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By H. H. Podgurski, H. E. Knechtel

Annealed Fe-Al alloys do not react readily to form AlN when held at 500ºC in NH3-H2 gas mixtures, but do so upon the introduction of dislocatims. Nuclea-tion of the nitride phase occurs on dislocation sites. In turn, the growth of the aluminum nitride particles causes the ferrite phase to yield plastically, generating more dislocations for the nucleation process. The nitride phase extracted from an Fe-2 pct A1 alloy nitrogenated at 500°C was identified as stoichio-metric aluminum nitride with a hexagonal crystal lattice. THIS investigation reveals the role that dislocations play in initiating and sustaining the nitriding reaction in Fe-A1 alloys. As early as 1931 the work of Meyer and Hobrock1 suggested that the initiation of the nitriding reaction could involve a nucleation controlled process. Recently Bohnenka2 depicted the gas-phase nitriding process below 600°C as one of mixed control limited by nitrogen penetration through the surface, by nitrogen diffusion, by aluminum diffusion, and by nucleation of the nitride phase, Fig. l(a). In our research in a comparable alloy (0.57 pct Al) at 575ºC, we have observed a nitrogenation which we feel is better described by Fig. l(b). In the case of a 2 pct-A1 alloy partially nitrided at 500°C we propose the profiles shown in Fig. l(c). For a complete and accurate description of the process, a concentration profile of the dislocation density in the test specimen would be needed. EXPERIMENTAL Nitrogenization was conducted between 500" and 575°C in a variety of NH3-H2 gas mixtures on three Fe-A1 alloys: 1) zone-refined iron + 0.16 i 0.2 pct Al—levita-tion melt, 2) zone-refined iron + 0.57 0.02 pct Al— levitation melt, 3) plastiron + 2 pct Al—melted by induction heating. To demonstrate the effect of dislocations on reactivity, both cold-worked and annealed samples were investigated. All nitrogenation rate studies were conducted gravimetrically with a gold-plated invar balance4 contained in a gas-flow system. To avoid contamination of the specimens in the reaction zone of the system, the reaction chamber was constructed of high-purity dense alumina. The activity of nitrogen was fixed by specific NH3-H2 gas mixtures whose compositions were continually monitored by calibrated thermal conductivity gages and checked by chemical analysis. Variations of ± 0.1 pct NH3 could easily be detected by both methods. Throughout this paper the activity of nitrogen is defined as PN3 /PH23/2 , where PNH3, and Ph2 are partial pressures in atmospheres. Electron transmission, density measurements, and chemical analyses were made on specimens before and after nitrogenating in order to reveal structural and chemical changes. Similar studies as well as X-ray diffraction studies were conducted on nitride extractions from the nitrogenated 2 pct-A1 alloy. These extractions were obtained by the use of an anhydrous bromine-methyl acetate solution which dissolves the iron and leaves the insoluble nitrides as a residue. Hardness profiles were obtained on cross-sections of partially nitrided specimens to demonstrate the extent of nitriding through the thickness of the specimens. RESULTS AND DISCUSSION The nitrogen activity in the NH3-H2, atmospheres was never allowed to reach a level capable of producing iron nitride (Fe4N). Hence, the term nitriding as used in this paper refers only to the formation of aluminum nitride whereas nitrogenation refers to the total uptake of nitrogen regardless of how it is distributed throughout the alloy. The weight increases observed during the initial stage of a nitrogenating treatment are due primarily to the solution of nitrogen in the ferrite phase, particularly when starting with annealed specimens. Because this initial nitrogenation rate in the case of the 0.57 pct A1 alloy, see Figs. 2 and 3(a), was most rapid the weight change that occurred thereafter might be attributed to the nitriding reaction with the exception of a small weight increment due to the irreversible pickup of oxygen by aluminum. The oxygen (<70 ppm) came from traces of H2O and 0, in the hydrogen and ammonia gases. On the basis of discrepancies between total weight increase and the increase in the nitrogen content of the sample as determined by chemical analysis, it was estimated and later established by activation analysis, that as much as 200 ppm of oxygen were taken up by a fully nitrided Fe-0.57 pct A1 specimen at 575°C. Most of the oxygen could have been picked up from the nitriding atmosphere on the surface of the samples during cooling to room temperature. Even 50 ppm of water in the gas phase will become oxidizing to iron before the sample has cooled to room temperature. The lack of reactivity* of these alloys in the annealed

Jan 1, 1970

By P. Shahinian, M. R. Achter

P. Shahinian and M. R. Achter (U.S. Naval Research Laboratory)—We should like to point out another instance where concentration of impurities in grain boundaries led to an embrittlement. In this case an impure nickel (99.8 pct) developed many more in-tergranular cracks during creep in a nitrogen atmosphere than in vacuum.5 In comparison high-purity nickel (99.99 pct) exhibited a much smaller atmosphere effect. We concluded that the interartion of the nitrogen with nitride-forming impurities concentrated at grain boundaries promoted inter-granular cracking.

