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By F. E. Luborsky, K. T. Aust

RECENT interest has been shown in utilizing solid-state techniques for obtaining large oriented grains in the Alnico Alloys.1-4 Unfortunately, due to the inherent brittleness of these materials it is difficult to introduce sufficient imperfections by deformation to support the nucleation and growth of new, recrystallized grains. As a result, recrystal-lization methods for obtaining large grains, such as the strain-anneal technique, do not appear to be feasible. Steinort et a1.2 used a combination of a thermal gradient and internal strains to obtain large single crystals of Alnico 5 from a poly crystalline casting by annealing at temperatures above 1200°C. It was suggested that the strains were the result of the precipitation of the y phase which exists between -850° and 1200°C. The purpose of the present study was to determine if the grain size of the cast Alnico alloys can be markedly increased by solid state techniques involv-

Jan 1, 1963

By Arthur Notman

DESPITE the tremendous drop in the volume of domestic production of metals, their prices, and profits, the world as a whole has managed to produce and consume nearly as much as in 1937. Measured by production, 1937 was the record year for copper, lead, and zinc. The Copper Institute figures for 1938 (estimating December as equal to November) show that although apparent domestic consumption declined 309,422 tons, foreign consumption increased 133.035 tons. The total for 1938 was 1,971,790 tons compared with 2,148,177 tons for 1937. The domestic decline was 38.5 per cent, the foreign increase 9.9 per cent, and the total decline 8.2 per cent.

Jan 1, 1939

By E. H. Jr. Dix

OF all the alloying elements used in commercial aluminum alloys, copper stands out as by far the most important, and it is perhaps for this reason that the constitution of the aluminum-copper system has received the attention of a number of experimenters covering a period of approximately 20 years. It would be expected that during this time the equilibrium relations had been thoroughly and exactly worked out. In a general way this is true, but there is a surprising lack of agreement in the details of the high aluminum end of the diagram, particularly in regard to the solid solubility of copper in aluminum, which has been given variously as 2 per cent. to 5 per cent. at the eutectic temperature. The importance of this is much greater than might at first appear to one unfamiliar with modern commercial aluminum alloys. This is true because, with one exception, the susceptibility of the strong alloys to heat treatment depends, in part at least, upon the solid solubility relations of copper in aluminum. In 1919, Merica, Waltenberg, and Freeman1 published the first detailed information on these solubility relations. They found that the solubility of copper decreases with falling temperature from about 4 per cent. at 5.25° C. to about 1 per cent. at 300° C. and is apparently still diminishing at lower temperatures. In 1921 there was published a brief account of the results obtained in the National Physical Laboratory, Teddington, England.2 This laboratory, however, reported that 5 per cent. of copper is soluble in aluminum at 540° C., and that this amount decreases to about 3 per cent. at 20° C.

Jan 2, 1926

By AIME AIME

OVER-ALL operations of the oil industry, as measured by production of crude oil and consumption of products, are almost exactly of the same magnitude as a year ago. Does this mean that the great oil industry has been undisturbed by the war? Has this industry, so vital to the prosecution of the war and to the maintenance of our way of life, been unaffected in its operations? No indeed - changes within the industry are great. It has been called upon to revamp its trans¬portation methods so as to move about one fourth of the total amount of crude and refined products by railroad tank car instead of by ocean-going tankers. Its fundamental internal economy, based on maximum gasoline yield from a barrel of crude, has been relegated to memories of the past. Rationing of oil products, which has been forced upon us in face of an abundant supply, is not only disagreeable medicine but is in itself completely disruptive to the marketing end of the-business.-

Jan 1, 1942

By W. Hume-Rothery

RECENT interest has been shown in utilizing solid-state techniques for obtaining large oriented grains in the Alnico Alloys.1-4 Unfortunately, due to the inherent brittleness of these materials it is difficult to introduce sufficient imperfections by deformation to support the nucleation and growth of new, recrystallized grains. As a result, recrystal-lization methods for obtaining large grains, such as the strain-anneal technique, do not appear to be feasible. Steinort et a1.2 used a combination of a thermal gradient and internal strains to obtain large single crystals of Alnico 5 from a poly crystalline casting by annealing at temperatures above 1200°C. It was suggested that the strains were the result of the precipitation of the y phase which exists between -850° and 1200°C. The purpose of the present study was to determine if the grain size of the cast Alnico alloys can be markedly increased by solid state techniques involv-

