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By Robert S. Archer, L. W. Kempf

It is now well known that the structure of aluminum-silicon alloys can be refined in a rather remarkable manner, with consequent improvement of physical properties, by certain treatments applied to the molten metal shortly before casting. The differences between the treated and the untreated alloys are so marked that special terms are used to distinguish them, the untreated alloys being referred to as "normal" and the treated alloys as "modified." The first practical method of accomplishing this result was that of A. Pacz,1 which consists in treating the molten metal with a salt flux of which the active ingredient is sodium fluoride. The result can also be brought about, and in a more economical manner, by the addition of small quantities of metallic sodium (or potassium) to the molten alloy shortly before casting.2 The action of the Pacz flux evidently consists essentially in the production of free sodium by the reaction of sodium fluoride with aluminum. The changing of a normal alloy to a modified alloy is referred to as "modification" and any process for accomplishing this result is a "modifying" process. Modified aluminum-silicon alloys were introduced several years ago, and it has been demonstrated both in the laboratory and in commercial practice that it is no simple matter to produce castings having the maximum or nearly the maximum properties which under favorable circumstances can be obtained. The alloys are rather sensitive to small changes in chemical composition, and the modifying process must be carried out in a very particular manner to obtain the best results. Extensive experimental work has been carried out in the laboratories of the Aluminum Co. of America with the object of determining the conditions that must be observed to make these alloys of the greatest possible value. It was necessary to learn how to control the modifying process

Jan 1, 1926

By H. A. J. Wilkens, H. B. C. Nitze

From time to time papers treating of specific cases of Southern gold-mines and mining have appeared in the Transactions of this Institute, as well as in other journals and publications. Mr. George I?. Becker, of the United States Geological Survey, made a reconnaissance of the Southern Appalachian gold-belt during the fall of 1894; the results of his investigations are published under the title of "A Reconnoissance of the GoldFields of the Southern Appalachians," in the Sixteenth Annual Report of the Director of the United States Geological Survey, 1894-95 : Part III., " Mineral Resources of the United States." Mr. Becker has treated the subject mainly in a scientific geological manner. We present this paper to the members of the Institute as requested by the Secretary last May, with the object of covering the ground from a more practical and technical standpoint. The notes for this paper were made in a large measure from personal observations, gained chiefly during the past summer on a trip through the field. In connection with this trip we collected a suite of typical hand-specimens, representing the gold-ores and wall-rock from the more important localities. This collection forms a part of the exhibit

Jan 1, 1896

By F. C. Kelley, L. L. Wyman

In order to clarify and amplify the existing data concerning the action of the cementing material in cemented tungsten carbide alloys, the authors have initiated this investigation of the entire range of cobalt-tungsten carbide alloys. Inasmuch as the ultimate objective is relative to what actually goes on during the sintering of cemented tungsten carbide materials, this work was necessarily restricted to heat treatments similar to those used in actual production of these materials. In the course of numerous experiments, the authors have noted several conditions that indicated that there was a solubility to be considered. Among these factors are the following: 1. Many of the alloys showed a much larger amount of binding constituent to be present than could possibly be accounted for by the cobalt content. 2. In many areas, grains of the carbide constituent are much larger than the particles of carbide originally added. In addition, these grains are of very regular contour. 2a. In samples of cemented tungsten carbide which had been fused in the atomic hydrogen torch in the presence of excess binder constituent, immense grains are formed, and their shapes are very regular. This is also true when the cemented tungsten carbide of 13 per cent. Co content is fused alone in the atomic hydrogen torch. Contrary to general expectation, chemical analysis of this material, after fusion in the atomic hydrogen torch, checks the analysis of unfused material. 3. In making the cemented tungsten carbide materials by the process of exerting the pressure at the time of heating a certain portion of the ' contents squeezed out of the mold. Chemical analysis has shown that this material contains approximately 12 to 20 per cent. of tungsten. The microstructure shows a cored dendritic structure interlaced with eutectic network, and some graphite, as shown in Fig. 1. 4. Thermal analysis of these materials has consistently indicated an arrest point close to 1350" C.

