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By G. A. Beske, P. Hilsch, J. Wulff

The effects of the growth precipitates on the su-perconduching properties of an Al- 15 al. pel Zu alloy have been studied using magneization, transition lem-perature, and residual resistivity measurements. Aging at 230C for 1/2 to 11 he produces an increase in Hfp, Ike field of first penetration, and tut increase in trapped flux. The upper critical field, Hc2 remains constant for such aging tunes. Aging at 200°C produces a decrease in Hfp and an increase in trapped flux. The transition temperature remains constant at Tc - 1.227° ± 0.02°K for aging at 220°C for tims of from 1/2 to 10 hr, and for aging at 200°C it remains constant at Tc. = 1.18° i 0.02°K for times from 1/2 hv to 26 hr. The observed behavior indicates that the superconducting matrix when aged at 220°C behaves tike a type U su-perconducior, but when aged at 200°C behares like a type I superconductor. The magnetization changes after aging can be attributed to the growth and clutnge in distribution of the precipitate in a matrix of fixed composition. IT has been realized for some time that the superconducting properties of alloys are highly structure-sensitive. This is evident in the work of Mould and Mapother1 who examined the properties of an aluminum alloy. Precipitation effects have also been briefly mentioned in other studies.2-4 Bonnin and coworkers5 have observed a sharp inc rease in trapped flux in an A1-Mg alloy when the residual resistivity reaches a value that indicates it is a type II superconductor. Recently Blanc, Goodman, and Nemoz5p have reported on precipitation effects in A1-Ag alloys. Detailed studies of precipitation in Pb-Sn and Pb-Cd alloys made by Livingston6 serve to show that the upper critical fields are enhanced by quenched-in solute. Furthermore. at various stages in the precipitation process? the upper critical field is determined largely by the remanent solute. The observed magnetic hysteresis and trapped flux in such alloys result from the interaction between precipitate and the flux filaments in the mixed state. The flux trapping appears to depend largely on the precipitate distribution and is greater if the superconductor is type II than if it is type I. To examine the effect of precipitation in another alloy system, particularly one in which the composition of the superconducting phase does not change significantly during the course of precipitation, the Al-Zn system seems interesting, especially in view of the transition temperature and resistivity studies of Chiou and seraphim.' Furthermore, the recent detailed electron-microscope studies of an Al-Zn alloy by Richards and Garwood8 provide a guide for relating superconducting properties to changes in structure. For these reasons, magnetization, transition temperature, and residual resistivity measurements for varying times of heat treatment at two temperatures were made with a -15 at. pct Al-Zn alloy. The results are reported in this paper. I) EXPERIMENTAL The alloy used was prepared by Cominco Products Inc. from 99.9999 A1 and 99.999 Zn. It was chill-cast, swaged, and drawn to 0.125-in.-diam rod. The analyzed composition was 15.6 at. pct Zn (31.1 wt pct). A jeweler's saw was used to cut the 0.125-in.-diam rod into the 0.875-in. lengths needed for magnetization measurements. The ends of the cylinders were slightly beveled to remove the sharp edges. A portion of the original 0.125-in.-diam rod was drawn into 0.010-in.-diam wire and used for transition temperature measurements. Specimens were suspended from wires within a vertical furnace during heat treatment. All were homogenized at 500°C for a minimum of 3 days and subsequently solutionized for times in excess of 6 hr. The solutionizing temperature was held constant to +3°C. Individual specimens were homogenized, quenched, and aged several times and no effects indicating loss of zinc were noted. The suspended specimens were quenched by cutting the wires and allowing the specimens to fall into a silicone oil bath held at the aging temperature. They were then isothermally transforked by aging in the same bath used for quenching. After aging for the required time (approximately 10 min aging was necessary before the upper critical field reached a fixed value), they were briefly (1 to 2 sec) dipped into an acetone bath at room temperature to remove adherent oil and then immediately transferred to liquid nitrogen where they remained until inserted into the helium bath (usually within an hour). The temperature of the aging bath was held constant to +3°C for longer aging times. The cryostat used for the measurement of superconducting properties consisted of outer and inner dewars for liquid nitrogen and liquid helium, Stokes 6-in. booster diffusion pump and Stokes Model 212 mechanical pump, temperature controller to measure and control the temperature of the helium bath, and a superconducting solenoid with inserted search coils to provide the magnetic field and measure the magnetic moment of the specimens. A schematic diagram of the cryostat is shown in Fig. 1. An ultimate temperature of 0.85°K was reached with this apparatus. The temperature controller used is similar to the one described by Blake and chase.' A 0.5 pct Allen-Bradley carbon resistor and a nichronle heater (200