Jan 1, 1963

By Peter Greenfield, Paul A. Beck

Thirty binary systems of vanadium and chromium group transition elements with second and third long period transition elements were explored in regard to the intermediate phases formed. It was found that the phases predominating in these systems are s, AB type with ordered a-tungsten or C8 structure, close-packed-hexagonal with small unit cell dimensions and, finally, phases isomorphous with 1-manganese. IN recent years, considerable information has become available concerning the intermediate phases in binary systems of the transition elements. Thus, the s phase has been found to occur in most of the binary systems of vanadium, chromium, and molybdenum with the group of elements manganese, iron, cobalt, and nickel.' It was observed that, while the rr phases formed by chromium with manganese, iron, or cobalt possess a considerable temperature range of stability, particularly in the Cr-Co system, the corresponding s phases with molybdenum are limited to a temperature range of less than 400" above about 1200°C. Goldschmidt' reported v phases of tungsten with iron and cobalt, and these are apparently stable only at (and above?) 1400°C." Exploratory work in this laboratory with Fe-W and Co-W alloys of approximately 60 atomic pct W annealed at 1300°C did not produce X-ray patterns suggesting the presence of a phase. It appears then that the phases of iron and cobalt with the chromium group elements decrease in stability as the two components are chosen from long periods further removed from each other. From the available information, it might be concluded that the controlling factor is the increasing difference in atomic radii between the components. In contrast to the a phase, the phases formed by iron and cobalt with chromium group elements' are stable only when the latter have large atomic radii (molybdenum and tungsten); the corresponding phases with chromium do not occur. When the difference in atomic size becomes still larger (r,/r,, approaching the ideal value of 1.225), the u and p phases are replaced by Laves phases (AB,), as in the alloys of iron and cobalt with columbium," tantalum." and titanium."-" However, atomic size certainly cannot be the sole determining factor, since, for instance, in contrast to the very stable (Mo, Co)p phase, no such phase occurs in the Mo-Ni system even though the atomic diameters of cobalt and nickel are nearly the same. Similarly, chromium and cobalt form a a phase in a wide temperature range," but the corresponding s phase in the Cr-Ni system is missing. It has been shown that the composition of the u phase in various binary and ternary systems of transition elements in the first long period may be correlated in a fairly quantitative manner with the number of electron vacancies. The influence of electronic structure is probably present also in binary and ternary phases' and to some extent, apparently, even in Laves phases." " Although the absence of phases in the Cr-Ni and Mo-Ni systems has not as yet been explained on the basis of electronic structure, it appears reasonable to suspect a connection. One of the great difficulties in arriving at well founded rules in regard to the alloying behavior of transition elements lies in the lack of reliable information concerning the details of their electronic structure in the metallic and alloy form. The theoretical penetration of this field appears to be beset by very considerable difficulties, even when the complications due to alloy formation are disregarded. Another great source of uncertainty is the scarcity of phase diagram information even for binary systems of the transition elements so that only a very limited basis is provided for generalizations as to the occurrence of intermediate phases. For instance, very few binary phase diagrams of second and third long period transition element systems have so far been published. The present work was undertaken in order to survey the various types of intermediate phases occurring in 30 binary systems of elements of the group vanadium, columbium, tantalum, chromium, molybdenum, and tungsten with the elements rhenium, ruthenium, rhodium, palladium, and platinum. For most of these binary systems phase diagrams are very incompletely or not at all known, as will be further reviewed.*

