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By R. F. Steigerwald

The effects of heat transfer on the corrosion behavior of type 304 stainless steel in boiling water have been studied. Heat transfer conditions increase the tendencies of the stainless steel toward stress-corrosion mucking when the water is contaminated with Cl-. Surface preparation is the most important variable in determining the severity of the stress-corrosion problem in water with a given Cl- content. Heat treatment, chemical cleaning, and degree of wet film boiling also affect the corrosion of stainless steels used as heat transfer surfaces in boiling water. An up-paratus for corrosion testing under controlled heat transfer conditions is described. THE principal objective of this investigation was to study the corrosion behavior of AISI Type 304 stainless steel in boiling high-purity water under conditions of heat transfer. The principal variables in the study were: a) boiling conditions: limited boil, agitated boil; b) metallurgical structure: annealed or sensitized; c) surface condition: rolled, pickled, or ground. The results of the study should elucidate the role of heat transfer in the corrosion of stainless steel in boiling high-purity water and provide a base line from which to assess the severity of this type of corrosion. Although there has been an investigation of the effect of heat transfer on the corrosion behavior of stainless steels in alkaline waters,' work on the corrosion of stainless steels under heat transfer has been largely confined to various acid solutions.'-4 Furthermore, the study of the corrosion of stainless steels in high-purity water has been generally restricted to auto-clave and instream testing in superheated (e.g., 300°C) water and steam.5'6 Cooling water problems led to this study of the corrosion behavior of type 304 stainless steel in high-purity water at its atmospheric boiling point. In addition to the effects of heat transfer, this study also considered the influences of the type of boiling,7 metallurgical structure, and surface condition on the corrosion behavior of stainless steel in high-purity water. Two boiling conditions were investigated in this study: a) limiting boiling, i.e., when the heat-transfer surface had just reached the boiling point and boiling nucleated randomly over the specimen surface and b) agitated boiling, i.e., when a mild degree of superheat had been achieved on the specimen surface and boiling occurred generally over the specimen surface. Both boiling conditions are broadly classified as wet-film boiling. Originally, this program included the study of a third type of boiling, dry-film conditions. At dry-film boiling the temperature of the heat transfer surface is high enough so that it is covered with a continuous film of steam. Experimental difficulties made it impossible to study this kind of boiling with the available apparatus. Since surface condition affects heat transfer rates, three typical surfaces were chosen for study: a) as-rolled, the 2B finish received from the supplier, b) as-pickled, 30 min in 8 pct HNO3-1 pct HF, and c) as-ground on 120 grit paper. In order to evaluate the effect of improper heat treatment or welding on hot wall corrosion, both annealed and sensitized mi-crostructure were included in this study. EXPERIMENTAL Test Apparatus. The particular problems of interest in this investigation required a knowledge of the thermal gradient through the test specimen. From this gradient, the heat flux to the surface and the surface temperature could be determined. In order to satisfy this need, an apparatus similar to the boiling-disk apparatus of Fisher and whitney2 was designed. The solution is contained in a thermally-insulated, steel pipe lined with TEFLON resin. A stainless steel _______;________________________________________

Jan 1, 1970

By C. Jardine, D. Freudenreich

The system concept is to minimize costly unscheduled equipment breakdowns by replacing components earlier than their life expectancy. Periodic unit services are scheduled according to preset constraints. Service sheets are generated by matching a job and component master listing based on assigned cyclic component lives. The system can account for all man-hours reported, and history information can be selectively retrieved. By reducing unscheduled equipment shutdowns, this system allows for better manpower utilization and an overall improvement in equipment reliability and availability.

