Search Documents

By L. R. Shoenberger

Boron has been used to produce nonaging low-carbon sheet steel. Retention of the necessary minimum amount of about 0.006 pet partially killed the steel. Amounts exceeding about 0.012 pet increased the degree of deoxidotion, piping tendencies, and possibility of hot tearing in primary rolling. Semikilled practice resulted in good ingot yields and satisfactory surface quality. Aluminum added with the boron provided a protective de-oxidizer. Good drawobility was indicated by performances of the steel in a limited number of deep-drawing trials. Some problems with hot-tearing and boron-analysis procedures were overcome. Metal lographically, the boron semikilled steels revealed some structures not usually found in plain low-carbon steels. IN 1943 Low and Gensamer1 reported that strain aging, which hardens and embrittles ordinary low-carbon rimmed steel, was due to nitrogen and carbon, and that oxygen played a relatively unimportant role. Since then, many investigators have substantiated their findings and indicated that nitrogen is particularly potent. Commercially, today's most widely produced non-aging sheet steels for deep drawing are either aluminum killed or vanadium rimmed types. The difference in deoxidation practice, alone, is evidence that oxygen is apparently not an important consideration in control of strain aging. The fact that nitrogen is important is apparent in the consideration that has been given, knowingly or unknowingly, to the amount combined with aluminum and vanadium. Patents were granted to Hayes and Griffis2 for the processing of aluminum-killed steel, and to Epstein" for the manufacture of vanadium rimmed material. Certain prescribed steps in producing these steels can be correlated with the formation of the respective nitrides within certain temperature ranges below the usual hot-finishing temperatures. The potential nonaging properties of either type can be reduced or suppressed by cooling too rapidly to permit the aluminum or vanadium to combine with nitrogen. Subsequent suberitical annealing of the cold-rolled strip, however, normally forms the nitrides and produces the resistance to strain aging. Titanium-killed nonaging steel, described by Comstock,1 forms a nitride in the molten state and is essentially nonaging throughout its processing. Zirconium-killed steel, which was investigated briefly by the author,* appeared to have similar nitride- forming characteristics. It is known" that chromium can produce nonaging rimmed steel, but relatively little is known of the potentialities of some of the other nitride-forming elements such as boron, silicon, columbium, and cerium. In attempting to develop a new nonaging cold-rolled sheet steel with good drawability, the following factors were considered pertinent. Such a steel would necessarily have a low carbon content and therefore have a relatively high degree of oxidation when made in a basic open-hearth furnace. If the denitriding element were also a deoxidizer, a part of the addition would be lost as oxide. The degree of deoxidation would determine whether the steel is rimmed, semikilled or killed, and also could be expected to have an important bearing on ingot yields and ultimate surface quality. Assuming that the pattern for the production of cold-rolled sheets would not be changed to any great extent, the nitride must form in the molten steel, in hot rolling, in subsequent cooling, or in annealing. The nitride, once formed, should resist dissociation and be stable in the final product. Usually an excess of the nitride-forming element is required to combine with sufficient nitrogen. If the element used is a strong ferrite strengthener, a small excess may markedly decrease drawability. With aluminum and vanadium, about 0.03 to 0.05 pct in the steel is preferred. Epstein has said" that about 0.30 pct chromium is required. Titanium nonaging steels are hard unless a sufficient amount (about 0.30 pct) is added also to combine with the carbon. The cost of the necessary amounts of these latter two elements discourages commercial acceptance. Silicon was considered as a possible nitride former, but since amounts up to 0.10 pct in rimmed and semikilled steels do not induce marked resistance to strain aging, larger amounts are apparently required, which would tend to harden and strengthen the ferrite. Of the other elements mentioned, all but boron are expensive heavy-metal elements. Stoichi-ometrically, almost an equal weight of boron would be required to combine with the nitrogen—-ordinarily about 0.003 to 0.006 pct in scrap-practice open-hearth steels. Boron is a slightly stronger deoxidizer than carbon but is less powerful than zirconium, aluminum, or titanium. Thus a rimmed-steel practice might be possible. There is much in the technical literature concerning the hardenability effects of minute amounts of boron in killed steels but very little about its behavior in low-carbon material—particularly as a ferrite strengthener. The available data indicated a need for better information concerning the effects of boron in low-carbon strip steels. Experimental Work Development of a Boron-Treated Nonaging Strip Steel—Initial attempts to produce a boron-rimmed strip steel employed 3-ton basic open-hearth heats which could be teemed into molds large enough to sustain a normal rimming action. Boron as ferro-boron was added to the ladle in small amounts because of the reported hot-short character of aluminum-killed heat-treating grades containing more than about 0.005 pct boron. Actually, the amounts used, i.e., 1/8 and 1/4 lb per ton, would be large for