Jan 1, 1957

By R. M. Hudson

The removal of nitrogen from a nitrogenized low-carbon sheet steel that contained 0.011 wt pct N was determined during heat treatment in Hz-N, mixtures. TIze process followed a first-order rate law; that is, plots of the logarithm of nitrogen content in steel were linear with the time of treatment at a given temperature. The rate of removal increased with an increase in temperature from 900" to 1300°F. By 1400°F the rate in dry hydrogen had decreased to a value intermediate between the rates at 1200" and at 1300°F; in wet (2.47 vol pct water vapor) hydrogen the rate at 1400°F was less than the rate at 1300°F and nearly the same as the rate at 1200OF. The rate at a given temperature increased as the 3/2 power of hydrogen concentration in the atmosphere. While wet atmosplzeres were generally more effective than the corresponding dry atmosplzeres, the effect of water vapor was much less pronounced than the influence of hydrogen content. NITROGEN is the principal agent in the strain aging of ferrite, the effect of carbon being secondary.' To eliminate the return of the yield point after straining and aging, it is claimed2 that the amount of nitrogen in solution in steel must be reduced to 0.0002 wt pct. Strong nitride-forming elements (titanium, vanadium, zirconium, and aluminum) can act to eliminate strain aging by combining with nitrogen. It is extremely difficult to decrease the nitrogen content in commercial steels to the low level required by conventional coil annealing because of the poor contact between the strip surface and the reactive atmosphere. However, a variety of gas-metal reactions can be effected by use of the open-coil annealing method,3 in which the metal surface is fully exposed to the atmosphere. With this possibility in mind, the Applied Research Laboratory has studied the influence of time, temperature, and atmosphere composition on the removal of nitrogen from low-carbon sheet steel. MATERIALS AND EXPERIMENTAL WORK Samples from a commercial nitrogenized low-carbon steel (0.010 in. thick) in the cold-reduced condition were used. The chemical composition of this steel is given in Table I. The gas mixtures used are listed in Table 11. The moisture content in the "wet" annealing atmospheres was controlled at a +70°F dew point (2.47 vol pct water vapor) by passing the gas mixture through a glass tube packed with a solid mixture of 10 pct anhydrous oxalic acid and 90 pct oxalic acid dihydrate held at 127°F; this technique has been described previously.4 For "dry" atmospheres, the gas mixtures were passed through a cold trap immersed in liquid nitrogen. A hinged-top Hevi-Duty electric furnace was used with a Vycor-glass furnace tube. When the furnace was at the desired temperature, the gas mixture was passed through the furnace at a flow rate between 1.1 and 1.2 cfh; coupons (size 3 by 3/4 in.) of the steel were pulled into the center of the Vycor-glass

Jan 1, 1964

By Byron W. Cheever

While engaged in experimenting with the usual methods for estimating phosphorus in iron and steel, it occurred to me that potassium chlorate might be used to oxidize the carbon, and thus avoid the tedious and vexatious evaporations necessary for successfully carrying out the usual methods. After many trials, the following plan was adopted : Take, for analysis, of Bessemer or other low-carbon steels, from 3 to 5 grammes; of crucible steel, 10 grammes; of pig-iron, 1 to 5 grammes, according to the percentage of phosphorus supposed to be present. Of iron, high in phosphorus (1 per cent.), take 1 gramme. Place in a No. 4 evaporating dish the amount of iron or steel decided upon, cover with a funnel which will just fit inside the dish, and then add gradually HNO3, (1.20 specific gravity), using 12 C.C. of acid for each gramme of steel or iron taken. (A larger quantity of acid will be required for small samples.) When the full amount of acid has been added, and the violent action has ceased, place the evaporating dish on a sand-bath, add 10 C.C. HNO3, (1.40 specific gravity), and boil till the bulk of the solution is reduced about onehalf. Then add 10 C.C. HNO3, (1.40 specific gravity), continue the boiling, and add from time to time, during the next 15 minutes, small portions of pulverized KCIO3, till about 2 grammes have been added. (If the solution shows signs of going dry, more strong acid must be added.) This will precipitate the manganese, with some iron. Sometimes it happens that the manganese does not come down readily, and more KCIO3, or further concentration, or both, will be required. The process is not complete till the manganese is precipitated, which may be known by the appearance of a dark, mirror-like deposit on the dish, at the edge of the solution. Boil the solution 5 minutes after the last addition of KCIO3, and then add cautiously (to prevent sudden explosions) 5 C.C. strong HCl. This will dissolve the precipitated manganese and iron. Continue the boiling till the chlorine is all expelled, adding from

