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By D. G. Westlake

Polycrystalline tensile specimens of various Zr-0-H alloys have been tested at 298°, 178°, and 77°K. Solute oxygen and hydride precipitates in quenched alloys made individual contributions to the yield strength at 0.2 pct strain which combined to produce a resultant strength increment, a,., Ductility changes which were ohserved can he interpreted in terms of the various oxygen and hydrogen concentrations, testing tem -peratures, and dispositions of the hydride. ADDITIONS of oxygen in solid solution were known to increase the yield and tensile strengths of polycrystalline zirconium as early as 1951.' More recently, the critical resolved shear stress (CRSS) for prism slip in zirconium single crystals was also shown to be affected by the solute oxygen impurity.' This latter work also demonstrated that large increments of strength could be contributed by the finely dispersed zirconium hydride precipitates that are present in quenched Zr-H alloys.3 It was concluded that the combined strengthening due to alloying could be expressed by where to is the increase in the CRSS due to solute oxygen alone and TH is the increase due to finely dispersed hydride precipitates. Eq. [I] is analogous to one used to express the combined strengthening effects of work hardening and neutron radiation damage.4 Eq. [1] was verified only indirectly and for only small amounts of the impurities—up to 0.14 at. pct 0 and 0.63 at. pct H. The present investigation was undertaken to obtain a more direct verification of the validity of the form of Eq. [1] for this system and also to determine the combined effects of oxygen and finely dispersed hydride precipitates on the tensile strength and ductility of polycrystalline zirconium. EXPERIMENTAL PROCEDURE Tensile specimens were machined from the same rolled billet of Kroll zirconium used in the earlier study.' These measured 38 by 4.7 by 0.5 mm and had 10-mm gage lengths which were 2.8 by 0.5 mm. Each specimen was ß-annealed in vacuo at 1173°K for 15.5 hr and a-annealed at 1073°K for 4 hr to D. G. WESTLAKE, Member AIME, is Associate Metal l ur-gist, Metallurgy Division, Argonne National Laboratory, Argonne, III. Manuscript submitted July 17, 1964. IMD______________ give an equiaxed structure with grain diameters averaging 0.06 mm. Oxygen was added by allowing the metal to react with a known quantity of oxygen during the 0 anneal and known quantities of hydrogen were added during the a anneal. Each alloy was encapsulated in Pyrex under vacuum, annealed at 873°K for 4 hr, quenched into ice water, and polished by immersion in a solution of 46.75 vol pct H2O, 46.75 vol pct concentrated HNO3, and 6.5 vol pct HF (49 pct) at 298°K. Special heat treatments given to a few specimens are described in the results below. Tensile tests were done on an Instron machine and were begun within 20 min after the quench, except where specified otherwise. Tests at 298°K were in air, at 178°K in acetone, and at 77°K in liquid nitrogen. All tests were at a strain rate of 8x sec-1. RESULTS AND DISCUSSION Yield Stress at 298°K. The compositions of alloys and the corresponding yield stresses (0.2 pct strain) are given in Table I. A plot of the yield stresses of the oxygen alloys, A, B, C, and D, indicates that varies linearly with CO1/2, where Co is the oxygen concentration, Fig. 1. This is in accord with Fleischer's6 theory for solution strengthening if the oxygen atoms do not cluster, or the cluster size remains constant with increasing oxygen concentration. In Fig. 1, it appears that if one could prepare some oxygen-free zirconium its yield stress would be very low. Therefore, we shall assume that for the oxygen alloys is equivalent to O0, the strength increment contributed by the presence of oxygen. The relationship between0.2and Co is expressed by 0.2 = 31.3 CO1/2, when the yield stress is in kg per sq mm and the concentration is in at. pct. Each of the hydrogen alloys, Al, A2, A3, and A4, contained 0.081 at. pct 0 as an impurity. In Fig. 1, it appears that this small amount of oxygen makes a significant contribution to the strength which cannot be ignored when we evaluate the contribution of the finely dispersed hydride. Let us assume the validity of the following equation: a0.2 = (a2o+a2R)1/2 [2] which is analogous to Eq. [I] for single crystals, and calculate values of UH for the hydrogen alloys by using the experimental values of 0.2 and o (0.081 at. pct) = 8.9 kg per sq mm. For 0.36 at. pct H, oH = 6.47; for 0.72 at. pct H, OH = 11.30; for 2.16 at. pct H, OH = 19.4; and for 3.60 at. pct H,

