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By M. C. Flemings, T. Z. Kattamis

Dendrite morphology and grain size were studied in bulk samples of iron and nickel base alloys under-cooled up to 300°C. In the alloys studied, dendrite morphology gradually changes with increasing undercooling from the usual dendritic structure to a structure composed of cylindrical dendrite arms. At a critical undercooling of approximately 170°C in these alloys there is an abrupt transition to a fine-grained structure of spherical morphology. Final dendrite-arnz spacing of melts nucleated at less than the critical undercooling decreases with increasing undercooling and with decreasing distance from a chilled surface. Grain size of melts nucleated at greater than the critical undercooling decreases similarly with these factors. It is concluded that structure coarsening, with reduction of surface area as driving force, is the principal mechanism determining final dendrite-arm spacing in melts nucleated at small undercoolings and grain site in melts nucleated at large undercoolings. IN solidification of highly undercooled melts, nuclea-tion and growth of the solid is accompanied by a rapid release of latent heat of fusion. The heat release is sufficiently rapid in bulk specimens that it takes place essentially adiabatically with respect to the surroundings; hence the specimen heats up ("recalesces") to some maximum recalescence temperature. For bulk liquid metals and alloys, a simple thermal balance shows the undercoolings obtainable in bulk samples are not sufficient to lower the maximum recalescence temperature below the equilibrium solidus temperature. Hence, some liquid always remains at the end of recalescence; this liquid must solidify by rejection of heat to the surroundings. Metals, including iron and nickel base alloys, normally freeze with only a few degrees of undercooling. In general, nucleation begins on impurity particles present in the metal, at a "heterogeneous nucleation temperature" that is quite close to the equilibrium liquidus temperature. Very small droplets of metal can be undercooled considerably before nucleation occurs,1-4 presumably because subdivision of the liquid reduces the probability of solid impurity in a given droplet. Following early work on metal droplets,' a series of studies has shown that it is possible, without great difficulty, to undercool bulk samples of many metals and alloys. Undercoolings obtainable are approximately two tenths of the melting point for nickel, iron, copper, and other metals and alloys.5-9 Specimen sizes have generally been in the range of 50 to 500 g. Studies on undercooling to date have been concerned primarily with techniques of undercooling and with nucleation and growth kinetics. Only limited consideration has been given to dendrite morphology in under- cooled alloys. One such study, in bulk Cu-Ni alloy,8 showed that at small undercoolings a typical dendritic structure was obtained. At undercoolings the order of 175°C the structure of a Cu-40 pct Ni alloy became "ray or starlike", and a dense network of subbound-aries appeared. At still larger degrees of undercooling, of the order of 250°C, the structure became more random and included an ensemble of globular forms. Comparable results were obtained by walker10 on Cu-Ni alloys, and by Kamenetskaya et al.11 in research on Cu-Ni, Sb-Bi, Fe-Ni, and Fe-Cr alloys. In this work, study was made of the processing parameters influencing dendrite morphology and grain size in undercooled alloy melts. Experiments were specifically designed to show the effects of coarsening ("ripening") during solidification on final casting morphology. EXPERIMENTAL PROCEDURE Apparatus used was patterned after that of Walker,10 Fig. l(a). Melting was by induction under reduced pressure of helium. Two different types of crucible materials were used; there was no difficulty in obtaining substantial undercooling in both types of materials. Alumina crucibles were used for the bulk of the runs made, with a glass coating separating the metal from the crucible walls. Other runs were made using fused silica crucibles with or without slag coating. A graphite susceptor was employed around the crucible to aid in melting and to reduce melt stirring. The major portion of the experimental work was on

