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Discussion of the paper of C. W. Goodale and J. H. Klepinger, presented at the Butte meeting, August, 1913, and printed in Bulletin No. 50, August, 1913, pp. 1935 to 2010. PROF. JOSEPH W. RICHARDS, South Bethlehem, Pa.:-Mr. Chairman, I would like to call attention to one valuable feature of the paper which may interest some: I have worked a good deal with the Pitot tube, and have always had difficulty with what is called the static end of that apparatus, so much so that I became almost hopeless of securing good results with it. I find here, however, what is stated to be a perfectly satisfactory static end for the Pitot tube, satis factory under probably all conditions. I congratulate Mr. Klepinger on the design of that tube and the consequent improvement he has made in the technical measurement of the volumes of gases. I would also like to ask if the total volume coming out of the chimney per day could not be computed by chemical analyses of the SO and SO2 in the gases, and calculation on the basis of the known weight of.. sulphur going out in a day; so that the Pitot tube measurements . could be checked by a method independent of measurements in the flues. J. H. KLEPINGER :-I think the volume of gases could be determined in that way. Those of a chemical turn of mind would go. about it so, but I am not enough of a chemist to follow that method, and consequently I always look at the mechanical way to obtain the results.

Jan 11, 1913

By K. Thirumalai

Rock response to heating depends on properties of rock material and varies widely between different rock types. By dissipating energy, surface melting limits rapid heating and fragmentation of rocks achieved by surface heating methods. This study advances a concept of rock fragmentation by rapid internal heating of a localized inner volume of rock. The working of the method to achieve fragmentation of rocks (Charcoal granite and Dresser basalt) having poor response to surface heating is analyzed. Experimental data on elevated temperature rock properties required for the study are presented. Based on the properties of test rocks, a high frequency (50 MHz) dielectric heating method of generating localized internal heating was selected for experimental study. The test rocks were fragmented without melting under localized heating below 600ºC. The heated volume required for fragmentation was observed to be less than 2 percent of the test block volume. A practical application of the method for in situ fragmentation of rocks is suggested.

Jan 1, 1971

[†AARONSON, ALFRED E., Vice-Pres., Mid-Co. Petroleum Co., Mid-Co. Bldg. Tulsa, Okla. '18 ABADIE, EMILE R., Min. Engr Address wanted. '76 ¦ABADILLA, QUIRICO A. Geol. Dept. Cia. Mexicans de Petroleo "El Aguila," S. A., Edifico "El Aguila," Esq., Calles Aurora y Comercio,] [ ]

Jan 1, 1925

SME Membership Directory Listings of record March 31, 1072 SOCIETY OF MINING ENGINEERS OF AIME