Jan 1, 1885

THE members arrived at Ticonderoga, N. Y., at noon, Tuesday, October 15th, and were received by Mr. Cyrus Butler, Chairman of the Local Committee of Arrangements. During the afternoon the works of the American Graphite Company and the Horicon Iron Company were visited under the guidance of Mr. Butler, President of both companies, and of Mr. William Hooper, Superintendent. An excursion was then made, in carriages, to old Fort Ticonderoga, on Lake Champlain, after which the party were driven to the Rogers Rock Hotel, on Lake George. The first session of the Institute was held in the parlor of time hotel on Tuesday evening. Mr. Eckley B. Coxe, President of the Institute, opened the proceedings with the following address: I shall ask your attention, this evening, to a few reflections upon the subject of mining engineering as a profession in the United States, its past, its present, and its future, and its duties and oppor¬tunities with reference to the proper development of our great min¬eral resources. Thirty years ago, there were scarcely any mining engineers in this country, and but few in England, and there were no institutions where young men could be educated for the profession in the Eng¬lish language. France and Germany have been able for about a century to boast of mining schools of a high character, that number among their graduates such men as Humboldt, Weisbach, Rittinger, Combes, and Gruner. Of the few we then had worthy of the name of "mining engi¬neer," some had studied in the continental academies, and others were graduates in the school of practical experience, and had learned their profession in mines and smelting-works. Their work con¬sisted principally in making surveys and maps of mines and mining properties, geological reports, and analyses of ores ; but the mining engineer whom we often meet with now, who has studied chemistry, physics, mineralogy, geology, mechanics, and drawing; who is more or less familiar with machinery and its construction, and with the practical management of mines or smelting-works, and who is an expert in some one branch of his profession, would have been very difficult if not impossible to find in the United States. The induce¬ments held out to ambitious and talented young men to enter the

Jan 1, 1879

By H. H. Waller, D. L. Monroe, D. P. R. Smyth

ORIGINALLY slusher drift development was conventional, advancing the drift full 10x13-ft size at 6 ft per round. This proved dangerous and costly because the weak fractured rock of the orebody cannot be left raw for any length of time without its reacting with air to cause spalling. With this method of drift development ground conditions were worsened by many blasts and the length of time it was necessary for the drift to remain open. The problem was practically solved by driving 5x7-ft pilot drifts, then enlarging to 10x13-ft raw size by slashing with 50 to 60-ft diamond drill holes. Calculated explosive charges are used to avoid wall and roof shattering. Still more recently jacklegs and sectional steel replaced the diamond drills, resulting in the same work for less than half the cost, see Figs. 1 and 2. Crosscuts at right angles to the main haulage drifts, which cross through the center of the ore-body, divide the ore into 200-ft blocks. Eight slusher drifts on 50-ft centers draw from one block. The slusher floor is 11 ft above the rail, inclined at 1 pct grade, and the top is 18 ft below the undercut. The finished slusher drift is 102.5 or 120 ft long, depending on whether it is north or south of the crosscut. Drawpoints are staggered on each side at 17.5-ft centers. The completed drift is concreted and has an inclined ramp and a vent at the back. When crosscuts and gangways have been excavated and concreted and slusher stations installed, slusher drift development is carried out in 10 clear-cut stages: 1—Pilot drift is driven full length, 5x7 ft. 2—Station is excavated at half-way point in pilot drift. 3—Pilot drift is enlarged to slusher drift size by drilling. 4—Lower part of slash is blasted and mucked for floor concrete. 5—Floor is poured. 6—Inside upper half of slusher drift is blasted, mucked, and concreted. 7—Outside upper half of slusher drift is blasted, mucked, and concreted. 8—Drawpoints are excavated. 9—Drawpoints are concreted. 10—Concrete ramp and sheave protection recess are constructed at back end of slusher drift. A 5x7-ft pilot drift is driven full length on the center line of the proposed slusher drift using a jackleg and detachable bits on 7/8-in. hexagon steel. A 10-hp air-driven slusher and 36-in. scraper pull muck directly into cars in the main haulage crosscut, see Fig. 2. Operations are on a three-shift basis. One man mucks the previous round, drills, and blasts his round in a shift. Average advance is 5 ft per shift. When the pilot drift is completed, 7 ft of drift in the center section is enlarged to full raw slusher drift size of 10x13 ft, for the set-up to drill long slash holes. The pilot drift is slashed to full raw size from this station with jacklegs and tungsten carbide chisel bits on 7/8-in. sectional steel. Crews line the holes without trouble, working from controls established by the engineers, and the pattern of holes for the slash is arranged to give the least shattering effect