Jan 1, 1959

By C. G. Dunn

This note describes a method for revealing micro-structures in tantalum through an {hkl} effect which was found during a study involving amorphous and crystalline tantalum oxides. Three steps are involved. First, an amorphous film of Ta2O5 is formed anodically1 on the surfaces of the tantalum. The amount needed depents on the thickness of the substrate tantalum; 1600Å of oxide, however, is generally satisfactory in the 1/2 -mil (12 µ) to 3-mil thickness range. The film at this point is uniform in color. Second, the anodized specimen is heated to 800°C in. vacuo during a period of a few minutes and held at temperature for 5 min. During such a treatment some oxygen leaves the oxide through dissolution into the substrate tantalum (e.g., at 10-8 Torr oxide films thinner than about 800 completely disappear on 5-mil strip). Considerable crystallization of the amorphous oxide also occurs adjacent to the metal/oxide interface but not throughout the oxide thickness. The thickness of oxide needed as a residue is not too critical; values between 500 and 1000Å (optical estimate') may be most useful. (The presence of a residual oxide layer after the heat treatment usually is not apparent; in fact, in most instances the surfaces have a metallic appearance. This can be the case also for thicker residual films needed in the detection of a crystalline oxide phase by surface X-ray diffraction—e.g., if the initial oxide film is 3000Å thick, enough crystalline oxide is formed for X-ray detection.) The third step eliminates the metallic appearance at the surface and reveals (or produces) a varied colored film of tantalum oxide. Two methods can be used and both will be illustrated. If the specimen is dipped in 48 pct HF for a few seconds, the tantalum is found to be covered with a multicolored oxide. Moreover the colors correlate with the grain structure of the substrate tantalum through an orientation dependence of the type illustrated in Fig. 1, where results of an orientation analysis by the Laue X-ray method have been plotted. Other film conditions would have provided a different set of colors for the same orientations. Any such correlation, however, provides a basis for a qualitative assessment of the distribution of orientations in a large sample. The cold-rolled structure of tantalum foil produced by a recrystallization anneal and a cold-rolling reduction of 95 pct is not easily obtained by usual metal-lographic methods.' The structure, however, is easily revealed by the present technique, Fig. 2. The alternative third step is to reanodize the specimen. The optical nature of the final anodic film depends on the presence of the crystalline oxide phase; color variations indicate optical thickness variations in the film. As the reanodization voltage is increased from zero, straw and light brown colors appear (as usual), followed now by variations in color from grain to grain depending on {hkl} orientation. Suitable end points, which are determined by voltage and time, are easily established. Fig. 3, for example, shows the grain structure developed in 5-mil tantalum strip during a 30-min re-crystallization and grap-growth anneal at 1800°C. An anodic film of 1600Å thickness was added prior to the special 800°C anneal. Reanodization was done at constant current density (near 0.2 ma per sq cm) in an aqueous solution of H3PO4 (0.01 pct) and was terminated after the initial brown colors were replaced by a deep blue at approximately 30 v. Although good grain contrast can be obtained with bright field illumination, even greater contrast for black and white micrographs may be obtained with polarized light, as in Fig. 3.