Jan 7, 1972

By Joseph Lindmayer, Karl M. Busen

If silicon is in contact with silicon oxide, a heterojunction is formed which induces an inversion layer ("channel"). Influences of impurities and structural parameters on the channel are discussed. There seems to be no relation between surface damage in silicon and the channel. Phosphorz~s doping of the silicon oxide has no pronounced effect on the channel. Channels which were well above the range predicted by the heterojunction model were related to the action of H* at the silicon/silicon oxide interface. Channels which were well below tlze range predicted by the heterojunc-tion model were related to a transition region in the oxide adjacent to the interface. In support of the assumed transition region and the H+ are the ex-periments described on the paper. Furthermore, the concept of metastable OH groups in silzca, known from other publications, has been used to explain certain channel characteristics by the formation and the accommodation of hydrogen in the silicon oxide. THE electrical characteristics of a semiconductor device in many cases are influenced by the conditions of its surface. Because these conditions often are changing with temperature, time, ambient, or other parameters, numerous attempts have been undertaken to stabilize them by suitable processes. Several years ago Atallal studied the silicon/silicon dioxide interface and since then increasing attention has been given to the silicon dioxide as a means to stabilize silicon surfaces. This led to the evolution of the planar silicon devices where oxide layers are used to protect places at which the junctions are intersecting the surface. The formation of the oxide layers on silicon can be carried out by a variety of processes: high-temperature thermal oxidation (exposing the silicon surface to oxidizing agents such as 02, HzO, COz), evaporation of SiOz, or anodic oxidation of silicon. Originally the oxides were considered able to "passivate" the silicon surface and it was understood that they 1) protected the surface against any influence from the ambient and 2) stabilized surface conditions which were necessary for proper device performance. It soon was realized that the second quality was not always obtainable: Atalla and Tannenbaum showed that, in the process of forming a layer on doped silicon by thermal oxida- tion, electrically active impurities in the silicon near the interface are redistributed, thus giving rise eventually to the formation of unwanted charge distributions. The degradation of planar junctions during reoxidation of silicon was observed by Barson et a. Surface studies with silicon planar junction structures indicated that the breakdown voltage depended on the kind of procedure which was applied during or after oxidation.*" Yamin and worthinge report on charge storage and dielectric properties of SiOz films at elevated temperatures. Another influential parameter on the silicon surface is discussed by Lindmayer and usen,' namely the appearance of a surface potential on silicon as a consequence of the heterojunction formed by the silicon/silicon oxide interface. In the present paper the influence of impurities and structural parameters in silicon oxide in connection with the heterojunction is a particular object of our investigations. I) EXPERIMENTAL The material used was 10 ohm-cm p-type silicon slices with either damaged surfaces (mechanically lapped or polished) or damage-free surfaces (chemically polished). The majority of the slices were oxidized for 1 hr and 20 min at 1250°C in a steam + oxygen atmosphere generated by passing O2 through HzO at 90°C (wet oxygen). This led to oxide layers of about 9000 A. On some slices oxide layers were grown in pure oxygen (dry oxygen). By a photoresist process a set of 20 by 200 mil windows was then etched out from the oxide layer. The pattern of the windows is shown in Fig. 1. In a subsequent process n-type pockets with surface concentrations between 2 x 10" and 5 x 10" cm"3 were formed by phosphorus diffusion. This allowed ohmic contacts between the silicon surface and tungsten probes which for electrical measurements were placed into two adjoining windows and

Jan 1, 1965

By Paul J. Fopiano

SOME relationships between the flow characteristics of iron single crystals of 99.9 pct purity and the behavior of imperfections have been investigated. X-ray rocking-curve measurements and etch-pit counts were made as a function of plastic strain, and compared to the stress-strain curve obtained on a modified Polyani tensile machine. Crystals grown from rolled strips of vacuum-melted iron by the strain-anneal method1 had a high preference for a (110) longitudinal direction and a (211) face normal. The tensile specimens were prepared from 2 by i by 0.040 in. single crystals having a gage area of 3 by \ in. Rocking-curve measurements were carried out with a highly perfect germanium monochromating crystal in which the dazz spacing was matched to that of the dZl1 in the ir0n.l Well-collimated CuKal radiation was used throughout. These procedures practically eliminated errors due to geometrical and wavelength resolution. Inasmuch as the rocking-curve half breadth may vary markedly from point to point in the specimen being irradiated, the crystals were strained in place by mounting a hydraulic loading device on the double-crystal spectrometer. The rocking curves were taken after each increment of strain in the unloaded condition, since no observable difference was found in the rocking-curves between the loaded and unloaded states. The rocking-curve half breadths of the as-grown specimens were in the range 90 to 120 sec of arc when the beam irradiated an area of about -£ by -& in. on the specimen. DeMarco and weiss3 have shown that, for a well-colli- mated X-ray beam, irradiating about 10"! sq in. of the very same material, half breadths within 10 pct of the Darwin natural half breadth were observed. Since the rocking-curve specimens were stressed by the load-unload technique, the strain achieved at any given stress depended on the time of holding because of low-temperature creep. Fig. 1 shows the rocking-curve half breadth (also area/peak height) as a function of plastic strain for a relatively short holding time (2 to 5 min) at each stress level. For strains less than 0.1 pct the rocking-curve breadth is essentially constant; it is only for larger strains that there occurs a significant increase in this breadth. Where the holding times at each stress level were longer (by well over an order of magnitude) there occurs a significant increase in the rocking-curve breadth only after plastic strains of the order of 0.6 pct had been introduced into the specimen. This observation is related to the time dependence of creep phenomena and emphasizes the difficulty in comparing data obtained by two such different straining methods. Etch-pit results were obtained using a 2 pct nital etch on specimens strained in the range of 0 to 1 pct. Prior to etching, all specimens were annealed for 3 hr at 150°C, the carbon content being sufficient to decorate the dislocations for strains of at least 1 p~t.~ The data points were all taken from parts of the same single crystal which had been strained with short holding times at stress in increments of strain of the order of tenths of 1 pct. The (211) plane is particularly difficult to etch-pit in vacuum-melted iron and therefore it is felt that these values are as much as an order of magnitude low. Fig. 2 shows the etch-pit density as a function of plastic strain. The smooth curve passing through the data points is not meant to infer a quantitative correlation with the rocking-curve data. What is of interest, however, is the change in etch-pit density in the region of 0.2 pct plastic strain. The first three increments in strain (points 2,3, and 4) did not produce a measurable change in the etch-pit density while subsequent increments did produce a measurable change. While the absolute values of these results do not appear to be cor-