Jan 1, 1968

New York Meets first Wednesday after first Tuesday of each month. DAVID 11. BROWNE, Chairman. JOHN H. JANEWAY, Vice-Chairman. F. E. PIERCE, Secretary, 35 Nassau St., New York, N. Y. P. A. MOSMAN, Treasurer. LEWIS W. FRANCIS. BENJAMIN B. LAWRENCE. Boston Meets first Monday of each winter month. HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. HENRY A. WENTWORTH, Secretary-Treasurer, 60 India St., Boston, Mass. A. H. EUSTIS, F. G. STANTIAL. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane. Wash. D. C. LIVINGSTON. FRANK A. ROSS.

Jan 4, 1916

New York Meets first Wednesday after first Tuesday of each month. L. W. FRANCIS, Chairman, WILLARD S. MORSE, Vice-Chairman,. THOMAS T. READ, Secretary, Woolworth Bldg., New York, N. Y. P. A. MOSMAN, Treasurer. LOUIS D. HUNTOON. - WILLIAM A. POMEROY. Boston Meets first Monday of each winter month. HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. HENRY A. WENTWORTH, Secretary-Treasurer, 60 India St., Boston, Mass. ROBERT H. RICHARDS, ALBERT SAUVEUR. Columbia Holds four sessions during year. Annual meeting in September or October. FRANK A. ROSS, Chairman. RUSH J. WHITE, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. FREDERIC KEFFER, FRANCIS A. THOMSON.

