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By Vsevolod Krivobok

THE re-crystallization of metals has been the subject of much scientific investigation, some of which has resulted in a better understanding of this extremely important and interesting phenomenon. Unfortunately, while many have propounded theories of re-crystallization, but a few have presented experimental evidence as to how it takes place. If this can be determined the question, why re-crystallization occurs, may be answered more definitely. Re-crystallization in single phase metals consists of a complete rearrangement and re-sizing of the grains, of which the structure is composed, while the type of structure remains the same. That is to say, if the structure before re-crystallization is composed of a number of polyhedral grains of different shape and size, a particular spot after re-crystallization will be seen to consist of grains in no way different from the original except in size and shape. The re-crystallized grains may be smaller or larger, depending on the treatment received; and, while the re-crystallization may be brought about by means of heat treatment only in passing through a critical range, yet it is common knowledge that single phase metals subjected to cold working are possessed of a tendency toward re-crystallization, even if the heating does not reach critical range. The study of re-crystallization would, of course, be much easier if we had single crystals of any metal as the original material with which to study the phenomenon of re-crystallization, since it would permit the observation of structural changes at what amounts to enormous magnification, by changing the scale of the specimen. In metals of more normal grain size the crystal boundaries introduce complications, but the process, it may be assumed, is essentially the same. Such an opportunity

Jan 2, 1926

By A. Hultgren, G. Phragmén

Page Outline of Progress of Knowledge and Theories about Gas Evolution in Steel Ingots. and Its Influence on Crystallization and Segregation................ 134 Object of Present Investigation........................................... 148 Theoretical Discussion of Process of Solidification........................... 149 Gas Given Off from Rimming Steel during Solidification................... 149 Equilibrium Diagram of the Iron-carbon-oxygen Alloys................... 151 Solidification of Pure Iron-carbon-oxygen Alloys.......................... 157 Solidification when Carbon Monoxide Is Given Off at Constant Pressure... 157 Solidification when Gas Evolution Is Suppressed....................... 158 Schematic Application on Solidification of Rimming-steel Ingots.......... 159 Influence of Manganese, Sulphur and Phosphorus......................... 160 Experimental work..................................................... 162 Liquid Steel and the Mold Gas......................................... 162 Ingots Investigated and Methods Used.................................. 165 Ingot structure....................................................... 174 Structure of Rim Zone.............................................. 174 Structure of Core................................................... 181 Structures Obtained under Special Conditions of Freezing................ 182 Distribution of Metalloids............................................. 187 Other Observations Made............................................. 192 General Discussion of Solidification Process................................. 195 Condition of Liquid Steel before Casting................................. 195 Rimming Period...................................................... 202 Composition of Rim Zone............................................. 225 Freezing after Top Is Closed........................................... 228 Slag Inclusions and Ingot Scum........................................ 234 Reaction between Gas in Blowholes and Surrounding Solid Steel during Cooling 235 Summary.............................................................. 237 Appendix—Preparation and Etching of Ingot Sections....................... 238 References............................................................. 239 In 1934, Jernkontoret (The Swedish Ironmasters' Association) appointed a committee for the study of the structure of rimming-steel ingots and the various phenomena associated with their solidification. The members of the committee, including those who have joined it later, have been: I. Bohm, B. D. Enlund, B. Kalling, M. Tigerschiöld, S. Wohlfahrt and the authors. The present paper‡ is a somewhat

Jan 1, 1939

By G. Phragmén, A. Hultgren

Page Outline of Progress of Knowledge and Theories about Gas Evolution in Steel Ingots. and Its Influence on Crystallization and Segregation................ 134 Object of Present Investigation........................................... 148 Theoretical Discussion of Process of Solidification........................... 149 Gas Given Off from Rimming Steel during Solidification................... 149 Equilibrium Diagram of the Iron-carbon-oxygen Alloys................... 151 Solidification of Pure Iron-carbon-oxygen Alloys.......................... 157 Solidification when Carbon Monoxide Is Given Off at Constant Pressure... 157 Solidification when Gas Evolution Is Suppressed....................... 158 Schematic Application on Solidification of Rimming-steel Ingots.......... 159 Influence of Manganese, Sulphur and Phosphorus......................... 160 Experimental work..................................................... 162 Liquid Steel and the Mold Gas......................................... 162 Ingots Investigated and Methods Used.................................. 165 Ingot structure....................................................... 174 Structure of Rim Zone.............................................. 174 Structure of Core................................................... 181 Structures Obtained under Special Conditions of Freezing................ 182 Distribution of Metalloids............................................. 187 Other Observations Made............................................. 192 General Discussion of Solidification Process................................. 195 Condition of Liquid Steel before Casting................................. 195 Rimming Period...................................................... 202 Composition of Rim Zone............................................. 225 Freezing after Top Is Closed........................................... 228 Slag Inclusions and Ingot Scum........................................ 234 Reaction between Gas in Blowholes and Surrounding Solid Steel during Cooling 235 Summary.............................................................. 237 Appendix—Preparation and Etching of Ingot Sections....................... 238 References............................................................. 239 In 1934, Jernkontoret (The Swedish Ironmasters' Association) appointed a committee for the study of the structure of rimming-steel ingots and the various phenomena associated with their solidification. The members of the committee, including those who have joined it later, have been: I. Bohm, B. D. Enlund, B. Kalling, M. Tigerschiöld, S. Wohlfahrt and the authors. The present paper‡ is a somewhat

