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By S. A. Mersol, C. T. Lynch, F. W. Vahldiek

The room-temperature Knoop hardness of single -crystal titanium diboride has been determined. Variations in microhardness have been correlated with orientation and structural imperfections in the crystals. Maximum differences in hardness values of 750 kg per sq mm with respect to orientation and 450 kg per sq mm with respect to substructure were found. The effects of etchants, load on indenter, and degvee of cracking of indentation were studied. The average hardness was determined as 2800 kg per sq mm on the as-grown crystals. Annealing increased the average hardness to 3375 kg per sq mm. ThE microhardness of polycrystalline titanium diboride approximating the stoichiometric composition TiB, has been studied by several investigators. The values for the Knoop hardness number range from 2710 kg per sq mm (Khn = 2710 kg per sq mm) to 3400 kg per sq mm.'-4 Samsonov et al.' reported a Vickers hardness number of 3400 kg per sq mm (Vhn = 3400 kg per sq mm) at 120-g loads for a 98 pct Ti + B material of 96 pct theoretical density. Recently Dunegan measured the Vickers hardness and obtained 2060 kg per sq mm with a 10-g load (Vhnlo = 2060 kg per sq mm), 1425 kg per sq mm for Vhnloo, and 1320 kg per sq mm for Vhnlooo. We have obtained a Khnloo = 3000 * 350 kg per sq mm for hot-pressed polycrystalline TiB2 that was 99.1 pct Ti + B and 96.6 pct of theoretical density. The present investigation has been made on single-crystal titanium diboride boules, and is believed to be the first such study on TiB, crystals of known orientation. EXPERIMENTAL The single crystals were prepared by a Verneuil-type process using an electric arc by the Linde Division of Union Carbide Corp. The largest specimens were 6 mm in diameter by 12 mm long. The crystals were of theoretical density (4.50 g per cm3) with a Ti + B content of 99.8 pct. The major impurities present were: 0.03 pct (by weight) 0, 0.06 pct C, 0.01 pct Si, 0.05 pct Fe, 0.01 pct Cr, and 0.01 pct Ni. The crystals were boron-rich, the average boron content being 31.S7 wt pct (stoichiometric value is 31.12 wt pct), and titanium-poor, the average titanium content being 68.2 wt pct (stoichiometric value is 68.88 wt pct). Titanium was determined gravimetrically by cupferron precipitation and boron by titration of H3B03 from a NaOH-fused specimen after removal of titanium with BaC03. The outer edge of the boule accounted for some of the excess boron. An electron-microprobe analysis showed that the titanium content increased from 60.0 wt pct at the edge to 68.5 wt pct at D, ~ 1000 p, where D, = distance from outer edge (see Fig. 5). X-ray measurements indicate that the boules are single crystals with considerable substructure. Upon etching this structure is seen in the form of a Widmanstatten-type rhombohedral line pattern in the basal (c) plane and a parallel "lines" pattern in the prism (a) planes. A typical WidmanstHtten-type pattern is seen in in Fig. 1. Electron microscopy reveals that the lines are less than 1 p across, which does not allow direct electron probe or microfocus X-ray determination of their composition. The identity of the second phase has not been established. It might be a higher boride or a nonstoichiometric TiB2. On annealing above 2200°C the precipitate is dispersed and dissolves in the matrix. The best etchants found were HF/HNO/HO, KF(CN)$NOH/HO (Murakami's Etch), and A large number of other etchants were previously Studied. The acidic etchant produced an acicular or "needles" pattern in the (a) planes which is an etchant effect on the "lines" pattern.

Jan 1, 1965

By Wallace W. Key

The California pesticide industry in 1962 consumed about 30,000 tons of clay, talc, limestone, diatomite, sulfur, and other minerals as fillers (carriers and diluents) in pesticide formulation. This was 10 percent of the U.S. filler requirement for pesticides. About two- thirds of the California total was supplied by a few local mineral producers; the remainder came mainly from Florida, Georgia, and Wyoming. The objectives of this report are to provide data on quantities, sources, specifications, and market conditions for minerals used as fillers by California pesticide formulators. The study disclosed that specifications for mineral fillers have become more rigid and formulators have become more numerous in recent years. During 1962 over 1,200 firms registered 16,000 pesticide products with the Bureau of Chemistry in California. Factors which will tend to diminish future need for mineral fillers include the trend toward greater use of organic sprays rather than dusts and further development of biological controls, such as the development of sterile insect strains.

