2 (817°C) and CeCua (938°C), and three incongruent cornpounds, CeCu (516°C), CeCu, (796°C), and CeCu, CERIUM and copper have been suggested as possible diluents in a liquid-plutonium fueled reactor. As part of the determination of the Ce-Cu-Pu ternary phase diagram, a review Of the Ce-Cu system (798°C), are present in this system. Eutectics exist at 28 at. pct Cu (424°C), 74 at. pct Cu (756°C), and 91 at. pct Cu (876°C). The purity of the cerium used has an important effect on the results obtained by differential thermal analysis. was considered necessary. Previous work by Hanaman was conducted with relatively impure metal: 96.7 pct Ce with 2.5 pct other rare earths and 0.5 pct Fe as major impurities. The metal had a melting point of 715°C as compared to the melting point for pure cerium of 804°C as reported by Spedding and Daane.2 Results presented in this work were obtained primarily by differential thermal analysis (DTA) and metallographic examination of slow-cooled or quenched samples.

Jan 1, 1964

By W. L. Freyberger

In a study of the kinetics of flotation of coal, employing a single-cell continuous flotation system, Jowett and Safvi1 pointed out that it was experimentally impossible to float all of the coal which could be floated in a batch tests. On the other hand, deBruyn and Modi, in a discussion of their paper, suggested that under certain conditions the recovery of floatable material from a similar one-cell continuous system would have been 100%.2 Both of these pairs of authors make the assumption that a state of perfect mixing exist in the flotation cell. This assumption, usually made by investigators studying flotation kinetics in a continuous system, has been confirmed experimentally on several occasions. The work is summarized by Arbiter and Harris.3 It is the purpose of this note to demonstrate that, for conditions of perfect mixing, one of two conditions exist: 1) the recovery of floatable material is 100%, and the flotation is infinitely fast, or 2) the recovery of floatable material must be less than 100%. This theorem can be proved simply in the following manner: 1) If recovery, R, of the floatable material is 100%, the concentration in the tailing must be zero. This follows from the definition of recovery as

Jan 1, 1964

By F. Scott Carpenter

During the past several years, more frequent reference to Wollastonite has appeared in print, both in this country and abroad. The reason for this is the apparent growing interest in this mineral as it approaches commercial maturity. Twelve years ago, wollastonite was available in only limited commercial quantity. In 1933, a deposit in California was worked for a short time to provide a calcium silicate raw .material for the manufacture of mineral wool* It was not until the spring of 1953 that Cabot Corporation put into operation a modem commercial plant to produce this material in a variety of grades. These grades covered both a range of particle size and of particle shape. At that time, applications for wollastonite were largely speculative, although a few commercial applications in glass frits and welding fluxes did exist, For all practical purposes, it was a new material for which few commercial uses had been fully proven.