Jan 1, 1965

The opening session of the Institute was held at the rooms of the American Society of Civil Engineers, No. 4 East 23d Street, VicePresident R. W. Raymond in the chair. After a short introductory address by the chairman, the following names were presented by the Council for election as members and associates of the Institute. They were unanimously elected : MEMBERS. Abbott, James W.,.....Lake City, Col. Abbott, J. J., Jr.,...... Lake City, Col. Bartlett, J. C.,.....Cambridge, Mass. Billings, G. H.,.....Boston, Mass. Blake, Frank C.,.....Lafayette College, Easton, Pa. Dewey, Fred. P.,.....Lafayette College, Easton, Pa. Douglass, Samuel T.,. .. . Ann Arbor, Mich. Emmons, 9. F.,.....New York City. Engle, George U.,.....Philadelphia. Harrington, Dr. Bernard J.,. .. Montreal, Canada. Hayden, Wm. B.,.....Columbus, O. Hill, Leslie C.,.....Capelton, Quebec, Canada. Land, W. J.,......Atlanta, Ga. May, Wm. A.,.....Scranton, Pa. Mills, James E.,.....St. Louis, Mo. Moore, Charles W.,.... Montezuma, Ind. Page, William Byrd,.... Lexington, Ky. Putnam, Douglas, Jr.,.... Ashland, Ky. Richards, Henry,.....Dover, N. J. Boberts, Percival, Jr.,. .. . Philadelphia. Sackett, S. G.,......Brooklyn, N. Y. Schley, Wm. S.,.....Atlanta, Ga. Setz, Gustav,......Mine La Motte, Mo. Talhutt, John H.,.....Lexington, Ky. Torrey, Herbert G.,.... U. S. Assay Office, New York City. Wernlitz, Fred. W.,..., Cartersville, Bartow Co., Ga. Wiestling, Geo. B.,.....Mont Alto, Franklin Go., Pa.

THE opening session of the Institute was held at the rooms of the American Society of Civil Engineers, No. 4 East 23d Street, Vice-President R. W. Raymond in the chair. After a short introductory address by the chairman, the following names were presented by the Council for election as members and associates of the Institute. They were unanimously elected : MEMBERS. Abbott, James W., - Lake City, Col. Abbott, J. J., Jr., - Lake City, Col. Bartlett, J. C., - Cambridge, Mass. Billings, G. H., - Boston, Mass. Blake, Frank C., - Lafayette College, Easton, Pa. Dewey, Fred. P., - Lafayette College, Easton, Pa. Douglass, Samuel T., - Ann Arbor, Mich. Emmons, S. F., - New York City. Engle, George U., - Philadelphia. Harrington, Dr. Bernard J., - Montreal, Canada. Hayden, Wm. B., - Columbus, O. Hill, Leslie C., - Capelton, Quebec, Canada. Land, W. J., - Atlanta, Ga. May, Wm. A., - Scranton, Pa. Mills, James E., - St. Louis, Mo. Moore, Charles W., - Montezuma, Ind. Page, William Byrd, - Lexington, Ky. Putnam, Douglas, Jr., - Ashland, Ky. Richards, Henry, - Dover, N. J. Roberts, Percival, Jr., - Philadelphia. Sackett, S. G., - Brooklyn, N. Y. Schley, Wm. S., - Atlanta, Ga. Setz, Gustav, - Mine La Motte, Mo. Talbutt, John H., - Lexington, Ky. Torrey, Herbert G., - U. S. Assay Office, New York City. Wernlitz, Fred. W., - Cartersville, Bartow Co., Ga. Wiestling, Geo. B., - Mont Alto, Franklin Co., Pa.

Jan 1, 1877

IT is a pleasure for the translators to record their gratitude to the Seeley W. Mudd Memorial Fund of the American Institute of Mining and Metallurgical Engineers for underwriting the cost of publication of this volume, to the Printing-Office of the Yale University Press for doing an unusually fine printing job, and to the following for granting permission to reproduce the title pages of volumes in their collection: The Bibliothèque Nationale of Paris, for edition A of the Bergbüchlein; the Osler Library of McGill University, Montreal, for editions B and G of the Bergbüchlein and edition D of the Probierbüchlein; Mr. Herbert Hoover, Jr., for editions C and E of the Bergbüchlein and editions E, M, N, and 0 of the Probierbüchlein; the Parsons Collection of the Reference Department of The New York Public Library, for edition D of the Bergbüchlein; the Library of the Bergakademie Freiberg, for edition F of the Bergbüchlein and editions A, H, and L of the Probierbüchlein; the Herzog August-Bibliothek of Wolfenbüttel, for edition C of the Probierbüchlein; the British Museum. Library, London, for edition I of the Probierbüchlein; and the library of the University of California at Berkeley, for edition J of the Probierbüchlein. The cooperation of those who helped with the translation of the Bergbüchlein is acknowledged on p. 64. A. G. S. C. S. S.

