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By H. M. Howe

Page 1. Introduction............................514 2. Definitions.............................517 3. Brevity of the Heating........................517 I. THE HARDENING OF THE BORE..............517 4. The Hardening of the Bore.....................517 5. The Thickness of the Hardened Layer.................517 6. Martensitization..........................518 7. The Hardening Repetitive ......................519 8. The Temperature Cycle.......................519 9. The Hardened Layer is the Merged Layer............... 521 10. The Progressiveness of Merging....................521 11. The Progressive Thickening of the Hardened Layer from Round to Round. 523 12. Merging and Hardening are Cumulative................523 13. Three Additional Causes of the Progressive Thickening of the Hardened Layer 525 14. Progressive Roughening of the Bore..................525 15. Avoidance of an Endothermic Transformation.............525 16. Asymptotic Retardation of the Thickening of the Hardened Layer.....527 17. The Troostitic Layer........................ 529 18. The Usual Lack of Martensitic Markings................529 19. The Thickness of the Hardened Layer Should Increase with the Quantity of Heat Taken up by the Walls of the Bore.................530 20. The Decrease of the Thickness of the Hardened Layer from Breech to Muzsle 531 21. Phstic Deformation as a Contributory aCause of Hardening........531 22. In What Way May Plastic Deformation Hasten Hardening?....... 535 23. Possible Need of Coarsening.....................535 24. Carburization as a Cause of Hardening..........:.....536 25. Does Hardening Increase Erosion?..................-538 11. THE CRACKING OF THE BORE ...............539 26. Appearance of the Bore and Cracks in Elevation............539 27. The Cracks in Elevation in the Rear Ring...............539 28. The Cracks in Elevation in the Forward Ring.............540 29. The Copper Network in the Grooves.................540 30. The Cracking of the Lands......................541

Jan 1, 1918

Jan 1, 1967

By A. A. Bauer

The ?-to-? transformation has been studied in zirconium alloys containing 22 to 70 wt pct U. In this range of compositions the ? phase can be retained by quenching. Transformation to ? occurs by a nucleation-and-growth process. The diffusion of atoms to preferred lattice sites to yield a partially ordered structure apparently controls the rate of reaction. Alpha uranium and a zirconium precipitate from the supersaturated E phase initially formed in alloys outside the equilibrium E phase composition limits. ZIRCONIUM-Uranium alloys have long been of interest for reactor-fuel applications because of the low thermal-neutron cross section of zirconium. Considerable information is available on the various properties and behavior of these alloys1 although there had been a number of areas where information was incomplete. As part of a program to provide more detailed knowledge in these areas, the presently reported investigation was undertaken. The constitutional diagram of the zirconium-uranium system is shown in Fig. 1.' The system is distinguished by a region of complete solid solubility between the body-centered cubic ß-zirconium and ? uranium phases and the existence of an intermediate phase in the vicinity of 50 wt pct U. This intermediate phase, designated as E, is reported3 to have a primitive hexagonal structure with a = 5.03 and c = 3.08A. The structure is partially ordered with zirconium atoms at the 0, 0, 0 position and zirconium and uranium atoms located randomly at the 1/3, 2/3, 1/2, and 2/3, 1/3, 1/2 positions. While the E phase may be nominally designated as of UZr2 stoichio-metry, the random distribution of uranium and zirconium atoms permit a considerable range in composition. Of interest in the research performed were alloys in the range from 20 wt pct (10 at. pct) to 70 wt pct (47 at. pct) U. In this range of compositions the body-centered-cubic ? phase can be retained either completely or partially on quenching. The nature and kinetics of transformation of the ? phase were the subject of study. Proceeding concurrently with the presently reported work was an investigation by Kearns4 which has since been reported. Kearns studied alloys containing 50 to 60 wt pct U prepared from sponge zirconium. While the work reported here is for alloys prepared from crystal-bar zirconium and the techniques of study are to some extent dissimilar to those employed by Kearns, general agreement so far as results and interpretation can be reported. Experimental Techniques—Alloys were prepared and the transformation of the ? phase studied during interrupted-quench and quench-and-temper isothermal heat treatments by means of hardness measurements and X-ray diffraction and metallographic techniques. The isothermal transformation of the ? phase on quenching and tempering was investigated further employing dynamic-modulus measurements. Electrical resistivity and limited Hall coefficient measurements were also obtained as part of the study. Alloy Preparation and Heat Treatment— Alloys containing 15, 20, 22, 30, 40, 45, 50, 55, 60, and 70 wt pct U were prepared from as-reduced uranium and crystal-bar zirconium. The alloys were double arc melted by consumable-electrode are-melting techniques. The final ingots were forged and rolled at temperatures between 790" and 840oC to 1/4-in. rod and 1/8-in. sheet. Chemical analyses of the fabricated alloys were