Jan 5, 1915

By D. P. Kedzie, R. A. Dodd

The fatigue strength, fatigue hardening, and effect of fatigue deformation on subsequent age hardening of supersaturated Al(Cu) solid solutions have been determined as functions of alloy composition and temperature. The fatigue strength/tensile strength ratios, determined at 150°, 25°, and -195°C, decreased with increase in alloy content for all temperatures, but the F.S./U.T.S. ratios at -195°C decreased much more rapidly than did the ratios for 150" and 25°C. This suggested that strain aging and/or age hardening occurred during tests at higher temperatures. Additionally, the F.S./U.T.S. ratios at 150°C exceeded those at 25°C for all compositions, indicating greater strengthening during fatigue at 150°C. The effect of fatigue or tensile deformation at 150°, 25°, and -195°C on subsequent age hardening showed that the deformatzon increased the rate of precipitation and indicated that mechanically produced vacancies were probably formed during deformation. Fatigue hardening was studied at 150°, 25°, and -195°C, and the effect of room-temperature rests after 10 and 100 cycles was examined. The results confirmed that strain aging occurred at the higher temperatures . DURING the last 15 years various mechanisms of fatigue crack nucleation and growth based on dislocation and vacancy interactions, operating singly or collectively, have been proposed. The probable consensus of present opinion is that the fatigue process in pure metals essentially involves dislocation interactions, and that vacancies formed by such interactions play a minor or inconsequential role. However, there is some evidence that age-hardened alloys tend to overage during fatigue, probably by local vacancy-enhanced diffusion, and strain aging also might be important in selected cases. Furthermore, it has been established that the behavior of quenched-in vacancies in Al(Cu) and other solid solutions is composition-sensitive. Therefore, it seemed worthwhile to investigate various aspects of the fatigue behavior of supersaturated Al(Cu) alloys and to examine the results in terms of vacancy-enhanced effects. EXPERIMENTAL The alloys used in this investigation were prepared from 99.994 wt pet A1 and OFHC copper, the latter containing 0.04 pet 0 as the principal impurity. Six alloys were made, containing, by actual analysis, 0.58, 0.96, 1.96, 2.85, 4.45, and 5.51 wt pet Cu. They were induction-melted in air in graphite crucibles, cast as 7-in. by 7/8-in.-diam rods in graphite molds, and hot-rolled to 5/8 in. diam. The experimental work was a three-part program involving the determination of a) 10' cycle fatigue stresses as a function of alloy composition and temperature; b) the effect of fatigue deformation on subsequent aging of the supersaturated alloys; and c) fatigue hardening as a function of alloy composition and temperature. For determining the 105 cycle fatigue stresses, a portion of the 5/8-in. stock was machined into Krouse rotating cantilever beam fatigue specimens, 2 in. in length by 1/4 in. minimum diameter. These were tested at +150°, 25°, and -195°C (liquid nitrogen) on a Krouse high-speed machine, with special weights to provide lower -than-normal loading ranges, this being necessitated by the small load requirements of those alloys of lower copper content. For the high-temperature tests a small resistance heater was designed to clear the collets and fit in between the chucks, while for the low-temperature tests a hollow nylon cylinder was used, having closed ends drilled to pass a fatigue specimen, and positioned similarly to the heater. A plexiglass container completely enclosed the fatigue machine; rubber gloves fixed to ports in the walls enabled the machine to be operated from outside the box. A tray of magnesium perchlorate dried the air in the container and prevented both atmospheric corrosion fatigue at room and elevated temperatures and troublesome ice build-up at low temperatures. A total of ten to fifteen specimens was used for each combination of alloy composition and temperature. The result of each test was plotted on a standard S-N diagram, and the next stress was selected on the basis of the trends indicated by previous specimens. In this manner a small portion of the S-N diagram was constructed, and the 105 cycle fatigue stress obtained. Small Krouse fatigue specimens were also used to study the effect of cyclic prestrain on subsequent

Jan 1, 1964

By H. W. McCue, Henry Rogatz

Oil.—In the Texas Panhandle, 502 oil wells were drilled during the year 1940, with a total daily initial production of 139,187 bb1.—that is, 137 more oil wells drilled than in the previous year, with an increase in total daily initial production of 8219 bbl. The total daily potential of the field on Dec. 31, 1940, as determined by the Texas Railroad Commission, was 1,375,502 bbl., an increase of 30,825 bbl. over the previous year. On Dec. 31,1940, a daily allowable of 85,050 bbl., which was a decrease of 35 per cent over 1939, was assigned to the field to be produced from 4788 wells. The total amount of oil produced for the year was 26,788,590 bbl., making a cumulative total of 378,960,728 bbl. during the past 19 years. No new oil-producing acreage was discovered. Gas.—During the year, 92 gas wells were drilled, having a combined open flow of 2,402,900.000 CU. ft.; that is, 6 more than the number of wells drilled in 1939, with an increase in the open flow of 204,900,000 cu. ft. per day. The gas production for the year was 670,435,112,000 CU. ft., and the total gas removed from thc ground during

Jan 1, 1941

By Henry Rogatz, H. W. McCue

Oil.—In the Texas Panhandle, 502 oil wells were drilled during the year 1940, with a total daily initial production of 139,187 bb1.—that is, 137 more oil wells drilled than in the previous year, with an increase in total daily initial production of 8219 bbl. The total daily potential of the field on Dec. 31, 1940, as determined by the Texas Railroad Commission, was 1,375,502 bbl., an increase of 30,825 bbl. over the previous year. On Dec. 31,1940, a daily allowable of 85,050 bbl., which was a decrease of 35 per cent over 1939, was assigned to the field to be produced from 4788 wells. The total amount of oil produced for the year was 26,788,590 bbl., making a cumulative total of 378,960,728 bbl. during the past 19 years. No new oil-producing acreage was discovered. Gas.—During the year, 92 gas wells were drilled, having a combined open flow of 2,402,900.000 CU. ft.; that is, 6 more than the number of wells drilled in 1939, with an increase in the open flow of 204,900,000 cu. ft. per day. The gas production for the year was 670,435,112,000 CU. ft., and the total gas removed from thc ground during

Jan 1, 1941

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary. 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. Boston Meets first Monday, of each winter month. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON, FRANK A. ROSS.

