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By R. M. Hudson, P. E. Perry

Weight-gain data obtained by nitriding low-carbon sheet steel in an amrnonia CNH,) atmosphere indicated that the process obeyed a parabolic rate law. The calculated actization energy for nitriding in the range 964" to 1268°F agreed reasonably well with published data. At 1358"F, rate data indicated that the activation energy decreased. Weight-gain data obtained by uszng mixtures of NH3 -Nz at 1268°F containzng jrom 10 to 100 zol pct NH3 also obeyed a parabolic rate law. The rate of 'nitriding increased with an increase in the NH3 content of the gas Mixture. It is well-known that steel heated in gas mixtures containing ammonia (NH3) takes up much larger quantities of nitrogen than steel heated in nitrogen, both gases having a total pressure of 1 atm;' this phenomenon can presumably be attributed to the catalytic decomposition of NH3 on the steel surface to furnish nascent (monatomic) nitrogen. This process was studied bv Brunauer. Jefferson, Emmett, and Hend-ricks at furnace temperatures of 752" and 831°F2 using mixtures of NH3 in Hz. Englehardt and wagner3 reported that, at a furnace temperature of 914°F and under their experimental conditions, both nitriding and denitriding were controlled by the rate of gas-metal reactions at a steel surface rather than by the rate of diffusion of nitrogen in iron. The present study was undertaken to obtain information on the kinetics of nitriding low-carbon steel strip at higher temperatures so that practical rates for short-time strip-annealing treatments could be estimated. Variables studied included time: temperature, and NH, content in the annealing atmosphere. Mechanical and chemical characteristics of steel nitrided in this manner will not be considered in the present article. MATERIALS AND EXPERIMENTAL WORK The samples used were from a commercial low-carbon steel, 0.0244 cm thick, in the cold-reduced condition. The chemical composition of this steel is given in Table I. Panels were cut to 5.1 by 17.8 cm, degreased in toluene, and weighed just before treatment. Four specimens were nitrided under each of the experimental conditions. A study was made of the nitriding rate of steel in a 100 vol pct ammonia atmosphere, 740 mm pressure, at five specific temperatures within the range 964" to 1358°F. The nitriding rates of steel in ammonia-nitrogen gas mixtures containing 10, 18, 26, 50, and 100 vol pct ammonia, 740 mm total pressure, at 1268°F were also determined. All atmospheres used were dried by successively passing them through drying towers packed with soda lime and with Linde Molecular sieve Type 4A. Quoted gas compositions refer to those entering the furnace. Specimens were held in the constant-temperature zone of a vertical annealing tube furnace for times of 14, 3, 5, 10, or 15 min. Gas flow rates were maintained at 3.8 cu ft per hr, which was nineteen volume changes per hour for the system used. The rate of flow was selected to provide a high level of free NH3 for cracking on the steel surface where the ammonia gas is most effectively used as a nitriding agent. The vertical annealing tube furnace consisted of a Hevi-Duty tube furnace with a 2 1/2-in.-ID mullite ceramic high-temperature tube. The constant-temperature zone (controlled within 10°F) was about 10 in. long. After each specimen was degreased, a hole was punched in one end, for attaching the specimen by hook to a chain so that it could be lowered into or raised from the high-temperature portion of the tube by means of a power-driven winch. A stainless-steel access port with O-ring seals was connected by suitable glass-to-metal seals to the cool upper portion of the furnace tube. After the weighed specimen was placed in the access port, the furnace tube was evacuated to approximately 10"3 torr, and then the system was flushed thoroughly with the atmosphere under study. When the gas flow rate and constant-temperature zone of the furnace were established, the specimen was lowered into the constant-temperature zone. The atmosphere flowed from the top to the bottom of the vertical furnace tube and was then vented. For all these runs, during the first 3 min of the time the specimen was in the constant-temperature zone of the furnace the specimen was heating up to the tempera-