Jan 1, 1931

By H. K. Birnbaum, H. B. Aaron

he authors suggest that a number of the types of yield phenomena which have been observed in high-purity fcc metals are due to dislocation interactions bccurring at the surface of the crystals rather than due to volume effects. Since rather different inter-pretationS2,7,12,14,15,21-23 of these effects have been suggested, it is of some importance to ascertain the role of the surface in these yield phenomena. It should be first noted that the high-purity fcc metals appear to exhibit several distinct types of yield phenomena. The "unloading yield point" which is observed on reloading the specimen after removing the applied load has been found to be independent of the time of holding in the unloaded condition. If however the specimen is aged while under load and re-tested without removing the load, a yield point is observed which does depend on the aging time and tem-perature. Feng and Kramer suggest that the removal of the unloading yield point on removing sufficient material from the surface of the specimen indicates that the effect is associated with dislocation interactions at the specimen surface. Their observations are counter to those of Haasen and Kelly5 and Birnbaum.12 Since the unloading yield points are extremely small (-2 pct of the flow stress) the results of the surface removal will depend on whether the material is removed uniformly over the gage length. The introduction of small etch pits or the removal of more material from one portion of the specimen than from another will result in preferential yielding and obliteration of the yield point. With the normal electropolishing techniques it would be difficult to avoid these effects. The data obtained by Aaron and Birnbaum, Fig. 10, on aluminum polycrystalline specimens indicate that, although the unloading yield point and the strain-aging yield point are not simply additive, a time- and temperature-dependent yield point is observed under conditions where no creep is observed. This does not agree with the results of Feng and Kramer but does agree with the results on copper15 and gold.7~23 The source of the discrepancy may be the procedure used by Feng and Kramer to correct their time-dependent yield points for the effect of creep. Since the strain-aging yield point is not independent of the pre-aging strain rate, Fig. 11, the effects of creep cannot

Jan 1, 1967

By JOHN R. SUMAN

IT SEEMS particularly appropriate that the Institute's Regional Meeting should be held in Minnesota this year. Whether we like it or not, we cannot help looking at things now in the light of the World War and the all-out effort we, as a nation, are making to defend our resources, our institutions, and our way of life. The ability to do this lies in large measure in the ability to forge weapons of defense-the machines of war. The basic ingredients of any defense system, or war machine, are the raw materials of industry-iron ore, providing steel for guns, shells, tanks, and warships; coal for stoking the nation's furnaces; oil to furnish power for war planes, ships, trucks, and mechanized weapons; and all the other materials that play a vital role in the operation of modern armies and navies. The tremendous requirements of full-scale defense programs are indicated by the large number of commodities that are now under priorities because the supply is not sufficient to meet both defense needs and all normal civilian consumption. But out of all these items two are of paramount importance-steel and petroleum. In this age no nation can hope to main¬tain a position as a first-class power in the world without a highly developed industry, particularly the heavy industries based on steel, and without access to the necessary resources for those industries. In 1918, 70 per cent of the iron and steel production of the United States was required for defense purposes. In 1940, 15 per cent of our iron and steel production was consumed for defense purposes, and with the acceleration of the defense program, it appears that the proportion of steel output required for defense purposes will reach 40

Jan 1, 1941

I;. D. Godshall, Everett, Wash. (communication to the Secretary) : In Mr. Morse's interesting paper several statements occur which seem to require correction and comment. This is the more appropriate, since Mr. Morse has mentioned me by name, and has cited my "Review of the Russell Process,"* so that silence on my part might be taken as indicating an assent which I cannot give. On the first page of his paper Mr. Morse says that the " goingback " of chlorination was " the only difficulty encountered at Aspen," and adds that he has " never seen any explanation " of the cause. The plain inference is that he now fills this complete