Jan 1, 1967

Before hostilities between the colonies and Great Britain began in 1775, most of the coal used in the northern colonies undoubtedly came from England, with some supplies for New England coming from Nova Scotia; in New York and Philadelphia the supply came from England with some from the Virginia mines. Table 4 shows data obtained from the Public Records Office, London, for the years 1768-1772. This table supplements Table 3, which records only a few shipments from Richmond in 1768 and 1769; as there was no coal shown in imports coastwise in 1769 in Table 4, and only two small shipments in 1769 in Table 3, there may have been a cessation of shipments then, for some reason not now known. In Table 5 are incorporated all the data in the first two, with a few earlier years, and an attempt is made to estimate the amount used during the period by allowing for coal exported. With the small total tonnages a carryover from one year to another makes a large difference in the annual figures, but over the period the result may be fairly indicative of the amount of coal used before the Revolution. According to present day ideas the quantity of coal used during that war was very small, but apparently it was badly needed for the manufacture of the small amount of munitions made in those troublous days. As Philadelphia was the leading city along the Atlantic coast, and as the southeastern part of Pennsylvania was the leader in making iron, as well as making rifles, it is natural that the first call for coal came from there. At first, procuring supplies such as coal, powder and sulphur was handled by a Committee of Safety, which later became a Council of Safety and later this committee's functions were turned over to a Board of War, functioning with the military organization of the colony. . The organizations of the several colonies were slightly different, but Pennsylvania, Maryland and Virginia followed this scheme generally. Later in the war the Congress began to make arms for the troops, and it is difficult now, with the few records available, to tell when the state functions ceased and those of Congress began. On December 5th, 1775, the Committee of Safety

Jan 1, 1942

Occasionally it is interesting, and sometimes useful, to review the past for early references to our industry, and to learn of the trials and travail passed through before it arrived where it now is- and the results of such a review follow. Some time ago one of our modern playwrights and poets, Arthur Guiterman, turned to coal, with the following result: Afar in the Carboniferous time I grew in Paleozoical slime, A lepidodendron with boughs on my stem And lepidostrobuses grew out of them. My roots in the mud of the ages I spread And up to the heavens I vaunted my head, I throve in the heat of tropical sun, And now I am coal at two dollars a ton

Jan 1, 1939

By Samuel S. Wyer

The following abbreviations have been used in the text: Cassier's, Cassier's Magazine. Eng. Lond., The Engineer (London). Eng. Mag., Engineering Magazine. Eng. News, Engineering News. Eng. Rec., Engineering Record. Eng. and Min. Jour., Engineering and Mining Journal. Engng., Engineering. Jour. Assn. Eng. Soc., Journal of the Association of Engineering Societies. Engr., The Engineer (Chicago). Jour. I. and S. I., Journal of the Iron and Steel Institute. Jour. F. I., Journal of the Franklin Institute. Mar. Eng., Marine Engineering. Mem. Soc. Ing. Civ., France, Memoires de la Socie'te' des Inge-nieurs Civils, France. Pract. Eng., Practical Engineer. Proc. Engs. Soc. of W. Pa., Proceedings of the Engineers' Society of Western Pennsylvania. Proc. I. C. E., Proceedings of the Institute of Civil Engineers. Proc. I. M. E., Proceedings Institution of Mechanical Engineers. Trans. A. I. M. E., Transactions of the American Institute Mining Engineers. Sci. Am., Scientific American. Sci. Am. Sup., Scientific American Supplement. Zeitschr. d. V. D. Ing., Zeitschrift des Vereines Deutscher Inge-niezcre.