Jan 1, 1949

By J. H. Scaff, H. C. Theurer, E. E. Schumacher

The microwave region of the radio spectrum was effectively utilized in radar designs during the recent war and it has become of increasing interest in the field of communications. Work in this field has led to an important use for silicon—that of the point contact rectifiers†1 in the frequency converter of microwave (radar or radio) receivers—and has stimulated considerable interest in the electrical properties and preparation of silicon and its alloys. Silicon is an electronic semiconductor. Its conductivity at room temperature results principally from the presence of certain impurities. While for metals an increase in impurity content increases the resistivity, for semiconductors such as silicon the opposite occurs and, in general, the addition of impurities lowers the resistivity. Silicon materials may be classified into one of two groups depending upon the manner in which the impurities contribute to electrical properties. These have been termed for convenience p-type or n-type. P-type silicon develops a very large positive thermal emf against metals, has a Hall coefficient of positive sign and a low resistance direction in point contact rectification with the silicon positive with respect to the point. N-type silicon, on the other hand, develops a negative thermal emf against metals, has a Hall coefficient of negative sign and a low resistance direction in rectification with the silicon negative with respect to the point. Impurities which produce n-type silicon are called donors inasmuch as these elements contribute to electrical conductivity by donating electrons to an unfilled energy band in the silicon. On the other hand, elements which produce p-type silicon are known as acceptors as these impurities contribute to the electrical conductivity by accepting electrons from a filled energy band permitting what is known as conductivity by "holes" in which the sign of the carriers appears to be positive. A general treatment of the mechanism of conduction in semiconductors from the viewpoint of modern band theory has been given recently by Pearson,2 by Becker, Green and Pearson,3 and by Torrey and Whitmer.4 In this investigation boron and aluminum have been found to be acceptors, and phosphorus, arsenic, and antimony to be donors in silicon. Data on the effect of boron and phosphorus on the electrical properties, when present singly and in combination, have been acquired. These data are discussed in the present paper. Raw Materials Used and Methods for Adding Seeond Constituents Silicon from two sources was used in this work and these will be referred to as A and B respectively. Silicon A is a material of high purity supplied by the Electro Metallurgical Co. It is prepared by chemical purification of "commercial" silicon obtained from the arc furnace reduction of SiO2. It contains 99.8 pct silicon, minimum, with small amounts of calcium, iron, aluminum, boron, and phosphorus as the principal impurities. This material was extensively employed in these studies as well as in the commercial preparation of rectifier materials. Silicon B is a material of high purity from the du-Pont Co. It is prepared by a pyrolytic reduction of Sicl4 and is free of analytically detectable amounts of boron and phosphorus. Its use permitted study of the effect of boron and phosphorus individually on the properties. This material contains, however, spec-troscopic traees of a number of metals, some of which affect electrical and rectification properties. Typical analyses for the two grades of silicon are given in Table 1. To make controlled additions of boron to the charge it was necessary to employ a low boron content master alloy since the quantity of boron to be added was usually only a few thousandths of one percent. The alloy containing nominally one percent boron was prepared by melting chemically pure boron with silicon A using the melting techniques for 320 g silicon

Jan 1, 1950

By S. G. Lasky

Abraham Lincoln is reputed to have said that if you want to chart a course to some destination, you have to know where you are starting from. In this instance we have to define our starting point in a double manner: 1) What was the theoretical basis of the Paley predictions? 2) What actually did the Commission predict, so that we can see how the predictions have worked out up to now as a basis for considering how they may have to be changed.