Jan 1, 1961

By L. L. McMurray

ILMENITE is the most important raw material for manufacture of titanium dioxide.1 Industrially, several other products are made from ilmenite, the most important of which are: ferrotitanium, ferro carbon-titanium, copper-titanium, titanium carbide and titanium nitride. The production of titanium metal is still in the laboratory stage because of the difficulty of extraction and as yet no important application for the metal has been found. Ilmenite has received considerable attention as an industrial raw material. Imports of ilmenite concentrates for the first nine months of 1941 were 156,737 short tons, the chief source being Travancore, India.2 Domestic production of ilmenite has here-tofore been confined to Amherst and Nelson Counties, Virginia, where a complex rutile, ilmenite, and apatite ore is mined and treated to utilize all three of these minerals. A recent report3 has described development of the large titaniferous magnetite ore body at Tahawas, New York, where it is expected that 800 tons of ilmenite concentrates, containing 48 per cent Ti02 will be produced daily. Additional domestic production is expected from a large ilmenite deposit recently opened in Caldwell County, North Carolina. Flotation tests indicate that a high-grade concentrate containing 53 per cent Ti02 can be made from the North Carolina ore. Prospecting of domestic ores in other areas has been reported.4 It appears that increased domestic production of ilmenite may well save considerable shipping space so vitally needed in these times. The composition and chemical structure of pure ilmenite is given by Dana as: FeO, TiO2; Ti, 31.6 per cent, Fe, 36.8 per cent, 02, 31.6 per cent. This composition is variable in that some iron or titanium may be replaced, giving a variable iron-titanium ratio. As an example, the iron-titanium weight ratio of ilmenite in Caldwell County, North Carolina, has been determined to be 0.94 (using 97.1 per cent ilmenite concentrate obtained by heavy liquids on minus 150-mesh ore) compared with theoretical 1.16. No rutile was noted in this ore to account for the low value. This North Carolina ore is free of magnetite, which is a common associate of ilmenite ores. In view of a large potential production from North Carolina, the Tennessee Valley Authority conducted a study of methods of concentration of that ore, of which the results are reported herein. THE ORE Five samples of ore were taken from the deposit at various exposed locations and were mixed for the study and testing. An attempt was made to proportion the amount of weathered and unweathered portions in making the composite sample, so as to approximate actual operating conditions. An examination of representative specimens of the sample showed the following general facts: I. The black mineral comprising nearly 70 per cent of the ore is ilmenite.

Jan 1, 1944

By AIME AIME

T HE Executive Board of the American Engineering Council held its fourth meeting at St. Louis on the first anniversary of the organizing conference which met in Washington on June 3,1920. Representatives of a number of the leading engineering organizations in the vicinity of St. Louis were present by invitation. The members of the Executive Board were guests of the Associated Engineering Societies of St. Louis. They were given a delightful ride about the city and were entertained at the Glen Echo Country Club at dinner. The special committee that had been appointed to draft resolutions to Mr. Hoover submitted the following, which were adopted : WHEREAS, our President, Herbert Hoover, has been appointed Secretary of Commerce in the Cabinet of the President of the United States, and WHEREAS, in consequence of his acceptance of this high public office, he has deemed it necessary to tender his resignation as President of The Federated American Engineering Societies.

Jan 1, 1921

By E. W. Wagy

The year 1927 witnessed numerous developments of significance in California. The State's shut-in production increased from an average of 58,000 bbl. daily in January to a maximum of 93,000 bbl. daily in August, and a total of about 25,000,000 bbl. was withheld from the market during the year. This not only lessened the effect of large production at Hunt-ington Beach, Seal Beach and Alamitos Heights, but also was a most effective conservation move. Since 1922, it is estimated that approximately 100,000,000 bbl. of oil that would otherwise have been produced have been held in the ground. I. Outstanding Field Developments of 19271 1. Long Beach Deep Sand. 2. Rincon (Seac1iff)Discovery. 3. Alamitos Heights Discovery. 4. Ventura Avenue Extension. 5. Round Mountain Discovery. 6. Mt. Poso Extension. 7. Potrero (Cypress) Discovery. 8. Buttonwillow Gas Development. 9. Goleta Discovery. 10. Union Avenue, Edison and Fruitvale Areas. (See Fig. 1.) II. Crude Production The most important factor in new crude production in 1927 was the Seal Reach field with its adjacent Alamitos Heights townlot area. Production increased from about 10,000 bbl. daily in January, to a peak of 66,000 bbl. in June. Huntington Beach finished the year 1926 with a production of 102,000 bbl. daily, which declined to 60,000 bbl. by the end of 1927. Due to production in these three areas and the tempering effect of shutting in numerous wells, the California production curve for 1927 was held at a fairly even level. Fig. 2, shows the State's production in 1927 and 1926 as compared with 1923, which was the year of excessive