Jan 1, 1970

By Morgan Walker

Intermittent injection of gas in gas-lift pumping is a variation of the common practice in that the gas is delivered to the well for a short period, called the "on time," followed by a period during which none is admitted, called the "off time," instead of being admitted continuously at a constant rate or by intermittent flowing in which it is occasionally delivered to the well in just sufficient quantity to flow off the accumulated head of fluid. The term "gas" is used throughout this discussion but it should be remembered that in so far as the operation is concerned either air or natural gas may be used. The equipment at the well is the same as commonly used in gas-lift installations and gas may be admitted to either the tubing or the casing. It seldom occurs that all the wells on a lease can be pumped economically by intermittent injection from one header. Wells that have flow characteristics which permit their being handled together have their intake lines grouped at a central compressor station. Well groups may consist of two or more wells. The total volume of gas delivered by each group of compressors goes to one well at a time through a quick opening valve, each well connected to the header receiving its charge of gas in turn. Special cases may require a deviation from this arrangement. The distribution of the gas to the different wells is effected by an automatic timing device which operates quick-opening valves on the intake lines. The timing mechanism may be actuated by electricity, liquid or gas pressure, The essential factor in the operation of the timing mechanism is that as one intake valve is closed another must be opened. Water-operated Timing Device Timing devices operate the intake valves either directly, or indirectly by pilot valves. Of the former type one that is operated by water and has given satisfactory service is shown in Fig. 1 and can be made on the lease. The horizontal cylinder is a piece of 10-in. casing about 7 ft. long, closed at each end and free to oscillate about a fulcrum at the center.

Jan 1, 1929

By K. K. Clark, W. H. Somerton

The feasibility of reducing pressures needed to fracture formations by heating the borehole intensively has been investigated on a laboratory scale. Reductions in fracture pressures of heated Bandera, Berea and Boise sandstone cores were observed at various confining pressures, simulating reservoir stress conditions to a depth of 5,000 ft. Both permeable and impermeable borehole boundary conditions were tested. Three heating conditions were used in the tests. One group of samples was heated in a furnace to a temperature of 600C, cooled to room temperature., and then tested for fracture pressures. Two other groups of samples were heated with a borehole heater to maximum borehole wall temperatures of 625 and 792C, then cooled and tested. In all cases, heated samples showed substantial reductions in fracture pressures compared to unheated samples. The higher temperature borehole heated samples showed the greatest reduction, amounting to 70 per cent in the extreme case. In actual application to wells, it was concluded that fracture pressures may be reduced by 20 to 50 per cent by intensive borehole heating before fracturing. INTRODUCTION Hydraulic fracturing of oil and gas wells is an accepted and effective technique for increasing well productivity in many areas, but is notoriously unsuccessful in other areas. The technique becomes less interesting for production stimulation purposes when excessive fracture pressures are necessary. Formations which do fracture but require high pressures, probably form horizontal fractures. There is good evidence to indicate that some formations do not fracture at all, but yield plastically under high pressure. Thus, any technique which will make formations easier to fracture or will reduce fracture pressures is potentially interesting to petroleum producers. Horizontal fractures generally occur in planes of weakness, such as bedding planes, and at pressures equaling or exceeding the effective overburden stress. In the unusual case where planes of weakness do not exist, a slightly higher pressure must be applied to overcome the tensile strength of the rock. In general, high fluid-loss fracturing fluids are conducive to the formation of horizontal fractures.1 Vertical fractures, when they do occur, are initiated at pressures generally lower than overburden pressure and are favored by low fluid-loss fracturing fluids or impermeable boreholes. The pressure necessary to create a vertical fracture in an impermeable, elastic medium can be predicted from the so-called "thick-walled cylinder" equation: Pf = 2 or+ st.............(1) where pf = fracture pressure or = radial stress st = tensile strength of medium. This equation indicates that to fracture it is necessary to overcome a tangential compressive stress, induced by and equal to two times the radial confining stress, plus the tensile strength of the medium. If the above equation held strictly true for rocks, very little could be done to reduce fracture pressure. The tensile strength of the rock might be reduced somewhat, but any change in st would be small compared to the magnitude of the tangential stress at reasonable subsurface depths. Laboratory tests have shown that actual fracture pressures exceed values predicted from Eq. 1 by factors of 1.4 to 28.6.1,2 Eq. 1 thus does not properly describe the