Jan 1, 1939

"Acta Metallurgica" Dennis Carney, '59 Alfred Noble Joint Prize Committee F B Foley, Dec '61 American Association for the Advancement of Science F T Agthe, Dec '59, William L Fink, Dec '60 American Geological Institute Arthur Montgomery, Oct , '59, F C Kruger, Oct '60 American Power Conference J P Weir, T D Hess American Society for Testing Materials

Jan 1, 1959

By O. W. Shimer, D. C. Helms, C. E. Brown

The early history and progress of anthracite stripping, from the first known operation at Summit Hill in 1821 through 1917, was covered in 1917 in a paper by J. B. Warriner,1 then chief engineer, now president of the Lehigh Navigation Coal Co., and stripping methods between 1917 and 1931 were the subject of a paper in 1931 by H. H. Otto,2 of the Hudson Coal Company. The present paper is confined to methods used today on pitching beds in the western middle and southern anthracite fields. The anthracite industry, not unlike other large industries, had been affected for more than a decade by the adverse economic conditions of the country. High development and operating costs and the competition of other fuels caused some collieries to be closed temporarily, while others were permanently abandoned. In order to obtain a larger tonnage at a lower development cost, a larger stripping program was put into effect by many companies. In 1932, stripping operations accounted for 3½ million tons, or 7 per cent of the total anthracite production of the year, and in the next 10 years this increased until more than double that amount, or over 14 per cent of the total production, was from stripping operations. These figures represent the total production of the entire anthracite region; unfortunately, the figures have not been separated from the different fields. There are some operations in the southern and middle western fields where the tonnage obtained from stripping amounts to more than 30 per cent of the total colliery production. Stripping operations on pitching beds present difficult problems. Owing to the various geological formations, a different situation is encountered in nearly every stripping pit; and because of the proximity of an overlying bed, it is very often necessary to load the entire overburden into trucks and haul it out of the pit to the dump area, although back filling and casting is done whenever possible. Beds in the areas described in this paper pitch from 20" to 90° and some are on the invert in many sharp folds and faults. Planning The more successful strippings have had adequate engineering analysis. Some work is being done without much preliminary planning, but many strippings would have failed completely if close supervision by the engineering department had not been maintained. Locations of stripping areas are determined as follows: I. By constructing cross sections over the areas and drilling sufficient diamond-drill or well drill holes to study the strata and to determine the location, thickness and pitch of the beds.

Jan 1, 1946

By Herbert Clark Hoover, Lou Henry Hoover

IN the last book I have explained the methods of delimiting- the meers along each kind of vein, and the duties of mine officials. In this book1 I will in like manner explain the principles of underground mining and the art of surveying. First then, I will proceed to deal with those matters which pertain to the former heading, since both the subject and methodical arrangement require it. And so I will describe first of all the digging of shafts, tunnels, and drifts on venae profundae; next I will discuss the good indications shown by canales2, by the materials which are dug out, and by the rocks ; then I will speak of the tools by which veins and rocks are broken down and excavated ; the method by which fire shatters the hard veins ; and further, of the machines with which water is drawn from the shafts and air is forced into deep shafts and long tunnels, for digging is impeded by the inrush of the former or the failure of the latter ; next I will deal with the two kinds of shafts, and with the making of them and of tunnels ; and finally, I will describe the method of mining venae dilatatae, venae cumulatae, and stringers.