Jan 1, 1928

By D. K. Deardorff, Haruo Kato

D. K. Deardorff and Haruo Kato (U. S. Bureau of Mines)—We wish to refute the 1875" 20°C value that Giessen, et al., report as the transformation temperature of hafnium. Although these authors state that their work along this line will be reported later, we can't leave their value undiscussed, for we believe it to be 125°C too high. Our value of 1750° 20°C, which the authors mention, has been substantiated in our laboratories by the use of three other methods. The first method of substantiation was by heating and cooling curves using a hafnium/tungsten thermocouple, the couple having first been calibrated against a t/Pt-10 pct Rh couple. The second method was by quenching and metallography of dilute Hf-Ta alloys. The third cussion, it may be pointed out that the observations of Rogers referred to large unidirectional strains where the internal cracks or voids appeared only after a strain of 32 pct or more. On the contrary the internal fissures observed, as a result of fatigue cycling, occurred for a total extension of some 5 pct and furthermore followed the directions of the slip zones. Finally, it is not our contention, as implied in Dr. Alden's last paragraph, that the tensile stress is an important factor in crack propagation. Indeed, in connection with the reference to the companion report, special note is made of the fact that "Deformation was apparently concentrated in grains which have a slip plane nearly perpendicular to the specimen axis and thus near the plane of maximum applied shear." This dependence of the growth of fissures on the orientation of the slip planes with respect to the direction of maximum applied shear is clearly shown in work on the torsional cycling of single crystals which has been submitted for publication. method was by heating and cooling curves with W/W-26 pct Re thermocouple. Counting the original resistometric method, four different methods have yielded 1750" 20°C as the transformation temperature of hafnium. All our work on determination of the hafnium transformation temperature has shown that the specimen under test must be quickly heated to and through the transformation temperature if the lowest possible transformation value is to be determined; otherwise a higher value not representative of pure hafnium will result. Speed was emphasized in all methods. In our resistometric work the corresponding voltage, amperage, and temperature readings were taken quickly and the transformation temperature was usually reached within 5 min total heating time. In the thermal analysis work involving Hf/W or W/W-26 pct Re thermocouples the transformation temperature was attained within three minutes total heating time, this time being less because the two variables were

Jan 1, 1963

By R. D. Mollison, C. F. Fogarty

Sulfur is widely distributed in nature. It is present in the earth's crust, the ocean, the meteorites that come to us from cosmic space and in practically all animal and plant life. According to Clarke,9 the earth's crust contains 0.06 pct sulfur. Large quantities of free or combined sulfur are found in coal, natural gas and petroleum. Mineral waters contain sulfates and hydrogen sulfide. Sulfur is rather plentiful in the crust of the earth; however, only under special circumstances can it be produced profitably. Sulfur is one of the cheapest raw materials used by industry; and, therefore, the economic feasibility of a given deposit is strongly dictated by the law of supply and demand on local as well as world-wide levels. The forms which are commercially important are elemental sulfur or brimstone, and the sulfides such as pyrite (FeS2), pyrrhotite (FenSn+1), chalcocite (Cu2S), sphalerite (ZnS), and galena (PbS); the sulfates such as gypsum (CaSO4,2H2O), anhydrite (CaSO4), and kieserite (MgSO4,H2O). Elemental Sulfur Elemental sulfur is found in many localities, generally in solfataras and gypsum type deposits. The solfatara deposits are found commonly in the neighborhood of active or extinct volcanoes as in Italy, Japan and Chile, or fumaroles associated with mineral springs such as the Mammoth Hot Springs in Yellowstone Park. Here the sulfur is deposited in tufas or other porous host rocks. This type of sulfur deposit probably results from the oxidation of hydrogen sulfide or the reaction of hydrogen sulfide with sulfur dioxide. Most of the world's supply of elemental sulfur comes from the gypsum-type deposits. Here the mineral occurs as either crystalline or amorphous sulfur in sedimentary rocks in close association with gypsum and limestone. This association is characteristic and occurs in almost all the great gypsum beds of the world, although sulfur is not always present in quantities of economic importance. Various theories have been advanced to account for this association. Bischof5 suggested that the sulfur came from hydrogen sulfide which resulted from the reduction of calcium sulfate by carbon or methane in accordance with the following reactions: CaSO4 + 2C= CaS + 2CO2 CaS + C02+ H2O = CaCO3 + H2S CaSO4 + CH4= CaS + C02+ 2H20 2H2S + 02= 2H20 + 2S All of the sulfur-bearing domes on the Gulf Coast have calcium sulfate in great quantity in the cap. They all show the presence of hydrocarbons. The oxygen for the final reaction could have been supplied by circulating ground waters. The principal objection to this theory is that temperatures of 700° to 1000°C are needed to reduce the sulfate to sulfide with carbon compounds. The geologic evidence is that the temperature of the sulfur-bearing domes of Texas did not exceed 100°C. Proponents of the theory say that geologic time or a catalyst replaced temperature. According to another theory the sulfur in the salt domes is the result of bacterial action. Sulfate reducing bacteria have been detected in sulfur cores and in the formation water issuing from salt domes. It has, therefore, been suggested that these bacteria converted the sulfate to sulfide which subsequently was converted to elemental sulfur.