Jan 1, 1964

By Y. Kondo, A. M. Gaudin

A combined method for sizing in the sub-micron range was developed using centrifugation and gamma emission. Its essential features are: 1) Centrifugation of suspended mineral in water carried out at 4°C where water has its maximal density and zero temperature gradient of density 2) Gamma activition of the sample suspension induced by irradiating it in a nuclear reactor prior to centrifugation 3) Measurement of the activity of a beam of suspension as it is sedimenting in the centrifuge, using a scintillation counter provided with a discriminator. Albite, the sodium feldspar, was used as feed to the comminution step, and the induced gamma activity of Na24 was measured. Dissolved sodium ion caused a a non-settling activity in the measurement. Other "noise" is due to scattered gamma radiation from albite particles in the centrifuge outside of the line of sight. These two activities were obtained sep arately and subtracted from the total activity counted. The relative solid concentration in the suspension under the collimating slit is proportional to this net activity. The cumulative weight per cent of undersize particles was calculated and plotted against size on logarithmic scales. The relationship was found to be linear down to about 30 mµ. The specific surfaces calculated from particle size distribution agree with those measured by krypton gas adsorption. The measurement of particle size distribution of comminution products has been of interest in clarifying the mechanism of the process. The Gaudin-Schuhmann equation1,2 relates the cumulative percentage undersize, y, to relative particle size x/k. The particle size, x, and the size modulus, k, together with the distribution modulus, m, characterize the particle size distribution, m is the slope of a plot of log (y) against log (x/k). This equation has been verified for ground particles down to 1 micron in size.3'4 For particle sizes smaller than a few microns, the precision and facility of sedimentation and microscope techniques become questionable. Use of a centrifuge which shortens settling time from weeks to hours is attractive. Many centrifugal methods have been proposed; however, determination of the solid concentration of the suspension at a reference level as a function of time is difficult, and sampling the suspension is likely to introduce errors. Measurement of particle size distribution by X-ray absorption in gravitational5 and in centrifugal6 sedimentation have also been tried. In these methods, the absorption coefficient for the solid is independent of size, since the wave lengths of the X-rays and gamma-rays are orders of magnitude smaller than the particles. Radiometric techniques7 in size distribution measurement have been developed within the last several years. They offer advantages over usual gravimetric and optical methods. PRINCIPLE OF METHOD The combined method of centrifugation and gamma emission for sizing in submicron range described in the present paper has the following essential features. 1) Centrifugation is carried out at 4 ± 0.1°C. Convection currents in the water phase due to density changes caused by temperature variation may disturb completely the settling system. To avoid this difficulty, the unique property of water having zero temperature gradient of density at 4°C is used. 2) Prior to size measurement the sample suspension is irradiated in a nuclear reactor and gamma activity induced. The gamma activity of the particles sedi-mented radially is measured by a scintillation counter provided with a discriminator. By this method, interruption of centrifugation by withdrawing samples is avoided and the counting rate at any time represents the solid concentration in the suspension at the level of the collimating slit of the centrifuge at the particular time at which the measurement is made. 3) By proper selection of the feed material and of the comminution device, gamma activities of foreign

Jan 1, 1964

By A. S. Appleton

The diffusion of carbon in Fe-Co-C austenites was studied as a function of cobalt concentration up to 12 at. pet, using an autoradiographic technique. The diffusion coefficient was found to initially decrease and then increase with increasing cobalt concentration, the trends being more marked the higher the temperature of diffusion. These effects were paralleled by variations in the activation energy and the constant for diffusion which, however, were found to be dependent also on the carbon content. The results are compared with the previously available data and their significance is discussed in terms of the kinetics of solid-state reactions in this systern. THE influence of cobalt on the diffusivity of carbon in austenite was first studied by Smoluchowski,' his data being that most commonly cited in works

Jan 1, 1964

By R. J. Arsenault

The yield drop that occurs in tantalum, Cu-AZ. and Ag-Al was investigated as a function of strain rate and at several temperatures. From the strain-rate dependence of the yield drop an activation volume was calculated and found to agree with that obtained from differential strain-mte tests. The temperature dependence of the yield drop can he explained in terms of the parameter temperature divided by activation volume. The yield drop is attributed to the rapid multiplication of dislocations during their motion. THE yield-point or yield-drop (upper yield stress minus the lower yield stress) phenomenon has been the subject of numerous investigations1-9 in both bcc and fcc metals. Also, there is no dearth of theoretical explanations10-20 to account for the yield-point phenomenon. The present explanations can be divided into two categories: the concept of dislocation locking and subsequent unlocking and the concept of multiplication of dislocations due to their motion. The Vottrell10,11mechanism of locking and unlocking, as applied to bcc metals, is the best known of the three proposed locking mechanisms. The two additional mechanisms, short-range order (SRO)7,16,17 and Suzuki-type locking,14,15 have been employed to account for the existence of yield points in fcc metals. The experimental evidence supporting the locking of dislocations, especially in bcc metals, is well-established. The dependence of the yield point on interstitial concentrations,' the kinetics of strain aging,2 and the observations by electron-transmission microscopy18 are some of these experimental results. The number of experimental observations supporting dislocation locking in fcc metals is not as extensive as in bcc metals. The unlocking of dislocations, which actually is supposed to account for the yield drop, is by no means well-established by experimental results for either bcc or fcc metals. The similar temperature dependence6 of the yielding and plastic flow is one of the experimental factors that cannot be explained in terms of the unlocking of dislocations. The mechanism based on the rapid multiplication of dislocations has been proposed by several investigators. 18-20 Johnston and Gilman19 have proposed a detailed model of yielding, which was later employed by Hahn21 to predict quantitatively the yield drop in iron. This mechanism was discussed in a previous paper22 and several limitations were pointed out. In the same paper it was shown that an activation volume could be obtained from the strain-rate dependence of the yield drop and that a correlation existed between the activation volumes obtained from the yield-drop tests and from differen-