Jan 1, 1966

On the following pages are abstracts of papers published by the Institute during the year 1934 as TECHNICAL PWLICATIONB, CONTRIBUTIONS, m bound volumes and in MINING AND METALLURGY. For abstracts of papers that appear In bound volumes in 1934 but that were published as TECHNICAL PWLICATIONS m 1932 or 1933, see the TRANSACTIONS for 1932 and the YEAR BOOK dated January, 1934. Many of the TECHNICAL PWLICATIONS have been reprinted In bound volumes Information regarding this disposition, and number of pages in each paper, may be found m the list beginning on page 92 Volume numbers are given as listed at the beginning of the index, page 99 The abstracts are grouped as follows:

Jan 1, 1935

By H. L. Riley, B. W. Gandrud

A froth flotation unit was added to the DeBardeleben Coal Corporation's Empire washer at Empire, Alabama, in the fall Of I94O following an investigation of possible ways and means of recovering coal values from settling-tank overflow or slurry. Officials of the DeBardeleben corporation hoped that some practical and reasonably economical way could be found for recovering fine coal from overflow water, although there had as yet been very little progress along this line in the Alabama coal fields. The Bureau of Mines was asked to cooperate in the project through its Southern Experiment Station, at University, Alabama. This paper presents a brief description of the process and the installation that resulted from the investigation of the overflow water or slurry problem at the Empire mine. The experimental data include' as a Part of this Paper were obtained during the course of the investigation in 1940 Since that time, however, the flotation unit has been running more or less continuously without significant operational changes and is still Performing pretty much in accordance with the data obtained in 1940. Flowsheet at Empire and Type of Coal Treated The Empire mine is developed on the Black Creek bed near the the border of the Warrior field. The coal in this bed is extremely low-ash and although there is an almost complete absence of bone coal and partings, the bed is so thin that, with mechanized mining, a high percentage of rock from roof and floor inevitably gets into the run-of-mine coal. The thickness of the Black Creek bed throughout the part of the Warrior field in which it is mined extensively is rarely over 30 in. and probably would average about 25 in, the coal is of the high-volatile A rank and of excellent quality, but as a result of admixture of roof and floor material, the run-of-mine product usually contains I ; to 20 pct rock by weight. he following is a proximate analysis on an "as-received " basis of a typical seam sample from the Empire mine:' moisture, 3.0 pet; volatile, 34.6 fixed carbon 58.3; ash, 4.1 This sample shelved 15,070 Btu per pound and 0.9 pct sulphur on a moisture-and-ash-free basis. In the Empire preparation plant the lump sizes above 3 in. are removed and hand-picked on a Marcus conveying Screen, the 3 to ? -in. size is removed by vibrating screens and washed in two Montgomery single-cell jigs, and the ?-in. to o slack is cleaned on four diagonal

Jan 1, 1949

By J. T. Crawford

Although nearly 10 pct of the total tonnage of coal produced annually within the United States is handled by bulk freighters on the Great Lakes, very little of the detail connected with it has been published other than occasional newspaper stories and publication of tonnage statistics. Of the total tonnage floated on the Lakes each year some 10,000,000 is stored and distributed from the port of Duluth-Superior, at the western end of Lake Superior commonly known as the Head of the Lakes. This port has the largest single area concentration of coal docks in the world. Since this area contains the largest ore docks, the largest movable material handling bridge, the largest and highest grain elevator and the largest coal bri-quetting plant in the world, it is entirely fitting and proper that here also should be located the largest coal dock and what we believe to be the world's largest clam shell. Of the sixteen coal docks operated by ten companies, five are owned and operated by the North Western-Hanna Fuel Co. which has two docks on the Superior, Wis., waterfront and three docks in Duluth, Minn. It is with these five docks that we are primarily concerned, General History In the summer of 1871 a small sailing vessel entered the harbor of Duluth-Superior with the first commercial coal cargo. All the coal brought up that first year did not amount to more than 3000 tons. During the year 1877 the first dock equipped for handling coal was built in Duluth. Coal receipts increased to 52,785 tons in 1879 the first year for which an official record was kept. Since then the volume of water-borne coal to the Head of the Lakes steadily increased to a maximum of 12,688,321 tons in the year 1923. This tonnage was nearly equalled in the year 1927 and the next highest tonnage recent year was in 1946 when 10,105,703 tons were unloaded. The average annual bring-up over a ten year period 1938 to 1947 was 8,605,231 tons. Approximately 30 pct of the coal unloaded at the Head of the Lakes is handled over the docks of the North Western-Hanna Fuel Co. Competition of other fuels coupled with expansion of coal fields in the mid-west have held coal receipts for Duluth-Superior at a relatively constant figure during the last eight years although the total tonnage of coal floated on the Great Lakes has more than doubled in the past 25 years. From the shovel and wheelbarrow method of unloading early cargoes to the horsepowered windlass derrick with a wooden tub was but a short step. The first movable coal handling, steam operated,