Jan 1, 1967

By H. J. Wasson

DEVELOPMENTS in Venezuela during the past few months have been obscured by the hap-penings in Seminole and, more recently, those in southwest Texas. The question has been asked whether or not the opening of these vast new, prolific areas in the United States may not have depressed prices to a point so low as to give the developments in the Caribbean countries a serious setback. Nothing of the kind, however, has taken place, and on the contrary, there has been demonstrated the fact that Venezuela can profitably produce great quantities of oil under existing market conditions, and at the same time finance the foundation for further large expan-sion in the future. The three big factors which contribute to place Venezuela in a unique position and tend to insure the steady expansion of its oil industry are, in the order of their importance: I. Reasonable oil laws backed by a sound govern-ment, which comprehends the all-important fact that the country's prosperity depends on the prosperity of its industries, in a word, perceiving that the goose which lays the golden egg merits considerate treatment. II. The low cost of placing Venezuela oil on our At-lantic seaboard; not over $0.60 per barrel. III. The uniformly high average production per well and the large area of some of the individual pools. Under these conditions Venezuelan producers may be expected to continue steady and profitable ex-pansion even in the face of further market slumps. Their position is analogous to that of the low-cost copper producers, and unless artificial barriers, such as tariffs, come into play, Venezuela will steadily grow in importance. Within less than five years it should be second only to the United States among the oil-producing countries of the world.

Jan 10, 1927

By Charles S. Barrett, F. W. Steadman

DEFORMATION bands of surprising regularity are found in large-grained polycrystalline copper after cold-rolling (Fig. I). Individual bands frequently are large enough to permit a determination of their orientation by means of etch pits and an optical goniometer. Measurements have been made on 21 areas in seven different grains, and these, combined with X-ray studies of nine single crystals that had been cold-rolled after mounting in a polycrystal-line block, have contributed to a better understanding of the preferred orientations in rolled copper just as similar studies have for rolled iron' and brass.2.3 Particular attention was given to determining orientations that are stable during rolling and to the manner of fragmentation and rotation of unstable grains. The possible role of twinning was also carefully investigated. The texture of polycrystalline copper after cold-rolling is well established by the pole figures that have been plotted by Schmid and Staffelbach,4 Iweronowa and Schdanow,5 and Brick and Williamson,3 all of which are in substantial agreement. There has been some divergence in the list of individual "ideal" orientations that have been used to describe the texture by these observers and others,6 although the orientation (110) [112]-that is, (110) parallel to the rolling plane and [112] parallel to the rolling direction-is generally recognized as the most prominent orientation and (I12) [111] one of the lesser orientations. Other orientations have been given by some observers as (236) [533], (100) [001], and (I 10) [001]. The texture of copper has also been described as (135) [533].6.1 The sum of these orientations provides a reasonable approximation to the complete pole figure, but it does not follow that these specific orientations are necessarily of fundamental significance, for the choice of indices is arbitrary, within limits. Furthermore, a detailed investigation of the ideal orientations in cold-rolled iron discloses continuous ranges of equally favored positions rather than definite positions of high stability,1 and similarly Brick's observations in a single crystal of a brass2 suggest that all orientations in the range between (110) [113] and (110) [117] are about equally stable. MATERIALS AND METHODS The material used was vacuum-cast electrolytic copper kindly supplied by L. L. Wyman, of the General Electric Co.* Slices 1/2 in. thick and 2 1/2 in. square, cut from the ingot, were rolled with 50 per cent reduction per pass to final thicknesses between 0.02 and 0.04 in., and etched to develop cube-face etch pits suitable for goniometric work.8 The etch was light on some strips and deep in others.

Jan 1, 1942

By Elmer W. Pehrson

NINETEEN FORTY-SIX was an eventful year for the mineral industries. Perhaps the most significant development was the socialization of industry in Great Britain, initiated in 1945 but carried to fruition in the coal industry in 1946. On Jan. 1, 1947, management of the coal industry will be vested in a National Coal Board, responsible to the Ministry of Fuel and Power. A sum of £164,660,000 has been provided to compensate private owners for assets transferred to the Board. The British coal industry has been a problem for many years. Production has declined to a point where serious shortages of fuel for domestic needs have developed. Exports have dwindled to a small fraction of the previous trade. Costs have increased greatly, and quality has deteriorated. The industry's physical plant has not kept pace with the rapidly mounting wage scales in recent years. Some claim that the best and most accessible coal reserves of Britain are heavily depleted. The industry has been harassed by difficult labor problems, including bad morale among the workers and a shrinking labor force.