Jan 1, 1982

By S. Saito, P. A. Beck

The crystal structure of MoNi3 was determined by means of X-ray diffraction. This structure is isotype with that of ovgered TiCu3. The lattice parameters are: a. = 5.064A, bo = 4.224A, co = 4.448A, and zf 0.157. If the orthorhombic distortion (slight relative to the corresponding orthohexagonal unit cell) is disregarded, the structure may be described in terms of a close-packed ordered atomic layer, stacked in the sequence: abab. The structztres of ordered TiCu3 and TiAl3 are homotectic. The three types of ordered hexagonal phases, iso-structural with TiNi3, MgCd3, and VCo3, are known to occur in AB3 alloys of transition elements of the first, second, ad third long periods. It was noted1 that phases with the TiNi3 structure occur selectively in alloys of Ti-group elements with Ni-group elements. In AB3 alloys of Ti-group and V-group elements with Co-group elements the AuCu3-type structure predominates.' The vCO3 structure, which was determined very recently,' has hexagonal symmetry, but the actual atomic arrangement here, too, is rather closely related to the ordered cubic structure of AuCu3-type. However, an ordered hexagonal close-packed structure of the MgCd3-type occurs in MOCO33 and WCO3.4 Consequently, the question arises as to whether or not the crystal structure of MoNi3 is also of the MgCd3-type. Grube and winkler5 found that MoNi3 has a hexagonal close-packed structure with a = 2.54A and c/a = 1.65. They pointed out that some additional weak diffraction lines could be observed in the powder pattern, which may have been due to an ordered atomic arrangement in this phase. However, no detailed information was obtained by them and the structure was apparently not further investigated by others. The present work was, therefore, undertaken in an attempt to determine in detail the structure of MoNi3, and to investigate the possibility of ordering. EXPERIMENTAL METHODS Alloys used in the present work were arc-melted in a water-cooled copper crucible under helium atmosphere. Electrolytic nickel and molybdenum, both 99.9 pct pure, were used. Chemical analyses were not made, but the melting loss was not higher than 2 pct for any alloy. Ingots were first homogenized at 1200°C for 48hr, quenched, heavily cold worked, and then annealed at 820" or 860°C for 1 week, followed by quenching in cold water. Powder specimens for X-ray work were prepared by crushing the heat-treated solid specimens. In order to remove strains, the powders were reannealed in evacuated scaled fused silica capsules for 6 hr at the same temperature at which the corresponding solid specimens were annealed. X-ray photographs were taken with an asymmetric focussing camera, using unfiltered CrK or CuK radiation. EXPERIMENTAL RESULTS The X-ray diffraction patterns of alloys containing 20.8, 25, and 26.4 at. pct Mo, homogenized at 1200°C, showed the face-centered-cubic structure of the Ni-base a-solid solution. It was revealed, however, by micrographic examination that the 26.4 at. pct Mo alloy contained in addition very small amounts of a second phase, in accordance with the phase diagram.6 On the other hand, the 20.8 at. pct Mo alloy after annealing at 820°C gave the X-ray diffraction pattern of the ordered face-centered-tetragonal MONi4.7 In this pattern several additional weak diffraction lines were also observed, corresponding to the strongest diffraction lines of MoNi3. The alloys containing 25 and 26.4 at. pct Mo after annealing at 820" or 860°C gave X-ray diffraction patterns, as shown in Tables I and 11, corresponding to MoNi3. Each one of the reflections which could be tentatively indexed on the hexagonal close-packed cell of Grube and Winkler,5 with the exception of the basal plane reflections, was split into a doublet, as seen in Table I. Since microscopically the alloy consisted of a single phase, it seemed probable that the lattice of MoNi3 is actually slightly deformed, as compared with the tentative hexagonal unit cell. In addition to these diffraction lines, several weak lines were also present, as shown in Table 11, which could not be indexed at all on the hexagonal close-packed cell considered. Satisfactory indexing of all diffraction lines observed was found to be possible by using an orthorhombic unit cell with ao = 5.064A, ft = 4.224A, and c = 4.448A. These values, whose accuracy is estimated to approximately ± 0.008A, correspond to 95.14A3 for the volume of the unit cell, and to an X-ray density of 9.50 g per cm3. If no attention were paid to the weak reflections listed in Table II, a reduced -unit cell of half the volume (a = 2.532A, b = 4.448A, and c = 4.224A), closely related to the orthohexagonal cell, might be used. The dimensions of the orthohexagonal cell of the same volume as the reduced cell are: a = 2.562A, b = 4.437 A, and c = 4.183A. It may be seen that in the reduced cell the a axis is slightly shorter, while the b and c axes are slightly longer than those corresponding to the orthohexagonal cell of the same volume. This slight orthorhombic distortion is re-

Jan 1, 1960

By O. W. Ellis

BEFORE entering upon a general discussion of the fascinating, but at present rather controversial, subject of gases in copper, the author feels that some attention should be directed to the work which has been carried out on the solubility of gases in metals. The outstanding contributions to our knowledge of this subject have been made by Sieverts and his collaborators(1) t and by Iwasé.(2) Both the German and the Japanese investigators employed apparatus of the same general design in their investigations. Full reference need only be made, therefore, to the German scheme, which is diagrammatically illustrated in Fig. 1. This, to use the words of Sieverts, which he employed in describing his Burette arrangement of apparatus at the 1928 meeting of der Deutschen Gesellschaft fur Metallkunde(1g): shows a diagram of the usual mode of procedure. A quartz flask contains the metal (for high temperatures a highly refractory porcelain FIG. 1.-SIEVERTS' APPARATUS FOR INVESTIGATING SOLUBILITY OF tube is used) and is connected with the rest of GASES IN METALS. the apparatus by means of a stopcock. The other parts consist of a burette divided into 1/10 c.c., a leveling tube, and art adjus-table mercury reservoir. The burette is connected on one side with the gas inlet and on the other side with the absorption flask; the connection can be interrupted by means of suitable taps. Another tap permits the connection of the flask and the Töpler pump. In an experiment the quartz flask is first exhausted and then a meas-ured quantity of gas is let in from the burette. In the first place the volume of the flask when empty is found by calibration with an inert gas. The pressure is read off on the level tube of the burette, and the temperature measured by means of a thermo-couple whose welded junction lies close to the outside of the quartz flask, which is heated in an electric furnace. In several experiments the quantity of absorbed gas was transferred to a burette by means of a pump and measured.

Jan 1, 1932

By James Gayley

The development of blast-furnace practice in America in the direction of large yields is mainly the history of our working since the year 1880, as the advancement that has been made in the last decade is greater than that in the third of a century previous. A new era in the manufactnre of pig-iron began in 1880 with the putting in blast of the Edgar Thomson furnaces. These furnaces at once leaped to the front as pig-iron producers, and have maintained that position—with but one brief interruption—ever since. I shall, therefore, confine myself mainly to a description of these works, showing the changes in design and practice by which these results have been achieved. In order to show more clearly the progress that has been made since 1880, I shall refer briefly to the best work that was done in the ten years previous to that time. The Struthers furnace, in Ohio, was one of the first to attract attention in the matter of large outputs. This furnace was 55 feet high, 16 feet in diameter of bosh, 9 feet in the hearth, and about 8 feet 6 inches at the stock-line. The fuel was raw coal. This furnace, in December, 1871, made 1602