Jan 1, 1965

By J. Buchwald, R. W. Heckel

THE DeHoff method' of analysis of ellipsoids of constant shape provides a quantitative metallo-graphic technique whereby the actual size distribution of the ellipsoids may be determined from polished and etched random planar sections. This method provides a useful metallographic tool since it appears to be the only method available for determining the size distribution of nonequiaxed second-phase particles. This method, however, assumes that the type of particle being studied is known to be either oblate or prolate of a fixed minor to major axis ratio, q. This, in general, means that one assumes either oblate or prolate ellipsoids of a given q and checks the total volume and surface area of the second phase as determined from the particle size distribution to values of these quantities determined by other techniques. Suitable check methods may be point counting, lineal fraction, and areal fraction methods for obtaining the total volume and the Smith and Guttman2 method of intercepts for obtaining the total surface area. If the initial guess at particle shape and q were incorrect, i.c., the volume and surface information obtained from the particle size distribution data does not agree with those values obtained by other techniques, another assumption must be made and the particle size dist distribution must be recalculated. A current study in this laboratory has involved a large number of these calculations. To facilitate the handling of the calculations, the DeHoff method was programmed in the FORTRAN language for an IBM 1620 computer. The purpose of this note is to briefly describe this program. The complete program along with a list of variable names, a sample input, and a sample output may be obtained from the senior author. Basically, the program provides for the calculation of particle size distributions for a series of q values for both oblate and prolate ellipsoids for each set of input data. The total volume of second-phase particles per unit volume are calculated for each calculated particle size distribution. The output of the program is arranged to allow a rapid comparison of the calculated volume and surface values to data obtained by independent check measurements. A condensed flow chart of the program in the notation of DeHoff1 is given in Fig. 1 The calculation of the number of particles per unit volume in the jth size class, Ni, according to the DeHoff method' is: where k(q) is the shape-correction factor given by DeHoff as a function of q for both oblate and prolate ellipsoids, A is the size-class increment, k is the number of size classes, ni is the number of particles in the ith class on the planar measurement surface, and B(j,i) are the saltykov3 coefficients which correct for measurement surfaces which do not pass through the major and minor axes of the particles. The values of /3(j,i) are included as a two-dimensional array in the program. Particular values of k(q) are included in the program in increments of q of 0.05. The first calculation is carried out for q = 1 (spheres), the second for q = 0.95 oblate, the third for q = 0.95 prolate, and so forth. The number of q values chosen for the calculation is determined by a control card in the input for each set of data.

Jan 1, 1965

By D. R. Mathews

Electrorefined vanadium was evaluated with respect to tensile properties and the effects of interstitial contaminants in the temperature range of 77° to 273° K. The yield strength of 18,500 psi and hardness of 63 diamond pyra-mid hardness (DPH) of electrorefined vanadium are approximately equal to that of iodide crystal bar vanadium. The ductile-brittle transition temperature was found to be below 77° K, but with 0.175 weight-percent oxygen or 0.10 weight-percent nitrogen, it increased to between 123° and 190° K. With carbon content up to 0.11 weight-percent, the transition temperature remained below 77° K. The yield strength of the interstitial-containing alloys can be expressed by: au = 7.5 + 480 (pct N) + 290 (pct 0) + 280 (pct C), where au is the upper yield stress in 1,000 psi at 273° K. Profuse deformation twinning occurred in the alloys tested at 77° K. However, twinning could be suppressed by dissolved oxygen or nitrogen in excess of 0.15 and 0.086 weight-percent, respectively. Carbon, even though present in excess of the solubility limit, did not affect twinning.

Jan 1, 1965

By P. E. Palmer, A. H. Daane, C. E. Habermann

Jan 1, 1965

By Joseph Grumer

The range of composition of gases synthesized from solid fuels which are exchangeable with natural gas on current gas appliances was evaluated by theoretical principles. These principles consider primarily the flashback, blowoff, and yellow-tipping characteristics of air-entraining burner flames. It was found that complete identity between the synthetic and natural product is not necessary. Gases such as may be obtained by hydrogasification of coal and other solid fuels without the removal of unreacted hydrogen offer advantages in flame characteristics. Between 25 to 37 percent hydrogen can be tolerated in the sendout gas.