Jan 1, 1955

United Engineering Trustees, Inc C E Reistle, Jr (to Oct '55), A B Kinzel, '56, Andrew Fletcher, '57, Philip Kraft (from Oct '55 to '59) The Engineering Foundation W M Peirce, '56, A M Gaudin, '58 Engineering Societies Library Board Frank T Sisco, '58, C H Behre, Jr Engineering Societies Personnel Service Board of Directors E J Kennedy, Jr, E H Robie Advisory Committee, Milwaukee F T Agthe Special Survey Committee C M Cooley American Standards Association Mining Standards Board E R Borcherdt, '55, Otto Herres, '55, J K Richardson, '56, E W Bullard, '56, Alternate

Jan 1, 1955

By V. C. Rogers

ALTHOUGH surveying at mining properties is fundamentally the same regardless of the method of mining, at Climax, due to the nature of the ground, the policy of advance development work, and extremes in climatic conditions, surveying practice has had to be revised to meet the specialized conditions of this particular type of mining operation. The company's mine is one of the largest underground properties in the United States. It has proved ore reserves of 275,000,000 tons, 60,000,000 tons of which have been broken. To date, 109,000 ft. of development drifting have been driven, as well as 40,926 ft. of development raising, 10,000 ft. of ventilation drifting and raising, 16,000 ft. of exploration drifting, and 206,000 ft. of diamond drilling. Normal production varies between 1.2,000 and 15,000 tons daily. Development work proceeds at a rate of 11/2 tons developed for every ton milled and with a development of 18,000 to 20,000 tons per day, the following crew is required to take care of mine and surface engineering

Jan 1, 1946

By B. C. Allen

Surface free energy and surface self-diffusion of solid molybdenum were studied in the temperature range 1600" to 2400°C using pressure-sintered bi-crystals. Comparison of groove angles formed in various surfaces perpendicular to the grain boundary indicate a maximum of 1 pct variation in surface free energy with crystallographic mientation. This anisotropy tends to decrease with increasing temperature. The surface diffusion of the bicrystals is equivalent to that of sheet with a mild (100) Preferred orientation. Anomalously low values found for bi-crystals with surface orientations of (OOl), (012), and (011) are rationalized in terms of anisotropy in surface free energy. THE effect of crystallographic orientation on surface free energy1,' and surface self-diffusion3,4 has been primarily studied in fcc metals. The object of this work was to study the effect of orientation on surface diffusion and surface free energy of bcc molybdenum using pressure-sintered bicrystals. EXPERIMENTAL WORK Materials and Crystal Preparation. Arc-melted molybdenum rod was obtained commercially and electron beam zone refined at 50 cm per hr at 10- 5 torr to form single crystals about 8 cm long and 0.65 cm diam. Three crystals were prepared with axial orientations about 1 deg from [001.], [011], and. [111]. To reduce the carbon content, the crystals were annealed 2 hr in 1.4 atm flowing wet hydrogen at 2050°C. Then the oxygen content was reduced by annealing for 2 hr in -30°C dewpoint hydrogen at 2020°C. The resulting impurity analysis is given in Table I. Bicrystal Preparation. The single crystal rods were cut into transverse slices with a thin silicon carbide abrasive wheel to produce specimens about 0.6 cm long. They were mounted in epoxy and surrounded by stainless steel washers. Cutting in half was done longitudinally at various angles to known crystallographic planes containing the cylinder axis according to Fig. 1. To reduce surface deformation resulting from the cutoff wheel and thus reduce parasitic grain boundary formation on subsequent annealing, about 0.003 cm was manually ground off each cut surface with 600 grit paper. Care was taken to keep the surface flat. After removal from the mounts, one half was generally ro-tated 180 deg with respect to the other to give a po- tential symmetrical tilt grain boundary between the two halves. In the other cases when low misorienta-tion angles were desired, the crystals were not rotated. On the basis of symmetry, sufficient bicrystals were prepared to cover the entire range of misorientations for symmetrical tilt boundaries. The misorientations, +, ranged from 0 to 45, 0 to 90, and 0 to 60 deg for [001], [011], and [111] bicrystals, respectively. One [Ill] twist bicrystal was prepared from 2 single crystal discs rotated 17 deg relative to each other. Each specimen consisted of two pieces which were placed in a cylindrical tantalum can. Sharp edges were rounded and the fit was made as snug as possible to reduce subsequent deformation during bonding. The assembly and crystals generally were vicuum outgassed at 900" or 1700°C and then electron beam welded in the can at l x 10-4 torr. After being leak checked, the samples were placed in an autoclave and hydrostatically gas-pressure bonded5 in four batches under helium at 10,000 to 18,000 psi at 1650°C for 3 hr. Satisfactory bonds were obtained in many cases, and most of the crystals bonded after two exposures. The results did not appear to be affected by the various pressures used, preannealing conditions, crystal orientation, or time-pressure-temperature route taken to the final bonding condition. After bonding, the tantalum cans were selectively removed in cold concentrated HF. Measurements indicated overall deformation was under 1 pct. The bicrystals were metallographically ground and polished flat and perpendicular to the axis. Examination showed the boundaries were straight and almost free of parasitic grains caused by extraneous local deformation. Annealing. In preparation for thermal grooving, the bicrystals were cleaned and annealed by outgassing at 10-5 torr at 1900°C and heating at 2300°C under 1 atm 99.996 Ar for 0.5 hr. The crystals were held in a closed 4-deck box made of molybdenum sheet, and were heated in a Ta-1OW resistance furnace. The ar-