Jan 1, 1891

By B. C. Allen

The interface energies of chronzium, molybdenunz. hugsten, and their solid-solution alloys Cv-35Re, MO-33Re, and UJ-25Re were studied at 0.6 to 1.0 of the absolllte liquidus ter)zpe,vature using fiz&apos;e )izethods. Liquid surface tension, yv , was deter mined clsing the pendant-drop and drop-weight methods. Results are, respectizlely, 1700, 2370, and 2480 +100 dynes per ct for the rhernium -containing alloys and essentially the same as tlwse reported for liquid chro)riln, trolybdenum, and tungsten. Average solid slrjace energy, rsv< xias ))zeasured using tlre fiber-extetlsion method. The ratio of ysS, the acerage high-angle grain-boundary energy, to ySV cclas jolnd fronz grain-bolzdary grooue angles fort)zed at the surface in an inert atrfizosphere. Absolllte iute?:face energies were deterawined using ?nultip/rase equilibria involzing suitable liquids of known surface tension (tin, silver). Interpretation of the experimented results in view of pvobable tenzperatzcre, orientation, and purity effects giz,e the follouling approximations in ergs per sq ctn: ysv (i2lo. Mo-33Re) - 2100, ySS (Mo, Mo-33Re) - 800, rr (defornzation twins in MO-33Re at 1200"C) - 800. ysV (Cr. Cr-35Re) - 2400. YSS (CY, Cr-35Re) - 1000. Probably Ylv- YSV- 2500 for tungsten and W-25Re, giving yss (It&apos;, W-25Re) - 900. The interface energies of solid and liqid ch?&apos;omiu?.z, nolybdenu?rr, and tungsten are not geatly aff&apos;ected by rhenium and therefore are not a ttlajor factor in the ductili zing rhenium effect in Croup VI-A metals. THE interface energies of the refractory Group VI-A metals, chromium, molybdenum, and tungsten, are not well-established. The objective of this investigation was to study the liquid surface tension, solid surface energy, and grain-boundary energy of these metals and compare them to those found for the bcc solid-solution alloys, Cr-35e,&apos; 0-33e,&apos; and -25e. Five techniques were used to measure interface energies in high-purity polycrystal rod, wire, and sheet at 0.6 to 1.0 of the absolute liquidus temperature. The alloys were chosen to see if there was any connection between interface-energy behavior and the ductilizing rhenium effecL4j5 EXPERIMENTAL WORK Materials. A description of the materials used is presented in Table I. Chromium rod was prepared by arc melting iodide process crystals supplied by Chromallo Cor., hot extruding, and warm swaging to 0.63-cm-diam rod.6 The sheet was prepared by rolling as-extruded rod to 95 pct reduction in area from a hydrogen furnace at 800" to 900°C and surface grinding off 0.02 cm from each face. Cr-35Re rod was prepared by arc melting sintered rhenium powder and iodide chromium crystals, warm rod rolling to 50 pct reduction in area in cans, and swaging to 60 pct reduction in area at 1100" to 1200°C. Some of the rod was warm-rolled to sheet and then surface-ground. Portions of swaged chromium and Cr-35Re were further reduced by swaging and drawing to 0.013-cm-diam wire by the General Electric Co. Mo-33Re and W-25Re rod, sheet, and wire were provided by Chase Brass and Copper Co. The molybdenum sheet consisted of two lots, both essentially the same except for the carbon content. Liquid Surface Tension. The liquid surface tension of Cr-35Re, Mo-33Re, and W-25Re was measured by a combination of pendant-drop and drop-weight methods using techniques already decribed." Following out-gassing, molten drops were formed on the ends of centerless-ground Mo-33Re and W-25Re rods by electron bombardment at 5 x 106 mm. Similar drops were formed on outgassed Cr-35Re rods by induction heating under 1 atm of 99.995 pct Ar. Solid Surface Energy. Solid surface energy was measured by conducting microcreep experiments on molybdenum, Mo-33Re, chromium, and Cr-35Re wires at 2350°, 2306, 1550°, and 180O°C, respectively. In preparation, gage marks -2.5 cm apart and -0.001 cm deep were circumferentially scribed on the wire with a razor blade. Weights of the wire material were then attached. Five to seven reasonably straight wires were hung in a container made out of the wire material. The free end was placed through a small hole in the removable top and secured by bending a small portion 90 deg. The containers not only tended to provide vapor-solid equilibrium for the wires but also protected them from gaseous impurities. They were nominally 2.5 cm in diam by 5 cm high and were made from extruded chromium rod, Cr-35Re arc casting, molybdenum bar stock, or welded Mo-33Re sheet. After deg re as ing, the assembly was outgassed at a relatively low temperature to 2 x 10"5 mm and then recrystallized 2 to 8 hr at the creep temperature in a rhenium-element resistance furnace. The static argon atmosphere was gettered by tantalum radiation shielding. Specimen temperature was measured optically to 25"C using calibration with known melting points and blackbody conditions. The wires generally developed a stable bamboo-type structure according to Fig, l(b), (c), and (d) and retained their gage marks [upper portion of Fig. l(d)]. One or two of the weights were clipped off to provide a low load for the creep anneal. To minimize the possibility of bending or breakage, the wires remained attached to the top of the annealing container which was held to keep the wires vertical. The distance between gage marks was

Jan 1, 1967

By Nathan C. Rockwood

LIME is a very general term applied to products of limestone, in popular treatises often incorrectly, including ground or pulverized limestone used in agriculture. When used without qualifying adjective, the term usually means burned or calcined limestone, or quicklime, or calcia. The corresponding calcined product of magnesite is magnesia. If the calcined rock is relatively pure calcium carbonate, the resulting lime is a "high-calcium" lime; if the rock is dolomite, or a combination of calcium and magnesium carbonates, the lime is a "dolomitic" or a "high- magnesium" lime. There are various grades in between, depending on the percentage of magnesium carbonate and other ingredients in the raw rock. For some industrial purposes only high-calcium limes are suitable; in other processing-as, for example, neutralizing acid wastes -the relative percentages of magnesium and calcium carbonates in the raw material are not important. Limestone is burned (roasted or calcined) in furnaces known as lime kilns by direct exposure to the hot gases and flames. When heated to incandescence, the carbon dioxide content of the rock is expelled, leaving calcium and magnesium oxides, according to the formula usually written: [ ] This thermal reaction is reversible, which requires that the lime be withdrawn from the "calcining zone" of the kiln about as fast as made. Pure calcium carbonate would lose 44 pct of its weight in the calcining process; dolomite, 48 pct. Generally, the lime will retain the approximate size and shape of the piece of rock from which it is made but some few limestones tend to break down into granules or dust. Hence lime (quicklime) comes from the kilns in lumps or granules and normally is packed in water- tight containers in these forms, or is pulverized after calcination.