Jan 1, 1960

By Charles Maier

IT has long been supposed that when crystalline materials are com-minuted the energy used in the production of increasingly smaller grain sizes is not entirely dissipated as heat but that a certain portion is "stored" as a part of the internal energy of the material. This portion usually has been called the "surface energy" of the particles. The practical interest of the Bureau of Mines in this subject in connection with the energy requirements of crushing processes has led to the author's attempt to measure the "stored" energy in finely divided calcite by heat-of-solution methods1. The experiments on calcite showed that "storage" of energy could not be proved for this material, because fine grinding caused a lack of chem-ical homogeneity evidenced by loss of carbon dioxide and subsequent adsorption of water on the surfaces of the calcite particles. When thermochemical correction was made for composition changes the cor-rected heat of solution was less for fine material than for coarse. Con-tinuation of the experimental work into the problem of comparing work and heat in the deformation of metallic crystals, where the calorimetric difficulties were less, showed, however, that in the case of copper and aluminum a real discrepancy between work and heat could be shown. similar results had previously been obtained by Farren and Taylor2 and Hort3 and more or less simultaneously with the author's work by

Jan 1, 1936

By G. R. St. Pierre, S. W. Gilby

The equilibrium vapors established over Fe-Cr-Ni alloys containing up to 50 pct Cr at 1600°C were determined by collecting the effusate from thoria Knud-sen cells. From these data, the activities of iron and nickel in the ternary alloys have been calculated. In a separate set of measurements, a mass spectrometer was used to determine the activities of the three components in a series of Fe-Cr-Ni alloys. In binary Ni-Cr melts, the activity coefficient of chromium referred to pure solid chromium as standard state is less than one at low chromium contents but is greater than one for melts containing more than 30 at. pct Cr. For Ni-Cr melts containing less than 10 at. pct Cr, In ?Cr = 0.15-0.92 N2. Ternary activity diagrams for Fe-Cr-Ni alloys are presented. In iron-rich alloys, the interactions between the three components are negligible; however, in nickel-rich alloys, the three principal interactions have significant positive values. THE activities of components in binary Fe-Ni alloys have been measured both in the solid solution1-3 and liquid solution4-6 temperature ranges. The determination for Fe-Ni melts have been made by three different methods: transpiration,4 Knudsen-cell effusion with analysis of an accumulated condensate,' and Knudsen-cell effusion with direct measurements of relative component intensities by mass spectrometric methods.6 The results obtained by the three different methods in three different laboratories are in excellent agreement and considerable confidence is placed in the activity coefficients for Fe-Ni melts. At 1600°C, the activity coefficients in dilute solution are ?°Ni = 0.66 and ?oFe = 0.40 for the pure liquid components as standard states. Measurements made on solid solution Fe-Cr alloys7-10 indicate that the component activities are slightly greater than ideal. The measured activities in iron-rich Fe-Cr liquid alloy11-16 indicate almost ideal behavior for this system. The recommended activity coefficient of chromium in dilute solution in liquid iron at 1600o C, ?oCr, is 1.18 when referred to pure solid chromium as standard state and 1.04 when referred to pure undercooled liquid chromium as standard state." The conversion factor of 1.14 is based on a melting point of 1857°C and an enthalpy of melting of 4047 cal per g at. for chromium.21,37 The activity coefficient of iron in dilute solution in liquid chromium has not been measured. Activity measurements on solid Ni-Cr alloys have been made by several investigators.17-20 During the review of this manuscript, Fruehan12 published the results of a study on liquid Ni-Cr alloys at 1600°C. He used galvanic cells22 with ZrO2(CaO) as the electrolyte and Cr/Cr2O3 for the reference electrode. His results indicate that ?oCr in nickel at 1600°C is about 1.01 when referred to pure solid chromium and about 0.89 when referred to pure undercooled liquid chromium as standard state. The activity coefficient of nickel in liquid chromium is unknown. The compositions of vapors freely evaporating from some molten Fe-Cr-Ni alloys have been measured by Lyubimov, Granovskaya, and Berenstein.23 Their results, combined with known vapor pressures, indicate strong positive deviation for chromium in iron-rich alloys and strong negative deviation for chromium in nickel-rich alloys. EXPERIMENTAL PROCEDURES This research was undertaken to determine the activities of components in ternary Fe-Cr-Ni melts containing up to 50 at. pct Cr. At the initiation of the research, we decided to use a Knudsen-cell method wherein a portion of the effusing vapor is condensed on a cold plate.' The composition of the equilibrium vapor for each alloy composition is determined in this method by holding the system under constant conditions for a period of time sufficient to collect enough condensate on the cold plate for chemical analysis. The activities of components in ternary alloys can be calculated from such vapor composition determinations by Eq. [1].24