Jan 9, 1916

New York Meets first Wednesday after first Tuesday of each month. . DAVID H. BROWNE, Chairman. JOHN H. JANEWAY, Vice-Chairman. . F. E. PIERCE, Secretary, 35 Nassau St., New York, N. Y. P. A. MOSMAN, Treasurer. LEWIS W. FRANCIS. BENJAMIN B. LAWRENCE. Boston Meets first Monday of each winter month. HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. HENRY A. WENTWORTH, Secretary-Treasurer, 60 India St., Boston, Mass. A. H. EUSTIS, F. G. STANTIAL. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash.

Jan 2, 1916

By FORTUNATO PEREIRA

(San Francisco Meeting, October, 1911.) I. GENERAL DESCRIPTION. The Department of Narino (formerly included in the Department of Cauca) is a narrow band about 170 km. (100 miles) wide in the southern part of the Republic of Colombia, FIG. 1.-SKETCH-MAP OF THE SOUTHWESTERN PART OF COLOMBIA. near the boundary of Ecuador, as shown in the sketch-map, Fig. 1. Its capital is Pasto, a small city of 25,000 inhabitants; the principal towns are Túquerres, Cumbal, Ypiales, Barbacoas, and Tumaco. The port on the Pacific ocean is Tumaco, and traffic in the interior is carried partly on the Patia river (steam navigation to the fluvial port of Barbacoas), and afterwards overland over poor roads by human bearers or on mule-back.

Aug 1, 1912

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman. A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, Chairman. FREDERIC KEFFER. Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON. FRANK A. ROSS.

Jan 10, 1916

By AIME AIME

DREAMS do come true at times, although it is evidently better to believe in engineers than to "believe in fairies" if most dreams are to be translated into fact. It was a fine dream that David H. Moffat had when he projected a railway directly west from Denver; a dream of opening a new empire in northwestern Colorado, and of quickening transportation from the Middle West to the Pacific slope. But Moffat had been a miner and had become a banker. He knew that dreams, untranslated into works, benefit no one and pleasure only the dreamer, so he employed an engineer, H. A. Sumner, to study and plan the route to be followed by the rails. Previous main lines had run to the north, the Union Pacific, or the south, the Santa Fe. The Denver and Rio Grande, it is true, wriggled its way bravely across Colorado but, in order to reach a point 74 miles in an airline west of- Denver, travelled 281 miles following two canyons and crossing Tennessee Pass at 10,240 ft. Valuable as such a road is, it could never accomplish what Moffat had in mind. It was known that no low pass could be found directly west of Denver but up to 9000 ft. the topog-

Jan 1, 1925

New York Meets first Wednesday after first Tuesday of each month. DAVID H. BROWNE, Chairman. PERCY E. BARBOUR, Vice-Chairman A. D. BEERS, Secretary, 55 Wall St., New York, N. Y. C. A. BOHN, Treasurer. Boston Meets first Monday of each winter month. W. E. C. EUSTIS, Chairman. R. L. AGASSIZ, Vice-Chairman. E. E. BUGBEE, Secretary-Treasurer, Mass. Inst. of Technology, Boston, Mass. ALBERT SAUVEUR, H. L. SMYTH. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON, -Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K: ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash. D. C. LIVINGSTON, FRANK A. ROSS.