Jan 3, 1960

By T. L. Joseph

A study is made of the amount of solution loss necessary to maintain the reducing power of the gas stream in the blast furnace. Curves are presented to show the effect of solution loss, moisture in the blast, and carbon dioxide from the flux on the nitrogen in the THE blast furnace process is based upon the counter flow of gases and solids. As CO, N, and H, flow upward from the combustion zones, oxygen is acquired from the descending charge. In the reduction of iron ore, a portion of CO is converted to CO, and similarly a portion of H, is converted to water vapor. The inert N,, from the air used in combustion, passes through the furnace with little change. Its concentration is, however, decreased by reactions such as direct reduction and solution loss which increase the volume of CO in the gas stream; Similarly the evolution of C02 from the limestone also dilutes the nitrogen. he purpose of this paper is to illustrate an idealized and simplified method of studying furnace processes by following changes in the gas phase between the tuyeres and the stock line. A more specific objective is to evaluate the effect of solution loss upon the CO/CO, ratio in that region of the furnace in which FeO is reduced to metallic iron. This last stage of reduction requires relatively high CO/CO, ratios to exceed the equilibrium requirements. Solution loss or the reaction of COZ with C to produce CO has a pronounced effect upon the ratio of the carbon gases and is necessary to maintain the reducing power of the gas stream if the consumption of coke is low. It will be explained later that indirect reduction followed by solution loss is stoichiometri-cally equivalent to direct reduction. Calculations will be made to show how the composition of the gas in the region of the mantle varies with coke consumption and with different amounts of solution loss. Such calculations show the condi- tions under which gasification of C with oxygen in the charge is needed to maintain the reducing power of the gas. Equilibrium conditions for FeO and the carbon gases will be used to establish a minimum CO/CO, ratio below which reduction will not proceed. The manner in which carbon is gasified in the furnace, at the tuyeres with oxygen in the air or above the tuyeres with oxygen from the charge, will be a basic feature of all calculations. It is hoped that greater interest in the use of top gas as a means of following furnace reactions will be aroused by the calculations and generalized curves which are presented. Bosh Gas Equations Subject to some alteration by the amount of moisture in the blast and by direct reduction, the gas leaving the combustion zones of a blast furnace has a definite composition. Because a relatively small amount of oxygen is acquired from the charge in the bosh and in the crucible, the products of combustion undergo little change until they enter the shaft. Bosh gas is, therefore, essentially the products of combustion of carbon in a deep fuel bed with air. The relative weights and volumes of reacting materials are expressed by the equation: 2~ + 0? + 3.76N, = 2C0 $ 3.76NZ [I] Air Bosh Gas -air = 79% N? = 3.76) 21% 02 Starting with a known mass of C consumed largely by air, Eq 1, but partly by water vapor, Eq 2, the volume and C + H2O = CO $ H? [21 composition of the bosh gas can be calculated and subsequent changes followed as reactions take place at various elevations in the furnace. As shown in

Jan 1, 1952

By W. C. Ellis

IN an ingot of germanium solidified progressively from the bottom by a method&apos; devised by J. H. Scaff and H. C. Theuerer, examination discloses ex- IH. C. Torrey and C. A. Whitmer, Crystal Rectifiers. p. 364. 1948. New York. McGraw-Hill Pub. Co. tensive twin relationships. A slice taken about midway in a cylindrical ingot approximately 3/4 in. in diameter and 1 1/2 in. in length, after etching and polishing to delineate different orientations, is shown in fig. la. The orientations of the regions designated with letters were determined by Laue X-ray back-reflection methods and plotted on stereograms. The orientation relationships of the designated components were determined by comparing the values for the nine angles between the three respective cube poles of each orientation with the values calculated in a formal treatment of octahedral multiple twinning in cubic crystals. Germanium, diamond cubic in structure, has the octahedral twinning habit. I am indebted to K. H. Storks for the calculation of the angular relationships of cube poles in octahedral twinning to four orders. The set of values for the nine angles is distinctive of the order of twinning. Confirmation for a multiple twin relationship is obtained from the determined indices of the mirror planes. These exist for all orders of twinning through the third and for some of the fourth." If the orientations are not those for twinning, then the nine angles for the cube poles do not correspond in value and distribution to those formally calculated. Since all nine angles must correspond in values and distribution of values to the calculated ones, the Laue method with a precision of one or two degrees is adequate to establish or deny with confidence the existence of multiple twins. Regions of the same orientation can also frequently be identified by the optical reflections. For example, the narrow twin bands in A at 2: 00 o&apos;clock have orientation B1. The interesting twin relationships shown schematically in fig. lb were found for the section in fig. la. Most of this slice was made up of orientation, A, appearing in widely separated regions. Of the four possible first order twins of A, three were present in this slice and are designated by B with subscripts. Four second order twins of A are designated by C with subscripts. It is worth emphasizing that two of these, C, and C,, are second orders of A through the first order missing in this section. Two regions, designated by D with subscripts are third order twins of A. D2 is a sixth order twin of D,. All orientations found were ascribable to multiple twinning, as if the orientations in this section originated earlier in solidification from a single nucleus. The presence of extensive multiple twinning to- gether with the absence of other orientations appears to be a characteristic result in many instances of solidification of germanium. Fertile conditions for twinning probably exist in the array of atoms in the diamond cubic structure. The high order twins in the section shown, it is reasonable to presume, are the result of progressive octahedral twinning through several generations in the material freezing earlier. Some of these generations do not appear in this section, it is suggested, because their orientations with respect to the growth direction were unfavorable for survival. The extensive twinning is probably promoted during solidification by constraint imposed by volume increase, and to an irregular growth front. Twinning may also be due, in part, to the attempt of the solidifying region to attain the orientation most favorable to the growth direction (maximum thermal gradient). The nucleus for a twinned orientation could have its origin in a "stacking fault" on the close-packed octahedral plane. Further work is being done in which the course of twinning throughout an ingot is being studied. The results appear to be important in the general theory of solidification.