Jan 1, 1965

By G. Baralis, P. Gondi, I. Tangerini, G. Scandola

The precipitation behavior of Zn-0.5 pct A1 alloy single crystals was studied by means of electrical resistivity measurements and by optical and electron microscopy. The single crystals for the resistivity measurements were prepared by an original method in - 100-p -thick sheets. The order of the precipitation kinetics ranged between 1 and 1.5. The dislocations play a relevant role in the first-order kinetics. Precipitation always occurs both on dispersed particles and on dislocations. Statistical examinations have shown that the first-order kinetics can have two different activation energies; i.e., the precipitation can have dz;fferent mechanisnrs which could not be identified, however, in the course of the research. During the tnetallographic exanzination of the precipitation structures a specific process of dislocation decoration was obsereed. The main purpose of this work was to study the contribution of dislocations to the precipitation. A number of authors have observed precipitation on dislocations and reference might be made to several monographs on the ubject.'' The possibility that dislocations also accelerate precipitation has been considered by Turn-bull3 and Fischer et al.4 The studies described in the present paper were carried out on zinc, chosen as a base metal owing to the ease with which dislocations can be introduced into it and because of the absence of excess vacancies after quenching in conditions where phenomena of accelerated precipitation still occur. Aluminum was preferred as alloying element because of the accelerated precipitation phenomena that resulted in a preliminary reearch. EXPERIMENTAL METHODS The observations refer to a Zn-0.5 pct A1 alloy. The zinc was 99.995 pct pure; a typical spectroscopical analysis is given in Table I. As a rule the alloy was subjected to homogenization, quenching, or slow cooling and annealing. Homogenization was carried out by heating at 390" to 410°C for 24 hr. From the homogenization temperature, some specimens were quenched and some slowly cooled at a rate of 2°C per sec. At this rate no precipitate was detectable under the optical microscope just after cooling. Quenching was carried out simply by dropping the specimens into water, aqueous ethylene glycol solution at -30" c, or liquid-nitrogen baths placed close to the homogenization oven. Vaseline oil baths were used with a thermal stabilization of 10-20 for both the aging treatments and the measurements; aging was generally carried out at 90" or 130°C. To avoid oxidation phenomena during heating, the vaseline oil baths had to be frequently renewed. The precipitation kinetics were studied by means of electrical resistivity measurements, using ans potentiometric method (reproducibility ± 5 x 10 5 v, that is 0.5 pct of the total voltage decreases on the specimens during precipitation). First, various types of specimens were tested, i.e., polycrystals, single crystals grown in capillary quartz tubes, and thin single-crystal sheets prepared by means of an original method requiring no container except for the natural oxide. Even if fully annealed, the polycrystals and the capillary grown single crystals showed resistivity in -creases, most probably due to dislocations introduced in the course of the measurements. Similar resistivity increases in pure zinc were noticed by another author. Only the single-crystal sheets showed no resistivity change; thus they were chosen for the subsequent tests. As already mentioned, these single crystals were obtained by using, as a container, the natural oxide on the zinc surface; the oxide strength is sufficient to maintain the original shape during melting with sheets up to 500 p thick. An initial zone melting and subsequent zone leveling, which led also to formation of the single crystals, were thus carried out on rolled sheets of the required thicknesses (- 100 p) and shape, lying on a flat silica surface. The resistivities were first evaluated by measurements at the liquid-nitrogen temperature. This method gave poor reproducibility, however, and this was attributed to the thermal cycles which had to be operated. To avoid cycles and handling, it was therefore decided to make measurements directly in the annealing oil baths; this required thermal stabilization at ilo-' "C. In this way only the resistance changes were measured. Specimens of pure zinc and of completely annealed alloy were always examined as controls together with those under consideration; only those measurement runs were taken into account where the reference samples showed no resistance increases. Again, the main inconvenience was due to oxidation and this was avoided by renewing the oil baths; even so data reproducibility was poor and the observations were therefore carried out on a large number (many hundreds) of specimens so as to provide indications of statistical value. For the transmission observations under the elec-