Jan 1, 1949

By John C. Branner

Five of the geologic horizons that yield oil in other parts of the world are represented in Brazil; namely, the Devonian, Carboniferous, Permian, Cretaceous, and Tertiary. Thus far, the first two have shown no evidences of being oil bearing within Brazilian territory. Not enough exploring has been done to permit trustworthy comparisons of the relative importance of the Permian, Cretaceous, and Tertiary as oil-bearing horizons in this country. The most important, indeed almost the only, information available relates to the locations of the areas and to the structural features of the several horizons. The theories regarding the physical conditions under which these rocks were laid down, however, I regard of the utmost importance. Permian Rocks of Permian age cover an enormous area in Brazil, extending from Rio Grande do Sul to Maranhao on the north, and to Matto Grosso on the west. These Permian rocks in many places are known to include oil-bearing shales and in some locations contain small veins of gilsonite. The geologic map of Brazil shows that the Permian area is widely distributed, but there is considerable doubt about the origin of some of the rocks. Some of the lower Permian beds in southern Brazil contain marine fossils, but in Minas no fossils have as yet been found in them, and in Bahia, at only one locality have a few Permian plants been found. Indications of oil have been found in the states of Sa0 Paulo, Parana, and elsewhere farther south, but wells drilled in the Permian of SaO Paulo near the Morro do Bofete did not find oil. One well has been started, by the Brazilian Government, in the Permian of Parana near Marechal Mallet, close to latitude 26" south, but thus far oil has not been found.

Jan 1, 1923

By John C. Branner

Five of the geologic horizons that yield oil in other parts of the world are represented in Brazil; namely, the Devonian, Carboniferous, Permian, Cretaceous, and Tertiary. Thus far, the first two have shown no evidences of being oil bearing within Brazilian territory. Not enough exploring has been done to permit trustworthy comparisons of the relative importance of the Permian, Cretaceous, and Tertiary as oil-bearing horizons in this country. The most important, indeed almost the only, information available relates to the locations of the areas and to the structural features of the several horizons. The theories regarding the physical conditions under which these rocks were laid down, however, I regard of the utmost importance. Permian Rocks of Permian age cover an enormous area in Brazil, extending from Rio Grande do Sul to Maranhao on the north, and to Matto Grosso on the west. These Permian rocks in many places are known to include oil-bearing shales and in some locations contain small veins of gilsonite. The geologic map of Brazil shows that the Permian area is widely distributed, but there is considerable doubt about the origin of some of the rocks. Some of the lower Permian beds in southern Brazil contain marine fossils, but in Minas no fossils have as yet been found in them, and in Bahia, at only one locality have a few Permian plants been found. Indications of oil have been found in the states of Sa0 Paulo, Parana, and elsewhere farther south, but wells drilled in the Permian of SaO Paulo near the Morro do Bofete did not find oil. One well has been started, by the Brazilian Government, in the Permian of Parana near Marechal Mallet, close to latitude 26" south, but thus far oil has not been found.