Jan 1, 1965

By A. C. Losekamp, R. M. Fincel, J. B. Conway

HIGH-TEMPERATURE thermal-expansion data for tungsten, rhenium, molybdenum, Mo-50Re, and W-25Re were obtained recently by means of a paired

Jan 1, 1965

By J. W. Leonard

This expanded and more detailed supplement to earlier published work1 is offered as a means to demonstrate the high empirical correlation which exists between the readily measured coal bench scale test parameters of volatile matter (d & a.f.), Hard-grove grindability index (HGI), Koppers cone bulk density (BD) and pulverization level (% passing a 1/8-in. screen) to the less readily measured full scale coke stability index. Thus, Fig. 1, 2 and 3 represent the correlated test data contained in Tables I, II and III respectively. Ninety-six coals are correlated so that 97% of the resultant cokes fall within two points and 100% fall within three points of the actual tested coke stability indices. The main generalizations which can be drawn from the correlation of these coals are as follows: 1) The coke stability indices for higher bulk density coals (46.0 BD to 50.6 BD) appear to be largely influenced by differing combinations of factors for coals above and below a pivotal point of approximately 36% to 37% volatile matter. Below this pivotal volatile matter coke stability index appears to be influenced largely as a result of changes to the coal volatile matter and pulverization level. While above this pivotal volatile matter coke stability indices appear to be dependent on the coal hardness, as measured by the HGI, and to some extent upon coal volatile matter. Pulverization appears to have little influence on the coke stabilities of the harder coals (52 HGI to 58 HGI) of greater than 36% to 37% volatile matter. 2) The coke stability indices for lower bulk density coals (41 BD to 45.9 BD) appears to be largely influenced by changes to coal volatile matter and pulverization level for softer coals above approximately 58 HGI. 3) The main empirical observation to be drawn from these results is that for coals above approximately 36% to 37% volatile matter the quantities of hard and soft constituents as measured by the HGI are important when defining coal rank for correlation to the coke stability index.

Jan 1, 1965

By Nicholas J. Grant, A. W. Mullendore, Paul Predecki

The Duwez technique of splat cooling in which a molten droplet of metal is accelerated and made to impact on a cold, highly conducting substrate was investigated.- An apparatus for producing "splat" was constructed employing an explosive powder charge to accelerate the molten metal. Transport of the molten metal just prior to impact with the substrate was studied by means of high-speed photography. The molten particles are small spherical droplets from about 1 to 50 µ diameter. The average cooling rates for aluminum, silver, and a gold alloy splatted on nickel substrates at room temperature were determined experimentally and were found to vary from 18 to 5 x 10' C per sec. The heat-transfer coeficients for pure aluminum and pure silver splats cooled on nickel substrates at room temperature were found to be 2.7 to 6.8 and 13.6 to 54.2 cal per sec sq cm 'C (2 to 5 x 104 and 1 to 4 x 18 Btu per hr sq ft OF), respectively. Solidification rates in pure aluminum and silver splats were calculated. "SPLAT cooling" is a term describing a technique for extremely rapid freezing and cooling of molten metals and alloys to room temperature or below. The technique was developed by Duwez et al.' in 1960, and after refinement2 consisted in transferring a few tenths of a gram of molten metal to near sonic velocity to strike a suitably placed cold copper surface. Upon impact, the metal spread into a thin nonuniform film called a splat, about 10-4 cm thick. The splat particles produced in this manner were thin enough in some areas to be suitable for transmission electron microscopy, without further treatment, and, together with X-ray data, yielded a variety of structures which would be classified as follows: 1) supersaturated solid solutions (increase in solubility limit), 2) metastable crystalline stoichiometric and non-stoichiometric intermediate phases ( in Au-20.5 at. pct Si and in Au-14 at. pct Sb, respectively), 3) amorphous alloys, 4) retained high-temperature phases, 5) alloys having equilibrium phases present, but with unusual, markedly altered structures. The crystalline phases present in splats were usually extremely fine-grained and had low dislocation densities. Present interest in splat cooling centers around a study of the unusual structures produced by the technique, their contribution to alloy theory, and the possibility of the development of new or unusual properties. In addition, the technique is being examined for the production of bulk quantities of new high-strength alloys for low- and high-temperature use. Although a number of alloy systems have already been investigated by the technique, relatively little is known about the mechanism of splat formation and the physical conditions encountered by the metal during solidification and cooling. The purpose of this work was: 1) to determine the velocity, shape, and size of the molten metal droplets just prior to impact with the cold substrate; 2) to try to estimate or measure solidification rates, heat-transfer coefficients, and cooling rates in splats. EXPERIMENTAL TECHNIQUE Splatting Apparatus and Procedure. An apparatus similar to the type originated by Duwez et a1.,2 but employing an explosive charge to accelerate the molten metal, was used. A "Ramset" fastening tool (a gun normally used for driving studs into concrete, steel, and so forth) was mounted vertically above a resistance-heated graphite crucible as shown schematically in Fig. 1. A splat product was produced by melting a few tenths of a gram of metal at the position shown in Fig. 1, and then exploding a powder charge in the breach. The shock wave thus generated traveled down the barrel into the furnace, ejecting the molten metal through the 0.06-in.-diameter hole at the bottom of the crucible. The ejected metal was impacted on a high-conductivity metallic substrate where it formed a splat. High-Speed silhouette Photography. In order to investigate the size and shape of the ejected, molten metal just prior to impact with the cold substrate, high-speed silhouette photographs were taken, and are shown in Figs. 2 and 3. These photographs were obtained with the aid of an Edger-ton, Germeshausen, and Grier microflash unit and a submicrosecond flash drive equipped with a variable time delay. Two types of triggers were