Jan 1, 1896

By J. A. Roberson, Robert A. Rapp

From the observation of platinum wire marker movement in the oxidation of columbium at high lemperatures and low oxygen pressures, predonzinant cation diffusion in CbO, has been demonstrated. The Cu,0 molecule was used as an oxidizing species to study the nature of the porous scale and the location of the reduction site in the oxidation of colum-bium. The Cb205 scale contains microporosity and forms by alternate ionic diffusional growth and fracture. The oxidation of columbium at high temperatures and very low po, results in a relatively compact and protective Cb205 layer. THE observation of marker movements during oxidation is one means for the identification of the mobile ionic species in an oxide lattice. Previous marker experiments in the oxidation of columbium have all resulted in the markers being found on the outside surface of the Cbz05 scale. The Cr203 powder markers of Klopp et a1.,' the gold film marker of Kofstad and ~jijllesdal,' and the platinum wire marker of Cathcart et a1 .3 were found at the oxide/gas interface for oxidation temperatures ranging from 450" to 120O0C. However, in all experiments relatively high oxygen pressures were used. As discussed by Mrowec, even the interpretation of marker experiments in simple scales containing only one compound is not without ambiguities. In brief, it can be said that a marker may be found almost anywhere in the scale layer if the metal oxidizes by cation diffusion through the scale; the position of the marker depends upon morphological happenings in the scale. When considering marker movement in a polyphase scale one must proceed with extreme caution. For example, in the past (and present) work markers have never been found at the columbium-scale interface, and one might infer that the oxygen ion is mobile in CbO and CbO,. However, only trace quantities of CbO and CbOz have been present on any of the specimens, so no firm statement is justified on this basis. Despite previous experimental work, considerable doubt still exists concerning the role of the oxides CbO and CbOz in the oxidation of columbium. The identification of the mobile ionic species in CbO and CbOz from the observation of platinum wire markers was one goal of the present investigation . The linear kinetics of columbium oxidation at high temperatures (T - 1000°C) suggests that the Cbz05 scales which form on columbium are porous. From mercury absorption measurements on a Cbz05 scale formed at 500"C, Aylmore et al.' reported a minimum volume fraction of connected voids equal to 0.15. While these scales often appear to be quite porous when viewed in metallographic cross section, they are so brittle that metallographic preparation is likely to exaggerate any porosity originally present. In this investigation, porosity developed during the oxidation of pure columbium and present at the high temperature was detected by oxidizing specimens in sealed evacuated capsules containing large compacts of mixed copper and CuzO powders. wooda has demonstrated that the CuzO, or (CuzO),, molecule is volatile and that oxygen is transferred by the CuzO molecule from a Cu/CuzO mixture to materials having a greater affinity for oxygen. For each molecule of CuzO that is reduced at a sink for oxygen, two atoms of copper are deposited. Quantitatively, essentially all of the oxidation carried out by a Cu-Cu20 compact results from a displacement reaction involving the CuzO molecule. When a metal which oxidizes to form a porous scale is exposed to the CuzO vapor, the CUZO molecules are reduced in the pores leaving a deposit of metallic copper to mark the site of the reduction. This technique has the rather unique advantage that any copper-coated pores found in the scale are unambiguously related to the reduction site in the growth of the scale under consideration. Pores or cracks which form in a msition*- external to the reduction site or which occur as a result of cooling or handling of the specimen will not exhibit the copper deposit. EXPERIMENTAL PROCEDURE Marker experiments were made on columbium metal, and on pellets of CbO which had been pressed and sintered. Platinum wire markers (0.001 and

Jan 1, 1968

By Frederic Brunton

I. INTRODUCTION THE smelting plant of the British Columbia Copper Co. at Greenwood, B. C., now closed because of the decline in the price of copper due to the European war, is of special interest to metallurgists for several reasons. It was successfully smelting in blast furnaces the lowest grade copper ore of all plants in America. In order to do so, it had to run at' very high efficiency, which necessarily required a large tonnage per square foot of hearth area, together with the minimum amount of labor and other costs. The furnaces smelted daily 2,250 tons of ore (6.62 tons per sq. ft. of hearth area), carrying 0.85 per cent. of copper, at a smelting cost of $1.18 per ton. The entire plant required 130 men to operate it and keep up repairs, showing a labor efficiency of about 17.5 tons per man per day. In the present paper, the method of obtaining these results is shown. Most of the information contained in this description I obtained as Assistant Superintendent, during the two years preceding the present shutdown. Other sources of information to which I am indebted are: The British Columbia Copper Co., Ltd., by Alfred W. G. Wilson, in The Copper Smelting Industry of Canada; Greenwood Smelting Works, by J. E. McAllister, Engineering and Mining Journal, vol. xci, pp. 1011 to 1015 (May 20, 1911); and Description of the Copper Smelter of The British Columbia Copper Co., by W. L. Bell, in Transactions of the Canadian Mining Institute, vol. xvi, pp. 151 to 154 (1913).