Jan 1, 1970

By F. R. Hensel

The present study was made to determine the laws governing the formation of the primary? crystal structure during solidification. Most of the experiments were carried out on chill castings, but from the resiilts it will be possible to draw certain conclusions as far as sand castings are concerned. It is necessary to discuss first a number of theories, which are generally adopted for explaining the structure of an ingot. Usually, the structure of an ingot consists of the following three zones (Fig. 1): (1) a chill layer of small at-random oriented crystals; (2) a layer of columnar crystals; (3) a zone of equiaxed crystals. The tensile properties of the chill layer and the equiaxed range are usually much better than in the columnar range, particularly the planes that are formed by the columnar crystals growing from two sides at right angles have low tensile properties. This is one of the reasons why columnar crystals in ingot structures are undesirable.

Jan 1, 1937

By Luis Toron, Salvador Cortes-Obregon

THE Oaxaca coal fields, shown in Fig. 1, are located in the Alta Mixteca region in the states of Oaxaca, Puebla, and Guerrero. Known out crops are scattered over 3125 square miles. It is probable that further exploration will reveal a more extensive area of deposits. The region is of great importance to Mexico, as at present the only sources of coal are the fields near the U. S. border. Steel mills are also located in the North, and finished products must travel 600 to 800 miles to the area of consumption in central Mexico. The Oaxaca coal, only 120 miles south of Mexico, D.F., lies close to several iron ore deposits. If this coal can be used in steel production is will be possible for the Mexican steel industry to reach new dimensions, commensurate with the growing industry of the central region. Coal can be utilized in thermoelectric plants in this area, which lacks not only petroleum and natural gas but also electric power. It can be used as domestic fuel, replacing charcoal and firewood.

Jan 5, 1954

By W. V. Green

The creep-rupture behavior of commercial powder-metallurgy tungsten rod is reported for temperatures of 2250°, 2500°, 2700°, and 2800°C, stresses up to 7000 psi, and times up to 4 hr. The temperature dependence and the stress dependence of creep rates are evaluated. Rupture time is fitted to the Larson-Miller parameter and compared to lower-temperature and higher stress results reported by pugh.4 THE tensile strength of single-crystal wire1 and of polycrystalline wire2 have been measured by Goucher. More recently Bechtold3 and pugh4 have studied the mechanical properties of tungsten rod between room temperature and 1200°C. Since tungsten has the highest melting point of all metals, it should retain useful strength to very high temperatures, and should find many applications in missiles, rockets, and so forth. Therefore, the mechanical usefulness of polycrystalline tungsten rod was investigated in the 2250" to 2800°C temperature range by short-time creep-rupture tests. MATERIALS TESTED Creep specimens were machined from 1/2-in. round commercial tungsten rod which was manufactured from powder by cold pressing, sintering, and hot swaging. Purity reported by the vendor was 99.95 pct W. Spectrochemical analyses showed "traces" (less than 0.01 pct) of silicon, iron, and titanium, and "faint traces" (less than 0.001 pct) of calcium and manganese. Carbon content was 30 ppm and nitrogen content was 70 to 110 ppm. No oxygen analysis was obtained. Room-temperature stress-strain tests on the as-received tungsten gave badly scattered results. Threaded end specimens broke at the threads. When these specimens were retested using shoulder grips, the specimens broke at the shoulders. No fractures occurred in the gage lengths. The fracture stresses were: 127,000; 137,000; and 154,000 psi for three specimens which fractured at the shoulders. The microstructure of the as-received tungsten rod is shown in Fig. 1. SPECIMENS USED Fig. 2 shows the two types of creep specimens tested. The threaded-end type specimen, which was used in most tests, had a 3/4-in. gage length and 1/4-in. gage diam. The cone-end specimen, which was used primarily to investigate the effects of a smaller gage diameter and the practicability of the modified grips and specimen, had a 3/4-in. gage length and a 1/8-in. gage diam. In both cases, the gage length terminated at 0.005-in. high shoulders which served as fiducial marks for optical strain measurements. Surface finish on the gage length was 16 µ-in. rms. Creep rates and rupture times were not significantly different for the two types of specimens and were not affected by electropolishing the specimens before testing. TESTING PROCEDURE The constant-load creep-testing machine used has been described by Smith, Olson, and Brown.5 In it the specimen is held vertically by grips of similar material and on the axis of a cylindrical tungsten or tantalum heater-tube. The specimen is loaded by means of the specimen grips, a pull rod (which is sealed to the chamber lid by a vacuum-tight bellows), a mechanical lever system, and hanging dead weights. Both specimen and grips are heated by radiation from the heater-tube, which is heated by its own electrical resistance. An optical system views the incandescent specimen through slits in the radiation shielding and heater-tube. The optical system projects an enlarged image of the specimen gage length on a ground-glass screen. Periodic gage-length measurements are made on this image with two cathetometers. Thorium oxide coatings on the specimen threads or conical end surfaces completely prevented diffusion-welding of specimens to grips, and were used