Jan 1, 1950

By Arnold S. Epstein

Tlze green electroluminescence occurring at liquid-nitvogen temperature in epitaxial gallium phosphide diodes is exarnined using the donor dopants silicon and sulfur. Zinc is used as the p-type diffusant. Two tt~ain peaks are found, namely til 0.56 and 0.535 p. The intensity of the gYeen peak occurring at 0.56 is found to oary as -4"' wlzere Jf is the forward current density and to first order appears to be dependent on the concet~tvation of ionized donovs. Tile vadintive lifetinze fov this process is -10-'sec. The intensity of the 0.56-p lu~ninescence is nt least several ovdevs of magnitude greate,, at liquid-nitvogen temperature than that noted jor the 0.538 radiation for current densities up to about 35 amp per sq cm. The variation oj- the intensity of. the 0.538-p peak with current density caries according to the donor dopant. With sulfur as the donor one has a J12 dependence, whereas when silicon is the donov a J1.5 dependence is noted. Tl~e above can be fitted to a In molecular process (in first order) such as a band to band recombination. The constant B fir band to band vecombination) is found from our experitt~etlt to be of the order of 2 CZI cm per sec, zcl~ereas for tlze impurity vecombination peak (0.56 p]) tile A cotzstor~t is of the order of. 7 x 10-' cu cm per sec. The structuve o/. the diodes at liquid-nitvog-en tett~peruture is oj tlze double injection type, and by carefi~lly selecting. the thickness of the structure one can regulate the onset of the 0.538-p radiation. The diode clzavaclevistics follow an I-Vx laiv where x is >1. Llregatiue resistance in these structures con be correlated with saturation of tlze 0.56- peak. ThE development of high-purity, large single crystals of epitaxially grown gallium phosphide is the ultimate aim of the studies to be reported. While a number of papers and reviews' have been presented on properties of gallium phosphide grown from gallium solution and from the melt, less attention has been paid to the properties of epitaxial gallium phosphide grown from the vapor. In the studies to be reported we have examined the effects of shallow donor impurities, primarily silicon and sulfur, at liquid-nitrogen temperature, on both the electrical and green electroluminescent properties of carefully characterized single-crystal epitaxial Gap. I) EXPERIMENTAL PROCEDURES A) Material Preparation and Properties. The samules used in this investigation were single-crystal n-type epitaxial gallium phosphide. he single crystals were synthesized from the elements by vapor transport and epitaxial deposition on single-crystal gallium arsenide substrates. Typical transport agents used were chlorides. The growth procedures are described in more detail in Ref. 2. The samples were grown in the (111) orientation and had thicknesses up to 480 . Following the growth, the GaAs substrate was removed from the epitaxial Gap by etching in nitric acid. The Hall effect and resistivity of these n-type samples were measured as a function of temperature and analyzed for impurity content and compared with spectroscopic emission analysis. The results are given in greater detail in Ref. 3 but a summary is noted in Table I. In Table I, AED denotes the donor ionization energy, Nd is the donor impurity concentration, lvA is the acceptor impurity concentration, NI is the total impurity concentration, Rip vs temperature is the measured Hall mobility-temperature relationship from liquid nitrogen to about 400"K, n(77"K) is the measured carrier concentration at liquid nitrogen, and R/p(77'~) is the measured Hall mobility at liquid nitrogen. Good agreement is noted between electrical and emission analysis for the major donor impurity, silicon, in the two materials where it is a major constituent. In the case of the two samples SC90-6 and AP138-3(111) B which were sulfur-doped the ionization energy found from the electrical data is in good agreement with that reported for sulfur.4 The acceptor impurities are not known, although from the presence of magnesium in the samples as indicated by emission analysis and its known role as an acceptor in GaP,4 magnesium could be present as an acceptor. Similarly, since silicon is known to be an amphoteric impurity4 it may also be present as an acceptor in the Gap.* The *A small band has been noted at 0.625 11 in samples SC90-6, SC76-4, and SC77-4, suggesting according to Ref. 5 that sillcon could be present as an acceptor In these samples since these authors have found this peak to represent a donor-silicon emission. presence of calcium deduced from emission analysis is not correlatable with the electrical analysis and its presence as an electrically active impurity should be questioned. B) Sample Preparation and Diode Fabrication. The original slices were of the order of 2 sq cm in area witi the (111)B face up. The material was cleaved and sectioned and the best pieces selected (i.e., those which visually appeared to have the least strain and defects). The samples were polished, lightly etched, and cleaned in trichloroethylene. Zinc was diffused in a closed tube at 800°C to form a p-n junction. Diodes were made from these samples. The depth of junction varied, but did not exceed 10 p depth. The back side of the slice was lapped back and a low-resistance n-type contact was formed (at 600°C in forming gas) to an Au-Mo tab with a hole in the middle for

Jan 1, 1968

By AIME AIME

Russell B. Paul, Chairman of the Special Committee on Divisional Relationships, presented the interim report of his Committee which was published in the September, 1945, issue of MINING AND METALLURGY and a copy of which is incorporated in the official minutes of this meeting. The following specific actions were taken by the Board of Directors in relation to the six recommendations in the Summary of the Report as published: (1) Mr. Haider, Chairman of the Petroleum Division, presented the formal request of his Executive Committee that the headquarters of the new Secretary of the Petroleum Division be established in Dallas, Texas. After lengthy discussion in which the point was made that the success of this program would depend upon effective co-operation between the Chairman of the Division, the Secretary of the Petroleum Division, and the Secretary of the Institute, the request was approved. The new secretary will be selected by the Division and will be employed by the Institute in the capacity of an Assistant Secretary. (2) The following item in the report was approved:

Jan 1, 1945

By DOOLITTLE E. M.