Jan 1, 1970

By Robert H. Hafner, Irvin R. Kramer

In recent years considerable interest has been shown in surface-alloyed metals, particnlarly those of chromium (chromized steels), which have excellent corrosion resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high tem- peratures of 1200º to 1400ºC. (2200° to 2550°F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- mon salt, and heated for approximately three hours at 930º to 1040°C. (1700º to 1900ºF.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900º to 1000ºC., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a Chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1943

By Robert H. Hafner, Irvin R. Kramer

In recent years considerable interest has been shown in surface-alloyed metals, particnlarly those of chromium (chromized steels), which have excellent corrosion resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method1 employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high tem- peratures of 1200º to 1400ºC. (2200° to 2550°F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- mon salt, and heated for approximately three hours at 930º to 1040°C. (1700º to 1900ºF.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900º to 1000ºC., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a Chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1943

By Arthur F. L. Bell

Discussion of the paper of ARTHUR F. L. BELL, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 105, September, 1915, pp. 1769 to 1799. WILLIAM A. WILLIAMS, San Francisco, Cal.-Is the Union Avila plant run as a topping plant or as a dehydrating plant? A. F. L. BELL, San Francisco, Cal.-Both. It takes off an average of 20 per cent. water besides topping the oil. Part of the crude oil is run through an electrical separator before running to the topping plant, but the entire crude averages about 20 per cent. when it enters the topping plant. DAVID T. DAY, Washington, D. C.-I suppose most of the work contemplated in these large topping plants is simply to deal with topping the oils with only a small percentage of water in them. A. F. L. BELL.-Not more than 2 per cent. of water can be handled in ordinary stills without causing trouble. At our Gavotte refinery, where the oil runs from 15 to 30 per cent. water, we carry 20 lb., pressure oil our stills to hold the framing down, we can do that with small stills, with large one's it would not be safe; but with a retort, the quantity of water contained in the oil does not affect its working. It simply means additional fuel to evaporate the water.

Jan 12, 1915

By Robert H. Hafner, Irvin R. Kramer

IN recent years considerable interest has been shown in surface-alloyed metals, particularly those of chromium (chromized steels), which have excellent corrosion [ ] resistance under a variety of severe conditions, and may undergo bending and flanging operations without spalling. An early method' employed to produce a high-chromium case on steel was developed by Kelley in 1921. It consisted of heating a low-carbon steel in intimate contact with powdered chromium in the presence of hydrogen at temperatures sufficiently high to permit diffusion of chromium into the steel. The usefulness of this process was limited because the extremely high temperatures of 1200° to 1400°C. (2200° to 2550 F.) caused excessive grain growth and warpage. Louenstein and Ulmer2 packed iron castings in ferrochromium and com- [ ] mon salt, and heated for approximately three hours at 930° to 1040°C. (1700° to 1900°F.). A recent and more practical method of depositing chromium on steel surfaces has been developed in Germany by Daeves, Becker and Steinberg3-8 and in Russia by Izgaryshev and Sarkisov.9 This process consists of passing gaseous chromium chloride over the steel to be chromized at temperatures of 900° to 1000°C., or packing them in a porous, ceramic material that previously had been saturated with chromium chloride. They reported obtaining a chromized layer, 0.004 in. thick, on low-carbon steels. Later, Daeves4 established a relationship between the carbon content

Jan 1, 1942

By Kent W. Pilz

Wet dust suppression can be achieved by 1) confinement of the dust within the dust producing area with a curtain of moisture, 2) wetting of the dust by direct contact between the particles and droplets of moisture or 3) the formation of agglomerates too heavy to remain airborne, or too heavy to become airborne, by combining small dust particles with each other and with the droplets of liquid. From the standpoint of economy, availability and safety, water is the ideal fluid; however, it is not as effective for dust suppression as when small percentages of specially formulated dust control compounds are blended with it. Performance of dust control com pounds is related to surface active agents and surface activity. In all liquids there is an attractive force between molecules which varies inversely as the sixth power of the distance between molecules. Thus, in the liquid phase where molecules are crowded together, the intermolecular forces are powerful; whereas in the liquid-vapor phase where the molecules are relatively far apart, these forces diminish rapidly. In the body of a fluid there is an uneven distribution of forces resulting in an inward pull called surface tension. The force which keeps two surfaces apart or causes them to coalesce is termed interfacial tension. Fluids of high surface tension exhibit poor wetting, spreading and penetrating qualities. Water has the unusually high surface tension of 72.75 dynes per cm at 20°C.