Jan 1, 1960

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

By J. Spreadborough, D. LaW. King, E. Anderson

Tmzsile tests were performed on Armco iron samples, at various ternpe.ralures and strain rates, ocer a wide range of grain sizes. Analysis of the data suggests that the plot of the lower yield stress, against d-1/2,where 2d is the acerage grain diameter, is not linear (as is often assumed) but is concave toward the d. axis over the range of d-from 7 to 53 . The different values of the parameters obtained by other workers can be explained, in part at least, by the observed curvature. This curvalure is shown to be consistent with a model of yielding based on dislocation pile-ups; however, the values of obtained by fitting our data to this model differ appreciably from the values generally reported. The equation proposed by Cottrell, viz.: is a plausible empirical fit to the experimental results. The purpose of this paper is to comment on the validity of the widely used linear relationship first proposed by all' and Petch and coworkers2"4 between ay, the lower yield stress, and 2d, the average grain diameter, for bcc metals, viz.: Many workers, see Refs. 2 to 7 and Table 11, have fitted this equation to their experimental results and have obtained acceptable fits over the relatively narrow range of grain sizes used by most of them. Indeed, in some cases, so few data points were available that any more sophisticated fit would have been irrational. In most of the interpretations,'-' oi is thought to be a measure of the friction stress accompanying dislocation movement, and ky was originally inter- preted as a measure of the dislocation locking but is now believed by Cottrell" to be a function of the dislocation creation rate. In the "unpinning" theories, k, is equated to where od is the unpinning stress and 1 is the average distance from the boundary of the grain where yielding is taking place to the nearest dislocation source in an unyielded grain. Other considerations (see, for example, Refs. 11 and 12) lead to equations with a similar form to [I] where different meanings may be attributed to the parameters. While there are doubts as to the physical significance of the parameters i and k, they continue to be used by many workers; interpretations of the variations in the behavior of ferrite materials following certain treatments, e.g., aging,'3 neutron irradiation,14 have been given frequently in terms of these parameters. Some theories of the mechanical behavior of bcc metals are based on this relationship. We have investigated experimentally the oy - d-'lZ relationship for Armco iron over a wider range of grain sizes and with more data points than those given in published results. The analysis of our data suggests that the oy—d-'" relationship is not linear but is in fact concave towards the d-'I2 axis. RESULTS AND DISCUSSION The experimental work was carried out on 3-mm-diam Armco iron rods which were prepared by wire drawing from 5-mm-diam rods. By annealing in vacuum at temperatures between 7000 and 1200°C for various times, grain sizes from 7 to 20,000 grains per sq mm were obtained, the grains in all cases being regularly shaped. Grain sizes were measured by lineal interceptand by area methods; only specimens with Amax/A values of 3 to 6 were used in the Petch-Hall plots (where A is the average area of a grain and Amax is the area of the largest grain observed). For all the specimens used, the number of grains in a cross section exceeded 50, which should be adequate to avoid grain size effects.'= Tensile tests were performed at 296", 219, and 17l°K, using