Jan 1, 1965

By John E. Crawford

A year ago, if I had the pleasure of addressing you, I would have discussed ocean mineral resources from a promotional standpoint. I would have described exciting indications of mammoth tonnages of sea-floor industrial minerals. I would have attempted to fire your imaginations as to the potential of a nation having the technologic know-how to exploit its submerged boundaries. As a first step toward this capability, I would have solicited your support for a Bureau of Mines? program aimed at determining the industrial worth of marine minerals and devising techniques and hard- ware for their recovery. We still need your support, but recently we have ventured out of the realm of planning and into your Government's first program in marine mineral engineering. Today, I wish to describe what we have done within the framework of existing research problems and our possible goals. I will be brief so as to allow ample time for questions, and I can do this with confidence because our program is so new that I need not be chagrined at not having all the answers.

Jan 1, 1965

Recently discovered Carboniferous bentonites are variable in charadeI and thickness, but being altered aeolian, ash-fall tuffs, they are probably extensive. Most are the Ca-montmorillonite type without the natural swelling characteristics of the Wyoming deposits, but their situation, thickness, and response to beneficiation through cation exchange may give them some potential as sources of future economic deposits.INTRODUCTIONLoughnan and See (1959) gave an account of bentonites and fuller's earth deposits of New South Wales. The most likely potential industrial sources were those occurring in the uppermost formations of the Newcastle and Singleton Coal Measures (Permian) in the Hunter Valley and deposited during epochs not marked by strong contemporary vulcanicity.One feature of the record of known occurrences at that time was the absence of bentonites from the thick volcanic sequences of the Carboniferous, but since this paper appeared, many bentonite beds have been discovered by the writer in the Carboniferous facies formerly known as the "Kuttung Series".The purpose of this contribution is to report briefly on the occurrence, genesis, mineralogy, and economic potential of these deposits which augment possible sources of bentonite near major industrial centres on the eastern seaboard.The potential world demand for bentonite would increase markedly with the trend to pelletization in the steel industry, if its use in this field became more general. More detailed mineralogical studies will be presented in later publications.STRATIGRAPHIC DISTRIBUTIONBentonite occurs at irregular intervals throughout a thick sequence of dominantly continental, plant bearing strata...