Jan 1, 1969

By J. B. Bassett, E. S. Rowland

The experimental work reported herein firas inspired by the publication of a paper by Grange and stewart, in which it was suggested that at low chromium contents the effect of this element on the Ma point was greater than at higher chromium contents, It was argued that, if a small increase of chromium in solution in austenite caused a sharp lowering of the M, point, it might lead to an explanation of occasional unsolved stress cracking of SAE 52100 during heat treatment. Commercial hardening is carried out at temperatures of incomplete solution, leaving carbides available to enrich the austenite during any inadvertent increase in temperature, such enrichment of the austenite in chromium content would lower the M, point nearer room temperature where cracking is more likely to occur. According, it was decided to investigate the effect of chromium, in quantities between o and 2 pet, on the M, point of commercial steels. Fig I summarizes the data available on chromium steels. For purposes of comparison, the M, temperature values were corrected by means of the Grange and Stewart formulas to (I) Hypoeutectoid compositions: 0.50 pct carbon and 0.80 pct manganese (z) Hsereutectoid compos-sition': 1." pet carbon and O.35 pct manganese. Only the steels having compositions reasonably close to these corrected values were included, because large adjustments inevitably introduce increased error such as are experienced in using the formula. The straight lines of Fig I were drawn by the authors. These data obviously do not settle the question Of the effect Of chromium On the Md Oint, particularly at low chromium contents. While it is fairly well established that chromium causes the M, to be lowered when present in quantities of I pet Or more, Grange and Stewart1 have suggested that in small amounts (less than 1 pet) it is more effective in lowering the Ma point, while Klier and Troiano2 have suggested that in small amounts it is less effective in lowering the Ma point. Payson and Savage3 concur with Klier and Troiano and further suggest that the effect is not linear at these concentrations. Rose and Fischer4 report that small amounts of chromium actually raise the Ma point of a 0.20 carbon steel. Material Two series of 35 Ib induction heats were melted for this work, the analyses of which are given in Table I. One series was aimed at 0.50 pct carbon and 0.80 pct manganese with chromium additions in 0,25 pet increments from o to 1.5 pct with a single heat at 2.0 pct Cr. This series was considered necessary because the commercial heat treatment of SAE 52100 does not generally introduce more than about 0.60 pct carbon in solution in the austenite. The high

Jan 1, 1949

By F. F. Claussen

The method of making silver ingots in use at this Mint being radically different from that employed at any other Mint of the United States or, so far as known to me, any Mint in the world, there may be some interest in a description of the apparatus used and a brief history of its distinguishing feature, viz., the rotary ingotmould, which, though not a recent improvement, is comparatively unknown. The furnaces used for silver-ingot-melting are four in number and have a capacity of some seventy thousand standard ounces of silver per day of eight hours. This output is increased, when the exigencies of the service demand it, to one hundred thousand ounces. They are built of fire-brick and elevated 21/2 feet from the floor of the melting-room, in order to have space to place iron boxes and to work, in case a crucible breaks in the furnace and its contents run into the ash-pit. The furnaces are circular in horizontal section, 2 $ feet in diameter and 29 feet high inside in the clear, and rest on castiron plates, with top-plates of the same, and sides encased in boileriron. The furnace-covers are also of cast-iron, dome-shaped, and are handled by means of a small crane and lever. The furnaces stand in sets of two, and one crane and one ingot-machine serves two furnaces. The crucibles used are made specially for this purpose of a mixture of black-lead and fire-clay; the size known as No. 200 will contain and safely melt, without danger of slopping over, from 8600 to nearly 10,000 ounces of standard silver; and this is the usual weight of the ingot-melt at this Mint, as against 1800 ounces at the Carson City mint and 2600 to 3000 ounces at Philadelphia and San Francisco. Each crucible will endure, on the average, ten melts. The crucible stands in the center of the furnace, on the bottom of an old one, cut down to a height of about three inches. The fuel used is coke. Experience has shown that, notwithstanding the higher first cost, Connellsville coke is cheaper than Alabama coke and much more suitable to the work. A small triangular black-