Jan 1, 1906

By E. S. Leaver

THE presence of soluble base metals in precious-metal ores usually precludes cyanidation as the best method of treatment. The laboratory experiments described in this paper show the possibility of cyanidation of gold-silver ores containing less than 0.5 per cent, of cyanide-soluble copper and the effect of zinc in the cyanide solution. PART I.-COPPER IN CYANIDATION The proposed process of cyanidation of precious-metal ores containing copper is based on the regeneration of about 80 per cent., of the cyanide used in the dissolution of the copper. The method of regeneration involves a combination of the sulfide and the acid precipitation of the copper and silver. The resultant solution is made alkaline with lime, and the gold is precipitated with zinc dust. Solubility of Copper Minerals in Cyanide Solution In order to determine the solubility of copper minerals, including metallic copper, under the usual conditions for cyanidation, experiments were conducted with synthetic ores. Each ore sample was prepared by mixing the particular pure copper mineral with barren sea sand. Both the mineral and sand were ground to pass 100 mesh before they were thoroughly mixed. The percentage of copper in each head sample was determined by direct assay, excepting the metallic copper sample, which was computed on weights before mixing. Table 1 gives the results.

Jan 1, 1929

By Franklin R. Carpenter

Pyritic smelting, so-called, as practiced in the Black Hills is pyritic smelting only in the sense that Dr. John Percy uses the expression in his " Metallurgy of Silver," where he describes a process for smelting dry silver-ores in connection with iron pyrites, to form a regulus. The ores treated by this process in the Black Hills are very siliceous, averaging about 74 per cent. of silica, from 10 to 20 of iron oxide, 4 or 5 of alumina, and from 2 to 4 of lime. In 1889, while Dean of the South Dakota School of Mines, I took up the question of their smelting. There were neither copper- nor lead-ores in the Hills; hence pyrite and pyrrhotite, of which there are large deposits, were employed to form a regulus. This mixture of pyrite and pyrrhotite, besides being absolutely barren of gold and silver, carried an average of 30 per cent. of silica. The only basic material available as a flux for the great excess of silica in the ores and in the pyrite was a dolomitic limestone. Moreover, the local coke gave 24 per cent. of ash, 60 per cent. of which was silica—as unpromising a set of conditions as can well be imagined. We had before us the examples of Mr. W. Lawrence Austin, of this Institute, who had experimented at Toston, Montana,"

Jan 1, 1901

By P. H. Royster

On the Continent, ferromanganese has been produced in the blast furnace almost continuously since 1876, but little definite information concerning the practice is to be found in technical literature, and almost nothing in the way of a theory of the manganese furnace. In this country, prior to 1904, but one company had attempted its production in a serious way, and none of the operating data or other information from this company has been, or is, available to the public..In the last 5 years, as a result of the restriction of imports, a number of furnaces have been blown in on this alloy, with the result that in 1918 as many as 18 furnaces were in blast. The majority of the men in charge of these furnaces had had little previous experience in such operations; so the Bureau of Mines, in the summer of 1918, undertook the collection of data from ferromanganese furnaces. Operating data were collected by the Bureau from eleven ferromangahese furnaces, which will be referred to throughout this paper as furnaces A, B, C, F, G, I, J, K, L, M, and P; the dimensions of seven of the furnaces are given in Table 1. The companies from whom this information was obtained, and to whom should go the credit for whatever value this information may possess, are the Bethlehem Steel CO.,