Jan 7, 1915

By R. M. Douthwaite, G. Birkbeck

The effect of grain size and specimen dimensions on the occurrence and magnitude of a yield point drop in pure iron has been examined. The tests were done at room temperature. The results indicate that gain size is the critical factor determining whether a yield drop occurs. The specimen diameter:gain size ratio does not influence the magnitude of the yield drop for the range of gain size and specimen diameters investigated. HUTCHINSON,' petchY2 and worthington3 have investigated the grain size dependence of the upper yield stress (uUYP) and the yield point drop, ouyp - aLYP, in Armco iron, mild steel, and Si-Fe, respectively. These authors used center-annealed wires to avoid stress concentration from specimen shoulders and to ensure uniformity of the applied stress. Coarsegrained specimens show no yield point drop; the yield point drop then increases as d-'I2 increases (where d is the grain diameter). These results can be understood in terms of Petch's analysis2 in which the magnitude of amp depends on the strain rate in the (limited) number of grains deforming plastically at the upper yield point. If N grains per unit volume are undergoing plastic deformation, the strain rate in the deforming grains is l/Nd3 times higher at the upper yield stress than when the whole specimen deforms homogeneously. If N is constant and independent of grain size at uUyp, then all the grains are deforming when ~d~ = 1, so there is no yield point drop. At finer grain sizes, the yield point drop is given by: where AU, is the friction stress increase corresponding to a tenfold strain rate increase. Christ, Smith, and Burton studied the upper yield point in 0.050-in.-diam wire specimens prepared from zone-refined iron. Each end of the 2; -in. specimens was soldered to a & -in. diam steel ball and the load applied through the two balls. There was a yield point drop in specimens with grain diameters less than 0.1 mm; no drop was observed in specimens of grain diameter greater than 0.1 mm that were free from veining substructure, but specimens of grain diameter 0.129 mm, annealed in the y range, showed an upper yield point. and this was associated with the presence of a veining substructure in these specimens. Christ et al. suggested the upper yield point occurs when more than a specific number of grains fill the specimen cross section so a multiplicity of slip is required to initiate plastic deformation. Table I summarizes the published data on the grain size at which the yield drop disappears. On the basis of this data the ratio of specimen diameter:grain diameter = 5 to 27 appears to be the critical value for the occurrence of a yield point drop. Thus, petch2 interprets the appearance and magnitude of the yield point drop in terms of the limited number of grains deforming plastically at uuyp, whereas Christ et a1. consider that the occurrence of the yield drop depends on the ratio specimen diame-ter:grain diameter. The published data cover a wide variety of materials so some variation between the results is to be expected, but the size range covered in the data of Table I is rather limited. In an attempt to discover whether the specimen diameter:grain size ratio or the grain diameter is critical in determining

Jan 1, 1969

Jan 1, 1965

By THOMAS G. FEAR

THE COAL DIVISION started its share of the annual meeting Monday morning with a study of coal classi fication. A. C. Fieldner was in the chair. The report of the tellers of the ballot for division chairman, stating that Thomas G. Fear had been elected to that office, was read by M. D. Cooper. Mr. Fear acknowledged the honor in a few words. In reviewing the history of the Coal Classification Committee the chairman pointed out that this was its third symposium, the last previous one having been held at the 1930 Annual Meeting. Throughout its work the com¬mittee has had the active cooperation of the Canadian workers who are interested in the subject which should result in a uniform scheme of classification in Canada and the United States. F. E. Lathe, of the National Research Council, Ottawa, abstracted the first two papers of the session entitled "Determination of the Alkali-Soluble Ulmins in Coal," by Edgar Stansfield and K. C. Gilbart, and "Moisture Determination for Coal Classification," by the same authors. The third paper "Condition of Water in Coals of Various Ranks"' was presented by its author, A. W. Gauger. Written discussions of these papers were presented by H. C. Porter and Gilbert H. Cady. In the oral discussion which followed, W. T. Thom, Jr., brought out the advisability of considering age as a factor in classification. Mr. Fieldner favored retaining bed moisture as a partial classification basis, stating that a review of many coal analyses revealed a remarkable consistency in this item in samples from a given mine particularly where the moisture content was not high. Mr. Porter pointed out that the structure and porosity of coal often have much to do with its moisture content and that these vary in different parts of a seam, particularly in anthracite. Mr. Gauger expressed doubt as to whether the Stansfield method gives the true moisture content of coal, which is needed for classification purposes.