Jan 1, 1951

By George S. Ansell, John B. Hudson, Stephen A. Koffler

The permeability of hydrogen through the a phase of palladium has been measured by a low pressure permeation technique under conditions such that bulk diffusion was the rate-controlling process. The observed permeability is described by the equation: J = 1.80 x 1O-3 P½exp(-3745)/RT) cc(stp)/sec/cm2/en over a range of hydrogen pressure, P, from 2.9 x 10-5 m Hg to 5.0 x 10-3 cm Hg, and over a temperature range, T, from 300" to 709°K. The fact that the permeability shows a square root dependence on pressure and a reciprocal dependence on thickness was taken as evidence that bulk diffusion, rather than surface reactions, was the rate-controlling process. The permeability data were used in conjunction with the solubility data of Salmon et al., to determine the diffusivity of hydrogen through palludium as: D = 4.94 x 10-3 exp(-5745/RT) cm2/sec There was no influence of sub structural defects observed over the temperature range employed. From the permeability data obtained, coupled with grain size measurements, it was concluded that the ratio of grain boundary diffusivity to bulk diffusivity was less than 105 over the range of temperature investigated. THE diffusive mass transport of hydrogen in the a phase of palladium has been studied previously by numerous investigators.&apos; In spite of the large amount of attention this system has received, there is not good agreement between the results obtained in different investigations.&apos; This is due in part to the fact that the mass transport was surface-limited during some of these studies, rather than being diffusion-controlled3-5 The reason for the disagreement in other cases is not clear. These studies made use of such techniques as rate of absorption from solutions6 and gases,&apos; electrochemical potential,8 time lag,&apos; and permeation10,11 to determine the mass transport behavior. Of these, the gas permeability technique is the only method which allows an easy test to determine if diffusion is the rate-controlling mechanism, thus eliminating the uncertainty regarding the limiting transport processes inherent in the other techniques. The two most recent permeability studies are those of Toda10 and Davis." Toda determined the permeability of hydrogen in the a phase of palladium over the temperature range from 170" to 290°C, and over the pressure range from 36 to 630 mm Hg utilizing a steady-state gas-permeability technique. Toda&apos;s result was: J = 1.41 x 10-3 P½ exp(-3220/RT) where J = specific permeability in cc(stp)/sec/cm2/cm, P½ = square root of the inlet pressure in (cm Hg)½, R = Universal gas constant, and T = temperature in deg Kelvin. Davis11 also employed a steady-state gas-permeability technique over the temperature range from 200" to 700°C and over the pressure range from 0.02 to 760 mm Hg. His result for the permeability of hydrogen in the a phase of palladium was: J = 3.15 x 10-3 P½ exp(-A440/RT) In the range of overlapping temperature for these two investigations, the values of the specific permeability calculated from the above two equations differ by a factor of about 1.8. In the present investigation, the permeation of hydrogen in the a phase of palladium was determined over a wide temperature range, 27" to 436oC, and over the pressure range from 2.9 x 10-5 to 5.0 x 10-3 cm Hg. This temperature range overlaps that of the previous investigations of Toda and Davis, but also covers the lower temperature range which has never before been investigated. The lower pressure range used here avoided the interaction between the dissolved hydrogen atoms observed at higher hydrogen concentrations.&apos; MATERIALS The as-received palladium specimens were cold rolled from a casting and were supplied as 5.08 cm discs of 0.508 and 0.762 mm thickness. According to J. Bishop and Company specifications, the composition of the discs was 99.95 pct Pd, the balance being Cu, Ag, Au, and Ir. In order to obtain samples of varying grain size, the as-received discs were then heat treated. Sample 1 was treated for eight minutes in a nitrogen atmosphere at 810°C and then air-cooled. Sample D was heated first to 550°C in helium. The helium atmosphere was then immediately replaced by hydrogen and the temperature was slowly raised to 1220°C and held for 22 hr. The sample was then cooled to 550°C where the hydrogen was replaced by helium and the disc was further furnace-cooled to room temperature. Sample H was given the same heat treatment, only with hydrogen substituted for helium below 550°C. The reason that hydrogen was not used throughout the entire annealing cycle for samples D and H was to prevent the distortion encountered by low-temperature cycling in hydrogen observed by Darling." After these heat treatments were completed, the

Jan 1, 1970

By A. J. Ardell

SASS and cohenl (S-C) have recently reported some transmission electron microscope observations of an interesting effect which they call "veining". They observed veining in thin foils of solution-treated and (in certain cases) aged samples of a Ni-10.3 at. pct Ti-0.6 at. pct A1 alloy (assumed equal to 10.9 at. pct Ti). S-C suggest that veining in solution-treated samples is due to the selective electrolytic etching of titanium-rich regions in alloys which are otherwise homogeneous. They associate the veins with the discrete titanium-rich regions detected in a magnetic study of aging in this system by Ben Israel and Fine,&apos; and they also suggest that the initial strengthening of aged Ni-Ti alloys is due to these titanium-rich regions, rather than the formation of the coherent precipitate (Ni3Ti, L12 crystal structure).