(Canal Zone Meeting, November, 1910.) The following notes are contributed, not with the idea of offering a complete history of the development of this very important process as applied to the Leadville district, but with the hope that the practice, as it was carried out in the Bi-Metallic Smelter, may still be of interest to others. The Bi-Metallic Smelter, at Leadville, Colo., was the first to make a commercial success of the process described in the following pages, which consisted essentially of smelting raw silver- and copper-bearing sulphide ores in blast-furnaces to form a matte, which was generally re-smelted with siliceous ores for a second high-grade matte. Robert Sticht, in his excellent monograph on the subject,1 has outlined briefly the plant belonging to this company. He says, in effect: The Boulder, Mont., enterprise set the example for others with whom the patentee (w. L. Austin) had been negotiating, and the old La Plata lead-smelter at Leadville, Colo., was fashioned into a crude, temporary experimental plant for the Bi-Metallic Company, and the feasibility of the process demonstrated by a trial run. Subsequently, the plant was considerably improved, and, being supplied with very favorable ores, continued to run without interruption from August, 1892, to June, 1893. In September, 1893, smelting was resumed in a completely remodeled establishment, some $200,000 having been expended upon the new work. Thus, aside from the Montana experiments, which, under the direction of W. L. Austin, began as early as- 1885 2 at Toston, and continued with indifferent success for six or seven years, the Bi-Metallic plant at Leadville may be said to have * Formerly Superintendent, Bi-Metallic Smelting Co. + Formerly Chief Assayer and Chemist, Bi-Metallic Smelting Co. 1 Modern Copper Smelting, E. D. Peters, 7th ed., p. 415 (1895). 2 Trans., xvi., p. 259 (1887-88).

Dec 1, 1910

By J. W. Powell, F. H. Spedding

A complete review of the use of chelating agents in the sepa ration of rare earths by ion-exchange is given as well as a concise description of the recent pilot-plant operations of the Ames Laboratory. The two chelating agents which show the greatest promise are ethylenediamine-N,N,N',N'-tetraacetic acid and N'-(2-hydroxyethyl)ethylenediarnine-N,N,N '-triacetic acid. The first successful separations of rare earths by ion exchange were reported in a collection of papers which appeared in the November, 1947, issue of the Journal of the American Chemical Society.1'9 Some of this work was performed at the Ames Laboratory of the A.E.C., the remainder at the Oak Ridge National Laboratory. The processes developed at Oak Ridge, as well as some of the early Arnes methods, employed 5 pct citric acid-ammonium citrate eluant at low pH and were carried out on either H+-state or NH:-state resin beds. These techniques were successful for the separation of small quantities of either naturally occurring or radioactive rare earths and are still used for the isolation of rare-earth activities from fission products. Concentrated citrate is not economical, however, for use in moderate or large-scale rare-earth separations. For this reason, the Ames Laboratory turned its attention to lower concentrations and higher pH's in order to make more effective use of the eluting agent.10-14 Although elutions have been performed successfully over a wide range of conditions, 0.1 pct citrate at a pH of 8.0 is highly recommended for use on H+-state resin beds.15,16 Elu-tion with 0.1 pct citrate in the pH range from 5 to 9 brings about the separation of the constituent rare earths into a series of flat-topped elution bands which progress down the resin bed, head to tail, without actually pulling apart as do the rare-earth peaks which develop when trace quantities are eluted with 0.25M (5 pct) citrate at low pH's. Because of this, elution with 0.1 pct citrate at pH 8.0 do not produce pure rare earths unless sufficient quantities are present to provide developed bands which are at least several inches long on the columns. Although other eluting agents have proved more effective than citrate solutions, articles concerning the use of citric acid for separating rare earths still appear in the literature occasionally. For example, Ketelle and Boyd17 reported some further studies on the separation of rare earths with 5 pct citrate in 1951. They used 270 to 325 mesh Dowex-50 columns at 100°C and a pH of 3.28. vickery18 compared the effectiveness of a number of eluants for the separation of rare earths on NH+4 state Dowex-50 in 1952. He found that citric acid was more efficient than acetic, malic, tartaric, and aminoacetic acids. In 1953, Mayer and Freiling18 reported that citrate was inferior to malate, glycolate, lactate, and EDTA for the resolution of Sm-Eu and Y-Tb mixtures on 250 to 500 mesh, NH+4-state, Dowex-50 at 87°C. pinta20 used 5 pct citrate in the pH range 2.8 to 3.4 to obtain some rare earths for analytical work the same year. Trombe and Loriers21 reported the use of citric acid in their laboratory to separate rare earths in kilogram quantities. Lariers and Quesney22 reported some separations with citrate in 1954. They used 5 pct citrate at pH 2.8 to separate yttrium and the yttrium-group rare earths from the cerium-group rare earths. briers23 used 5 pct citrate at pH 3.2 and 90°C as late as 1956 to isolate thulium in fair purity. For the separation of tracer quantities of rare earths, Mayer and Freiling19 have recommended pH 5.00, 0.24M lactate at 87 °C on 250 to 500 mesh, NH+4-form Dowex-50. Freiling and Bunney24 have also employed lactic acid for the separation of fission-product rare earths. Cunninghame, Size-land, Willis, Eakins, and Mercer25 have reported a 4-hr separation of Y, Eu, Sm, Pm, Nd, and Pr with 1M lactic acid at pH 3.25 on Zeokarb-225 at 87°C. Stewart, et al.,26 reported separation factors for rare earths distributing between Dowex-50 and 0.25M glycolic acid. stewart27 also reported a 30-61 separation of Y, Tm, Er, Tb, and Lu tracers with buffered, 0.25M glycolic acid containing 0.05 pct Aerosol OT. The resin bed was 400-mesh Dowex-50 (X12). The pH of the ammonia-buffered eluant was 3.5. Various aminopolyacetic acids have also been used to obtain varying degrees of separation of the rare earths. In 1951, Fitch and Russell28 investigated iminodiacetic acid (IDA) and nitrilotriacetic