Jan 7, 1916

New York Meets first Wednesday after first Tuesday of each month. DAVID' H. BROWNE, Chairman. JOHN H. JANE WAY, Vice-Chairman. F. E. PIERCE, Secretary, 35 Nassau St., New York, N. Y. P. A. MOSMAN, Treasurer. LEWIS W. FRANCIS. BENJAMIN B. LAWRENCE. Boston Meets first Monday of each winter month. HENRY L. SMYTH, Chairman. ALFRED C. LANE, Vice-Chairman. HENRY A. WENTWORTH, Secretary-Treasurer, 60 India St., Boston, Mass. A. H. EUSTIS, F. G. STANTIAL. Columbia Holds four sessions during year. Annual meeting in September or October. STANLY A. EASTON. Chairman. FREDERIC KEFFER, Vice-Chairman. LYNDON K. ARMSTRONG, Secretary-Treasurer, P. O. Drawer 2154, Spokane, Wash.

Jan 3, 1916

By T. A. Rickard

"The chief aim in style ought to be absolute precision", said Flaubert. "There is only one noun that can express your idea, only one verb that can set that idea in motion, and only one adjective that is the proper epithet for that noun." Let this be your motto. The engineer tries to be exact in all his measurements; he should measure his language with similar exactness. The technical term is a word of precision. It is not only precise, it is a word-saver. To the unscientific the earth is "a ball slightly flattened at the poles, something like an orange". To the scientific it is "an oblate spheroid". A similar contrast between the precision of the technical term and the vagueness of common words is afforded by a conversation between Ivanhoe and Rebecca: "' What device does he bear on his shield?' asked Ivanhoe. 'Something resembling a bar of iron, and a padlock painted blue on a black shield.' 'A fetterlock and shacklebolt azure', said Ivanhoe "-using the technical terms of heraldry. It is good style in writing, however, to adapt your manner of expression to the intelligence and experience of the person or persons to whom the writing is addressed. The description of a mine should be worded differently according as it is intended to inform a mining engineer, a director, or a bishop. REMEMBER THE READER. It is as incorrect to write in a technical way for a non-technical reader as to write in a popular way for a technical or scientific reader. That style is best which enables the writer to place himself in the closest mental touch with his reader, to establish the maximum of sympathetic understanding. Let your precision be\ proportioned to your accuracy. You should not try to be precise in matters that do not admit of