Jan 1, 1932

By FRED T. WILLIANS

INTRODUCTION. THE Park City mining-district is distinctively a camp of few properties, 5,000 acres, or one-third of the entire district, being under the management of but three companies. As a rule, the ore-bodies lie deep, with no outcrop, except where erosion has formed the deeper canyons and gulches. Ontario canyon exposed the famous Ontario ledge, and Woodside gulch showed the first ore of the Silver King Coalition mine. The Quincy ore-bodies were first brought to light in upper Empire canyon, and Thaynes canyon was instrumental in aiding the prospector during the early days of the camp. There are 22 shafts which have reached a depth of at least 500 ft., ten a depth of 1,000 ft., five a depth of 1,300 ft., and two a depth of 2,000 ft. The amount of lateral development has been proportionally extensive, including six long tunnels, four of which are in 3 miles, with a fifth now being driven. The Ontario lower drain-tunnel is now more than 4 miles long. The formations are sedimentary, dipping about 30° NW. and N., and traversed by many fissures, dikes, and faults. The principal ore-bodies are found associated either with the contact of the basal Ontario quartzite and the overlying limes, or on a quartzite stratum within the limes, or in the fissures, or along some of the porphyry dikes. The district covers the intersection of the Uintah and Wasatch ranges, which explains the existence of large folds and faults, and fissures of great length, width, and depth. In a general way, the geology of the district consists of a basal quartzite dome, which has been exposed by erosion at the Ontario property. The Ontario fissure lies entirely within this formation. Flanking this dome on the west, north, and east lie

Jun 1, 1911

By Julian Avery

IN its dual role of pig-iron smelter and gas producer, the blast furnace is a remarkably satisfactory and efficient apparatus. Many metallurgists and engineers have pointed out, however, that since the primary function of the blast furnace is to produce pig iron at the lowest possible cost, its function as a gas producer should be subordinated to this primary pur-pose. During the past 10 years or more, improvements in blast-furnace technique and economy have, in fact, been directed primarily to increasing efficiency in the use of the reducing power of the gases produced by com-bustion of coke at the tuyeres, to reduce iron ore within the furnace. The net over-all result is a decrease in the fuel value of the top gas per unit of volume, and per ton of pig iron, which is evidently more than offset in value by the corollary saving in coke and the possibility of increased furnace capacity, for otherwise there would be no point in making such improvements. The purpose of the present paper is to suggest that, while progress has been made in this direction, there is another approach to the problem of increasing the chemical and thermal efficiency of the blast furnace in its primary role as a pig-iron smelter, which appears to offer possibilities of improvement in over-all economy of a different order of magnitude than results thus far obtained by the use of other expedients. The present argument is based in large part upon the hypothesis that the effi-ciency and economics of pig-iron smelting are seriously and adversely affected by the phenomenon known as "solution loss," and that the problem of solution loss can be successfully attacked by increasing the over-all pressure; i.e., the "top pressure" under which the furnace is operated. It is indicated that pressure operation may also be expected to result in concomitant benefits, which may be summed up as generally improved operating conditions, together with a substantial saving in fuel and/or a substantial increase in furnace capacity.

Jan 1, 1938

By F. C. Farnham

THERE has been very little, if any, uniformity in the reference datum used for magnetometer surveys. It has been the practice to choose a base station at which the magnetic field is assumed to be normal and call the difference in field strength between a given station and this base the anomaly at the given station. For small-scale surveys latitude and longitude corrections may or may not be applied, but for large-scale surveys such corrections usually are applied. The United States Coast and Geodetic Survey maps showing lines of equal magnetic intensity are commonly used to determine the normal latitude and longitude variation by scaling values from the map for given points and computing the change per mile north and the change per mile east. This method has been quite satisfactory for isolated surveys, but when two surveys originating at different base stations were extended until they joined, difficulty arose, not only because of discrepancies between base-station values, but also because of differences between the latitude and longitude correction factors used for the separate surveys. It is the purpose of this paper to describe a reference datum for magnetometer surveys which, it is believed, will eliminate most of the difficulty arising from this source. In order to be satisfactory, a general datum for magnetometer sur-veys should be as close as possible to the observed field and still he based on some assumed distribution of magnet poles, in order that the "normal" value of any component of the field for any given point may be computed to as many significant figures as desired. Such a field has been com-puted, and a comparison of the intensity of its vertical component with the average vertical intensity for the United States as shown by the U.S.C.G.S. map of lines of equal intensity for 1935 is shown in Fig. 1.