Jan 1, 1967

DAVID THOMAS 1871 R. W. RAYMOND 1872-1874 A. L. HOLLEY 1875 ABRAM S. HEWITT 1876 T. STERRY HUNT 1877 ECKLEY B. COXE 1878-1879 WILLIAM P. SHINN 1880 WILLIAM METCALF 1881 RICHARD P. ROTHWELL 1852 ROBERT W. HUNT 1883 JAMES C. BAYLES 1884-1855 ROBERT H. RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B. POTTER 1888 RICHARD PEARCE 1889 ABRAM S. HEWITT 1890 JOHN BIRKINBINE 1891-1892 H. D4. HOWE 1893 JOHN FRITZ 1894 J. D. WEEKS 1895 E. O. SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1943

DAVID THOMAS 1871 R. W. RAYMOND 1872-1874 A. L. HOLLEY 1875 ABRAM S. HEWITT 1876 T. STERRY HUNT 1877 ECKLEY B. COXE 1878-1879 WILLIAM P. SHINN 1880 WILLIAM METCALF 1881 RICHARD P. ROTHWELL 1852 ROBERT W. HUNT 1883 JAMES C. BAYLES 1884-1855 ROBERT H. RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B. POTTER 1888 RICHARD PEARCE 1889 ABRAM S. HEWITT 1890 JOHN BIRKINBINE 1891-1892 H. D4. HOWE 1893 JOHN FRITZ 1894 J. D. WEEKS 1895 E. O. SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1942

By Frank M. Howell, Claude E. Schmidt

To counteract the spiralling costs of labor and materials against the fixed sale of its product, namely, gold at $35 per oz, Homestake Mining Co. has revised the milling flowsheet once and effected increases in the daily milling rate twice in the past 12 years. During this period the mining department has been able to hold production costs steady by increased productivity through technical improvements and utilization of the most modern mining by CLAUDE E. SCHMIDT and FRANK M. HOWELL, JR. 46-MINING ENGINEERING, APRIL 1963 equipment. The flowsheet alteration occurred during 1951-1953 when the two crushing plants at the shaft head frames were converted to a three-stage crushing system with the third stage closed circuited to produce a minus 5/8-in. product as rod mill feed.

Jan 4, 1963

DAVID THOMAS 1871 R. W. RAYMOND 1872-1874 A. L. HOLLEY 1875 ABRAM S. HEWITT 1876 T. STERRY HUNT 1877 ECKLEY B. COXE 1878-1879 WILLIAM P. SHINN 1880 WILLIAM METCALF 1881 RICHARD P. ROTHWELL 1852 ROBERT W. HUNT 1883 JAMES C. BAYLES 1884-1855 ROBERT H. RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B. POTTER 1888 RICHARD PEARCE 1889 ABRAM S. HEWITT 1890 JOHN BIRKINBINE 1891-1892 H. D4. HOWE 1893 JOHN FRITZ 1894 J. D. WEEKS 1895 E. O. SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1941

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

By M. Cohen, R. T. Howard

The purpose of this paper is to direct attention to the lower part of the austenite transformation diagram, or TTT curves, where considerable uncertainty still exists as to the blending of the bainite and martensite reactions. The dissimilarities between these two low temperature transforrnations have been summarized recently by Troiano and Greninger.' Of particular importance to the present work is the fact that martensite formation, unlike bainite formation, is not suppressed by the fastest quenching rates attainable. However, most of the investigations in this direction have been concerned primarily with the start of the martensite transformation (Mg) during cooling, rather than with the quantitative aspects of the subsequent reaction on either further cooling or isothermal holding. Several years ago, Cohen2 suggested a form of transformation diagram which reconciled, at least schematically, the isothermal characteristics of the bainite transformation with the insuppressible nature of the martensite transformation. In essence, the diagram consisted of a family of horizontal lines (representing the progress of the austenite-martensite reaction during quenching) which were interrupted in point of time by the bainite family of C-curves extending down from higher temperatures. This picture received later support by metal-lographic3 and dilatometric4,5 studies, but the techniques employed were not sufficiently critical to substantiate some of the details. Elmendorf6 and Grange and Stewardi have shown that the Greninger-Troiano metallographic technique8 may be used not only for M, determinations, but for studying the course of further austenite decomposition. In fact, the latter investigators have observed the amount of martensite formed as a function of temperature below M, in fourteen commercial steels. In the present paper, the Greninger-Troiano technique has been combined with the lineal method of Howard and Cohen9 to provide a unique, quantitative treatment of the austenite-martensite reaction. Furthermore, isothermal transformations have been similarly measured on holding at temperatures above and below M., thus permitting a fairly detailed presentation of the lower part of the conventional austenite transformation diagram. Experimental Details Materials The steels, listed in Table I, were selected for study because they exhibit a satisfactory range of M. temperatures and have not received as much attention as the lower carbon grades. They were prepared as 30 lb induction furnace heats in the laboratories of the Vanadium-Alloys