Jan 1, 1931

By R. L. Fullman

IN the investigation of metallurgical transformations and the relationships between microstructure and properties of metals, it frequently is desirable to obtain a measurement of the relative amounts of the various phases present and of the mean size of particles into which each phase is dispersed. The relative amounts of the phases can be measured by the classical methods of area, lineal, and point analysis,1-5 in accordance with the principle that the volume fraction of a phase, the fraction of a polished cross section occupied by the phase, the fraction of a random line occupied by the phase, and the fraction of randomly arrayed points occupied by the phase are all equal. The validity of this relationship depends only on the attainment of a truly random sample of area, length, or points, and not on the size, shape, or distribution of the particles constituting the phase. Smith and Guttman8 have derived a relationship between the interface area per unit volume S, and the measurable quantities L., the interface length per unit area on a cross section, and NL, the number of interfaces per unit length intersected by a random line. Their equation, Sv = — L8 = 2NL is also valid regardless of the distribution of particle sizes and shapes. In contrast to the situation concerning measurement of relative fractions of phases and of interface area, the measurement of particle sizes in opaque samples has not been subjected to a complete analysis. It has been common to measure some lineal or area dimension of particles on a polished cross section and to use the mean value as a qualitative measure of particle size. In the present paper, quantitative relationships are established among the various mean dimensions on a polished cross section and the actual dimensions of the particles present. Particles of Uniform Size Spheres: If a metal sample contains particles of a phase a dispersed in the form of spheres of uniform size, a polished cross section through the sample will reveal circular areas of phase a with radii from 0 to ?, the radius of the spheres. Consider a cube of unit dimensions to be cut from the sample. If a cross section parallel to one of the cube faces is examined, the average number of particles per unit area (N,) equals the number of particles per unit volume (Nv) times the probability p1 that the plane would intersect a single sphere positioned at random within the unit cube. Since, of the various possible positions for the cross-sectional plane over the unit length from top to bottom of the cube, only those positions existing over the length 2r would lead to the plane intersecting the sphere, the probability of intersecting a single sphere is just 2r. N8= Nvp1 = Nd-2r [1] Applying the equality of area and volume fractions, the relationship is found between sphere size and average area s of uniform spheres intersected by a random cross section, 4 - f = NV V = Nr . — pra = N s = Nd . 2rs S = —pr2 [2] A similar analysis reveals the average traverse length across spheres of uniform size when random lines are passed through the sample. If a randomly oriented unit cube is cut from the sample and a randomly positioned line is passed through the cube parallel to a cube edge, the number of spheres intersected by the line (Nl) equals the number of spheres per unit volume times the probability p1 of the line hitting a single randomly placed sphere in the cube. Since possible positions of the line occupy unit area, and possible positions for which it will pass through the sphere occupy an area of pr2, the probability of the line hitting a randomly placed single sphere is pr2. NL = Nv p1 = Nvpr2 [3] Combining this relationship with the equality of volume and lineal fraction, the desired relationship is obtained between radius and mean lineal traverse length -i, for spheres of uniform size. 4 - - 3 l=4/3r [4] Circular Plates: Consider a sample containing particles of a phase a in the form of circular plates of uniform radius r and thickness t, where r >> t. If the plates are randomly oriented, as in a sufficiently large sample of a fine grained polycrystalline material, area and lineal analysis may be carried out with parallel cross-sectional planes and lineal traverses. If the plates are not randomly oriented, it is necessary to randomize the orientation of the cross-sectional planes and traverse directions. Let a unit cube be cut from the sample, and a cross-section plane be passed through the cube parallel to one of the cube faces. The number of plates cut by the cross-sectional plane per unit area is equal to the number of plates per unit volume times the probability of a plate intersecting a single randomly positioned and randomly oriented plate in the cube. If J is the component of the plate diameter in the direction normal to the cross-sectional planes, the probability of a plane cutting a single randomly oriented plate is equal to J, the mean value of J for all possible orientations of the plate. Let 4 be the dihedral angle between a plate and the cross-sectional plane, and let p?, d? be the probability that a plate makes an angle between 4 and ? + d? with the cross-sectional plane. Then for ran-

Jan 1, 1954

By S. A. Bradford

Internal-oxide precipitates in decarburized a iron alloys were studied by microscopic and X-ray methods. Diffusion of oxygen is primarily trans-granular, although large amounts of manganese or PhosPhorus cause preferred grain boundary dimsion at temperatures below 1450OF. Transgvanular internal oxidation follows the parabolic rate law with an apparent activation energy of 60 kcal per g-atom for decarburized rimmed steel and around 50 kcal per g-atom for higher alloy contents. The internal oxide is (Fe,Mn)0. Evidence was found for a miscibility gap in the FeO-MnO system. UNTIL very recently, the internal oxidation of metals was studied primarily as a scientific curiosity or, in a few cases, as a means of strengthening alloys by precipitation hardening. However, with the recent development of low-carbon enameling sheet steel, internal oxidation has become a problem of practical importance to the steel industry. For example, in 1961 it was reported1 that internal oxidation of steel can occur during decar-burization by open-coil annealing and will reduce the notch ductility of the sheet unless the process is carefully controlled. The present study was therefore undertaken to learn more about the rates and mechanism of oxygen diffusion and oxide formation in iron alloys. BACKGROUND The process of internal oxidation has been well-defined in the literature:',' oxygen dissolves in an alloy, diffuses inward from the surface of the metal, and reacts to form a precipitate with the alloying element that will provide the most stable oxide. he growth of the finely divided so-called subscale, i.e., the internal-oxidation zone, depends on the diffusion rates of both the oxygen and the reactive element.4 Investigators have generally found that increasing the temperature increases the size of the oxide particles, the rate of subscale growth, and the tendency to transgranular diffusion. With very few exceptions, the square of the thickness of the internal oxide layer is directly proportional to the reaction time. Given two conditions easily satisfied for iron systems— a) an oxygen solubility much less than the concentration of the alloying metal and b) an oxygen-diffusion rate to the oxide boundary much faster than that of the alloying element—then the general expression developed by Rhines and co-workers5 for the parabolic growth rate of the internal-oxide zone can be simplified to the following form: where Co and CM are, respectively, the solubility of oxygen and the concentration of the alloying element, DO is the diffusion coefficient of oxygen, O/M is the weight ratio of oxygen to metal in the precipitated oxide, and x is the thickness of the internal-oxide zone after an annealing time t. Both the oxygen solubility and diffusion coefficient can be approximately expressed as functions of temperature by Arrhenius-type equations: in which H and Q are, respectively, the heat of solution and the activation energy of diffusion. Consequently, the apparent activation energies calculated from Arrhenius plots are the sum of the heat of solution of oxygen in iron and the activation energy for diffusion of oxygen. The data, if not the interpretation, of Schenck et al.8 bear out the fact that oxygen diffuses in the atomic form. The general rate law for atomic diffusion is: the reaction rate being proportional to the square root of the pressure at low pressures. Benard and Moreau8 studied both the surface oxidation of Fe-Ni alloys and the gradual penetration of oxygen into the metal. They observed that oxide particles first form along grain boundaries and then grow to form continuous films that eventually envelop the grains. The parabolic rate law does not usually apply in these cases, especially at the higher temperatures. The oxide formed is wustite which gradually transforms into Fe3O4 and finally into Kennedy and coauthors8 examined Fe-Ni alloys with 26, 75, and 84 pct Ni oxidized at 800°C and