Jan 1, 1939

By Walter Crafts

KEYNOTE of the technical sessions of the Iron and Steel Division at the Annual Meeting was struck by Leo F. Reinartz in his Howe Memorial Lecture on "The Development of Research and Quality Control in a Modern Steel Mill." In describing recent developments in steel-producing practices at the American Rolling Mill Co. the co-ordination of practical observation and directed research with operations was stressed and was shown to have resulted in economical production of steels of uniformly high quality. Empirical methods based on inaccurate and incomplete experience resulted in the production of commercial products of variable quality and were recognized as inadequate; a research program was therefore initiated that has been justified by its fruits. To name a few outstanding achievements such as Armco iron, steel for electrical sheets, wide continuous strip of superior surface and quality, and non-aging steel is not sufficient to summarize the results of this increasing effort toward better steel products. In addition to the development of new products the faithful observation of operating procedures, the co-ordination of the resulting information, and the standardization of processes have made the steel of today much more uniform and thus more economical and useful to the nation.

Jan 1, 1943

By T. A. Rickard

Freeman, the English historian, said that he had learned from Macaulay "never to be afraid of using the same word or name over and over again if by that means anything could be added to clearness or force. Macaulay never goes on, like some writers, talking about `the former' and `the latter', `he', `she', `it', and `they', through !clause after clause, while his reader has to look back to see which of several persons it is that is so darkly referred to". He might have learned also from Macaulay that a preposition makes a' feeble ending for a serious statement. How often do you hear `the former' and `the latter' in conversation? Good conversation is a guide not to be dis¬dained. When you must use `the latter', do not confuse it with `the last'. Cheap labor, cheap fuel, and cheap transport are essential, the latter [last] being particularly important in base-metal mining. The apparatus may be used to determine such gases as hydrogen sulphide, chlorine, oxides of nitrogen and some others, as well as sulphur dioxide. In the case of the latter two, etc. The two last mentioned are "sulphur dioxide" and "some others". He should have stated which two, and he should have avoided that wretched phrase "in the case of ". Pinning may be partly prevented by use of chalk, oil, or turpentine. The latter [last] is best. I "Partly prevented" is a poor phrase. `Prevented! is a word that does not lend itself readily to modification. He means `checked' or `corrected'.

Jan 1, 1931

By H. B. Pulsifier

THE following report on the structure of copper is the result of work done in the laboratory of the Rome Wire Co. early in 1925. Previous work had indicated to the author that excellent results might be expected if a suitable technique in surfacing and etching could be developed. The resources of the Rome Wire Co. enabled this metal to be studied more intensively than previously, although none of the materials were investigated exhaustively. The material presented is hardly more than a preliminary summary of the most obvious character of the metal; a much longer research would have been necessary to solve many of the pressing problems connected with the casting and working of copper. The Rome Wire Co. has generously released the paper; to Dr. E. H. Darby, technical supervisor of the company, are due particular thanks for his appreciation of the importance of metallographic study of copper and for his effective support in the prosecution of the work and in making its publication possible.