Jan 1, 1960

By C. A. Gibbons

AFTER nine years of extremely de- pressed business, marked mostly A with red ink on the balance sheets of most coal companies and with an increasing internal competitive struggle for diminishing markets, somewhat of a change appeared during 1939. Shipments increased and prices generally firmed, giving the coal industry increasing optimism and encouragement for the future. Specifically, it now appears that bituminous coal production for 1939 will approximate 378,000,000 tons, and anthracite production will approximate 47,500,000 tons, bituminous production being around 14 per cent ahead of 1938 and anthracite production 12 per cent better. The curve on p. 31, showing both bituminous and anthracite production, furnished by the bituminous coal division of the Department of the Interior, shows graphically most of the 1939 monthly production and clearly illustrates the increased production.

Jan 1, 1940

By J. R. FINLA

THE three great war periods of recent times involving the-chief industrial, commercial, and military nations of the world have been the following: 1. Wars centering around the French Republic and Napoleon Bonaparte, .1791-1815;. involving every nation in Europe, parts of Asia Minor and *North Africa., and the United States of America. 2. Wars in Europe, Asia, and North -America beginning with the Crimean War, 1854-56, the British Empire, France, Sardinia, and Turkey against Russia; the Sepoy rebellion in India, -1857; -war of France . and Sardinia against ..Austria in Italy, .185.9; :the Taiping rebellion in China, 1861; Civil War in , America, 1861-65; French. occupation .of .M Mexico, .1863; Prussian war against :Denmark, :1864; (Prussia and Italy against Austria sand various -south German : states, 1866; :the Franco-German War, 1870.7,1.

Jan 1, 1931

By OTTO HERRES

TITANIUM is estimated to be the ninth most plentiful element, ranking after iron, aluminum, and magnesium, and ahead of copper, lead, and zinc. Vast quantities of titanium are widespread throughout the world in ore deposits and beach sands. Before the war, processing plants were operated in England, France, Italy, Czechoslovakia, Norway, Russia, Australia, United States, and Japan. In spite of its widespread occurrence, however, the U. S. Department of Justice has held the titanium industry to be a world monopoly and action was taken in the Federal court during the summer of 1945 to enjoin international patent and marketing agreements and to restore free competition. Possibly the rather surprising lack of public familiarity with this industry of international importance arises from its astonishingly rapid development and growth in the strong hands of some of the greatest chemical companies in the world, including the important foreign companies, Imperial Chemical Industries (British), Montecatini (Italian), I. G. Farben (German), and Titan Kogko Kabushiki Kaisha (Japanese). The rapid growth of the titanium industry in the United States is indicated by a tenfold increase of ore imports in the 1930 to 1940 decade before the war began to affect shipments from overseas. The fact that the industry formerly derived practically all ore for chemical processing in American plants from foreign sources probably also accounts for lack of general public knowledge of titanium. In 1939, to meet the requirements of increasing demand for the white pigment. titanium dioxide, more than 250,000 tons of titanium concentrates moved to this country, principally from the Travancore coast of India where the ilmenite concentrate from the beach sand runs as high as 60 per cent in titanium dioxide. Global warfare put a stop to shipping and thus gave rise to the development of titanium mining on a substantial scale in the United States during 1941.