Jan 1, 1964

By R. N. Dokken, J. F. Elliott

A high-temperature solution calorimeter was used to measure directly the partial molar heat of mixing of nickel in the Cu-Ni system, 0 to 15 at. pct Ni and 1200°C; of silver in the Cu-Ag system, 0 to 50 at. pct Ag and 1100°C; and of cobalt in the Cu-Co system, 0 to 6 at. pct Co and 1200°C. The heats of fusion of copper and silver were also detervnined directly. The results of these investigations are as follows: Cu-Ni: HM = [2.64 + 0.25Xm JXNiXCy kcal/g-U~OI Cu-Ag: HM =[4.00 + 0.31XAglXAgXCu kcal/g-atom Cu-Co: HF~ = [8- 5X~,]X& kcal/g-atotn Cu, AH, = 3290 * 275 cal/g-atom Ag, AH, = 2890 * 250 cal/g-atom The performance of the calorimeter was enhanced by improving the operational and control procedures, particularly the temperature-wieasuren~ent method and the solute-addition practice. The interpretation of the experimental data was improved by developing machine computational techniques that increased the speed, flexibility, and accuracy of the treatment of the data. THIS paper reports further measurements of the heats of solution of liquid metals with the high-tem- perature solution ca1orimeter.l Measurements were made of the partial molar heats of mixing in the following liquid alloys: Cu-Ni, Cu-Ag, and Cu-Co. In addition the heats of fusion of copper and silver were also determined. The apparatus and the experimental procedure were essentially those of Benz and Elliott.2 Several modifications in the experimental method and the means for interpreting the data were incorporated in this study to improve the results. The operation of the calorimeter and its characteristics will be described only briefly here. The