Jan 1, 1926

By D. K. Deardorff, Earl T. Hayes

An improved technique is described for the accurate determination of melting points of metals in the temperature range 1500' to 2500°C. The improvements consist of gradient heating and refinements in cavity preparation to obtain true black-body conditions. The melting point of hafnium, as determined by this method, is set at 2222°±30°C. This is over 200°C higher than one of the values reported earlier. Discrepancies in the previously reported values for the melting point of hafnium are explained. The melting points of zirconium and titanium are found to be 1855O±15OC and 1668°±10°C, respectively. Reproducibility of results was ±3OC. PRIMARILY, this report is being made to correct a 1975o±25oC1 value for the melting point of hafnium, and to present an improved method for melting point determination. As a matter of interest, the technique was also applied to determining the melting point of zirconium and titanium. There is a wide difference in the melting point of hafnium as reported by competent investigators. DeBoer and Fast' reported a value of 2230°±500C, and later work of McPherson, as reported by Aden-stedt, placed the melting point at 1975o±25oC. Zwikker" calculated that the melting point was 2430°C. In resolving this discrepancy, improvements were made in the procedure for determining the melting points of refractory metals in the range 1500" to 2500°C. Special techniques are necessary to determine the melting point of these metals accurately. Since the metals oxidize in air above 900oC, the determinations must be carried out in an inert gas or vacuum. Also, every known refractory contaminates them to some extent. In addition, the attainment of true black-body conditions is always difficult. DeBoer and Fast actually determined the melting point of Hf-Zr as-deposited iodide process alloys and extrapolated to 100 pet Hf. McPherson employed a tungsten wire suspension similar to that described by Schramm, Gordon, and Kaufmann,1 and used hafnium metal produced by the iodide process. There was no apparent reason for the wide spread in melting points, since the quality of the metal was very good and the work was under the direction of highly competent investigators. Retracing some of this work revealed one understandable error in the case of hafnium, and led to development of an improved technique for determining melting points of reactive metals in the range 1500" to 2500°C. Material Crystal bar hafnium, zirconium, and titanium were used for this work, with analyses as shown in Table I. The hafnium was of the highest purity that has been prepared, though not as pure as the zirconium and titanium. At the instigation of the Pittsburgh Area Office of the AEC, a special lot of Hfo2 was purified, converted to the tetraflouride, and bomb-reduced with calcium, all at the Iowa State College Laboratories. This crude hafnium metal was then refined by the iodide process at the Foote Mineral Co. All specimens were cut with a Sic wheel, ground, pickled, and dried carefully before use. Procedure General Tungsten Suspension Method—In this method, a small specimen is suspended by a fine tungsten wire in a slender, induction-heated tungsten or tantalum cylinder, all under vacuum. The melting point is determined by heating the specimen slowly while observing it with an optical pyrometer focused upon a portion of the specimen that radiates as a black body. This means that there should be no reflected radiation, either from colder objects near the pyrometer or from hotter surfaces. The induction heater would be the only hotter object and, if it is slender enough, the specimen will attain the same temperature. Often a slender hole is drilled into the specimen as a source of black-body radiation. This was the general method used by McPherson in obtaining his value of 1975°C for the melting point of hafnium. In trying to repeat this work, it was found that the points of contact between the

Jan 1, 1957

By K. Mukherjee

A quasi-thermodynamic calculation is presented for estirt~ating vacancy Parameters in fcc metals. For fcc metals the equilibrium vacancy concentration at the melting point can be approximated by a constant mole fraction. The Gibbs free energy of formation of the vacancies can then be expressed as a simple function of the absolute melting temperature alone. From this description the formation energy Ef, the vibrational entropy Sv, and the formation volume of a vacancy can be calculated in terms of known thermodynamic parameters. The calculated values are in good agree-rnent with available experimental results. IT appears that many of the physical parameters associated with lattice defects can be empirically related to thermodynamic melting parameters.'-7 Besides the implicit correlations between melting phenomenon and point defects, the melting temperature itself at atmospheric pressure can be used as a reference temperature for the purpose of comparison of vacancy concentrations in a given crystal class. The concentration at the melting point then corresponds to the maximum vacancy super saturation in the crystalline state at a fixed pressure. For pure fcc metals such as Au, Cu, Al, Ag, Pb, and Pt the mole fraction of vacancies at the melting point8 is of the order of 10*"3 to 10"1. The equation expressing the equilibrium vacancy concentration at the melting point contains three parameters: the formation energy, the vibrational entropy, and the absolute melting temperature, see Eq. [2]. Since these three parameters cover a wide range of values8 in the above-mentioned metals, it can be assumed that in other fcc metals, for which no reliable data are available, the mole fraction of vacancies at the melting point most likely lies in the range 10~3 to lO"4. This is then the basis of the calculations described in this article. Within this range the mixing entropy can be linearized and the vibrational entropy, the formation energy, and the vacancy formation volume can be calculated in terms of known thermodynamic constants. 1} LINEARIZATION OF MIXING ENTROPY The Helmholtz free energy of a crystal containing n vacancies at the melting point can be writteng as where Ef, T,, k, and S, are the formation energy of a vacancy, the absolute melting temperature, Boltz-mann's constant, and the vacancy formation entropy, respectively. After applying Stirling's approximation in Eq. [l] and minimizing with respect to n where (n/N), is the equilibrium vacancy concentration in mole fraction at the melting temperature at 1 atm pressure. If instead of setting (6~/6n) = 0 immediately after Stirling's approximation in Eq. [I], the configurational partition function is simplified, then some useful and significant results can be obtained by utilizing the experimental inforrnation After applying Stirling's approximation and rearranging is plotted as a function of (n/N) in Fig. 1. The points, not all of which are shown, are fitted by a straight line substituting from Eq. [5] into Eq. [I] and minimizing with respect to n combining Eqs. [6] and [2] It must be emphasized that Eq. [7] is only a crude approximation based on an oversimplified model of