Jan 1, 1949

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1938

DAVID THOMAS 1871 R. W. RAYMOND 1872-1874 A. L. HOLLEY 1875 ABRAM S. HEWITT 1876 T. STERRY HUNT 1877 ECKLEY B. COXE 1878-1879 WILLIAM P. SHINN 1880 WILLIAM METCALF 1881 RICHARD P. ROTHWELL 1852 ROBERT W. HUNT 1883 JAMES C. BAYLES 1884-1855 ROBERT H. RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B. POTTER 1888 RICHARD PEARCE 1889 ABRAM S. HEWITT 1890 JOHN BIRKINBINE 1891-1892 H. D4. HOWE 1893 JOHN FRITZ 1894 J. D. WEEKS 1895 E. O. SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1944

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898 JAMES DOUGLAS 1899-1900

Jan 1, 1952

By Warren Howes, C. O. Anderson, Robert E. Illidge, M. D. Harbaugh, S. J. Burris

The Tri-State zinc-lead mining district embraces an extensive area, including the northeastern part of Ottawa County, Oklahoma, the southeastern part of Cherokee County, Kansas, and adjacent portions of Missouri, mainly in Jasper County. The Oklahoma-Kansas portion of the district, in the vicinity of Picher, Okla., has been the principal producing area since 1917, and the present milling practice in that section is the subject of this paper. This district is the largest zinc-producing field in the United States. In 1926 it produced 55 per cent of the nation's zinc and 15 per cent of its lead, and in 1933 it produced 35 per cent of the zinc and 10 per cent of the lead. From 1842 to 1933, inclusive, the total output of the district was 18 1/2 million tons of zinc and lead concentrates valued at 818 million dollars. Of this production, the Oklahoma-Kansas, or Picher, field yielded over 9 million tons valued at over 400 million dollars. Mining operations in the Oklahoma-Kansas field near Picher and Baxter Springs began in 1915. The mills built it that time consisted merely of gravity concentration plants employing jigs and tables and the same flow sheets as had proved satisfactory with the free-milling ores such as were mined in the Joplin-Webb City fields in Missouri. The Kansas-Oklahoma ores proved to be much richer but also more refractory to treatment than those in the Joplin area, and contained a considerable percentage of zinc mineral not freed by the amount of crushing usually practiced in preparing the ores for jigging. Thus the old Joplin type of mill, with its usual two or four jigs and a few tables, proved inadequate and resulted in excessive tailings losses sometimes as high as 50 per cent

Jan 1, 1935

E.T. CONNER;. Scranton;. Pa-I had the honor of being associated with Mid. Griffith in an investigation of the Scranton mine cave problem several years ago; in the course of which we investigated rather carefully the bearing strength of various materials that might be utilized for, the support of over We found that there were no reliable data as to the resisting strength, for instance, of gob pillars or timber cogs or cribs, nor as to the amount of compression that might be expected under a given burden. We made a series of tests at the Fritz engineering laboratory of Lehigh University, from which we, reduced certain conclusions, subject, however, to further test before they could be definitely recommended. Onr study of the subject was later checked by a commission appointed by the Governor of the State of Pennsylvania, to investigate the same subject the subsidence of the surface, and the danger entailed thereby. The State, commission made a series of tests on a much more ambitious scale at Pittsburgh, in the laboratory of the U. S. Bureau of Mines, and their tests agreed quite closely with those that Mr. Griffith and I had made. As the result of our study, we determined that the most elastic support is the ordinary timber cog or crib, while the most rigid support is a