Jan 1, 1949

By W. W. Stephens, W. J. Kroll, H. P. Holmes

THE only two methods for producing commercial quantities of malleable zirconium, up to now, have been using magnesium reduction of the anhydrous chloride under a neutral gas, and using purification of raw zirconium by the iodide dissociation method on a hot filament. The purity of the metal obtained by the latter process is about the same as that resulting from the chloride reduction, with the exception of the oxygen content, which may be about 0.05 pct lower in the iodide metal. Even traces of oxygen have a strong hardening effect on zirconium. Since, in the iodide process, the impurities, Si, Al, Fe, Ni, and Mg in the raw zirconium used, are carried over, it would appear uneconomical to use this method of refining solely to eliminate the traces of oxygen, unless very soft metal is desired. One important step to improve the iodide method, namely, dissociating pure iodide made from carbide and recycling the iodine, which would change this refining process into a method for extracting zirconium from the ore, has not yet been made. The Bureau of Mines, by using the chloride reduction, wanted to produce quantities of a reasonably pure and malleable metal at low cost for large-scale industrial use. This aim has been achieved, and a pilot plant permitting production of 600 lb of malleable zirconium per week will be described (fig. 1). Briefly, the Bureau of Mines process consists of reducing purified gaseous anhydrous zirconium chloride with fused magnesium under a noble-gas atmosphere. The reaction product, magnesium chloride, and any excess magnesium metal present are removed from the sponge zirconium in the next step by fusion and evaporation in a good vacuum at about 925°C. In this process, care is taken to keep air out of contact with the hot metal, which otherwise would contaminate the product with oxygen and nitrogen. Both these impurities embrittle zirconium even when present in an amount as low as 0.1 pct. A number of previous reports1-3 describe the method and the various improvements that finally led to a workable process. The major steps made were the production of large quantities of carbide, which is the raw material for producing the chloride, its chlorination with reasonable efficiencies, and the elimination of iron trichloride contained in the raw chloride, as well as that of the zirconium oxide which is always present in this product. The physical nature of the anhydrous chloride, which sublimes at 331°C at atmospheric pressure and melts at 420°C under a pressure of 25 atm, made it necessary to provide a special safety device on the purification and reduction vessels in the form of a lead-alloy seal, permitting escape of excess gases if pressure tended to build up. The main difficulties encountered in the reduction and in the following step, salt separation in a vacuum at elevated temperature, were caused by the material from which the reaction pot was constructed—iron. This metal reacts with zirconium at about 940°C with formation of a eutectic. The last step, salt separation by evaporation of the magnesium and magnesium chloride in a vacuum, is quite unconventional and has not been used before on such a scale. It is only due to the improved construction of high-vacuum pumps, especially oil-diffusion pumps, that such a method could be used. The various steps of the Bureau of Mines process, as described in the general outline above, may be summarized as follows: (1) production of the carbide, (2) chlorination of the carbide, (3) purification of the raw chloride, (4) reduction of the pure chloride with fused magnesium, (5) separation of excess magnesium and magnesium chloride in vacuum at elevated temperature, and (6) melting of the sponge obtained. Production of Carbide The arc furnace, described in a previous report,&apos; was improved both to reduce the graphite consumption caused by the burning of the bottom plates and to concentrate the heat in order to obtain better power efficiency. This was achieved by providing the bottom with graphite plates entirely embedded in refractory bricks, the contact with the current being made with three water-cooled copper plugs. Figs. 2 and 3 show the arrangement. The crucible, made

Jan 1, 1951

Data for 1962 world-wide, non-communist bloc geophysical activity, including geochemistry, are now available through the Society of Exploration Geophysicists. This information was made available to the AIME Geophysics Unit Committee through the courtesy of Charles L. Elliot, Mining Coordinator for the SEG. The data were compiled from 245 responses to 496 questionnaires mailed (49%). The data for the U.S. are a realistic representation of actual activity, followed by Asia, Canada, Europe, Australia, Africa and Latin America in order of decreasing reliability.

Jan 9, 1963

IN the decade beginning 1850, the development by William Kelly in I the U.S.A. and Henry Bessemer in England of the pneumatic method of refining pig iron, known as the Bessemer process, gave the world the first method of producing low-cost steel in large volumes. Briefly, the Bessemer process consists of blowing air through liquid blast furnace iron in a refractory-lined vessel known as a converter. The air enters the iron in the furnace bottom through tuyeres, and during its passage through the iron removes the carbon, manganese, and silicon by oxidation. The heat produced by oxidation is sufficient to raise the temperature of the liquid metal to normal steel casting temperatures and, in addition, to melt some scrap. In the 1860&apos;s, the open hearth process was introduced which in the early part of the twentieth century surpassed the Bessemer process in steel production. In the early 1870&apos;s, Thomas and Gilchrist discovered that phosphorus could also be removed if lime were added and the converter lined with basic refractory; the modification is known as the basic Bessemer process and is used in Europe. Bessemer steel usually contains between 0.010 and 0.020 per cent nitrogen and between 0.05 and 0.10 per cent phosphorus which influences the properties. Henry Bessemer,1 in 1856, recognized the possibility of using oxygen in the converter process, but the cost was prohibitive. This interest was associated with the theoretical balance of the Bessemer process. Experimental work&apos; has indicated that bottom blowing with pure oxygen results in serious converter bottom and tuyere erosion. Dilution of the oxygen by steam has been observed to be an effective means of maintaining low-nitrogen content of the steel and at the same time reducing bottom and tuyere erosion. A further advantage is that the fume emission characteristic of Bessmer operation is reduced. The addition of steam to the oxygen, however, reduces scrap-melting capacity due to the endothermic reaction characteristics of steam. The possible advantages of refining methods for steel using high-purity oxygen have been recognized for over a hundred years, but the develop-