Jan 1, 1967

By J. J. Jonas, J. L. Uvira

Equipment was constructed which permitted the hot compression of 99.8 pct Armco iron and 2.8 pct Si steel at constant true strain rates of 0.05 to 1 per sec over the temperature range 600" to 1000°C. A maximum true strain of 1.9 could be attained, followed by immediate quenching or by isothermal annealing. True stress-true strain curves were obtained, and the steady-state flout stress, a, strain rate, i, and temperature, T, were found to fit the following expression: The constants A, a, n', and AH were determined for the two ,materials. The activation energies obtained for Arrnco iron and silicon steel are 66 and 80 kcal per mole, respectively, and approximate those for seu- diffusion and for creep. This indicates that hot compression is a diffusion-controlled thermally activated process. THE hot compression of iron and steel is usually carried out in the austenite temperature range,1"7 as this is the one of greatest interest with respect to industrial hot working. However, a disadvantage of testing in the austenite range is that the hot-worked structure is destroyed by the phase transformations taking place during cooling. The present study was therefore carried out in the ferritic temperature range, and the hot-worked substructures were preserved by rapid quenching after deformation. The substructural results will be described in a separate paper, and the present communication is restricted to the strain rate/stress/temperature relationship observed during hot working. The results of hot-compression testing are usually given in the form of true stress/true strain curves, with a different curve for each temperature/strain rate ~ornbination.',~,~ Sometimes simple algebraic equations are fitted to the curves, so that certain extrapolations or interpolations can be performed.1'2'5 These equations are, however, devoid of mechanistic interpretations. The present study was undertaken to show that hot compression can be described by an equation of the type used in creep studies. That is, it will be shown that the temperature dependence of the strain rate in hot working is well-represented by an Arrhenius term, with an activation energy similar to that for creep. Also it will be seen that the stress dependence of the strain rate is similar to that for creep EXPERIMENTAL METHOD AND MATERIALS The investigation was carried out with the following three ferrous materials: 1) Armco iron; 2) Armco iron with 0.26 pct Mn; 3) 2.8 pct Si steel. The first two materials were utilized for investigations performed in the temperature range 600" to 800°C; the last one was used for tests at temperatures from 600" to 1000°C. The materials were of commercial purity,* as shown in Table I. Cylinders of five different sizes were prepared by strain annealing. The resulting mean grain diameter was 3 mm in the 1-in. Armco iron and 2 mm in the other sizes and grades. Different ratios of diameter/height were used to enable the determination of the coefficient of friction. The specimen faces were provided with concentric grooves, which acted as lubricant holders during compression, as recommended by English and ~ackofen' and others.2'9 Powdered glass lubricants were applied to the samples before hot compression to decrease friction and barreling, following the practice of previous investigator~.~~~~~~~~ Different mixtures of glass powder were used for each temperature, after the determination of suitable compositions by experiment.'' Equipment for Hot Compression. Hot-compression tests were carried out on an adapted 150-ton vertical hydraulic extrusion press and also on a modified high-temperature creep machine. The modified extrusion press was used for temperatures up to 800°C. The following items were added to the press: a) a high-temperature furnace with built-in upper and lower platens; and b) a transmission assembly, which permitted the attainment of logarithmically decreasing crosshead speeds. These accessories are described in detail in Ref. 11.

Jan 1, 1969