Jan 1, 1946

"Located at Canyon Ferry on the Missouri River, 17 miles from Helena and 63 miles from Butte. River drainage area 15,570 sq. miles. Built in 1898.DAM: Rock-filled, wooden crib, 490' long and 39' feet at maximum head; also masonry core, earth bulk-head 300' long and granite masonry abutments.SPILLWAY: 473' long, crest elevation 3660.5; steel flashboard system 10' high.PENSTOCKS: 10 main penstocks, 12' diam., about 40' long, leading from canal to turbines, each supplying 1 pair turbines.WHEELS: 4 main center discharge, horizontal units, each 1 pr. of 42"" wheels made by Dayton Globe Iron Works, and 6 main units, each 1 pr. of 45"" wheels made by S. Morgan Smith Co., all 157 r. p. m., normal head 34', and direct coupled to generators.GENERATORS: 10 W. E. & M. Co., Kodak Type, revolving armature, 750 k-w., 157 r. p. m., 550 v., 3 phase, 60 cycle alternators.OPERATION: The plant has large water storage and can carry peak loads to 12,000 h-p. It is the central control station for the system."

Jan 1, 1913

By S. T. Wlodek

The scale md subscale reaction products were identified and their rates of formation were studied in air over the range 1600" to 2000°F (871 " to 1149°C) for periods of up to 400 hr and for hoth the solution-annealed and aged conditions. The effect of prior sltrface preparation on suhscale oxidation was also studied The general oxidation behavior of both Ni-Cr-Mo-Al-Ti type alloys was similar. A surface film of a, Al2O3, forms immediately on exposure Subsequent oxidation continued at a linear rate (QL = 55 * 5 kcal per mole) as colonies of Cr2O3 nucleated at the A12O3/gas interface Further oxidation proceeded at a paraholic rate zvhiclz could he fitted to two successive rate constants. During paraholic oxidation, and depending on temperature, the scale consisted of Cr2O3, NiCr2O4 , and TiO2 with traces of NiO. In the case of Rene 41, the activation energy of both paraholic processes was 66 * 3 kcal per mole suggesting that diffusion of cations tlzrozrgh Cr2O3 was the rate -determining process. An unusual decrease in the oxidation of Udimet 700 at 1900°F where a spinel of Ni(A1,Crh0, zuas the predominant reaction product prevented the accurate assignment of activation energies for this composition. In both alloys internal oxidation of Al2O3 commenced shortly after parabolic scaling was observed. Prolonged exposure prod7tced intemal oxidation of TiN, and in Udimet 700 a complex Mo-Ni nitride was also found. At 1900oF, the subscale reactions in Udimet 700 undergo an inversion which parallels the decrease in surface oxidation; internal oxidation ceases hut is replaced by the formation of "spherodized" 3.' colonies. Surface-preparation techniqtles which introduce appreciable working, such as coarse surface grinding or grit blasting. increase the amount of alloy depletion and internal oxidation in Reni 41. The reverse is true of Udimet 700 for which electropolished or mechanically polished specimens show much more subscale oxidation than strongly worked stirfaces. The strongest commercial nickel-base alloys presently available are generic to the Ni-Cr-Mo-A1-Ti base which exploits the precipitation of Ni3(A1,Ti) as the main strengthening mechanism, while relying on solid-solution strengthening by molybdenum and chromium reinforced by the pre- cipitation of carbides to attain maximum properties. This study characterizes the oxidation behavior of Rene 41, the strongest alloy of the Ni-Cr-A1-Ti type commercially available in sheet form, and Udimet 700, whose higher aluminum and titanium content allows it to exhibit one of the more attractive combinations of high-temperature properties available in a wrought product. The scaling processes of complex, type nickel-base alloys have received relatively little attention. Malamand and vidal as well as Poulignier et al.2'3 have determined the composition gradients across the metal/oxide interface produced by high-temperature oxidation and considered the effect of surface perature, Limited weight-gain data has also been published by Fere 5 for alloys of this type and Radavich6 has identified the reaction products on Udimet 500 and Inco 702 after oxidation at 1832°F. Reference can, of course, be made to the excellent reviews of Kubaschewski and Hopkins7 or Ignatov and Shamgunova8 for a summary of the data available on the oxidation of binary and ternary alloy systems which are related to the more complex alloys considered here. EXPERIMENTAL The analyses of the different commercial heats studied are given in Table I. Using the experimental procedures previously established,9 continuous weight-gain data were obtained on both heats of Rene 41 sheet (A and B) and 150-mil-thick slices of cast Udimet 700. Subscale oxidation reactions were followed by static exposure of cylindrical specimens obtained from swaged Rene 41 (Heat C) and Udimet 700 (Heats E and F). In brief, continuous weight-gain tests were performed on specimens with a surface area of 10 to 12 sq cm. These were abraded through 600 grit Sic paper, electropolished to 2p rms in an electrolyte of 10 pct H2So4 in ethanol, and lightly etched in 10 pct HCl in ethanol before final washing and rinsing in ethanol. All continuous weight-gain data were obtained in dried (-70°F dew point) flowing (1 liter per min) air to an accuracy of +0.1 mg. Subscale oxidation processes were followed by the metallographic examination of 0.5-in-diam by 1.0-in.-long specimens. After an initial center-less grinding, various additional surface treatments were employed to determine the effect of surface preparation on subscale oxidation processes. Before exposure in zirconia crucibles, all samples were lightly etched in 10 pct HCl-ethanol, washed in ethanol, and dried. The depth of internal oxidation was measured to ±0.00025 in. on unetched specimens mounted so as to provide a taper mag-