Jan 1, 1964

Discussion of the paper of John H. Hall, presented at the New York. Meeting, October, 1913, and printed in Bulletin No. 79, July, 1913, pp. 1247 to 1256. WILLIAM &apos;R. WEBSTER, Philadelphia, Pa.:-I would like to call ,attention to the fact that the results of the ordinary tension and bend tests do not always give us the information we want even if we figure out the amount of work done. You want a bending test of sufficient width and full thickness. In the case of eyebars, for instance, I have had experience with a 10- by 1-in. eyebar which gave perfectly good results in a full-size test of the finished bar. The 10- by 1.5-in. and 10- by 1.75-in. eyebars from the same heats-of steel were absolutely worthless in full-size tests. The narrow bending tests from all these bars gave good results. Bat after going into the matter fully, we found that if pieces about 3 in. wide and full thickness were used for the. cold bending tests, the heavier material would not stand this test, but failed. That is, in order to check the quality of the rolled bar you should have a wide piece of full thickness for cold bending, as the narrow pieces give misleading results. J. E. JOHNSON, JR., New York, N. Y. :-I would like to ask if there have been any tests made to compare the results of Charpy tests with the true dynamic test similar .to the Wohler test, except that the piece is subjected to a tensile or compressive stress and to alternating stresses in addition, at the same time. This seems to me to approach more nearly than any other test to the conditions of actual service. where the piece is under a fixed initial stress plus a highly variable and often alternating stress. Some tests were made on this plan in England within a year or two. The test piece was Subjected to either a tensile or compressive stress of known amount and simultaneously to alternating stresses in addition. Such a. test as this gives information which we cannot get by a tensile test or even from the tensile strength multiplied by an. elongation. Such tests, however, are exceedingly tedious and require long periods of time in order to obtain valuable results. If material could be subjected to these dynamic tests and the same material to the. Charpy shock test, and if some reasonable qualitative relation could be established between the results of the two tests, then we could assume that the shock test, which is so simple and easy to make, was a measurably accurate test of the dynamic qualities of the material. At present it does not seem

Jan 12, 1913

By K. A. Semlak, F. N. Rhines

NFILTRATION is a term used to designate that i- process by which the pores of a metal powder are filled with a relatively low-melting liquid metal through the action of capillary forces. This is accomplished in practice either by heating the porous body in contact with the solid infiltrant metal above the melting point of the latter, or by preheating the porous body separately and then dipping it into the liquid metal. The liquid, as it sweeps through the porous body, replaces the gases progressively, thus yielding a relatively dense product in a short time.&apos; Liquid-phase sintering, which is related to infiltration, is a process by which a mixture of two or more metal powders is sintered at a temperature between the liquidus and solidus of the ultimate alloy.&apos; According to Cannon" liquid-phase sintering can be divided into three stages which he calls liquid flow, accommodation, and solid sintering. The largest density increase occurs during the first stage, where the lower melting component melts and, driven by capillary forces, flows among the particles of the higher melting component, where, after dissolution of the bonds between the solid particles, it moves them into close packing. This happens so quickly that little has yet been learned of its mechanism. A study of the rate of capillary rise of a liquid metal in a higher melting metal-powder compact may be expected, therefore, to contribute not only to a firmer understanding of the process of infiltration as such but also to a more extensive knowledge of what occurs during the initial stage of liquid-phase sintering. Theoretical Basis In order to derive a mathematical expression of the rate of infiltration, it has been assumed that a powder compact consists of a great many parallel capillary tubes and that the rate of rise of a liquid in an average capillary channel represents the rise in the entire compact. For a straight capillary, assuming that Poiseuille&apos;s law obtains for the non-stationary state and that wetting is very rapid, Ligenza and Bernstein&apos; have derived the following differential eauation of motion where h is the height of rise of the column of liquid at time t, R, is the radius and 1 the length of the capillary, t) and 7, the viscosities of liquid and air, respectively, p and p, the density of the liquid and air, respectively, y the liquid-gas surface tension, 0 the liquid-solid contact angle, and g the acceleration due to gravity. The term on the left of Equation [I] represents the rate of change of momentum of the contents of the capillary tube. On the right the terms represent, respectively, the forces due to a) surface tension, b) viscous resistance, c) gravity, and d) end-drag effect. Equation [I] is not amenable to explicit solution, but for a tube of sufficiently small radius, the rate of rise may be slow enough so that the rate of change of momentum and end-drag terms may be neglected. The validity of this simplification was established by Ligenza and Bernstein&apos; by graphical differentiation of observed data obtained from organic liquids rising in glass tubes. The solution of this simplified case is:

Jan 1, 1959

By J. J. Frawley, W. J. Childs

Experiments were carried out to induce grain refinement during solidification by applying vibrational energy (freq 20 kc) to small specimens of bismuth, tin, and bismuth-tin alloys. The results show that if the intensity of the applied sound -field is not great enough to fragment the growing dendrites of a pure metal, no grain refinement is observed and the pain size of the dynamically nucleated specimens is the same as the grain size of a specimen statically supercooled the same amount. Bismuth specimens did not show any grain refinement; whereas, the tin specimens did show grain refinement. This phenomenon is the result of the difference in growth habit between the bismuth and tin dendrites. The bismuth-tin alloys showed grain refinement and, in addition, the segregation pattern was changed. THE solidification process is a change in phase requiring the nucleation of the solid phase from the liquid and the growth of this solid phase at the expense of the liquid phase. Since many physical properties and also the integrity of a casting are dependent on the solidification process, understanding and controlling this process are very important.&apos; A good example in the controlling of a cast structure using heterogeneous nucleation theory is the reduction of grain size in aluminum castings by nucleation catalysis.2 This mechanism of nucleation catalysis has been explained by Turnbull.3 Another technique for grain refinement, which has received much attention but the mechanism has not been fully understood, is to vibrate the solidifying melt. Vibrations can be applied to the melt either by vibrating the mold directly or by introducing a vibrating rod into the melt.4-13 Three mechanisms have been proposed to explain this phenomenon: 1) The mechanical fragmentation of the original dendrites that grew into the melt. These crystals or fragmented dendrites act as new growth sites. 2) The nucleation of new grains in the liquid by the generation of very high pressure pulses caused by cavitation in the liquid. 3) The remelting of the dendrite arms during the solidification process. This mechanism is operative only in alloy systems and would be enhanced by stirring or mechanical vibration. The purpose of this investigation was to determine the mechanism that will increase the number of grains when mechanical energy is introduced into a solidifying melt. APPARATUS The unit used to generate the ultrasonic vibrations was manufactured by the Redford Co., and is similar to the one used in ultrasonic soldering. Fig. 1 is a sketch of the major components used for generating ultrasonic vibrations. The crystal transducer assembly consisted of four lead zirconate ti-tanate piezoelectric crystals in an aluminum holder. An acoustical horn, which was fabricated from stainless steel, was attached to the holder by a set screw. The resonant frequency of this unit was 20,000 cycles per sec. A Pyrex crucible, 4 in. in diam and 4 in. high, was contained in a hole in the top of the horn. The piezoelectric crystals changed volume when excited by an electric signal, thereby generating a sound signal which passed through the horn. The crucible was coupled to the horn by a liquid silicone oil. The purpose of the couplant was to transmit the soundwaves from the horn to the crucible. Without the couplant, much of the sound energy would be lost. The energy transmitted was sufficient at the resonant frequency used, so that acoustical cavitation always occurred in the molten metal. The presence of acoustical cavitation was detected by the characteristic hissing sound emitted from the liquid. EXPERIMENTAL PROCEDURE The influence of ultrasonic vibration on the grain refinement of bismuth, tin, and bismuth-tin alloys was studied. These metals were chosen because of their low melting temperature and the relative ease with which they can be thermally supercooled. The following procedure was used for obtaining large amounts of supercooling. Pure bismuth (99.999+), which was received in bar form, was mechanically broken into pieces small enough to be accommodated in a 50 ml beaker. About 200 to 300 g of bismuth and a few grams of SnCl2 as a flux were placed in the 50 ml beaker and melted by induction heating. The melt was held for 20 min at

Jan 1, 1970

By John M. Hartman

The high temperature of the blast of modern furnaces renders it desirable that the pipe conveying the blast into the furnace crucible shall transmit and radiate as little heat as possible. To accomplish this, the pipe shown in the accompanying sketch was devised and patented. It consists of a slide-valve, leg-pipe, and belly-pipe, which are held together and to the tuyere by a system of levers and links. The slide-valve is superior to the old throttle-valve. The legpipe is formed of two thicknesses of wrought-iron pipe, with a space of half an inch filled in with clay and brick. The belly-pipe is made in the same way as the leg-pipe, and terminates in a globe face to suit the tuyere. The quarter turn is made extra thick, of cast iron, and the cap on the end is lined with clay also. The catches, A, B, C, are merely for convenience in putting the pipe together. The joints D and E are globe faces, and allow the pipe to adjust itself to any angle. The eye-piece is made of violet glass, which cuts off the glare from the bright coals in the furnace and allows a close examination of the interior, so that any water dropping or vapor can be detected. The glass does not become coated with dirt, like mica. Since good running of furnaces is shown by a bright tuyere, it is necessary to have a good eye-piece to examine them. To detach the pipe, a man lifts the weights, the side rods are then slipped off the bell crank under the quarter turn, the link under the belly-pipe is unhooked, and the pipe carried away. The same process is reversed to put the pipe together. The nozzle is changed by taking off the cap, G, drawing the nozzle through the belly-pipe, and inserting another. In this way the change can be made quickly, without taking down the pipe. On the old tuyere pipe bolts with brass nuts were used, which burned up and gave trouble. In other cases key-bolts were used, making it difficult to adjust the pipe. Bolts make too rigid a joint, and there is no provision for movement from contraction or expansion. As the temperature of the blast increases there is more expansion, and where rigid joints are

Jan 1, 1879

By John M. Hartman

THE high temperature of the blast of modern furnaces renders it desirable that the pipe conveying the blast into the furnace crucible shall transmit and radiate as little heat as possible. To accomplish this, the pipe shown in the accompanying sketch was devised and patented. It consists of a slide-valve, leg-pipe, and belly-pipe, which are held together and to the tuyere by a system of levers and links. The slide-valve is superior to the old throttle-valve. The leg-pipe is formed of two thicknesses of wrought-iron pipe, with a space of half an inch filled in with clay and brick. The belly-pipe is made in the same way as the leg-pipe, and terminates in a globe face to suit the tuyere. The quarter turn is made extra thick, of cast iron, and the cap on the end is lined with clay also. The catches, A, B, C, are merely for convenience in putting the pipe together. The joints D and E are globe faces, and allow the pipe to adjust itself to any angle. The eye-piece is made of violet glass, which cuts off the glare from the bright coals in the furnace and allows a close examination of the interior, so that any water dropping or vapor can be detected. The glass does not become coated with dirt, like mica. Since good running of furnaces is shown by a bright tuyere, it is necessary to have a good eve-piece to examine then. To detach the pipe, a man lifts the weights, the side rods are then slipped off the bell crank under the quarter turn, the link under the belly-pipe is unhooked, and the pipe carried away. The same process is reversed to put the pipe together. The nozzle is changed by taking off the cap, G, drawing the nozzle through the belly-pipe, and inserting another. In this way the change can be made quickly, without taking down the pipe. On the old tuyere pipe bolts with brass nuts were used, which burned up and gave trouble. In other cases key-bolts were used, making it difficult to adjust the pipe. Bolts make too rigid a joint, and there is no provision for movement from contraction or expansion. As the temperature of the blast increases there is more expansion, and where rigid joints are