Jan 1, 1888

By R. C. Dalzell, A. E. Wells

In 1866, Thomas Graham1 called attention to the volume of gases, three times the volume of the sample, evolved from a meteoric iron heated in an evacuated porcelain tube. From that time to this the occurrence and significance of gases in metals have been the subject of investigation by many workers, among whom Sieverts,2 Iwasé3 and 0. W. Ellis4 stand preeminent. Sieverts and Iwasé concerned themselves with the solubility of a number of gases in metals in the liquid and solid states. They determined the absorption coefficients of these gases, and in all cases found a sharp change in solubility at the melting point of the metals. Ellis analyzed the gases evolved by solidifying copper and those occluded by the solidified metal. Lobley and Jepson5 endeavored to determine the effects of hydrogen, carbon monoxide and nitrogen on the porosity of copper that was allowed to solidify in the presence of each gas after 30 min. exposure to it in the

Jan 1, 1930

By Charles H. Behre

This paper deals with recent geologic studies in the slate belt of Northampton, Lehigh and Berks counties, Pennsylvania. The work was conducted under the auspices of the Pennsylvania Topographic and Geologic Survey. Three years have now been spent in detailed consideration of the economic geology of this region. In the field, particular attention was paid to the bearing of geology on quarry development and property valuation and the object of this paper is to summarize the results from that viewpoint. Excellent studies of a somewhat similar nature have already been carried out by Bowles,' but with the emphasis upon the details of quarrying and fabricating methods, rather than upon the geologic relations. The Northampton-Lehigh-BeRks District Location The region here discussed lies in east-central Pennsylvania and extends southwestward from Delaware River, on the New Jersey line, to the Schuylkill in north-central Berks County. It is an elongated belt occupying the northern sections of the three counties mentioned and lying along the southern edge of Blue Mountain. Its length is about 50 miles and its average width five or six, though in places it attains a maximum of 10 miles. There are no large cities in the region, but about 10 miles south are Reading, Allentown, Bethlehem and Easton. Railroads serving the slate belt are the Delaware, Lackawanna and Western, and the Pennsylvania along the Delaware River, the Lehigh Valley and Central of New Jersey along the Lehigh, and the Pennsylvania and Philadelphia and Reading on the Schuylkill. In addition, two railroads—the Philadelphia and Reading and the Lehigh and New England—cut obliquely through the slate region to reach the more isolated communities. Transportation facilities are thus excellent. The slate deposits of these three counties are conspicuously unified, both economically and geologically. In general type of marketable

Jan 1, 1928

By Thomas Harris

This paper. was written in conjunction with the work being undertaken by the Technical Committees on Classification of Coal, and an effort has been made to compile information relative to the use of coal for stationary steam generation in order to use this information to assist the Committee on Classification of Coal for the ultimate purpose of elimination of losses both by the' reduction of indivi-dual effort and waste in the consumption of material. Under the auspices of the National Association of Purchasing Agents, a questionnaire was drawn up to develop this information from stationary steam plants throughout the United States. in order to consolidate the information de-veloped from the many hundreds of boiler tests on coals consumed by various coal¬burning equipment. These questionnaires covered: 1. The company reporting, location and method of delivery to the plant. 2. Complete coal date, including description of coals used (with. sufficient space to- include first, second and third, preference) on--source of coal used,- complete-analysis and factors affecting choice of, coal used. 3. Plant data, divided into - A. Hand fired, B. Overfeed stokers,. . C. Underfeed stokers, D. Traveling grate stokers, E. Pulverized coal, and included complete description of furnace data, draft data, coal-burning rate, type of stoker, type of pulverizer, efficiency date and remarks.