Jan 7, 1972

By John Chipman, Minu N. Dastur

This paper presents equilibrium data on the reaction of water vapor with vanadium dissolved in liquid iron at 1600°C. The thermo-dynamic behavior of vanadium and oxygen when present together in the melt is discussed. A deoxidation diagram is presented which shows the concentrations and activities of vanadium and oxygen in equilibrium with V209 or FeV2O4. STUDIES of the chemical behavior of oxygen dissolved in pure liquid iron1-3 have served to determine with a fair degree of accuracy the thermody-namic properties of this binary solution. The practical problems of steelmaking, however, involve not the simple binary but ternary and more complex solutions. Only a beginning has been made toward understanding the behavior of such systems. The silicon-manganese-oxygen relationship was studied long ago by Korber and Oelsen4 and more recently by Hilty and Crafts." The carbon-oxygen reaction was investigated by Vacher and Hamilton6 and by Marshall and Chipman.7 A number of deoxidizing reactions have been studied empirica1lys'10 with the object of determining the appropriate "deoxidation constants." The work of Chen and Chipman" afforded a clear-cut view of the effect of the alloy element, chromium, on the thermodynamic activity of oxygen in liquid ternary solutions. These investigators determined the oxygen content of experimental melts which had been brought into equilibrium with a controlled atmosphere of hydrogen and water vapor and were able to show that the presence of chromium decreases the activity coefficient of oxygen. They determined also the conditions under which the two deoxidation products, Cr2O3 and FeCr2O4, were formed and showed that the activity of residual oxygen is considerably less than its percentage. It was the object of this investigation to apply a similar method to the study of molten alloys of iron, vanadium, and oxygen. Vanadium was once considered a moderately potent deoxidizer, but this is now known to be erroneous, in the light of its behavior in steelmaking practice. Its reaction with oxygen retains a certain amount of practical interest in that a high percentage of one element places a limit on the amount of the other that can be retained. As a deoxidizer it will be shown that vanadium lies between chromium and silicon. Experimental Method The apparatus was that used by the authors3 in their study of the equilibrium in the reaction: H2(g) +O = H2O(g);K,= [1] PII., ao Crucibles of Norton alundum or of pure alumina were used. The latter were made in this laboratory and were of high strength and low porosity. Under conditions of use they imparted no significant amount of aluminum (less than 0.01 pct) to the bath. Temperature measurements were made with the optical equipment and calibration chart of Dastur and Gokcen.= The charge was made up of calculated amounts of ferrovanadium (20 pct V) and clean electrolytic iron totaling approximately 70 g. The first few heats were made in alumina crucibles with an insufficient amount of vanadium so that no oxide of vanadium would be precipitated under the particular gas composition. All the heats were made at 1600 °C under a high preheat and with four parts of argon to one part of hydrogen in the gas mixture to prevent thermal diffusion. The rate of gas flow was maintained constant at 250 to 300 ml per min of hydrogen. The time for each heat was three quarters of an hour after the melt had melted and attained the required temperature (1600°C). The water-vapor content of the entrant gas mixture was gradually raised in succeeding heats, keeping the vanadium content of the melt constant. This was controlled by manipulation of saturator temperature. A point was reached when for a given H2O:H2 ratio some of the dissolved vanadium was oxidized and appeared as a thin, bright oxide film on top of the melt. By raising the temperature of the melt it was possible to dissolve the oxide film which reappeared as soon as it was cooled down to 1600°C. The temperature readings taken on the oxide film were consistently higher by 80" to 85 °C as observed by the optical pyrometer. The heat was allowed to come to equilibrium under a partial covering of this oxide film. At the end of the run the power and preheater were shut off and the crucible containing the melt was lowered down into the cooler region in the furnace. This method of quenching proved quite