Jan 1, 1965

By W. O. Philbrook, K. M. Goldman, G. Derge

THIS is the third in a series of papers from the Metals Research Laboratory dealing with the transfer of sulphur across the iron-slag interface in a carbon-saturated system. The first paper' showed that the transfer obeyed first-order kinetics. The second' presented detailed evidence in support of the three-stage mechanism: FeS(Fe) FeS(slag) FeS(slag) + CaO(sing) ? CaS(slag) + FeO(slag) FeO(slag) + C ? Fe + CO. This emphasized the role of an iron-sulphur complex as the transfer agent across the interface and as an essential intermediate in the overall process. The present paper shows the influence on the process of the individual elements, carbon, silicon, manganese, and phosphorus, the alloying elements normally present and of interest in commercial blast furnace operations, aluminum, which has a pronounced accelerating influence, and nickel and copper, which are common minor impurities in the raw materials. The experimental methods and procedures for interpretation of data are the same as described earlier.1,2 Induction heated, graphite crucibles were used, and sulphur-free slag was added to the molten iron containing sulphur and the selected alloy. Slag samples were taken at regular time intervals and analyzed for sulphur and other components of interest. The authors wish to state specifically that these experiments were not intended to simulate industrial blast furnace operations. However, they do represent a study of the kinetics and mechanism of sulphur transfer at the slag-metal interface under specified laboratory control of the major variables in the system. It is believed that the results can be usefully applied to the blast furnace if consideration is given to the differences which are known to exist between the two conditions. A rigorous evaluation of the accuracy of rate studies is difficult. Recognized sources of error include sampling and analysis of both slag and metal, temperature measurement and control, selection of zero time, composition of the gaseous atmosphere over the reaction system, and extraneous sources of sulphur from the graphite crucible and reagent materials. In this study carefully standardized procedures were followed consistently in order to minimize the errors. It is believed that the reproducibil-ity of duplicate runs indicates that errors have been rendered negligible relative to the observed effects from intentional variables. For example, original experimental points for duplicate runs are shown in Figs. 1, 2, 7, etc. In most cases in this paper the drawn curves represent an average of at least two heats. The spread in sulphur values at a given time ranges from 0.02 to 0.08 pct, which is a small frac-tioi of the total values ranging up to 2 pct S in slag. In the systematic study of the influence of alloy additions, each element was added over a range of concentrations. The two slags used in this study were designated as "acid" or 1530 and "basic" or 1545. They had the nominal compositions given in Table I. Rates were measured in the temperature range 1500" to 1650°C. Data will now be presented to illustrate the various features of the study. Silicon The first alloying element examined was silicon, because its presence is unavoidable in any silicate slag system through the reaction y/2SiO2(slag) + xM?y/2Si(liq.Fe) + MxOy where M is any reducing agent such as iron or carbon. It is known that the attainment of equilibrium by this reaction is extremely slow and probably not reached in the blast furnace." The influence of silicon on the final stages of the sulphur reaction has also been studied.' It has been shown5 hat silicon increases the activity of sulphur in iron. For such reasons silicon may also be expected to influence the kinetics of the reaction. The observed effects will now be described. The general procedure was to melt 530 grams of ingot iron in a graphite crucible, 3 in. OD, 2 1/4 in.

Jan 1, 1955

By Charles T. Holland, David A. Olsen

Considerable work has resulted in the development of a formula by which the strength of coal pillars for an L to T ratio of up to 12 may be estimated. One of the factors involved in this formula is the coefficient of friction between the coal pillar and the adjacent rock with which it is in contact. This paper presents the results of studies on sandstone, limestone, shale and coal and the coefficient of friction between coal and the other three under wet and dry conditions. With the coefficients of friction thus determined and the use of results obtained earlier by Meikle and Holland, it seems probable that coal pillar strength may be more closely estimated. Several investigators1-3 have found that the com-pressive strength of cubical coal specimens can be correlated by an equation such as

Jan 1, 1969

By Richard A. Pomeroy

This mine, known also as the A very Mine, is situated on Petite Anse Island, Iberia Parish, Louisiana. The island is about four miles from Vermillion Bay, an arm of the Gulf of Mexico, and is one of four islands or hills surrounded by the sea-marsh, as shown in the accompanying map. (Fig. 1.) A fifth, Joe Jefferson's Island, or hill, is some distance from the sea-marsh. These five islands: Belle Isle, Cote Blanche,Grand Cote, Petite Anse and Jefferson, appear to be the tops of submerged hills, and occupy a line having nearly a northwest trend. To the north are a series of hillocks that extend at intervals to the hills of Northern Louisiana, which in turn appear to run into the Ozarks of Arkansas. Near the mine there is sandstone, also a thick vein of lignite. Bones of the mastodon have been

Jan 1, 1889