Jan 1, 1918

PRESIDENTS DAVID THOMAS 1871 R W RAYMOND 1872-1874 A L HOLLEY1875 ABRAM S HEWITT 1876 T STERRY HUNT 1877 ECKLEY B COXE 1878 - 1879 WILLIAM P SHINN 1880 WILLIAM METCALF 1881 RICHARD P ROTHWELL 1882 ROBERY W HUNT 1883 JAMES C, BAYLES 1884-1885 ROBERT H RICHARDS 1886 THOMAS EGLESTON 1887 WILLIAM B POTTER 1888 RICHARD PEARCE 1889 ADAM S HEWITT 1890 JOHN BIRKINBINE 1891-1892 H M HOWE 1893 JOHN FRITZ 1894 J D WEEKS 1895 E G SPILSBURY 1896 THOMAS M. DROWN 1897 CHARLES KIRCHHOFF 1898

Jan 1, 1937

By Klaus Schwerdtfeger

The equilibria in the Cr-N system have been investigated in the temperature range 1100° to 1310°C by reacting chromium powder with Nz-Hz gas mixtures. The solubility of nitrogen in chromium in equilibrium with chromium subsitvide ("Cr,N") is given by Chromium subnitride is nonstoichiotnetric; its nitrogen content is always less than that corresponding to the formula CrzN. The lattice paranzeters of quenched samples have been measured; c, and a. parameters are found to increase with increasing nitrogen content. The growth rate of the subnitride layer on chromium plates was measured by a thermogravimetric technique, using a silica spring balance. The self-diffu-sivity obtained from the theoretical analysis of the parabolic rate constant is found to decrease with increasing nitrogen content, i.e., with decreasing vacancy concentration in the nitrogen sublattice. The intrinsic nitrogen diffuivity is derived from another series of rate measurements using "CrzN" plates; the intrinsic diffusivity, DN = 3.2 X 10-a cmZ sec-' at 1200 C, is found to be essentially independent of- the subnitride composition. The concentration gradient was measured in a chromium subnitride layer by the X-ray method and found to be consistent with the derived diffusivity value. TWO chromium nitrides are known to exist:' the nonstoichiometric subnitride "CrzN" and the nitride CrN. In the present work the kinetics of the formation of chromium subnitride from chromium and nitrogen have been investigated at 1100" and 1200°C. In additional experiments the relevant equilibria have been measured. The data are used to evaluate the diffusivity of nitrogen in chromium subnitride. Since chromium nitrides are often found in chromium-containing steels, the results are expected to be helpful in the interpretation of the chemical reactions between chromium steels and nitrogen. Equilibria in the Cr-N system have been determined by several investigators.2"3 The rate of nitriding of chromium was measured by Arkharov et a1 .' in ammonia in the temperature range 800" to 1200°C. The parabolic rate law was observed. Due to the undefined nitrogen activity of the ammonia atmosphere, it is dif- ficult to interpret these rate data theoretically. An additional difficulty arises from the fact that the two-layer scale consisting of CrN and "Cr2N" was formed at the temperatures below 1030°C. The rate of nitriding of technical chromium (95 pct) was measured by Zaks in nitrogen at -1 atm in the temperature range 800" to 1300°C. EXPERIMENTAL METHODS The chromium samples were reacted with Nz-HZ gas mixtures in a vertical tube furnace, wound with Pt-10 pct Rh resistance wire. The gas-tight reaction tube was of high-purity recrystallized alumina. In nitrogen solubility measurements the nitrogen content of chromium was determined by the Kjeldahl method, on samples quenched in the cold part of the furnace. The nonstoichiometry of the subnitride and the nitriding rates were measured thermogravimetrically using a sensitive (+0.1 mg) silica spring balance. For the equilibrium measurements samples of 1 g of chromium powder contained in high-purity alumina crucibles were used. In order to remove most of the oxygen and nitrogen impurities from the chromium, the samples were initially annealed in purified hydrogen until a constant weight was obtained. The chromium plates (approximate dimensions 2 by 1 by 0.08 cm) used for the rate measurements were machined from ingots obtained by arc-melting of iodine-processed chromium. According to manufacturers' specifications the purity of the chromium powder was 99.9 pct Cr and that of the iodine-processed chromium 99.99 pct Cr. Our own spectroscopic analysis of the chromium powder yielded 0.02 pct Fe, 0.05 pct Mn, 0.05 pct Si, and 0.02 pct Ti as major impurities with all the other detectable elements below 0.005 pct. The nitrogen partial pressure of the gas phase was controlled by mixing prepurified hydrogen and nitrogen with constant pressure head capillary flowmeters. Oxygen and water vapor were removed from the mixed gas by passing it through columns of platinized asbestos (450°C) and anhydrone. The gas flowed upward in the furnace with flow rates of 300 to 500 cu cm per min (25"~). Gas tightness of the furnace system was ensured by pressure checks at regular intervals. The furnace temperature was controlled electronically in the usual manner. The reported temperatures were measured with a Pt/Pt-10 pct Rh thermocouple and are estimated to be accurate within ±$C The X-ray measurements were made with a Debye-Scherrer camera and a diffractometer using chromium radiation {\Ka = 2.29092A). EQUILIBRIUM MEASUREMENTS The experimental results of the equilibrium measurements are contained in Tables I to In. Fig. 1 shows the solubility of nitrogen in solid chromium in the temperature range 1100" to 1310°C. In Figs.