Jan 1, 1965

By A. J. Boyer, T. R. Meadowcroft

An experimental determination has been made of the efject of surface diffusion on the vapor pressure obtained in a Kwudsen cell. The results show that a knife-edge orifice in a molybdenum lid may give erroneous results for the vapor pressure of silver. when a correction suggested by winterbottom and Hirth is made, the results become meaningful. Experimental work with cylindrical orifices in molyhdenz~m lids and knife-edge orifices in ceramic lids shows that good vapor-pressure results may he obtained when the orifice is designed so that ejfusion is the only significant source of weight loss. THE Knudsen effusion cell technique has been used by many investigators to study relative and absolute vapor pressures over metals and alloys at elevated temperatures. As a result of this interest, some theoretical studies have been made of geometric factors affecting effusion from the orifice of a Knudsen cell. A review of these studies has been made by Margrave.1 Recently, Winterbottom and Hirth2 have suggested that a physical effect, that of condensation, surface diffusion, and re-evaporation, may seriously affect Knudsen cell measurements, especially when a knife-edge orifice is used. Inasmuch as many of the present vapor-pressure data have been obtained using knife-edge orifices. it was felt that an experimental evaluation of the effect of surface diffusion on Knudsen cell measurements would be of value both in the design of the cell orifice and in establishing realistic estimates of the limits of error for existing data. The experimental program was in two sections. Firstly, measurements of the vapor pressure of silver were made in cells with cylindrical and conical orifices in which the surface-diffusion contribution to the weight loss should be negligible. These results were correlated with existing data to give a reliable measure of the real vapor pressure of silver. Secondly, measurements made using knife-edge orifices were corrected using the surface-diffusion theory of Winterbottom and Hirth2 and were then compared to the real values. The experimental arrangement is shown in Fig. 1. The balance was an Ainsworth RV-AU-1 automatic recording microbalance capable of measuring weight changes of ±0.02 mg on a total load of up to 100 g. The temperature was measured by an optical pyrometer signted on the bottom of the suspended crucible. The temperature readings were calibrated in a separate experiment in which pyrometer measurements were made while at the same time thermocouple readings were taken of the temperature at the inside top and bottom of the crucible. The range of reproducibility with this technique was ±4°C. A constant voltage source maintained a temperature of ±2°C at 1200°C over 10 hr. Silver of 99.99 pct purity was used in nonporous alumina crucibles. Lids of molybdenum, tantalum, or magnesia were cemented to the crucible using a sodium silicate cement. Table I shows the characteristics of the lids used. The vapor pressure is obtained using the basic Knudsen formula:

Jan 1, 1965

Hatches Creek has been inactive since 1961, but with better metal prices, interest in the field is reviving.The mixed gravity concentrates which were unsalable in 1951 have been experimentally separated into salable wolfram, scheelite, and bismuth-gold concentrates, and a flow sheet incorporating magneticseparation and flotation has been developed.

Jan 1, 1965

By F. A. Jerabek, H. L. Hartman

This study presents results of investigations in a small model of segregation in discharged fill slurry, the quantity of solids escaping in the drain liquid, and the relationship of solids to slurry concentration and discharge rate. Compressibilities of fine fill material, in dry and wet states and individual size fractions, are compared. Two terms are frequently used in describing the hydraulic placement of fill material underground: hydraulic stowing is mostly associated with the underground flushing of coarse-sized fill material, such as coal washery refuse; while hydraulic backfilling refers to placement of small-sized fill material, e.g., sand or classified mill tailings, mainly in metal mines. Characteristically, in backfilling, only a few hours may elapse between the time the material is hoisted as ore and redeposited as fill underground. Hydraulic filling was first used about 100 years ago to control subsidence in coal mines. It was subsequently adopted in many mining operations all over the world, but its basic concepts have never been adequately studied and analyzed. This is not surprising, when one considers the number of variables involved in the hydraulic backfilling operation. Recently, much work has been done on the problems of transportation of slurries in pipes. Comparatively less research work has been done concerning the physical properties of fill material (compressibility, cementation, permeability, etc.). Very little work has been done on the problems of fill placing, distribution, and segregation of fill material discharged in the mine void. It is the purpose of this paper to explore two of the basic, lesser known aspects of filling: segregation and compressibility in discharged fill slurry. Difficulties in observing the behavior of hydraulic fill slurry during the pouring operation underground, and insufficient knowledge to conduct any kind of meaningful theoretical analysis, suggest experimental model studies. The tests described in the following sections were conducted in the Rock Mechanics Laboratory of the Department of Mining at Penn State.