Jan 1, 1923

By J. F. Kemp

The use of nickel-steel has directed increasing interest of late towards the deposits of nickel, and at the same time the parallel advance in our knowledge of the basic igneous rocks has rendered these deposits a subject of important geological inquiry. Investigations have led to some views, more or less new, on the igneous origin of certain ores, which, though not universally accepted, have a growing number of adherents. In Europe, the mines in Norway have been especially suggestive subjects of study, and others somewhat less generally known have also added their testimony; while in this country the great economic importance and scientific interest of the developments in the Sudbury district of Canada, have furnished the principal texts for the discourses that have appeared among us. The purpose of the present paper is to set forth these views through the medium of one interesting ore-body, of which but little has been written ; and, by the description of another, to place in contrast two different geological associations in which nickeliferous pyrrhotite occurs, and to indicate a generalization, based upon these different geological characters, and justified by the experience so far gained. To Prof. J. H. L. Vogt, of Christiania, Norway, is due the chief credit for the revival of interest in the geology of nickel. His important contributions* of recent date have made generally available

Jan 1, 1895

By R. L. Templin

THE increasing use of aluminum and its alloys in commercial fields has demanded a better understanding of their machining properties. This fact is exemplified by problems that have arisen in the automotive and airplane industries, but many in other fields might be cited. As pure aluminum and its alloys in their various commercial conditions show appreciable differences in their machining properties, it is not surprising that quite divergent solutions have been offered for the machining problems encountered. However, if the fundamental requirements of the most suitable cutting tools for these metals are understood, these machining problems lend themselves more readily to satisfactory solutions. Since the machining of free cutting brass and mild steel is understood by most persons accustomed to working these metals, it may serve our purpose better to first make a general comparison of the tools more commonly used in machining these metals with the tools most suitable for machining aluminum, then proceed to a more specific discussion of the individual stools.

Jan 1, 1927

By W. E. D. Jr. Stokes

THE application of aviation to mining and petroleum operations, on the basis of economy and attainment, has become a demonstrated fact. According to Dominion Government records, 30. Canadian companies engaged in air transportation with northland mining camps, carried 13,000 tons of freight in 1935, and in 1936 carried 16,000 tons. In addition, many mining companies used planes to transport prospectors with canoes, outboard motors, gasoline drums and supplies to remote locations, and one company maintained a plane to take radium-bearing ore from its mine on Great Bear Lake nearly 1000 miles south to the rail-way at Waterways, Alberta. Heavy pieces of mining machinery weighing 2 tons are being carried by Ford trimotor planes over the Andes, at an altitude of not less than 15,000 feet. At Bulolo, New Guinea, 17,500 tons of disassembled gold-dredging equipment has been flown over inaccessible terrain, while supplies and building materials for a, community of 1000 whites have been transported by airplane. A 31..4-ton shaft was carried on one notable trip, while at another time an automobile, 2 tons of rice and a large safe went over the mountains in one plane. Fig. 1 shows an electric generator that was carried by plane to Bulolo. Many large American oil companies operated fleets of planes during 19:36, ranging from fast, luxurious air liners for executives to elaborate geological prospecting units, ambulance planes, freight carriers and pipe-line repair crews. According to the U. S. Geological Survey, commercial firms photo-graphed 16,291 square miles during 1935, while the Government compiled from aerial photographs by the Geological Survey in the United States 85,544 square miles. It was found that information could be determined in a fraction of the time required by surface methods.

Jan 1, 1937

By H. H. Stoek

(Wilkes-Barre Meeting, June, 1911.) THE origin of the Mine-Rescue Service of the State of Illinois can be traced to two distinct sources, the work of the Rescue Station at Urbana and the Cherry disaster. During the early part of the year 1909, the Technologic Branch of the U. S. Geological Survey, now the Bureau of Mines, in connection with the Illinois Geological Survey and the College of Engineering of the University of Illinois, established at the University of Illinois, in Urbana, a branch rescue-station to supplement the work of the Pittsburg station of the Geological Survey. As a result of the work of training at the station in Urbana by R. Y. Williams, mining engineer, and James Webb, foreman of the Bureau of Mines, and the use of the helmets at several mine-accidents in the State of Illinois, . the people of the State were somewhat familiar with oxygen-helmets when the Cherry disaster occurred, in November, 1910. The oxygen-helmets were successfully used in connection with that disaster, and upon the recommendation of the Illinois Mining Investigation Commission, the Legislature of the State, assembled in special session during the winter of 1910, passed a bill appropriating $75,000 for the erection and maintenance of three rescue-stations, stipulating that they should be located in the northern, central, and southern parts of the State. The Act also provided that the stations should be in charge of a Commission of seven, two representing the United Mine Workers of Illinois, two the mine-operators, one the Federal Bureau of Mines, one the State mine-inspectors, and one the Department of Mining Engineering of the University of Illinois. This Commission was called together by the Governor of the State, Aug. 2, 1910, and since that time three stations have been located, built, and equipped: at La Salle for the northern