Jan 1, 1968

By E. A. Gulbransen, K. F. Andrew

The gas-metal reactions of zirconium are very interesting. The metal is extremely stable at room temperature to reactions with the several gases present in air and the metal will stay bright indefinitely. However, at temperatures of several hundred degrees higher the metal reacts readily with oxygen, nitrogen and hydrogen. This behavior, in addition to the fact that zirconium is one of the higher melting point metals which might have high temperature applications under the proper conditions, resulted in the work reported in this communication. There are several factors which indicate that zirconium might have good oxidation resistance at elevated temperatures. These are: (1) the high melting point of approximately 1860°C, (2) the high melting point of the oxide of approximately 2675°C, (3) the high degree of thermodynamic stability of the oxide to chemical reaction and the low decomposition pressure of the oxide and (4) the possible formation of a continuous oxide film since the volume ratio of oxide to metal is greater than unity. The unfavorable factors are: (1) the metal reacts to form nitrides, hydrides and carbides, (2) the oxide is soluble at elevated temperatures in the metal and (3) the oxide ZrO2 undergoes crystal structure transformations at high temperature. The oxidation resistance of this metal is not only a question of the rate of film formation but is complicated by the fact that the oxide and other reaction products dissolve in the metal which in turn will affect the physical and mechanical properties of the metal. The protection of the metal to nitride formation must be considered separately from the oxide problem. One unfavorable factor is that the volume ratio of the nitride to the metal is about unity. This indicates that a discontinuous film might be formed. This paper will present measurements on the rates of reaction of the metal with O2, H2 and N2 over a wide temperature and pressure range. The reaction in high vacuum and the stability of the several compounds formed will be presented. The results are correlated with fundamental rate theory and with the physical and chemical structure of the metal and film. Literature Although many papers have been published on the chemical reactions of zirconium with various gases, comparatively few are concerned with the protective nature of the metal and its reactions at normal pressures. The studies in the pressure range below 0.01 mm of Hg gas pressure are largely of interest in the nature of the adsorption of gases by hot filaments in high vacuum apparatus. The reactions of zirconium in this pressure range have been reviewed by Fast8 and by RaynOr.27 In spite of certain differences of opinion as to the maximum adsorption temperatures for various gases, the low pressure range is qualitatively understood. Some of these papers will be mentioned briefly here. 1. LOW PRESSURE Ehrke and Slack' find that oxygen reacts above 885°C and hydrogen above 760°C. Nitrogen does not react up to a temperature of 1527°C. Fast9 on the other hand observes that oxygen is absorbed above 700°C and nitrogen at temperatures exceeding 1000°C. Hydrogen is absorbed from 300" to 400°C and liberated between 500" and 800°C. It is readsorbed at 862°C and released above 862°C. Hukagawa and Nambo22 find a rather complicated picture for the absorption of oxygen. A rapid initial absorption is found between 180" to 230°C. Further oxygen is not taken up until a temperature of 450°C is reached. The optimum temperature for complete absorption is 650" to 700°C. Nitrogen is found to be completely adsorbed at 600°C. However some of the gas is evolved at higher temperatures. Their data on the absorption of hydrogen indicate some of the gas is removed at 550°C. Guldner and Wooten17 in a study of the low pressure reactions of zirconium with various gases observed that the reaction with oxygen occurs at temperatures above 400°C and that the oxide is formed. The reactions with carbon monoxide and carbon dioxide occur rapidly at temperatures of about 800°C with the oxide and carbide being formed. Zirconium reacts at temperatures of 400°C slowly and at 800°C rapidly to form the nitride and with hydrogen and water at 300°C to form the hydride and a mixture of the oxide and hydride respectively. 2. NORMAL PRESSURE DeBoer and Fast3 in a study of the electrolysis of oxygen in zirconium find that the metal absorbs up to 40 at. pct of oxygen without forming a new phase. The solubility of nitrogen in the lattice has been studied by de Boer and Fast4 and Fast10 and is found to be considerable. At higher temperatures the oxide dissolves in the lattice at an appreciable rate according to Fast10 and the zirconium surface becomes active. De Boer and Fast4 and Hägg18 have studied the solubility of hydrogen and find that at room temperature the solubility corresponds to ZrH1.95 Desorption occurs on lowering the pressure. Hydrogen is stated to be more soluble in the ß-form and the