Jan 1, 1965

By R. B. Falk, F. E. Luborsky

Small iron particles in mercury pow by diffusion of iron atoms through the mercury. Iron particles, with diameters about 200Å, have been stopped from gvowing in size, even up to the boiling point of mercury, by the addition of a third metal. The metal additives were classified according to whether they produced 1) negligible inhibition, 2) some inhibition, or 3) marked inhibition of the growth rate. Metal additives which resulted in a marked inhibition of iron-particle growth form a stable monolayer on the iron particles. Only those metals which may form compounds with iron showed this pronounced effect. The one exception was manganese. Metal additives which resulted in no inhibition of growth, showed no evidence for adsorption and could not form compounds with iron. None of the added metals, even those which strongly inhibited particle gvowth and thus had adsorbed on the particle surface, actually formed any compounds with iron at room temperature at the concentrations required for complete inhibition of growth. ThE stabilization of the size and shape of metallic particles dispersed in liquid metals has important technological implications in "homogeneous" nuclear reactor systems and in elongated particle magnets and is directly related to the problem of corrosion by liquid metals. Growth in these par-ticulate systems may occur by diffusion of atoms from surfaces of high energy, corresponding to a small radius of curvature, to surfaces of low energy or large radius of curvature. Thus, small particles dissolve and large particles grow to increase the average diameter of the particles. reenwood' has analyzed this diffusional growth of a system of particles containing a distribution of sizes and has obtained reasonable agreement with data on the growth of uranium particles in liquid sodium and UPb3 particles in liquid lead. Greenwood concluded from his analysis that the chief factors promoting stability of dispersed particles growing by a diffusion mechanism are large mean radius, high density, and low molecular weight with low values of the solute diffusion coefficient, the solubility, and the interfacial tension. In the case of elongated particle magnets the system of interest is that of iron particles dis- persed in mercury. Previous work,2 concerned with "spherical" particles in mercury, has indicated a diffusional growth mechanism similar to that discussed by Greenwood. It has also been shown3'4 that the addition of certain metals to Fe-Hg dispersions results in the formation of a monatomic layer of adsorbed atoms on the iron particles. In this paper we will show that this adsorbed layer provides the decrease in the iron-atom flux through the mercury necessary for size stabilization. The general features of the stabilization of the iron particles in mercury through the formation of this "coating", with many different metals, will be described. EXPERIMENTAL RESULTS Iron particles in mercury were prepared by elec-trodeposition,2, 4 and measurements2, 4 of coercive force HCi) and saturation induction (Is) were used to follow changes in size and composition during thermal aging in the mercury in the presence of relatively small amounts of an added metal. In Fig. 1 is plotted the aging behavior of spherical particle samples in the presence of some of the added metals to be discussed. The iron particles have an initial average diameter of 180Å. Each sample was aged for 20 min at each temperature in succession in the presence of a twofold to threefold excess of added metal over that required to form a monolayer on the iron particles. These are the same samples used previously3 to study the adsorp-

Jan 1, 1965

The Red Lake greenstone belt is an irregular mass of lavas sedimentary rocks and intrusives which is approxiately 35 miles long 18 miles wide and 7 miles deep. Basaltic volcamcs are the oldest rocks w1thm the belt. They are believed to have been laid down on an ancient crust which is at least 3 billion (3 x 109) years old and was composed partly of sediments. The basaltic rocks are overlain by acid volcanics and sedimentary rocks which have been complexly folded and are preserved as a down-folded remnant of younger rocks within the older crust. The volcanics and sedimentary rocks of the greenstone belt have been cut by intrusives with a wide range of composition. The emplacement of the intrusives and the accompanying regional metamorph-ism which terminated the orogenic activity in this area are believed to have occurred approximately 2.4 billion years ago. The basalts and many of the basic and ultrabasic intrusives undoubtedly had their source in the sub-crust or mantle. At least some of the granitic intrusives are believed to have had