Jan 1, 1879

By R. H. Goodrich

Development in this district during the year 1929 was little different from that of any other year despite the somewhat depressed condition of the oil business in general. The year was marked by: (1) An intensive geophysical campaign in the search of deep-seated salt domes; (2) the rather successful exploration and development of lateral sand production on the flanks of some of the older domes. Geophysical Exploration Geophysical work is confined almost exclusively to the torsion balance and seismograph. At the beginning of the year there were approximately 185 individual instruments of all types engaged in the search of structures in the Gulf Coast of Texas and Louisiana. This total includes 3 magnetometers, 83 torsion balances and 100 seismographs. The number of parties operating the torsion balances was 47; seismographs, 20; magnetometers, 3. It is estimated that 4,800,000 lb. of dynamite or other explosives were used in seismic exploration. During the year the torsion balance and seismograph were credited with having discovered the following salt domes: Texas, Danbury dome, Brazoria County, H. & T. B. R. Co., and Clodine dome, Fort Bend County, John Fredricks and Wm. Stanley, Satowsky Survey; Louisiana, Iowa dome, Calcasieu and Jefferson Davis Parishes, T. 9 S., R. 6 and 7 W., and Cameron-Meadow dome, Cameron Parish, T. 14 S., R. 13 W. Because of the secrecy maintained in these developments, it is somewhat hazardous to venture opinion as to the number of salt domes found during one year. The discovery of gas at Mykawa district and at Genoa district, in Harris County, Texas, is considered of more than passing importance, because there is indication in the performance of these two districts that commercial accumulation of oil and gas may be found in the Gulf Coast on structures other than the wore or less definite salt dome type. While it is generally conceded that the accompanying structure in these instances are deeply buried salt domes, it is a fact that neither the seismograph nor the drill have indicated the presence of salt.

Jan 1, 1930

By Thomas F. Donnelly

Discussion of the paper of THOMAS F. DONNELLY, presented at the San Francisco meeting, September, 1915, and printed in Bulletin No. 104, August, 1915, pp. 1759 to 1768. F. LYNWOOD GARRISON, Philadelphia, Pa. (communication to the Secretary *).-The paper is of value in giving the public some first-hand information regarding a copper property that from various causes has attracted considerable attention, especially in Philadelphia, and which has also been the source of several fantastic flotations that had little to recommend them. Since 1906, no work has been done on this property under my direction, with the exception of a topographic survey made last winter by Mr. Donnelly, which was intended as the first step in a sound and logical system of development. From 1906 to 1915, desultory attempts were made to develop these orebodies, but as the work was not in competent hands much money was wasted and even more disappeared in ways regarding which it is perhaps not best to inquire. The result is, this interesting property has now practically no more ore developed upon it than in 1906, despite the fact that a new 100-ton mill is being erected, although, as I have intimated, it is today not much more than a prospect. Turning now to the scientific and more agreeable side of the subject, it is interesting to note that these Santo Domingo copper ores are invariably found in volcanic tuffs and that, in a geologic sense, they are all very old, for there are no evidences of recent volcanic activity in the greater Antilles, of which this island is the second largest. The existence of copper in tuffs in different parts of the world is a notable fact. Often, if not usually, it is present in mere traces, but not infrequently we find it in sufficient amount to be of economic importance. Thus, for example, chalcopyrite and bornite occur in the Tertiary tuffs of Japan, and a number of producing copper mines of that country are either actually in, or closely associated with, rocks of this character. Whether the copper minerals are original primary ores in the tuffs, or were derived from accompanying eruptive dikes, appears not yet to have been determined in any instance. In most of the Japanese cases of which I can find any record the tuffs appear to be associated with shales and limestones. These Japanese copper ores also carry some gold, especially in the upper parts of the veins; in this they resemble the Santo Domingo deposits which not infrequently carry as much as $6 or $7 per ton of gold on the outcrop. As a rule the content of gold in both the Japanese and

Jan 12, 1915

By P. Dayal, L. S. Darken

THE migration of carbon in austenite under the influence of an electric current has been observed qualitatively several times.14 Lebedev and Guterman5 recently have reported quantitative measurements; their method consisted of welding a low-carbon to a high-carbon wire, passing current, and later estimating the carbon distribution metal-lographically. We believe the method reported in this paper is superior in principle since electrolytic migration and ordinary diffusion are not necessarily coupled as in the weld method; also for the first time the extent of migration is determined by combustion analysis for carbon. A uniform tubular specimen (S.A.E. 1045 or 1095) was mounted as illustrated in the figures. the whole assembly being in an atmosphere of purified nitrogen. Direct current (129 to 226 amp at 0.65 to 1.0 v) served as source both of heat and of potential gradient for carbon migration. The duration of experiment was 7.5 to 12 hr, during which time the temperature was controlled (±10°C) manually. The experimental conditions are indicated in the first five columns of table I. With this experimental arrangement, the temperature initially has a maximum value at the central plane. Also, in this vicinity (by virtue of the symmetry), the carbon entering any volume element is equal in quantity to that leaving; the loss or accumulation of carbon occurs near the electrodes since the carbon moves uniformly near the center and is "frozen" at the cold ends. Hence, providing the time of experiment is not sufficiently long to seriously influence the conditions at the central plane, carbon crosses this plane only under the influence of the electrical potential gradient and not under the influence of temperature or concentration gradient. The amount of carbon which has crossed this plane was determined by combustion analysis of the two halves of the specimen. The results of these analyses are shown in the sixth and seventh columns of table I. It will be noted that substantial amounts of carbon migrated from the anode portion to the cathode portion (except at 920°C, which temperature was too low to exhibit the effect in the allotted time). In spite of precau-tions taken, considerable decarburization occurred as may be seen by comparing cols. 8 and 5. In three cases (indicated by asterisks in table I) the specimen was ground on one side, polished, and examined metallographically before analysis. One specimen was normalized and re-examined. Micrographs of selected areas in specimens 4 and 6 are shown in figs. 1 and 2, respectively. Evidence of carbon migration from the anode toward the cathode is quite apparent. Fig. 2 shows abundant graphite as well as cementite in a region near the cathode. The temperature of this zone is estimated at about 800°C. In fig. 1, particularly in the micrograph on the extreme right (the right side of which is of unaltered carbon content), there is evidence of slight depletion of carbon in the immediate vicinity of the cathode as contrasted to the general increase in carbon of the cathode half of the specimen. Although this may be attributed in part to decarbur-ization, it is believed that it is occasioned also by thermal diffusion—migration (of carbon) from a cool to a hot zone4—a phenomenon superimposed upon the electrical migration. Evidence of carbon migration was visible particu-larly during the course of the high-temperature,