Jan 1, 1969

By Joseph A. Holmes

Although Venezuelan production attained a new peak in 1938, passing the 190 million barrel mark for the first time, there was a distinct flattening of the steep upward trend that marked 1937 and preceding years. The annual total of 190,231,780 bbl. was only 31/3 million barrels above the 1937 figure, an increase of slightly less than 2 per cent, which contrasts sharply with the 20 per cent increase of 1937 over 1936. As in the previous year, the Lake Maracaibo fields supplied approximately 73 per cent of the oil produced, Lagunillas remaining the largest single contributor in spite of a 17 million barrel decrease in its annual output. Tia Juana increased its percentage of the Venezuelan total from 14.1 per cent in 1937 to 23.4 per cent in 1938; La Rosa showed little change with 13.7 per cent; Quiriquire in eastern Venezuela was also little changed with 13.2 per cent; Mene Grande, the only other field of real importance, declined from 7.7 per cent of the total in 1937 to 6.6 per cent for 1938. Two new fields, Temblador and Bachaquero, began actively to ship oil during the year, and by November were averaging 7600 and 10,000 bbl. per day, respectively. The former is in eastern Venezuela, and the latter is the most southern of the proven Lake Maracaibo fields. (A map of Venezuela was published in Volume 127 of the Transactions.) Table 1 gives a complete résumé of Venezuelan production by fields for 1937 and 1938, and shows that 1,685,575,663 bbl. had been produced to Dec. 31, 1938. The percentage contributed by each of the principal fields to this total is shown in Table 3, as well as their trends over the past several years. From these data it is apparent that the Maracaibo Basin is the principal source of Venezuelan production, and will probably continue to hold this position for some years. At the year's end 2657 oil wells were producing, of which 2425 were in western and 232 in eastern Venezuela; 36 per cent were on natural flow, 57 ppr cent were pumping, and 7 per cent were on air or gas lift. Out of 523 wells drilled, 507 producers were completed in 1938, five less than in the previous year and nearly 100 less than in 1929. These

Jan 1, 1939

By Joseph A. Holmes

Although Venezuelan production attained a new peak in 1938, passing the 190 million barrel mark for the first time, there was a distinct flattening of the steep upward trend that marked 1937 and preceding years. The annual total of 190,231,780 bbl. was only 31/3 million barrels above the 1937 figure, an increase of slightly less than 2 per cent, which contrasts sharply with the 20 per cent increase of 1937 over 1936. As in the previous year, the Lake Maracaibo fields supplied approximately 73 per cent of the oil produced, Lagunillas remaining the largest single contributor in spite of a 17 million barrel decrease in its annual output. Tia Juana increased its percentage of the Venezuelan total from 14.1 per cent in 1937 to 23.4 per cent in 1938; La Rosa showed little change with 13.7 per cent; Quiriquire in eastern Venezuela was also little changed with 13.2 per cent; Mene Grande, the only other field of real importance, declined from 7.7 per cent of the total in 1937 to 6.6 per cent for 1938. Two new fields, Temblador and Bachaquero, began actively to ship oil during the year, and by November were averaging 7600 and 10,000 bbl. per day, respectively. The former is in eastern Venezuela, and the latter is the most southern of the proven Lake Maracaibo fields. (A map of Venezuela was published in Volume 127 of the Transactions.) Table 1 gives a complete résumé of Venezuelan production by fields for 1937 and 1938, and shows that 1,685,575,663 bbl. had been produced to Dec. 31, 1938. The percentage contributed by each of the principal fields to this total is shown in Table 3, as well as their trends over the past several years. From these data it is apparent that the Maracaibo Basin is the principal source of Venezuelan production, and will probably continue to hold this position for some years. At the year's end 2657 oil wells were producing, of which 2425 were in western and 232 in eastern Venezuela; 36 per cent were on natural flow, 57 ppr cent were pumping, and 7 per cent were on air or gas lift. Out of 523 wells drilled, 507 producers were completed in 1938, five less than in the previous year and nearly 100 less than in 1929. These

Jan 1, 1939