Jan 1, 1970

By K. Tangri, M. Chaturvedi

The addition of 0.5 wt pct Cu to Zr-2.5 Cb alloy increases the as -quenched hardness of the hexagonal martensitic a&apos; phase, produced by water-quenching bccß-Zr phase, by about 35 pct. This strengthening has been attributed to the solid -solution hardening of the matrix. On aging ternary martensite, a&apos; phase reverts to equilibrium a and Zr2Cu and ß-Cb precipitate out, mainly at the twin and grain boundaries, causing a secondary hardening of the matrix. COLD-worked Zircaloy-2 pressure tubes have been in use in power reactors for a considerable period of time. The search for a better material led to the development of Zr-2.5 wt pct Cb alloy which in the quench-aged condition develops 50 pct more strength than that of cold-worked Zircaloy-2, however, its corrosion resistance in water and steam in the temperature range of 316" to 400°C, in absence of neutron flux, is inferior to that of zircaloy-2.&apos; Work carried out by Ells et al.1 and Dalgaard2 has shown that the corrosion properties of Zr-2.5 wt pct Cb alloy can be considerably improved by the ternary addition of 0.5 wt pct Cu. This paper is concerned with the effect of 0.5 wt pct Cu on the formation of martensitic a and its aging characteristics in a Zr-2.5 wt pct Cb alloy. MATERIALS AND EXPERIMENTAL TECHNIQUES Zr-2.5 Cb-0.5 Cu (referred to as the ternary alloy) and Zr-2.5 Cb (referred to as the binary alloy) alloys, supplied by the Chalk River Nuclear Laboratories of the AECL were used. The detailed chemical analysis is given in Table I. Cold rolling and swagging with frequent intermediate anneal of 1000°C were used for the initial fabrication of the alloys. All the heat treatments were carried out after the specimens were wrapped in zirconium foils and encapsulated in silica tubes under a vacuum of 5 x 10-6 mm of Hg. For optical metallography and hardness measurements specimens were mechanically and then chemically polished in a 45 pct HNOj, 45 pct HzO, and 10 pct HF solution. Hardness was measured on a Vickers hardness tester using a 10-kg load. For each specimen at least fifteen indentations were made in order to obtain a representative value. The phase identification and structural analysis were carried out using X-rays and electron diffraction techniques. Wires of 1.5 mm diam reduced to 0.12 mm diam by chemical etching were used for making Debye-Scherrer powder patterns using Cu Ka radiation in a 114.6 mm diam camera. Carbon extraction replicas were prepared by etching the specimens, after depositing a layer of carbon on the metallographic specimen, in one part HF and thirty parts ethyl alcohol. Thin films were prepared by electropolishing heat-treated 3/4 by 1/2 by 0.005 in. thick strips using a modified Bollman-Window technique. The 10 pct perchloric acid-90 pct methyl alcohol bath was kept at -50°C and polishing was done at 5 to 10 V. The thinned specimens were washed in ethyl alcohol at -30º to -40°C and dried between filter papers. Replicas and thin films were examined in a Phillips 300 G electron microscope. For resistivity measurements thin strip specimens 0.02 by 0.3 by 10.0 cm long were used. The potential leads were spot welded to the specimens in order to maintain a fixed length for the initial and the final resistivity measurements. The resistivity was measured by a Kelvin bridge in a temperature controlled room. The temperature was maintained at 72º ±1°F and the accuracy of the resistivity measurements was 0.03 µa-cm. RESULTS As-Quenched Structures. In order to produce a homogeneous matrix to study the precipitation reaction the solution-treatments of both the alloys were carried out in the -field region. From the Zr-Cb phase diagram due to Lundin and cox3 ß/a + ß phase boundary for Zr-2.5 wt pct Cb alloy is 820°C. Ells et al.1 have reported this boundary for Zr-2.5 Cb alloy containing 1100 ppm 0 to be at 920°C. Also, the addition of 0.5 wt pct Cu reduces this temperature by 50°C. Therefore, the solution-treatments were carried out at 1000°C to ensure that the alloys were in ß-phase region. The soaking time was 1 hr and the specimens were water-quenched. The as-quenched hardness of the binary alloy was 245 Vpn whereas, that of the ternary alloy was 330 Vpn. The X-ray diffraction studies indicated that the as-quenched structure of both the alloys consists of martensitic hexagonal phase a&apos;, with a c/a ratio of 1.591, and some retained ß-Zr. The presence of a&apos; phase was further confirmed by thin film electron microscopy. Electron micrographs of typical ß-quenched structures of the ternary and the binary alloys are shown in Figs. 1 and 2, respectively. Fig. 3 shows the diffraction pattern from an area similar to that shown in Fig. 1. Although, the as-quenched hardness of the ternary alloy is about 35 pct greater than that of the binary alloy, the structure of both the alloys seems to be the same. The matrix of both alloys is heavily twinned and shows very few dislocations. Furthermore, there is no evidence of any precipitation taking place in either of the two specimens during quenching from the solution-treatment temperature. Aging Behavior of Martensitic a&apos;. The aging kinetics of the ternary alloy were followed by resistivity and hardness measurements. The as-quenched values