Jan 1, 1933

By Bernard H. Coyle, Robert N. Anderson, Judith A. Koperski

Between 6 and 8 million cars are shredded annually in the U.S. This shredded material is magnetically separated leaving a mixture of nonmetallics and nonferrous metals which can be further separated into its metallic and nonmetallic constituents. The metallic portion is a mixture of metalr; and alloys containing predominately zinc, and some aluminum, copper, and residual iron. Hydrometallurgical strategies are proposed for recovering the aluminum, copper, and zinc. The thermodynamic and kinetic behavior of the most promising alternatives to separation are discussed.

Jan 1, 1978

By Werner Langguth

SINCE the introduction of the improved method of precipitating gold from chlorine solution by SO2 and H2S at the Golden Reward chlorination-works, Deadwood, S. D.,* this modern method has been further adopted in the chlorination-works of the Portland Consolidated Company at Deadwood, and in those of the Black Hills Milling and Smelting Company at Rapid City, S. D. It has proved practically most successful in the handling of large quantities of gold solution, and constitutes up to date, with Mr. John E. Rothwell's most important improvement, namely, barrel-leaching under hydraulic pressure, the principal progress made in gold chlorination. The method of refining the gold sulphides which result from this method of precipitation, was introduced by me in 1890 at the Golden Reward works, and in 1892 at those of the Black Hills Company. It has not suffered any changes during the last three years, and is substantially as described below:

Jan 1, 1895

By D. Y. Geng, Syd S. Peng

This paper analyzes the effects of geology and mining methods on surface subsidence factor, angle of draw and angle of critical deformation based on the results of 40 longwall subsidence profiles in the Northern Appalachian coalfield. Several equations were derived to show the relationships between those parameters. Furthermore, the equations were transferred and plotted in the form of several monographs for convenience of applications.

Jan 1, 1982

By P. M. Robinson, M. B. Bever

THE heats of formation at 273°K of the compounds InBi, In2Bi, and TIBi2 have been determined by metal solution calorimetry with bismuth as solvent. The published information on the thermody-namic properties of these compounds is limited. The structure of the compound InBi (mp, 383°K) is tetragonal of the PbO (B10) type.1 The compounds In2Bi (mp, 362°K) and TIBi2 (mp of highest-melting composition, 486°K) are now believed to have structures of the NizIn (B8) type273 and not the A1B2 (C32) structures reported earlier.4, 5 The compounds In2Bi and TIBi2 have limited homogeneity ranges at room temperature, while the compound InBi has no detectable homogeneity range.' Samples of the compounds were prepared from 99.99 pet Bi (Mallinckrodt Chemical Works), 99.999 pet in (American Smelting and Refining Co.), and 99.99 pet Tl (Amend Drug and Chemical Co.) by melting the components in sealed, evacuated Vycor tubes. The compounds InBi and in2Bi were of the stoichiometric compositions. The compound TIBi2 contained 40 pet T1; this composition was chosen because at room temperature the alloy of stoichiometric composition does not lie within the homogeneity range.' The melts were held approximately 50°C above the liquidus for 8 hr and then quenched into iced brine. The samples were homogenized for 48 hr at temperatures 20°C below the temperature of complete solidification. Metallographic examination of sections taken from the center and the ends of the ingots did not reveal second phases or segregation . The heats of formation were determined as the difference in the heat effects on solution of a compound and of a mechanical mixture of its components added from the reference temperature of 273°K to liquid bismuth at 623°K. The details of the calori-metric procedure and method of calculation have been described elsewhere? The calorimeter was calibrated by adding bismuth at 273°K to the bismuth bath at 623°K. The calculated values of the heats of formation of the compounds, listed in Table I, are based on a value of 4.96 keal per g-atom for the difference between the heat contents of bismuth at 273" and 623oK7 No published values are available for the heats of formation of the compounds InBi and In2Bi. Hultgren et a1.7 have calculated a value of -0.50 i 0.10 keal per g-atom for the heat of formation at 423°K of the compound TIBi2 containing 40 at. pet T1 from heat-content measurements in the range from 398" to 700°K and the heats of formation of the liquid alloy. The difference between this value and the value of -0.66 * 0.01 keal per g-atom at 273°K is too large to be attributed to a difference between the heat capacities of the compound and the components over the temperature range 273o to 423oK7 However, the direct determination of the heat of formation by a calorimetric method should give a more accurate value. The heats of formation at 273°K of the compounds InBi and In2Bi lie on a straight line when plotted as a function of composition, Fig. 1. The compound In2Bi, therefore, appears to be barely stable with respect to its neighboring phases. In order for the free energy vs composition curve to be concave towards the composition axis, the entropy change on formation of In2Bi must be more positive than that on formation of InBi. As the compounds are ordered,2, 3, 8 there is no configurational entropy change on formation. The difference between the entropy changes on formation of the two compounds, therefore, is probably associated with the vibrational entropies. In view of the low heats of formation, the changes in vibrational entropy, due to changes in bond strength on formation of the two compounds, are likely to be small. Owing to the volume contractions on formation of the two compounds,5 the vibrational entropies probably decrease slightly but the decrease of the vibrational entropy of InBi is expected to be larger than that of In2Bi.