Dec 1, 1911

By R. W. Raymond

THE absence of a convenient glossary of terns connected with mining and metallurgy has long been felt by the general public. It is to meet this want, not to furnish a technical manual for experts, that the following glossary has been prepared. It originated in an attempt on my part to revise for publication the manuscript of a compilation prepared from the appendix of Yale's work on Mining Titles and one or two other sources, to serve as an appendix to a new work on mining law, about to be published by Mr. H. N. Copp, of Washington, D. C. This revision soon assumed, contrary to my original intention, the proportions of a reconstruction ; and with the consent of Mr. Copp, and for the purpose of receiving from my fellow-members valuable aid, I presented my still incomplete work as a paper at the Lake Superior meeting of the Institute, inviting from any quarter suggestions of new terms or better definitions to be incorporated in the glossary before its final publication. This invitation was so widely and generously responded to, that I cannot undertake to make in this place' individual acknowledgments to those members of the Institute, and professional colleagues outside of it, who hays favored me with ' assistance and advice. The labor bestowed upon this paper since its presentation, at the Lake Superior meeting has considerably exceeded that of its first preparation, as

Jan 1, 1881

By Guillermo Zuloaga

THE iron deposits of the Imataca Range of Venezuela, which occur along the Orinoco River, in the northern border of the Guayana High-lands, have lately attracted attention on account of their economic possibilities. Many deposits occur in this area; some of slight economic importance and others that may rank with the largest masses of high-grade iron ore of the world. The geology and the character of the ores seem to be remarkably similar to those of the large iron deposits of Brazil. In the investigation of the Venezuelan deposits a definite relationship has been found between the mineralization of the large orebodies and igneous intrusions, especially norites and granites. The following paper is the result of a field and laboratory investigation of the ore deposits. The field work was done during the months of February and March of the year 1929, partly in the company of Prof. W. H. Newhouse. The laboratory studies have been made in the Massachusetts Institute of Technology, under the supervision of Profes-sor Lindgren and Professor Newhouse.

Jan 1, 1933

A. R. Ledoux,New York City: The so-called combination method " is generally used in assaying bar copper for silver. It has been modified from time to time. Briefly outlined

Jan 1, 1901

By J. M. Hodge, H. M. Reichhold, R. D. Manning

The work reported in this paper represents the first of a series of investigations of the factors governing notch toughness in ferritic materials. This paper is concerned with two of these factors, namely, the effect of ferrite grain size, and the effect of an alloy content of 3.64 pct nickel. Every effort has been made to hold other variables constant in order to isolate the effects of these two. The compositions chosen for study were 0.02 pct carbon in order to eliminate the variable of carbide distribution, one steel being a plain carbon steel and the other alloyed with 3.64 pct nickel. Both steels were fully killed with silicon, without an aluminum addition, so that the variable of deoxidation practice was held constant. Finally, all samples were water quenched from 1200°F and tempered 24 hr at 300°F in order to hold the quench aging variable constant and to decrease the tendency for grain boundary carbide precipitation. The ferrite grain size was varied by heat treatment over the range of A.S.T.M. grain size numbers of about 2 to 6 in each steel so that the effect could be evaluated individually and the notch toughness of each steel could be compared at comparable ferrite grain sizes. Materials and Experimental Procedure MATERIALS The materials for this investigation were obtained from Battelle Memorial Institute as 250 Ib induction melts which were forged into 134 in. square bars and then rolled into 0.6 in. square bars. Both steels were deoxidized with silicon, the aluminum content being held to a minimum. Check analyses of these materials are shown in Table 1. HEAT TREATMENT FOR GRAIN SIZE The grain size was varied by varying both the cooling rate and the austeni- tizing temperatures. The heat treatments used and the corresponding grain size values are tabulated in Table 2. A semicontinuous network of grain boundary carbide was observed in the microstructure of both the plain carbon and nickel steels in the as rolled condition and an additional heat treatment was necessary to eliminate this variable. Therefore, all samples were water quenched from 1200°F and tempered 24 hr at 300°F as a final treatment before testing. This heat treatment served to eliminate to a great extent the grain boundary carbide network and to hold the quench aging effect constant. IMPACT TESTING Standard keyhole Charpy impact tests were machmed after heat treatment. A bath of acetone and dry ice was used for refrigeration of the samples down to temperatures of —94°F (—70°C) and a bath of either methyl-cyclohexane or isopentane, cooled by