Jan 1, 1970

By L. G. Huntley

Points out differences between the new, more liberal, law passed by the Colombian Congress and the law passed in 1919, gives a few facts about the pipe-line concession granted to a Canadian company, and tells of new drilling developments. PROBABLY the most important development in the Colombian oil situation during the past year was the passage by Congress of a new petroleum law, which went into effect Jan. 31, 1923. The principal points of interest in which this new law changes or improves the previous one are as follows: Law 120 of 1919 provided that one person or corporation could not acquire more than three exploitation zones. of 5000 ha. each, and royalties were based on a sliding scale, to wit: 6 per cent. royalty on lands 400 km., or more, from the ocean; 8 per cent. on lands 200 but not over 400 km. from the ocean, and 10 per cent. royalty on lands located less than 200 km. from the ocean. Rentals were fixed at 10 centavos per hectare for the first year; 20 centavos for the second year; 50 centavos, third year, and $1 (one peso) yearly thereafter. Under this law the term of the lease was fixed at 20 years and, at the discretion of the government, could be extended for 10 years additional. After the expiration of the lease and its corresponding extension, the machinery and other material placed upon the property would vest in the government. A bond of 20,000 pesos was also required of the lessee to guarantee faithful performance of his contract.

Jan 3, 1924

By R. P. Smith, L. S. Darken

FOR a high-purity iron-carbon alloy, the phases existing at equilibrium at temperatures slightly above the temperature of the metastable eutectoid are austenite and cementite (hyper-eutectoid) or austenite and ferrite (hypo-eutectoid) and those below the eutectoid temperature (carbdn content > 0.02 pct) are ferrite and cementite. Such an alloy, held in a carefully controlled and measured temperature gradient (about 1 cm per deg) which includes the eutectoid temperature, then quenched and examined metallographicall.y, provides a precise measure of the eutectoid temperature. The samples were hollow cylinders approximately 1.3 cm OD, 0.63 cm ID, and 2.5 cm long, which had been carburized to the desired carbon content at 1000°C with an appropriate hydrogen-methane mixture. In order to cool the samples to room temperature with a minimum change of carbon content and absence of cracks they were quenched in a Cerro Bend bath at 480°C, followed by a water quench to room temperature. Three cylinders were suspended in the furnace1 in a purified helium atmosphere, by a closed end, thin wall, silica tube which also served as a thermocouple well. The top and bottom cylinders served only as a means of making the temperature gradient along the center cylinder more uniform. The temperature was determined with a platinum-platinrhodium thermel calibrated by comparison with a thermel certified (* 0.5OC) by the National Bureau of Standards. After holding in the temperature gradient for 24 to 72 hr the samples were quenched in Cerro Bend at 480°C, followed by

Jan 1, 1960

By Henry Emmett Gross

Two types of decline curves are considered and their applications are discussed. The first is the well-known semilogarithmic decline curve having the rate of production plotted on the logarithmic scale and the time on the horizontal scale. The other curve is the percentage of oil in the fluid versus cumulative production, and it is plotted on Cartesian coordinate paper. These curves are illustrated by carefully and adequately labeled graphs. Where conditions permit application of both types of curves for rationally determining the reserves of a well, both should be applied and the most conservative reserve should be chosen. Formulas are given for determining the economic limits. For a semi-l~~arithmic~decline curve the formula is: A = B X C X D X E X F or B = A/C ? D X E X F A = total monthly operating cost (average of past year), B = economic limit in barrels of oil per day, C = days in an average month = 30.4, D = market price of crude per barrel, E = 1-royalty, F = 1-gross production tax, G = water production in barrels per day at the economic limit, H =per cent oil in fluid at economic limit. The economic limit for a per cent oil in the fluid curve is: H = B/B+G X 100 The semilogarithmic decline curve is treated first. Straight-line extrapolations on semilogarithmic paper follow the compound interest compound discount law, hence the ensuing formulas derived from this law may be used in computing reserves for such extrapolations: [1___1/(1+Y)]