Jan 1, 1964

By I. B. Cadoff, J. C. Bilello, R. Rosenberg

Diffiusion of magnesium into the surface of LiF crystals to controlled depths and subsequent heat treatments provided a wide range of surface zone harahesses and structure, The bend strength of the LiF crystals was increased by as much as an or-dev of magnitude. Ductility was achieved when dislocation generation occurred in the diffusion zone or when dislocations penetrated to the surface from the intevior. A critical surface hardness of 130 to 140 kg per sq mm was found helozu which generation could take place in the diffusion zone and ahoue which the zone was impenetrable, This hardness was obtainable by several methods, among them the aging of quenched MgF2 -LiF solutions to produce MgF, precipitation. Maximum hardness was ohtained in quenched specimens with no visihle evidence of MgF,. Diffusion-zone formation followed a parabolic rate law and an activation energy of 20.9 kcal per mole was obtained for the process. RECENTLY, the properties of ionic crystals as related to surface condition have been receiving much attention, specifically the transitions between ductile and brittle behavior. Originally Joffe 1 showed that NaCl crystals could be made ductile by immersion in water and related this to the elimination of surface microcracks. Aerts and DeKeyser 2 and Gorur 3' have subsequently shown that ionic crystals are inherently ductile and are embrittled through contact with air. Machlin and Murray4 hypothesized that a layer of NaCIO3 produced by contact of ozone with NaCl induced embrittlement by acting as a barrier to outward dislocation flow. westwood,' Rosenberg and Cadoff,9 and Bilello and cadoff' have reported surface strengthening of LiF crystals by coating with a magnesium compound and then heat treating for adherence. The major effect of the coat was to inhibit dislocation-slip lines from reaching the specimen surface. westwoods showed microcrack formation and fracture to be caused by slip-band interactions at the surface. The material presented in this paper is an extension of the work reported earlier by Bilello, Rosenberg, and cadoff'6,7 and illustrates the wide range of surface properties and bulk behavior obtainable by use of heat-treated magnesium-diffused surface regions in LiF crystals. EXPERIMENTAL PROCEDURE The LiF single crystals were obtained from the Harshaw Chemical Co. Some batch to batch variation was observed; therefore all specimens for a given test series were cleaved from the same crystal. The typical dimension used was 1 by 0.1 by 0.40 in. Surface damage resulting from cleavage was removed by chemically polishing in a 2 pct NH4OH solution. Each group of specimens was given a vacuum anneal at 700°C for 4 hr to provide a base standard for measuring comparative effects of various surface treatments. To produce the reacted surface zone, the annealed specimens were immersed in a boiling suspension of MgF, in doubly distilled HzO, agitated slbwly for 30 sec, removed, and dried at room temperature. Uniform coatings of MgF, were deposited with a thickness of approximately 5 mils. It should be noted that this technique can be modified for use with crystals which are soluble in water by using boiling absolute alcohol as the dissolving medium. This was found effective for the coating of NaCl with MgF2. The diffused surface zone was obtained by annealing the coated samples at elevated temperatures in a vacuum of lob4 mm Hg. Penetration depth was controlled by varying the annealing time from 1/2 to 28 hr. After heat treatment, the samples were tested for bend strength and hardness. Load was applied by four-point bending in a hard-beam testing jig. Four-point rather than three-point bending was used to provide a wide area of constant stress and to minimize the effect of localized inhomogenities in the specimen. The deflection rate was 8 x min-' and the distance between knife edges was 1/4 in. Load-time curves were obtained from a chart recorder coupled to the machine and converted to resolved shear stress on the shear plane vs deflection, as plotted in the figures. The unstressed portions of the sample outside of the two outer knife edges were used for the microhardness studies. Microhardness measurements were made with a Bergsman tester attached to a Reichert metallograph. All hardness impres-