Jan 1, 1950

By Jay R. Burns

Two magnesium sand-casting alloys are commonly favored in the United States. These are referred to as H and C alloys (Dow Chemical Co.) or AM265 and AM260 alloys (American Magnesium Corporation). Both are of an aluminum-zinc-manganese type. H alloy contains 6 per cent aluminum and 3 per cent zinc and is characterized by relatively good toughness. C alloy contains g per cent aluminum and 2 per cent zinc and is employed where high yield strength and pressure tightness are required. Examination of magnesium castings poured in Europe and England,1,2 however, demonstrates that H and C alloys are replaced by A8 and AZ91, respectively. That is, A8 represents a magnesium alloy having superior toughness while AZ91 is suitable for high yield strength and pressure-tight applications. The basic difference between the American and European alloys is that the foreign alloys employ a somewhat higher aluminum content and less zinc than is found in H and C alloys. The mechanical properties of the alloys, when divided into high and low-aluminum groups, are quite similar, as determined from separately cast foundry-control type test bars.3 In this paper the decrease of mechanical properties caused by any given amount of microporosity is measured for H, C, A8, and AZ91 alloys. The relative susceptibility of each of the four alloys to microporosity is also determined. Typical mechanical properties and nominal chemical analyses are reported in Table I. [ ] The apparent similarities between the two alloys in each group have led to considerable discussion as to the relative merits of each of the compositions.2 Popular points for comparison between the alloys have been the relative susceptibility of each of the four alloys to microporosity5 and the effect of this microporosity on their mechanical properties. It is primarily intended, in this paper, to show the