Jan 1, 1920

By R. E. Pray, M. C. Fuerstenau, J. D. Miller, B. F. Perinne

Quartz cannot be floated with potassium amyl xanthate as collector at any pH. Complete flotation is achieved with certain minimal additions of amyl xanthate and Pb from pH 5.8 to 8.5 and with amyl xanthate and Zn from pH 7.5 to 8.1. The active species of these metal ions responsible for activation are shown to be PbOH and ZnOH No flotation was effected when Cu and Mg were added as activators. Previous work1,2,3,4,5,6,7 has shown that quartz may be floated in the presence of sulfonate or soap when the following two criteria are met: 1) some portion of the added metal ion has hydro-lyzed to its first hydroxy complex, and 2) a precipitate of the metal-collector has formed. Since sulfonate and soap, two substantially different anionic collectors, conform to these criteria, this phenomenon may well be expected to be of a general nature. In this view then, it would appear that any anionic collector, including xanthates, should also float quartz when these two criteria are met. The object of this paper is to demonstrate the conditions under which quartz will respond to flotation in the presence of potassium amyl xanthate. EXPERIMENTAL MATERIALS AND TECHNIQUES Quartz was prepared by leaching the sized sample (48 x 150 mesh) with HC1 until no iron could be detected in the leach liquor. Conductivity water, made by passing distilled water through an ion exchange column, was used in the investigation. Potassium amyl xanthate was selected as collector. Purification of this reagent was effected with the following method: 1) a laboratory sample of potassium amyl xanthate was dissolved to saturation in hot ethyl alcohol and filtered several times while still hot, 2) the filtrate was cooled, during which time potassium amyl xanthate crystallized out of solution; the xanthate was then separated from the solution by filtration, 3) the amyl xanthate was dissolved in fresh hot ethyl alcohol and filtered, 4) step (2) was repeated, 5) the crystalline potassium amyl xanthate was washed with ethyl ether five times, and 6) the xanthate was dried for 24 hours under continuous vacuum. Inorganic impurities are insoluble in hot ethyl alcohol whereas dixanthogen is soluble in ethyl ether. Five-gram charges of 48x150 mesh quartz were conditioned for 3 min in 125 cc of solution containing the reagents and were floated with the small-scale cell and procedure described in previous papers.478 Reagent grade HCl and NaOH were used for pH adjustment, while reagent n-amyl alcohol was added as frother. Frother addition is necessary with this technique, but it should be mentioned that data, similar to those shown in Fig. 2 for 1 x10-4 mole per liter Pb++ and 1 X 10-4 mole per liter AX-, were also obtained with a Hallimond cell in the absence of frother. EXPERIMENTAL RESULTS Clean quartz could not be floated with amyl xanthate at any pH. Flotation was achieved under certain conditions, however, when various metal ions were added to the system. The activating ions used were lead, zinc, copper and magnesium, added as reagent grade chloride salts. Lead as Activator: The effect of Pb++ as activator was examined at five different additions of amyl xanthate (Fig. 1, 2 and 3). When 1x 10-5 mole per liter xanthate was added in the presence of 1 x 10"4 mole per liter Pb ++, no flotation was obtained at pH 6.5 or below, while a recovery of about 60% was effected at pH 7. When the pH was increased to 7.8, no flotation was again obtained, Complete depression was noted from pH 7.8 to about 10, at which point a recovery of about 30% was achieved. At about pH 11, the precipitate of lead amyl xanthate which was present below this pH dissolved and complete depression occurred. When 2.5x 10-5 mole per liter xanthate was added with the same lead addition, no flotation was obtained at pH 5.8 and below, whereas a recovery of