Jan 1, 1964

By Larry Kaufman, Martin Schatz

The effect of pressure on the extension of the ? loop in the FeSi system has been determined by means of metallogvaphic studies and hardness measurements performed on a series of high-purity Fe-Si alloys containing 7.5, 11.0, and 13.9 at. pct Si, respectively. These mensurements, performed at 42 kbar and temperatures up to 1200oC, indicate that the ? loop is expanded to about 10 at. pct Si at 42 kbar as opposed to a maximum extension of 4 at. pct Si at 1 atm. Comparison of the experimental results with thermodynamic predictions of the pressure shifts yields satisfnctory results. DURING the past few years, several studies have been performed in our laboratory1-' in order to determine the effect of high pressure on phase equilibrium in pure iron and iron-base alloys. The purpose of these studies has been to elucidate the effects of high pressure experimentally and to compare the observed results with predicted pressure effects derived on the basis of known thermody-namic and volumetric data at 1 atm. These studies have included work on pure iron2,5,7 as well as Fe-Ni,1,5 Fe-cr,l,5 and Fe-c4-6 alloys. In addition, Tanner and Kulin3 have reported results of pressure studies on two Fe-Si alloys containing 2.0 and 6.25 at. pct Si. At the time of this latter study, no detailed information was available concerning the difference in volume between the a (bcc) and ? (fcc) phases in the Fe-Si system as a function of silicon content. In order to compare their observations with calculated pressure shifts, Tanner and Kulin were forced to assume that silicon had no effect on the difference in volume between a and ? iron. The resulting discrepancy between their calculation of the a/? phase boundary at 42 kbar and the observed results led them to the conclusion that silicon additions probably decrease the difference in volume between a and ? iron. Recently: Cockett and Davis8,9 have reported de- tailed studies of the lattice parameters of a series of Fe-Si alloys at temperatures ranging from 20" to 1150°C. These measurements, performed on alloys in the bcc and fcc range, show that silicon does indeed decrease the difference in volume between a and ? iron. By correcting the calculations of Tanner and Kulin in line with the observed effect of silicon they were able to show improved agreement between computed and observed pressure shifts.' The present measurements were undertaken to provide additional corroboration of this effect, by extending the range of composition, in addition to exploring a situation where large extensions of a ? loop could result in impingement of the ? field with an ordered bcc phase (based on Feo.75Sio.25). I) EXPERIMENTAL PROCEDURES AND RESULTS The alloys investigated were obtained from Dr. F. Kayser of M.I.T. They were prepared at the Ford Scientific Laboratory by vacuum melting electrolytic iron and high-purity silicon. The melts were poured under an argon atmosphere into hot-topped steel molds. Subsequently the ingots were hot-worked down to 1/2-in.-diam rods. Three alloys containing 7.5, 11.0, and 13.9 pct Si were studied. Carbon, regarded as the principal impurity, analyzed at, or below, 0.001 wt pct for all of the alloys. Prior to pressure-temperature treatment, the rod was annealed for 24 hr in vacuum at 1000°C, water-quenched, and subsequently machined into 0.100-in.-diam by 0.100-in.-long specimens. Subsequent to machining, the specimens were again annealed and then examined metallographically. They were found to exhibit a clear coarse-grained ferrite similar to Figs. 10 and 110 of Ref. 1 and Fig. 2 of Ref. 3. Subsequently, specimens of each alloy were equilibrated at 42 kbar at various temperatures in supported piston apparatus.1,3,4,6 Three specimens, one of each alloy, were wrapped in platinum and exposed simultaneously. The pressure-temperature cycle consisted of increasing the pressure from ambient to 42 kbar at 25oC, heating rapidly to the desired temperature, holding for 15 min, and quenching to 100°C, followed by slower cooling to 25°C and pressure release. The temperature was measured with a Pt/Pt-13 pct Rh thermocouple which was not corrected for pressure effects. Subsequently, specimens were examined metallographically and by

Jan 1, 1964

By Robert D. Saltsman

The inadequacy of our knowledge of the coal combustion process has long been recognized. This was expressed very well by Spicer and Finney (1). "The control of combustion processes in industry and the design of the equipment necessary for efficient burning to take place have always been very much branches of an industrial art rather than of an exact science. This has been especially true of the utilization of coal, a substance so hetrogeneous and complex in character that all too little is known about its chemical and physical composition.' During the past several years one branch of coal utilization, that of high temperature carbonization; has made significant advances from being an art into being an exact science. This has been accomplished by the development of petrographic techniques for identifying, measuring, and determining the thermal properties of the organic materials which affect the carbonization of coal and the correlation of this information with a pre-existing standard of coke quality, the stability index.

Jan 1, 1964