Jan 1, 1952

By B. Chalmers, L. Bäckerud

The growth temperature of dendrite tips has been measured in a binary alloy system, Al-Cu, as a function of rate of formation of solid phase. Metallographic examination has rerealed the dendritic structure dereloped during different stages of the freezing process and factors influencing the undercooling, such as solute buildup, surface tension, and kinetic effects, have been estimated. Practical implications of the results are discussed. THE development of a dendritic growth pattern during the solidification of metals and alloys has an influence at least equal to that of grain size on the properties of the casting or ingot being produced. and consequently much interest has been devoted to the study of this phenomenon. A review of the knowledge gathered up to 1964 has been given by Chalmers.' Among recent publications in the area the works of Jackson et al 2 and Flemings and his coworkers3,4 are of special interest. This work is an experimental study of the factors which influence the development of a dendritic pattern during the solidification of a typical binary alloy system, A1-Cu, when there is no heat source in the liquid. This means that the temperature and the temperature gradient are controlled by the heat extraction from and latent heat evolved by the growing crystals. EXPERIMENTAL PROCEDURE Samples were prepared from a master alloy made up of aluminum, 99.995 pct, and copper. 99.99 pct, of the concentrations given below and of sufficient size to fill cylindrical graphite molds of 35 mm ID and 35 mm height. Bottom. wall. and lid of the graphite molds were all of 6 mm thickness, Fig. 1. Thin ceramic thermocouple shields could be introduced at different positions in the sample through holes in the lid. The assembly was heated in a small vertical resistance furnace to a suitable temperature. 700° to 720°C. which is well above the melting point of the sample. It was thereafter taken out of the furnace and chilled at selected rates, and the temperature changes in the sample were recorded. For high sensitivity in the temperature recordings, a reference thermocouple was held in a solidifying pure aluminum melt. which was very well insulated and therefore was at a constant temperature. 660°C, for nearly half an hour. The thermocouples were connected so that the difference voltage was fed into the recorder of which the most sensitive range was 1 mV. Temperature variations could be read to within 0.l°C. The thermocouples used were of the Chromel-Alumel type (28- or 38-gage wires) and the recorder a two-pen Moseley strip chart recorder. The different rates of chilling were obtained in the following way. a) The graphite crucible was wrapped in one or two layers of an insulating. feltlike material (Fiberfrax paper from the Carborundum Co.). The drop in temperature per unit time after complete solidification could thereby be varied from 8" to 18°C per min. This corresponds to a rate of heat extraction in the given samples from 0.08 to 0.17 cal cm-' sec-I. 6) The bare graphite mold was placed free on a piece of firebrick. The measured temperature drop was around 50°C per min (-0.5 cal cm-" ' sec- I). c) By blowing compressed air through a tube with many holes surrounding the mold in a ring shape. the rate of heat transfer could be raised to 150' to 200°C per min (-1.7 cal cm-3 sec- I). d) Cooling rates around 1000 C per mill (-9.4 cal cm-3 sec-l) were obtained by substituting the air in the device used in c by water. The range of cooling rates used in these experiments correspond to technical casting processes from slow solidification as obtained in sand molds to very rapid freezing which occurs in some continuous casting and welding processes. EXPERIMENTAL RESULTS The A1-Cu system was chosen for the experiments: the relevant part of the phase diagram is reproduced in Fig. 2. Observation of the Center Temperature. When a thermocouple is inserted in the center of the melt. the type of cooling curves obtained at slow solidification rates differs little from numerous published curves from similar systems. and the solidification pattern

Jan 1, 1970

The Colorado Scientific Society, Denver, Colo Charles Henderson, President, 519 U. S Custom House, Denver, Colo. Beginning in 1882, up to. about 1919, the Society published 11 volumes containing many valuable papers From the informa¬tion at hand, the papers in those volumes are now only available in libraries or on file at institutions. Vols 12 and 13 are the current volumes, and the list of the geologic papers contained in them are given here For any information as to price and availa¬bility, address the above. Vol 12 (1929-31) No 1, The geology of the Sangre de Cristo Mountains, by J H Johnson, 2, Relation of the ore deposits of the southern Rocky Mountain region to the Colorado Plateau, by B S Butler; 3, Mosquito Range and the Leadville district, by C H Behre, Jr , 4, Geologic history of the Front Range, by T S Lovering, 6, Revision of geologic structure and stratigraphy in the Ouray district, by W S Burbank, 7, Localization of ore in the schists and gneisses of the Mineral Belt of the Front Range, by T. S. Lovering, 8, Relation of the ore deposits of the southern Rocky Mountain region to the Colorado Plateau, by J. B. Tenney; 9, Preliminary geologic map of the Alma mining district, by Q D. Singewald and B S Butler, 10, The Climax molybdenum deposits of Colorado, by B S Butler and J W. Vanderwilt, 12, Localization of ore bodies at Rico and Red Mountain, by G. F Collins, and Geology of Mount Lincoln and Russia mines, by Q D Singewald and B S. Butler. Vol 13 (1932- ): No. 1, Preliminary geologic notes on Galena Mountain, by J. W Vanderwilt, and High plains of Colorado and New Mexico (Late Tertiary history), by F. M. Van Yuyl and J M. Coke