Jan 1, 1964

By Earnshaw Cook, H. S. Avery, J. A. Fellows

TEe increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni; 16 per cent Cr, 35 per cent Ni; 12 per cent Cr, 60 per cent Ni; etc.) in recent years has been accompanied by continued demands by the consumer for improvement in properties. The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties. To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created. It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloys presented in a companion paper. The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized. The Creep Test Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure. The creep-test iaboratory constructed for the American Brake Shoe and Foundry Co. is designed to permit I000-hr. tests in the temperature range of I200° to 2 200°F. with a choice of applied stress extending from jo to 50,000 lb. per sq. in. in increments of 50 lb. per sq. in. To simplify the calculation of weight combinations, the loading beams (Fig. I) are provided with counterweights to eliminate the tare. The precision of the knife-edges (10:I ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a I-gram weight attached to the loading shackle. Check of the loading weights proved the maximum error to be 0.06 per cent. Axial alignment is provided by crossed knife-edges in the grip seats. The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U.S. Steel Corporation. An 80 per cent Pt, zo per cent Rh No. 19 B. and S. gauge wire is used as the heating element. The details of -construction are shown in the radiograph reproduced in Fig. 2. The windings are held in place on an alundum tube with aludum cement; the distribution of turns is adjusted to give a maximum temperature gradient of , I°F. over a 4-in. gauge length (Fig. 3). To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length. Sixteen-inch coupons are used „ to reduce the temperature of the threaded joints and thus to facilitate removal from the grips. Thermal losses are minimized by refractory insulators cut to shape and surrounded by diatomaceous ear,th. The taps

Jan 1, 1942

By J. A. Fellows, Earnshaw Cook, H. S. Avery

TEe increased use of heat-resistant alloys (26 per cent Cr, 12 per cent Ni; 16 per cent Cr, 35 per cent Ni; 12 per cent Cr, 60 per cent Ni; etc.) in recent years has been accompanied by continued demands by the consumer for improvement in properties. The manufacturers of these materials, of necessity, have resorted to more critical studies of the basic causes of variations in fundamental properties. To keep pace with the need for augmented information, previous techniques of investigation have been refined and new test methods and instruments created. It is the purpose of this paper to describe the apparatus, experimental technique and precision of measurement that were employed in the exploration of properties of heat-resistant alloys presented in a companion paper. The detailed precautions in experimental procedure essential for attainment of accurate and comparable data at elevated temperatures cannot be too highly emphasized. The Creep Test Since the fundamental concepts of creep testing have been recognized for the past 20 years, present interest is restricted to refinements in equipment and experimental procedure. The creep-test iaboratory constructed for the American Brake Shoe and Foundry Co. is designed to permit I000-hr. tests in the temperature range of I200° to 2 200°F. with a choice of applied stress extending from jo to 50,000 lb. per sq. in. in increments of 50 lb. per sq. in. To simplify the calculation of weight combinations, the loading beams (Fig. I) are provided with counterweights to eliminate the tare. The precision of the knife-edges (10:I ratio) is such that a 10-gram weight placed on the upper specimen grip will be exactly balanced by a I-gram weight attached to the loading shackle. Check of the loading weights proved the maximum error to be 0.06 per cent. Axial alignment is provided by crossed knife-edges in the grip seats. The furnaces are similar in design to those of Crane and Company, Battelle Memorial Institute, and the U.S. Steel Corporation. An 80 per cent Pt, zo per cent Rh No. 19 B. and S. gauge wire is used as the heating element. The details of -construction are shown in the radiograph reproduced in Fig. 2. The windings are held in place on an alundum tube with aludum cement; the distribution of turns is adjusted to give a maximum temperature gradient of , I°F. over a 4-in. gauge length (Fig. 3). To avoid sharp temperature differentials at the ends of the test section, the length of the furnace is four times the gauge length. Sixteen-inch coupons are used „ to reduce the temperature of the threaded joints and thus to facilitate removal from the grips. Thermal losses are minimized by refractory insulators cut to shape and surrounded by diatomaceous ear,th. The taps