Jan 1, 1939

By Henry Emmett Gross

Two types of decline curves are considered and their applications are discussed. The first is the well-known semilogarithmic decline curve having the rate of production plotted on the logarithmic scale and the time on the horizontal scale. The other curve is the percentage of oil in the fluid versus cumulative production, and it is plotted on Cartesian coordinate paper. These curves are illustrated by carefully and adequately labeled graphs. Where conditions permit application of both types of curves for rationally determining the reserves of a well, both should be applied and the most conservative reserve should be chosen. Formulas are given for determining the economic limits. For a semi-l~~arithmic~decline curve the formula is: A = B X C X D X E X F or B = A/C ? D X E X F A = total monthly operating cost (average of past year), B = economic limit in barrels of oil per day, C = days in an average month = 30.4, D = market price of crude per barrel, E = 1-royalty, F = 1-gross production tax, G = water production in barrels per day at the economic limit, H =per cent oil in fluid at economic limit. The economic limit for a per cent oil in the fluid curve is: H = B/B+G X 100 The semilogarithmic decline curve is treated first. Straight-line extrapolations on semilogarithmic paper follow the compound interest compound discount law, hence the ensuing formulas derived from this law may be used in computing reserves for such extrapolations: [1___1/(1+Y)]

Jan 1, 1939

By J. David Lowell

On a low desert ridge six miles south of Cairo lie the remains of the world&apos;s earliest known mining town, Maadi of predynastic Egypt. Copper artifacts, including ingots and an ax head which was spoiled in casting, indicate that copper ore was smelted in Maadi, and radio- carbon dating has placed the activity at least as early as 3300 B.C. This is the oldest documented date for the use of smelted copper, the first industrial metal used by man. Copper was mined and smelted almost as early in Asia Minor and on the island of Cyprus, but the greatest development of the budding copper industry was in Egypt, where specific historical records show that about 10,000 tons of copper metal were produced in the period from 1850-1580 B.C. Contrast this production of 35 tons per year with the present world production of about 7 million tpy.

Jan 1, 1970

By C. E. Birchenall, M. H. Davis

The rate of oxidation of titanium in the temperature range 650° to 950°C has been measured. &apos;The linear rate law obtained is explained by interface reaction control of the process. Tracer experiments indicate the oxygen diffuses in at least one phase of the scale. THE kinetics of oxidation of titanium, principally at low temperatures and under varying oxygen pressures, have been reported.¹,² In the present investigation the rates of oxidation of titanium have been determined by the gravimetric method in the temperature range 650" to 1000°C under 1 atm of oxygen. Some of the scales formed were powdered and an endeavor was made to identify the phases present by X-ray diffraction. Alexander and Pigeon1 ascribe a logarithmic rate law to the growth of thick films formed at temperatures up to 565"C, and Gulbransen and Andrew&apos; suggest that the parabolic rate law holds up to 600°C. In both cases large initial deviations from those relationships are apparent and no explanation is offered. In the present experiments it is shown that a linear rate law holds in the temperature range 650" to 1000°C, and it is suggested that the initial deviations observed are due in part to a spurious surface area effect and also to the high solubility of oxygen in titanium metal. Positive information on the mechanism of oxidation is not available, but oxygen ion diffusion through the lattice is inferred from the re- sults of trace experiments. X-ray analysis of the scale confirms Gulbransen and Hickman&apos;s&apos; observation on the presence of rutile TiO². Experimental Details The titanium used in these experiments was prepared by the reduction of titanium tetrachloride with magnesium and was used in the form of rolled sheet. Samples approximately 0.040x0.5x0.75 in. were cut and polished to a fineness of 4/0 on metal-lographic polishing papers. Individual samples, suspended on a platinum wire, were lowered into the hot zone of a furnace, in vacuo, by means of a winch, and oxygen was admitted after the desired temperature was attained. The increase of weight of single samples oxidized for fixed times at certain temperatures was determined by weighing the sample before and after oxidation on a chemical balance. In these instances the sample was used for only one time at one temperature. In some cases the course of oxidation was followed by attaching the sample to a sensitive spring balance and noting periodically the extension of the spring with time of oxidation. Kirkendall type experiments were carried out by marking the surface of the titanium prior to oxidation with a solution containing radioactive silver. After drying, the specimen was heated in vacuo to decompose the silver nitrate used, leaving a small amount of metallic radioactive silver on the surface. Following oxidation, these samples were mounted, ground, and then placed in intimate contact with

Jan 1, 1952

Jan 1, 1933

By John V. Hamme

ONE of Tungsten Mining Corp.&apos;s Vance County, N. C., mill near Henderson was the installation of a new crushing plant with a capacity of 45 to 50 tph. During 1953 the milling rate was jumped from 650 tons to 800 tpd simply by expanding existing facilities, eliminating bottlenecks, and making changes in the existing and new circuits. Previous expansions in 1951 and 1952 raised mill capacity from 300 tons to 650 tpd. In its latest move, Tungsten Mining decided that expansion of existing facilities would be more economical than building that normal production was uninterrupted. For the engineering and design of the new crushing plant and mill expansion the services of the Southwestern Engineering Co., Los Angeles, were obtained. The Southeastern Construction Co., Charlotte, N. C., carried out construction, alterations to existing facilities, and the installation of equipment

Jan 10, 1954