Jan 1, 1965

By J. A. Jr. Church

I. EARLY FURNACES. COPPER blast-furnace construction in America has long recognized a general standard in the rectangular mater jacketed shaft with separate forehearth. The details, however, and especially those relating to shaft dimensions, have had to meet a great variety of conditions, and show no uniformity whatever. Selecting a few of the present day Western plants, we find furnace lengths varying from 12.5 to 87 ft., widths at tuyere level from 42 to 84 in., and heights above tuyeres from 5 ft. 4 in. to 22 ft. 4 in. ; and comparing present designs with those of the past, we meet contrasts no less striking. Unlike its transverse section, the length of a furnace has come to depend rather on the size of unit desired than on the requirements of smelting ; and if the question of length be ignored, several of the various existing designs can be grouped together on the basis of a common transverse section. This section, having a width at tuyere level of 56 in. and a height above tuyeres of 18 ft., was developed at Great Falls, and the story of its development contains some interesting features. Ground was broken for the Great Falls works in the spring of 1891. About a year later, the concentrator was able to begin operation, followed within the next few mouths by the Brueckner, reverberatory, and converter departments, and in April, 1893, by the first blast fur-

Jan 7, 1913

By D. B. Reger

DAVID B. REGER.-T Want to 'add that since this paper was prepared a well is now being; drilled it the location recommended do the last page. It was not, however, done at my instance; it was done at the instance of Dr. White, the State- Geologist of West Virginia, who has been trying for several years to induce the large oil and gas companies to make a test of some of these, deep sands in West Virginia and a well is now just being started in Wood County, right at this immediate

Jan 4, 1917

The practice of fine-grinding is now being so succeesfully carried on in some fields, notably in West Australia, and its advisability has been so frequently pointed out,l that the matter in this paper is not put forward as new; its chief object being to call attention to the importance of fine-grinding in the treatment of comparatively low-grade oree. I' have been engaged daring the last five years in the cyanide-treatment of ores in the Ohinemuri district (North Island), New Zealand, and I consider that, in the near future, extremely fine-grinding (almost sliming) will become a very im-