Jan 1, 1933

By W. G. Pfann

In zone-melting, a small molten zone or zones traverse a long charge of alloy or impure metal. Consequences of this manner of freezing are examined with impurerespect to solute distribution in the ingot, with particular reference to purification and to prevention of segregation. Results are expressed in terms of the number, size, and direction of travel of the zones, the initial intermsofsolute distribution, and the distribution coefficient. IF a charge of binary solid-solution alloy is melted and then frozen slowly from one end, as for example in the Bridgman method of making single crystals,' coring usually occurs, with a resulting end-to-end variation in concentration. Such coring, or normal segregation, is undesirable where uniformity is an object. On the other hand, for certain systems, it can be utilized to refine a material by concentrating impurities at one end of the ingot.'. ' In the present paper a different manner of freezing will be examined with respect to the distribution of solute in the ingot. A number of procedures will be indicated which have in common the traversal of a relatively long charge of solid alloy by a small molten zone. Such methods will be denoted by the general term zone-,melting, while the process described in the preceding paragraph will be called normal freezing. It will be shown that, in contrast to normal freezing, zone-melting affords wide latitude in possible distributions of solute. Segregation can either be almost entirely eliminated or it can be enhanced so as to provide a high degree of sttparation of solute and solvent. A number of simplifying assumptions will be invoked which, while not entirely realizable in practice, nevertheless provide a suitable point of departure for more refined treatments. Moreover, our own experience with zone-melting has shown that, for certain systems at least, the analysis holds quite well. The present paper will be confined to a discussion of principles and a general description of procedures. Comparison with experiment is planned for later publication. Normal Freezing Before considering zone-melting, segregation during normal freezing will be reviewed briefly. If a cylinder of molten binary alloy is made to freeze from one end as in Fig. 1, there usually will be a segregating action which will concentrate the solute in one or the other end of the ingot. If the constitutional diagram for the system is like that of Fig. 2, then the distribution coefficient k, defined as the ratio of the concentration in the solid to that in the liquid at equilibrium, will be less than one and the solute will be concentrated in the last regions to freeze. If the solute raises the freezing point, then k will be greater than one and the solute will be concentrated in the first regions to freeze. The concentration in the solid as a function of g, the fraction which has solidified, can be expressed by the relation: C = kC0 (1-g)k-1 [I] where C, is the initial solute concentration in the melt. Eq 1 is based on the following assumptions: 1—Diffusion in the solid is negligible. 2—Diffusion in the liquid is complete (i.e., concentration in the liquid is uniform). 3—k is constant. Concentration curves representing eq 1 for k's from 0.01 to 5.0 are plotted in Fig. 3. This equation, in one form or another, has been treated by Gulliver,³ Scheuer,4 Hayes and Chipman5 for alloys and by McFee2 for NaCl crystals. It is derived in Appendix I. It should be pointed out that the k which is calculated from the phase diagram will be valid only in the ideal case for which the stated assumptions are correct. In all actual cases, the effective k will be larger than this value for solutes which lower the melting point, smaller for solutes which raise the melting point, and will probably vary during the beginning of the freezing process. For simplification it will be assumed that the ideal k is valid. Zone-Leveling Processes The processes of this part are designed to produce a uniform, or level, distribution of solute in the ingot. Single Pass: Consider a rod or charge of alloy whose cross-section is constant and whose composition, C2, is constant, although permissibly varying on a microscopic scale." Such a charge might be a rapidly frozen casting or a mixture of crushed or powdered constituents. Cause a molten zone of

Jan 1, 1953

By B. K. Larkin, H. R. Bailey

A model Of heat flow in an underground combustion process is studied. This model includes convection effects and thus is more general than previous studies which considered conduction as the only mechanistn for heat transfer. Both linear (tube run) and radial (field application) geometries are considered. The effects of ignition heaters, vertical losses and finite source width are considered for the linear case. The results are in the form of equations and are presented in graphical form for a number of cases. Convection effects increase frontal temperatures about 25 per cent over those computed for conductive transfer for typical field operating conditions. This increase in temperature is a result of heat being transported toward the front by the injection gas. Even greater temperature increases are realized as the per cent oxygen in the injection gas decreases. It is well known that compression costs are of considerable importance in estimating the economic feasibility of underground combustion. By assuming an ignition temperature for the combustion fuel, predictions of limiting conditions on fuel density and injection rate necessary to sustain the combustion zone are made. For typical field conditions, at least 0.75 lb/cu ft of fuel are needed with air as the injection gas. If the injection gas is 10 per cent oxygen and 90 per cent nitrogen, this figure is 0.69 lb/cu ft. INTRODUCTION The possibility of increasing oil recovery by underground combustion has been considered for many years. Recent field tests indicate that the underground combustion process is technically feasible. The economic feasibility depends to a large extent on the amount of air which must be injected to sustain combustion. Prediction of the success of employing underground combustion in a particular reservoir must be based on existing field tests, laboratory tube runs"' and solutions of mathematical or analog models. Vogel and Krueger5 devised an electrical analog of the heat transfer problem in an underground combus-ion process. They considered the problem of heat conduction from a cylindrical source with increasing radius assuming no vertical losses. Bailey and Larkin and Ramey solved the corresponding problem including vertical losses by considering a mathematical model of the conduction process. Ref. 9, 10 and 11 also present information related to the subject study. The present paper generalizes these results to include both conduction and convection mechanisms for heat flow. A model of the conduction-convection process is described. The partial differential equations governing this model are written and solved for a number of cases of interest. The formulas are evaluated and the results are presented graphically. A CONDUCTION-CONVECTION MODEL Description of the Model A number of models are employed in this paper, each of which approximate a particular physical situation depending on the geometry, i.e., linear or radial flow, the type of vertical heat losses, the nature of the source, etc. The geometry for both the linear and radial case is shown in Fig. 1. A particular linear model is described in this section, and variations from this model are described in later sections of the paper. Consider a homogeneous, semi-infinite porous prism with lateral sides insulated as shown in Fig. 1. The left end, x = 0, is heated for a time t, with a plane heater supplying a constant heat flux and during this time; gas (nitrogen) is passed through the pores of the prism at a constant mass flux. At time t, the heater is turned off and air is injected in place of the nitrogen. This causes combustion to take place, and a uniform source of width 1 is formed which moves at a constant velocity v, to the right. The frontal velocity v, is related to the gas velocity v,, through stoichiometric considerations