Jan 1, 1951

By Gerald Edmunds

CASTINGS of pure metals and many alloys usually have a coarse-grained structure characterized by long columnar grains throughout the main body of the casting. Frequently, the surface exhibits finer, some-times nearly equiaxed grains, and such grains may also compose other parts of the casting. This paper deals primarily with determinations of the grain-orientation textures of the columnar and surface grains of polycrystalline zinc castings. It includes some results upon a cadmium casting and a magnesium casting. A hypothesis is devel-oped to account for the observations on columnar grains and to use as a basis for predicting orientations in other cast metals. A general description of the position of the columnar grains in castings is that their long axes are approximately parallel to the direction of the thermal gradient during crystallization. Thus, in cylindrical castings the columnar grain axes tend to be radial, and in large flat castings where most of the cooling is through one or both of the large mold surfaces they tend to be perpendicular to the mold surfaces. At the edges and corners the direction of heat flow and there-fore the position of the grains is more com-plex. Actually observation shows that even in castings made in flat molds the cooling seems to be somewhat irregular, since columnar grains tend to emanate from certain areas of the cooling surface, indicat-ing that thermal contact was better there than in neighboring areas.

Jan 1, 1940

By A. B. Kinzel

IT is with sincere appreciation and a deep sense of responsibility that I accept the honor of delivering the Howe Memorial Lecture. In our time metallurgical research has delved into phenomena ever more complex in character, so that much of this work must be done by organized teams. We, of the Union Carbide and Carbon Research Laboratories and the Electro Metallurgical Co., are truly a team and the lecture which is to follow is due largely to a few of the outstanding members of that team here cited and well known to you in their own right: John Lamont, whose work deserves special recognition, Walter Crafts, William Forgeng, William Binder, Robert Fowler, and David Swan. Thus it is a fitting pleasure to accept this honor for the research institution which I represent. Henry Marion Howe was truly inspirational and his breadth of view was such that he could use either the method of rigid proof or implied mechanism to further the broad understanding. But perhaps his outstanding characteristic was his sound judgment and his ability to weigh observations. The following is replete with observations and judgment as to their implication. We would like to feel that it is the type of dissertation which Howe, himself, would have enjoyed. Chromium carbides in stainless steel have, in a sense, been a key to the progress of the stainless steel industry. Brearley&apos;s first stainless steel, containing approximately 0.30 pct C, was successful because it differed from previous Fe-Cr alloys in that the carbides were present in such amount and form as to provide the stainless and cutting properties. Again, the 12 pct Cr die steels with a carbon content of 1.5 pct or more achieved their properties by virtue of the form and distribution of the chromium carbides. In the straight chromium steels with from 12 to 25 pct Cr, chromium carbide amount and distribution are once more the determinants with respect to physical properties and corrosion resistance. In each of the cases just cited the role of the carbide is in essence similar to that of iron carbide in carbon steel and this story is so well known that we need not dwell on it. In the austenitic stainless steels, the chromium carbide plays only a minor positive role with respect to mechanical properties, and for corrosion resistance the objective is to achieve maximum homogeneity. Thus the tendency has been to ever lower the carbon and correlatively the chromium carbide content of the austenitic steels. Today stainless steels with carbon less than 0.03 pct are beginning to find their true place, and this is being aided in major degree by our Company&apos;s introduction of a new type of ferrochromium having negligible carbon. The role of carbon in these austenitic steels has long been recognized, and a truly enormous amount of research has been devoted to the subject. Much has been learned about corrosion resistance, but the attack on the problem from the point of view of carbide precipitation and the nature thereof has left much to be understood. Because of its fundamental importance to the future of stainless steels, further study of the mechanism of carbide formation in austenitic steels is of interest. In the 18-8 Cr-Ni steels, which are typical of the austenitic class of steel, carbon is soluble in the aus-tenite to the extent of approximately 0.15 pct at 1832°F (1000°C). The solubility becomes less with decreasing temperature, so that at 1652°F (900°C) the solubility limit is approximately 0.06 pct, at 1472°F (800°C) it is about 0.03 pct, and at 932°F (500°C) it is approximately 0.01 pct. Obviously this is the ideal situation for the classical precipitation phenomenon. It is true that, in a sense, 18-8 austenite resulting from annealing is in a metastable state, and the phenomenon of ferritic precipitation from this austenite should be considered. However, in a so-called fully austenitic 18-8 steel this is secondary with respect to the carbides and can be neglected. A wide variety of chromium carbides is known. Only one chromium carbide, Cr,,C,,, frequently referred to as Cr,C, has been found in unmodified low carbon 18-8 steel. This, fortunately, simplifies the study of the precipitation phenomena. For this study an A.I.S.I. type 304 stainless steel of commercial quality was selected. Analysis showed C 0.07 pct, Mn 0.49 pct, Si 0.33 pct, Ni 9.34 pct, Cr 18.91 pct, and N 0.033 pct. As expected with this composition the steel was homogeneous after annealing except for a few pools of ferrite, which were disregarded in that their location was not coincident with subsequent carbide precipitation areas. On corrosion testing the steel was normal and typical of good commercial quality. Specimens 1/2xlx4 in. were annealed and subjected to precipitation heat treatment for 100 hr at 100" temperature intervals from 1000° to 1500°F and for ten selected intervals ranging from 5 min to 64 hr at 1300°F. These blocks were then cut into small pieces for metallographic studies. The first problem

Jan 1, 1953