Jan 1, 1965

By R. Taggart, D. H. Polonis, W. C. Gallaugher

In the Ti-Cu system, the a' phase can be produced over a wide range of alloy composition witJwut the retention of measurable amounts of the ß or ? phases. This paper reports on the decomposition of this hexagonal martensite phase front the standpoint of solute corzcentratiorz, tempering temperature, and coherency strain condition. The mechanism of precipitation during tempering comprises localized precipitation which is followed by discontinuous precipitation if sufficient coherency strains are present. The localized precipitation process in hypoeutectoid alloys is described by the generalized Johnson-hiehl equation and an activation energy of 46,000 cal per mole. In hypereutectoid alloys the corresponcEing activation energy is 51,000 cal per mole. The rate-controlling process has been proposed as the difision of copper along a' platelet interfnces. SEVERAL investigations have been reported concerning the kinetics of decomposition of the mar-tensitic a' phase in titanium binary alloys.' In the Ti-Mo system,' two modes of a' decomposition have been observed in the presence of /3 phase; one of these involves the precipitation of fine a from a', and the other involves diffusion across the a'-ß interface. In studies of the Ti-Cr system, Rostoker2 did not detect the formation of TiCr2 during tempering. In Ti-Ni alloys,3 the intermediate phase Ti2Ni has been found to precipitate directly from a' along the interfaces between plates. With the exception of the study of Ti-Ni alloys the previous investigations of tempering phenomena in substitutional martensites are mainly qualitative and do not present a detailed description of the precipitation processes. The following limitations restrict the correlation of the microstruc-tural processes and reaction kinetics during tempering in most binary-alloy systems. 1) A mixture of at least two phases characterizes the constitution of quenched alloys. 2) Difficulties have been encountered in obtaining uniform structures throughout quenched samples. 3) The reaction products, and in particular their morphology. have not been clearly resolved. 4) The martensitic a' phase forms over only a limited composition range for most titanium-base binary alloys. Gomez and polonis4 showed that the Ti-Cu system provides an excellent basis for investigating the tempering of a' over a range of composition without the complication of retained P or the transition w phase. In the present work the effects of solute concentration, tempering temperature, and coherency strain conditions are considered with reference to the over-all precipitation process in quenched alloys of the Ti-Cu system. Both microstructural observations and kinetic data are correlated to define the rate-controlling processes which govern the observed localized and discontinuous precipitation reactions. An earlier paper5 was devoted to a discussion of the modes of heterogeneous nucleation of Ti2Cu from the martensitic a' structure. The present paper will therefore emphasize the progress of the tempering reaction beyond the initial stages. EXPERIMENTAL METHODS The Ti-Cu alloys for this study were prepared by conventional arc-melting procedures. Chemical analysis revealed that the alloy buttons contained approximately 0.02 wt pct 0, 0.04 wt pct N, and within 0.1 wt pct of the intended copper concentration. The progress of the tempering reaction was followed by means of electrical-resistance measurements utilizing a Kelvin double bridge, microhard-ness readings with a 400-g load, and X-ray dif-fractometry patterns to reveal line-broadening effects. Metallographic specimens examined at magnifications greater than X1000 were shadowed with germanium to reveal fine structural details. Direct carbon replicas were prepared for the electron-microscopy studies. EXPERIMENTAL RESULTS Property Changes. The changes of microhardness that accompany the precipitation of Ti2Cu from a' are shown in Figs. 1 and 2. As the solute concentration increases the peak hardness, for a given tempering temperature, increases. In alloys of given composition the time to reach the peak hardness agreed with the time to attain maximum X-ray diffraction peak breadth, as shown in Fig. 3. The maximum hardness and the maximum line breadth increased with lower tempering temperatures, and the time to reach the maximum also increased. The a' peaks broadened during the initial stages of tem-

Jan 1, 1965

By B. Ramaswami

INTERNAL oxidation occurs readily in silver due to the rapid diffusion of oxygen in silver.' It has a marked effect on creep in polycrystalline silver2 and raises the critical resolved shear stress in single crystals of silver.3 However, the effect of oxygen on the work-hardening parameters of silver is not known. It is the aim of this paper to describe the effect of internal oxidation on the work-hardening characteristics of single crystals of silver and an Ag-0.1 at. pct A1 alloy. The materials used were: 99.99 pct Ag from Handy and Harman and 99.993+ pct A1 from Alcoa. Single crystals, 6 mm by 6 mm in cross section of silver and Ag-0.1 at. pct A1 of mo.5 orientation, i.e., the orientation with the Schmidt factor m = 0.5. were grown by the Chalmers technique.4 One set of specimens, referred to herein as oxidized specimens, was annealed at 940°C for 24 hr in a muffle furnace, in air, and furnace-cooled to room temperature. Another set of specimens, referred to as nonoxidized specimens, was annealed in oxygen-free helium at 940°C for 24 hr and furnace-cooled over a period of 7 hr to room temperature. The annealed single crystals were tested at room temperature in a floor-model Instron testing machine. The results are presented in Figs. 1 and 2. A

Jan 1, 1965

By Albert W. Deurbrouck

This report describes the preparation characteristics of 23 coal samples collected from nine of the more significant coalbeds of Fayette County, W. Va. In 1963 almost 5.4 million tons of medium to high volatile B coals of excellent quality for metallurgical and steam markets were produced in Fayette County. Of the 23 coal samples collected 11 would require some upgrading to pro-vide metallurgical quality products, 11 were acceptable as received, and 1 was a noncaking coal. Cleaning these coals to metallurgical standards would require only the removal of the sink 1.58 specific gravity material which would be quite easy as very little near-separating-gravity material was present at this gravity.

Jan 1, 1965

Jan 1, 1965