Jan 1, 1965

By H. I. NORTON, H. O. Hofman

ZINC smelters in the central western. States have established a very high standard of purity for blende-concentrates, viz., zinc 60, iron less than 3, and lead less than 1 per cent. The very low percentage of iron is made possible by the blende containing less than 0.5 percent of isomorphous iron sulphide and by the sparing occurrence of pyritic material in the large blende-deposits of southwestern Missouri and southeastern Kansas. The blende in these districts occurs in sub-Carboniferous limestone, and is associated with chert, residual clay, calcite, pyrite or rnarcasite and bitumen. The different minerals are coarse and therefore readily separated by mechanical washing from the blende, with the exception of pyrite and marcasite, as blende has a specific gravity of from 3.9 to 4.1, marcasite, from 4.85 to 4.90, and pyrite, from 4.95 to 5.10. The common procedure of dressing the ores is to crush in a breaker, size in a trommel with 0.5-in. holes, pass the over-size through roughing-rolls and then jig the ore, now reduced to 0.5 in. maximum size, in roughing multiple-sieve jigs. The products of these are waste-tailings, sine-discharge coarse concentrates, side-discharge coarse middlings and bottom-discharge fine middlings. The coarse concentrates are sent to the market. The coarse middlings are crushed in middlings-rolls and brought back into the system by feeding into the main trommel. The fine middlings are cleaned upon finishing-jigs. Any pyrite or marcasite present follows the blende and increases the percent-

Mar 1, 1905

Executive SIDNEY .J. JENNINGS, Chairman GEORGE D. BAR HON .I. E. JOHNSON, JR. EDWIN LUDLOW ROBERT M. RAYMOND Membership KARL EILERS, chairman LEWIS W. FRANCIS .1. E. JOHNSON, JR. LOUIS D. HUNTOON ARTHUR. L. WALKER Finance GEORGE D. BARRON. Chairman. CHARLES F. RAND BENJAMIN B. THAYER Library E. GYBBON SPILSBURY1 Chairman ALEX C. HUMIPHREYS3 GEORGE C. STONE .J. H. JANEWAY4 BRADLEY STOUGHTON Papers and Publications BRADLEY STOUGHTON, Chairman

Jan 10, 1918

By GORDON H. FISHER

During the year 1945, the drilling pace in West Texas increased above that in the year 1944, and represented the highest number of well completions since 2941. The 1680 new wells drilled 8,287,958 ft. of hole for a per well average of 4933 ft. This depth is approximately 30o. ft. deeper than the average for the year 1944. Although the deepest well drilled in West Texas (Phillips Petroleum Company's Ada Price No. 1, in Pecos County) was completed during the year. 1944 to a depth of 15,279 ft. and tested the Ellen-burger horizon, the producing depth record for West Texas was set during the year 1945 with the completion of Amerada Petroleum Corporation's Jones No. I-A, in the Jones Ranch field, Gaines County, which now is producing at 11,422 ft. from the Devonian formation.

Jan 1, 1946

I HAVE hitherto shown you as well as I knew how the procedure for those operations which are needed in melting on either a large or small scale, as you might need them. Now I wish to pass on to some other operations which, while related to the operations and power of fires and also to certain kinds of melting, are not wholly connected with the art of casting. First I wish to begin with the actual substance of the art of alchemy, which is sought and desired with so much zeal. Then, as a useful and ingenious thing, I wish to inform you of the art of distilling, and, afterwards, how you should operate a mint in an orderly fashion and without burden on the conscience. Then I shall tell you of the ironworker, the goldsmith, the coppersmith, and some others, as you will be able to see in their places.

Jan 1, 1942

Jan 1, 1959

LIST OF MEMBERS AND ASSOCIATES ARRANGED ACCORDING TO STATES AND TOWNS. ALABAMA. Aldrich, Aldrich, W. F. Anniston, Noble, A. E Bessemer, Fergusson, V. Bir¬mingham, Aldrich, T. H., Jr, Bowron, C. E, Bowron, J., Davis, F H, Dimmick, F. D., Hillman, Ludwig, C. P., McCarthy, M. E, McCormack, G B., McCrery, Ramsay, E, Shook, A. M. Ensley, McDonald, S., Shook, J. W. Gadsden, Lee, R. H., Jr. Gannts Quarry, Hiller, E Helena, Squire, J. Huntsvalle, Moss Le¬high, Toulmin. Ozmoor, Greenamyer, A. G. Rock Run, Garvin, J M. Selma, Saylor, B. F. A. Sheffield, Miller, D, I. Tuscaloosa, Lodge, J. Woodward, Wood¬ward, A. H. ALASKA Coppermount, Wiswell, H. J. Douglas Island, Macdonald, J Ellamar, Stevens, B. Fairbanks, Hamilton, A L Haines, Le Wald, E A. Jualin, Hoggatt, W. B. Juneau, Denby, Hampton, W. H , Thane, B L , Whipple, J. R. Ketchikan, Bar¬ber, J C , Parker, J. L., Reid, G D Nome, Garfield, C D. Snettwham, Tisdale. Teller, Hirshberg, M. R. Treadwell Caty, Kinzie, Stow, H. P. Valdez, Esterly, G. M, Hazelet.