Jan 1, 1906

By Klaus Detert, Joseph Ziebs

The progress of primary recrystallization has been studied in alloys of nickel with 0.01, 0.1, and 1.0 at. pct Ta. It can be shown that in one particular alloy containing 0.1 Ta and 0.02 02 a large grain structure (0.5 mm diameter) could he developed by primary recrystallization in thin sheetswhich were cold-worked to 97.5 pct reduction in thickness. Electron transmission microscopy demmstrates that this phenonmena was linked to the occurrence of fine precipitates at subboundaries. A discussion of how fine precipitates can exert under certain circumstances a rather distinct retarding effect on nucleation rate is included. IN a former investigation, the recrystallization and texture formation in a series of binary nickel alloys including pure nickel were studied.' Nickel alloys with some tantalum added displayed peculiarities during primary recrystallization which have been studied in more detail by the present investigation. The alloys were prepared by powder-metallurgy techniques similar to the previous investigations.' Pure metal powders were thoroughly mixed to obtain alloys with 0.01, 0.1, and 1.0 at. pct Ta, referred to as alloy A, B, or C, respectively. The metallic impurities were kept below 0.005 at. pct except iron and cobalt with slightly higher values, by using highly purified nickel and tantalum powders.' The mixtures were pressed into bars and sintered at a temperature of 1300°C. The sintering atmosphere was either high vacuum, dry hydrogen, or wet hydrogen. The sintered rectangular bars were rolled 60 pct to a thickness of 3 mm, then annealed under dry hydrogen at 1000°C and again cold-rolled to about 97.5 pct reduction of thickness. After this heavy deformation, the sheet thickness was 0.07 5 mm. In order to study primary recrystallization which occurred in measurable times between 400" and 600°C, samples of the rolled sheets were annealed in a salt bath at various temperatures for various times in order to study the progress of recrystallization by hardness measurements and microscopic examination. For optical observation, the samples were polished and etched in a solution of 65 cu cm HNO3, and 18 cu cm acetic acid in 20 to 100 cu cm H2O, depending of the particular sample and annealing treatment. For transmission electron microscopic observations, thin foils were prepared by the combined window and Bollmann techniques.273 The electrolyte consisted of 23 pct perchloric acid and 77 pct acetic acid held at 15°C. Polishing was performed at a current density of 0.4 amp per sq cm. The examination of the thin films was accomplished by a Siemens Elmiscope-type electron microscope operating with an accelerating voltage of 100 kv. RESULTS The progress of primary recrystallization was very accurately followed in these alloys in order to establish the time when recrystallization started and ended during an isothermal anneal. Table I gives some of the data obtained by these studies. The time for beginning is a mean value, where somewhat less than 5 pct of the matrix has recrys-tallized. The end of recrystallization is the time when at least 95 pct of the matrix has recrystal-lized. Listed are three different B alloys, with 0.1 Ta distinguished by different sintering atmospheres which influence the rate of primary recrystallization. By the above method, the state of the grain structure when primary recrystallization was completed, but grain coarsening had not started, could be clearly defined. The average grain diameter of the recrystallized matrix is also given in Table I. The grain size did not depend on the temperature of the isothermal anneal. With one exception the grain size of the primary recrystallized matrix was found to be rather fine

Jan 1, 1965

By S. Zador, C. B. Alcock, K. Sudo

Measurements have been made of the standard free enevgies of formation of the sulfates of cobalt, Cupric copper, nickel, and ferric iron in the temperature range of 750° to 950°C. Dynamic gas-solid techniques have been employed in which oxide-sulfate and basic sulfate mixtures were placed in a stream of gas of controlled SO3 potentials. Thermal analysis and thermogvavimetry were used as detection methods, and it was found THE formation of sulfates during the roasting of sulfide ores is now considered to arise in many cases from the interaction of sulfur trioxide in the gas and the metal oxide which is formed on the sulfide as a first step.' As a preliminary to the investigation of the kinetics of sulfate formation during roasting, measurements have been made of equilibria from which the free energies of formation of cobalt, copper, nickel, and iron sulfates can be that the range of temperatures which could be investigated and the choice of method was largely controlled by the kinetics of these gas-solid reactions. The results are compared with previous results obtained from static measurements with which they agree quite well, and calculations have been made employing themal data to interrelate the present results with those for other sulfates. calculated. The method used has been to expose the solid sulfate (or basic sulfate) to a controlled flowing gas mixture of SO,, 02, and SOs and to observe the temperature of decomposition. The onset of decomposition was detected by thermal analysis or thermogravimetry. EXPERIMENTAL METHODS The thermal-analysis method was similar to that employed by Dewing and Richardson.' The sulfate was dehydrated at 250°C in air, and placed in a small alumina crucible which was held by a quartz ring in the hot zone of a horizontal furnace. The reaction tube of this furnace was made of mullite.