Jan 1, 1942

By W. C. PAGE

HARVEY S. MUDD has the unusual distinction of having virtually inherited a Directorship in the -A.I.M.E., for he was appointed to the Board to fill the unexpired term of his father in 1926. Since then he has served as a Director continuously until 1936, and now he is a candidate for Vice-President. One of the first words that young Harvey tried to say was "ore," for he was born in Leadville, Colorado, in the heyday of that camp, where Seeley W. Mudd for years ran the Small Hopes mine. Stanford and Columbia gave him his mining education, and the Shattuck-Arizona, at Bisbee, his first job. Afterwards he examined many

Jan 1, 1937

By AIME AIME

SHORTLY after he started his professional career, the subject of this sketch acquired the sobriquet "Moose" Allen. At the time he was engaged in geological exploration it1 the Canadian wilds. The nickname was given .him because of the wide, straight trail that he broke with unusual speed when going through the bush. Like a moose he was strong, energetic, and determined. To a considerable degree, Rolland Craten Allen today displays the same characteristics in larger affairs-business, civic, and professional. It is his habit to study a problem thoroughly, to decide u11on the best course of action, and then to pursue that course with vigor and

Jan 1, 1936

By W. M. Albrecht, W. D. Klopp, R. I. Jaffee, B. G. Koehl

Kinetic studies were made of the reactions of tantalum with oxygen, nitrogen, and air at 400o to 1500°C. The tantalum-oxygen reaction is linear from 500° to 1250°C. The tantalum-nitrogen reaction follows a cubic rate law at 400° to 700°C and a parabolic rate law at 800" to 1475°C. The reaction behavior in air is initially parabolic followed by a transition to linear behavior. In the search for high-temperature materials, considerable interest is being shown in the refractory metal, tantalum. It is the third highest melting metal with a melting point of 2996°C. Also, tantalum has excellent ductility, making it one of the most workable refractory metals. In considering high-temperature applications of tantalum, the oxidation kinetics of the metal must be known. Such information also serves as a basis for the development of corrosion resistant tantalum-base alloys. Therefore, this study was made to investigate the reaction of tantalum with air, nitrogen, and oxygen. LITERATURE Several oxides of tantalum have been reported. The pentoxide, Taz05, is the only oxide of tantalum whose identity has been established. A high-temperature modification, aTa2Os, has been reported by several investigators.1-4 A low-temperature phase, ßTa2O5, undergoes an allotropic transformation at 1320o to 1350oC. 5-8 Four other oxides of tantalum have been reported. The oxides TaO2, TaO, and Ta4O have been reported by schonberg.9 A suboxide Ta2O, was observed by Wasilewski 6. However, the presence of oxides lower than Ta2O5 is questioned by Lagergren and Magneli.7 In oxidation studies, vermilyeal0 and Peterson, et al.,12 reported one possible phase intermediate between Ta and Ta2O5. Only Ta2O5 was formed in the tantalum air reaction, as reported by Michae1.l3 Several studies have been made on the kinetics of the tantalum-oxygen reaction. vermilyeal4 investigated the range 50° to 300°C and found that the rate of growth of a thin adherent oxide film could be described by the Cabrera-Mott theory. Gulbransen and Andrew15,18 studied the reaction kinetics of tantalum in oxygen pressure of 1/10 atm at 250° to 450°C. At all temperatures the reaction followed the parabolic rate law for periods up to two hours. The oxidation behavior in the range 500" to 1000°C was found to be linear at oxygen pressures of 0.2 to 600 psi according to Peterson. et al.l1 At very low pressures (1 x 10-3 to 2 X lo-' mm of Hg) Gebhardt and seghezzi17 reported linear oxidation at 800° to 1500°C. The reaction of tantalum with air is similar to the reaction with oxygen. Studies have been made by Waber, et a1.,12 and Michae1.l3 Two nitrides of tantalum, TaN and Ta2N are known. Their structures have been determined by Brauer and Zapp 18,19 The tantalum-nitrogen reaction kinetics have been investigated by Gulbransen and Andrews. 15, 16 The reaction follows the parabolic rate law at 500° to 850°C at a nitrogen pressure of 1/10 ,atm. At the same temperature, the tantalum-nitrogen reaction is much slower than the tantalum-oxygen reaction. EXPERIMENTAL TECHNIQUES Material— The material used in this study was high-purity, electron-beam-melted tantalum obtained from the Temescal Metallurgical Corp. The hardness of the as received ingot was 76 Vhn. The analysis of the material is given in Table I. Methods—Cylindrical specimens of tantalum approximately 0.9 cm in diam and 0.5 cm in length

Jan 1, 1962