Jan 1, 1946

By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939

By C. C. Singleterry, D. L. Katz

The critical phenomena have been studied during the past century but our knowledge of the critical temperatures and pressures of complex hydrocarbon mixtures still is very limited. The critical temperatures and pressures of pure substances have been examined in large numbers120 and in great detail.11.17 No experimental determinations of the critical phenomena have been reported on such complex hydrocarbon systems as a reservoir fluid. The critical temperature is defined by Taylor18 as follows: "there is some temperature for each gas above which the gas cannot be liquefied. This temperature is called the critical temperature." The critical pressure of a pure substance is the vapor pressure at the critical temperature. It should be noted that these definitions refer to a given substance in the pure state and do not mean that the pure substance cannot be liquefied in the presence of a second constituent. The normal procedure for obtaining the critical temperature of a substance is to heat it in a glass tube 1,20 under pressure until the meniscus between the liquid and vapor phase disappears, although other methods, especially for mixtures, have been used.13,14 However, when considering oil and gas reservoirs, it is more enlightening to consider a critical phenomenon that occurs when a mixture of oil and gas are compressed at a reservoir temperature until the meniscus disappears because the two phases become equal in composition. This conception, along with erroneous applications of the definition of the critical phenomena of a pure substance to that pure substance when it is part of a complex mixture, has caused confusion even among persons familiar with the classical theories. The purpose of this paper is to discuss the critical phenomena of pure substances and mixtures and to report experimental data on a mixture of

Jan 1, 1939

By J. C. Swartz

New measurements of graphite and cementite solubilities in ferrite have been obtained to resolve disagreements among previous data. To measure graphite solubility, specimens of iron were equilibrated with rarious carburizing atmospheres at temperatures be-twee~z 480" and 1435°C. The carbon activity of each atmosphere relative to graphite was taken from published data. After quenching from each equilibration treatment the concentration of carbon (typically 10 pprn by wt) was determined from the height of the Snoek peak in the internal friction spectrum. A few inclividual analyses by combustion support the reszdts of Smith on the solubility of graphite near the eutectoid temperature. Combination of these combustion and internal friction analyses determines In a, (at 0.01 wt pct) = 24,000/RT - 12.72, where a, is the activtity relative to graphite in ferrite at fixed cornposition. The same specimens were used to determine the solubility of self-stressed cementite precipitates. The results indicate solubilities of 6.3, 23.2, and 68 pprn carbon by wt at respectively 400°, 500". and 600°C. The once large discrepancy between the cementite solubility determined by internal frictiori and that calculated from flee energy data has been almost completely resolved. A recent study1 (hereafter designated I) on the solubility of cementite in a iron did not fully resolve the disagreement among previous data. The remaining disagreement is illustrated by the phase diagram in Fig. L The data of I are represented by the line labeled "stress-free" cementite. They determine a heat of solution of cementite of (14.8 * 0.2) kcal per mole which contrasts with the (20 * 1) kcal per mole derived from Smith's graphite solubility2 and the formation energy of cementite.3 Toward resolving this disagreement we have obtained new data on the solubilities of graphite and cementite. METHODS As in I the Snoek peak in the internal friction spectrum was used to measure the concentration of carbon dissolved in ferrite. This method relies on the relation C=kQ-1 [1] in which C is the concentration of dissolved carbon, Q-I is the Snoek peak height, and k is a proportionality factor which is a function of the peak temperature, polycrystalline texture, and other parameters characteristic of the ferrite lattice. To determine true heats of solution via Eq. [1], it is necessary to establish that k is independent of the temperature from which the specimen is quenched. Some evidence on this point is contained in a separate report.* Additional evidence is shown by the data points in Fig. 1. These represent the Snoek peaks of two specimens carburized to about 10 ppm C, copper plated, and quenched first from 888º then from 588°C. The copper plate was removed before each Snoek peak measurement. These data show that there is no detectable dependence of k on quenching temperature. The solubility of graphite was determined by repeatedly carburizing various specimens of iron wire with gas mixtures of known carbon activity relative to graphite. To cover a wide temperature range within the a phase boundaries it is desirable to use as low a carbon concentration as is compatible with reasonable precision. With the present internal friction apparatus the best compromise of these desires is a concentration near 10 wt ppm. The dashed line in Fig. 1 was used to approximate the activity of carbon* for

Jan 1, 1970