Jan 1, 1965

A B Cummins President James C Gray, President-Elect J W Woomer, Past President C E Lawall, Eastern Regional Vice-President Donald W Scott, Central Regional Vice-President H C Weed, Western Regional Vice-President Nathaniel Arbiter, Treasurer John Cameron Fox, Secretary AIME 29 W 39 St New York 18, N Y

Jan 1, 1960

By D. L. Ritter, N. J. Grant, B. C. Giessen

Forty-six alloys covering the complete concentration range of the Nb-Rh system were examined by metallographic and X-ray methods; solubility limits of terminal ad intermediate phases and transformation and solidus temperatures were determined. There are nine intermediate phases; two eutectic, five peritectic, two eutectoid, and three peritectnid reactions were encountered. The experimental methods and the constitution diagram are described in Part I. Part 11 deals with the crys -tallography and relation of the intermediate phases. The Nb-Rh system was selected for study for three reasons: first, it was hoped that the anticipated similarity of the Nb-Rh phase diagram to the Ta-Rh1 and Ta-Ir2 diagrams treated earlier (see also Ref. 3) and to the Nb-1r4 diagram treated simultaneously would allow a crystallographic and comparative evaluation of the intermediate phases in these related systems; second, it was likely that the previous experimental methods could be carried over without significant change; and third, it was expected that the interesting mechanical properties of the a1 phase of the Ta-Rh and Ta-Ir systems would also be encountered in similar phases of the new systems, and that these phases could be investigated more closely. The phase diagram had not been treated fully in the literature; only brief surveys of some intermediate phases were found.5-7 It was attempted to cover the details of the phase boundaries, Part I, as well as to present the crystallography of the intermediate phases, Part 11. EXPERIMENTAL METHODS Specimen Preparation and Treatment. The following high-purity starting materials were used. 1) Niobium powder, 99.8 pct pure, mesh size -60 +200, from Wah Chang Corp., Albany, Ore. The analysis furnished by the supplier showed the following major impurities: Ta, <500 ppm; Zr, <500 ppm; 0, 300 ppm; Fe, 280 ppm; Ti, <I50 ppm; W, Si, <100 ppm; C, N, 30 ppm; all other impurities, <30 ppm. 2) Rhodium powder, ground sponge, 99.9+ pct pure, mesh size -80, from J. Bishop Co., Malvern,

Jan 1, 1964

By Calvin Pierson, R. S. Dean, E. P. Barrett

Wrought iron and steel have been prepared from limonite, hematite, and magnetite ores by gaseous reduction, compacting and squeezing the resulting product at high temperature and finally melting the wrought iron so formed. The structure, analyses, mechanical and magnetic properties of the products are given. It is found that the structure of iron ores is best studied by subjecting them to gaseous reduction and using metallographic technique on the resulting sponge iron. In this way the cell structure of iron ore is clearly shown. The wrought iron made by heating compacted sponge iron to 1450" C., and forging, shows a cell structure inherited from the ore. This cell structure is further preserved in melting and casting the wrought iron. The probable relation of the properties of the materials to this inherited cell structure is discussed.

Jan 1, 1935

By Calvin Pierson, R. S. Dean, E. P. Barrett

Wrought iron and steel have been prepared from limonite, hematite, and magnetite ores by gaseous reduction, compacting and squeezing the resulting product at high temperature and finally melting the wrought iron so formed. The structure, analyses, mechanical and magnetic properties of the products are given. It is found that the structure of iron ores is best studied by subjecting them to gaseous reduction and using metallographic technique on the resulting sponge iron. In this way the cell structure of iron ore is clearly shown. The wrought iron made by heating compacted sponge iron to 1450" C., and forging, shows a cell structure inherited from the ore. This cell structure is further preserved in melting and casting the wrought iron. The probable relation of the properties of the materials to this inherited cell structure is discussed.

Jan 1, 1935