Jan 1, 1910

By Elmer Weber, W. M. Baldwin

Solid lead obeys a single parabolic weight increase vs. time law. In contrast, liquid lead undergoes three successive parabolic weight increases vs. time laws, the first of which has a low constant relative to the latter two. The conversion times for the change from one parabola to the next decrease with increasing temperature. IN recent reports on the subject,1,2 it was noted that zirconium and titanium scale in air by a complex mechanism. The scale first forming on the metal is protective to the extent that it gives a low constant, K, for Tammann's, and Pilling and Bedworth's parabolic equation: w² = Kt [1] relating weight increase, w, due to chemical reaction of the metal with the air, and time, t. After hundreds of hours of apparent stability in some cases the first scale yields to another that offers little protection to the metal. This transition from one scale to another, from a slow parabolic oxidation reaction to a fast one, was not due to impurities in the atmosphere or incidental effects (changing environment, etc.) but was a specific behavior of the metal itself, the transition occurring at definite times (dependent on temperature) and showing other reproducible traits. In view of this behavior how can long-time service behavior be predicted from short-time laboratory tests, not only in the case of these metals, but in any case? Certainly a systematic study of the type of scaling behavior described above—wherever it is found—would help to answer this question. The present paper is a report on the behavior as it is found in lead—the only metal to the authors' knowledge for which the behavior has been described at all, if inadequately, for our present purpose.* At least four oxides of lead are known, of which one occurs in two allotropic forms. They are ß (red) tetragonal PbO stable up to 486°C;8 a (yellow) orthorhombic PbO stable from 486°C up to its dissociation temperature in air at about 2300°C;9 minium or Pb3O4 which from the dissociation pressure data given in Fig. 1 decomposes to PbO at 540°C in air; lead sesquioxide or Pb2O3,; and lead dioxide or PbO2 which, according to Fig. 1, decomposes in air at 400°C to minium. In view of the high dissociation temperature of PbO, lead will scale up to at least its boiling point. Further, it is known that oxygen is almost insoluble in liquid lead.'V his implies a fair probability that an oxide scale would not dissolve in the molten metal and would afford the same protection to lead in the liquid state as in the solid. All of the oxides of lead for which specific gravity data are available are more voluminous than an equivalent weight of metal or a lower oxide from which they might form, hence the scales will be in compression. Lead oxides are known to be ductile, so it would be anticipated that they would form coherent nonporous scales. It is not surprising to learn, then, that both solid and liquid lead scale according to the Tammann, and Pilling and Bed-worth law.14,15 (Gruhl states that at 600°C and above lead oxidizes linearly with time because of "spitting" of the scale.) The parabolic constants K reported by various investigators3,14-16 are badly scattered, however, as shown in Fig. 2. The oxides formed on solid lead were described as being reddish-brown but were not chemically identified by Pilling and Bedworth.15 Gruhl's descripdin³ of the appearance of the scales On his liquid samples indicates that a (yellow orthorhombic) PbO is formed initially on the specimens but gives Way eventually—at least at temperatures below 486 °C— to .ß (red tetraunal) PbO, and that below 540°C minium—Pb3O4 :is firmed at an even later time as an overlay on either the red or yellow PbO. Fig. 3 is a graphical interpretation of Gruhl's description. Gruhl does not indicate any change in the parabolic scaling rate as yellow PbO converts to red. He does indicate that minium reduces the scaling rate, al-

Jan 1, 1953