Jan 1, 1950

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

H. H. Bleakney (Dept. of Mines and Technical Surveys, Ottawa, Canada)— The work of Dr. Machlin and his colleagues at Columbia University is so scholarly that one hesitates to take issue with them. Nevertheless the writer feels compelled to enter a demurrer to the mechanism of intercrystalline cracking proposed in this paper. The principal obstacle to its acceptance is found in its preoccupation with purely mechanical influences and its disregard for the chemical effect of impurities. The writer believes that the destruction of metallic cohesion by concentration of impurities at the grain boundaries is a necessary and sufficient condition for the development of intercrystalline cracking; and he believes that discussion of the numerous mechanical explanations proposed should wait until some valid objection to the chemical hypothesis has been advanced. It is nearly twenty years since Gillett" drew attention to the possibility that the chemical influence of precipitation might be the cause of intercrystalline cracking. As early as 1935, Greenwood'" remarked that grain-boundary precipitation of impurities in lead appeared to promote intercrystalline cracking. Again in 1939, Scott commented as follows on a paper by Thielemann and Parker:'" "There are at least two familiar phenomena that can influence grain-boundary cohesion: 1) intergranular oxidation; and 2) grain boundary precipitation. An important consideration in this work, therefore, is to determine which, if either, of these factors is responsible for the low values of cohesive strength observed." In 1952. the writer presented evidence," some original and some abstracted, which indicated that in copper, silver, aluminum, lead and iron, intergranular cohesion was a function of the purity of the metal. In 1954 Glen, discussing a paper by Ridley and Tapsell14 indicated his belief in a precipitation mechanism for the intercrystalline embrit-tlement of molybdenum steel and suggested that with an absolutely pure metal it would be almost impossible to obtain an intercrystalline crack. This suggestion has

Jan 1, 1959

EXECUTIVE COMMITTEES OF LOCAL SECTIONS Arizona E. P. MATHEWSON, Chairman W. V. DECAMP, First Vice-chairman F. W. MACLENNAN, Second Vice-chairman E. D. GARDNER, Secretary-Treasurer, U. S. Bureau Of Mines, Tucson, Ariz. MICHAEL CURLEY J. P. HODGSON HENRY F.1 ASTER CLYDE E. WEED Boston Meets first Monday each winter month GEORGE A. PACKARD, Chairman FRANKLIN B. RICHARDS, Vice-chairman F. LEROY FOSTER, Secretary-Treasurer Rooms 8-219 Mass. Inst. of Tech., Cambridge, Mass. G. W. METCALFE D. H. MCLAUGHLIN

Jan 1, 1932

W. M. PEIRCE, Chairman J. L. CHRISTIE, Past-chairman E. H. DIX, JR., Vice-chairman ALBERT J. PHILLIPS, Vice-chairman E. M. WISE, Secretary International Nickel Co., Bayonne, N. J. W. M. CORSE, Treasurer Executive Committee W. H. BASSETT, JR. R. H. LEACH' D. K. CRAMPTONR. F. MEHL J. A. GANN W. E. REMMERS G. O. HIERS H. J. ROAST JEROME STRAUSS Finance Committee J. L. CHRISTIE, Chairman W. M. CORSE C. H. MATHEWSON T. S. FULLER H. S. RAWDON

Jan 1, 1934