Jan 1, 1947

By K. M. Fagin, D. W. Carter

Six new oil fields were discovered in the East and East Central Texas district during 1942. The Coke and Quitman fields, in Wood County, at this time appear to be the two most important oil discoveries for the year. The. four other oil fields discovered were Concord, in Anderson County; Kildare, in Cass County; Weiland (ClubLake), in Hunt County; and Larissa, in Cherokee County. The Rodessa lime in the Chapel Hill field, Smith County, provided the only new oil zone in older fields. The Hawkins field, Wood County, was the most active in drilling operations, 125 new wells being completed during the year. The Chapel Hill field tied the Coke field for second place with 30 completions each. The third most active field was Kildare, with 10 completions. Like the other oil-producing districts of the country, wartime restrictions reduced the number of oil and gas-well completions to 265 in 1942, compared with 964 completions in 1941. This represents a drop of 72 per cent and only a little more than one half enough to replace the 437 producing wells abandoned in the district during the year. Tn addition, the number of producing wells temporarily shut down nearly tripled, far two principal reasons: (I) the rule of the Petroleum Administration for War preventing operators from equipping more than, one well on each 10 surface acres with pumping or artificial-lift equipment, and (2) the Railroad Commission's issuance of various orders permitting the transfer of allowable for wells having high water-oil ratios and high gas-oil ratios to other wells capable of producing the same with less waste of reservoir energy. No changes were made in prices of crude oil in the district during 1942. Production and Probation The district produced 158,928,281 bbl. of oil and distillate during 1942, compared with 163,566,695 bbl. during 1941, which represents a decrease of 3 per cent. The East Texas field produced 120,680,595 bbl. of oil, compared with 130,377,793 during 1941; a reduction of 9,697,198 bbl., or 7.4 per cent. The production of this field represents 75.9 per cent of the district total, compared with the 79.7 per cent that it furnished in 1941. The district had an estimated basic daily oil allowable of 623,242 bbl. on Dec. 31, 1942. Approximately 31.8 per cent of the production in Texas during 1942 was supplied by this district, compared with 33 per cent during 1941- Changes in the annual production of newer and flush fields in this district are attributable either to a difference in the number of wells producing during the year or to changes in basic allowable and number of shutdown days due to shifting market dconditions brought on by the war. All regularly prorated fields in the district were shut down 123 days. Major exceptions were the East Texas field, closed128 days; Hawkiis, shut down 106 days; and Cayuga, Sulphur Bluff, Talco, and Rodessa, which

Jan 1, 1943

By D. W. Carter, K. M. Fagin

Six new oil fields were discovered in the East and East Central Texas district during 1942. The Coke and Quitman fields, in Wood County, at this time appear to be the two most important oil discoveries for the year. The. four other oil fields discovered were Concord, in Anderson County; Kildare, in Cass County; Weiland (ClubLake), in Hunt County; and Larissa, in Cherokee County. The Rodessa lime in the Chapel Hill field, Smith County, provided the only new oil zone in older fields. The Hawkins field, Wood County, was the most active in drilling operations, 125 new wells being completed during the year. The Chapel Hill field tied the Coke field for second place with 30 completions each. The third most active field was Kildare, with 10 completions. Like the other oil-producing districts of the country, wartime restrictions reduced the number of oil and gas-well completions to 265 in 1942, compared with 964 completions in 1941. This represents a drop of 72 per cent and only a little more than one half enough to replace the 437 producing wells abandoned in the district during the year. Tn addition, the number of producing wells temporarily shut down nearly tripled, far two principal reasons: (I) the rule of the Petroleum Administration for War preventing operators from equipping more than, one well on each 10 surface acres with pumping or artificial-lift equipment, and (2) the Railroad Commission's issuance of various orders permitting the transfer of allowable for wells having high water-oil ratios and high gas-oil ratios to other wells capable of producing the same with less waste of reservoir energy. No changes were made in prices of crude oil in the district during 1942. Production and Probation The district produced 158,928,281 bbl. of oil and distillate during 1942, compared with 163,566,695 bbl. during 1941, which represents a decrease of 3 per cent. The East Texas field produced 120,680,595 bbl. of oil, compared with 130,377,793 during 1941; a reduction of 9,697,198 bbl., or 7.4 per cent. The production of this field represents 75.9 per cent of the district total, compared with the 79.7 per cent that it furnished in 1941. The district had an estimated basic daily oil allowable of 623,242 bbl. on Dec. 31, 1942. Approximately 31.8 per cent of the production in Texas during 1942 was supplied by this district, compared with 33 per cent during 1941- Changes in the annual production of newer and flush fields in this district are attributable either to a difference in the number of wells producing during the year or to changes in basic allowable and number of shutdown days due to shifting market dconditions brought on by the war. All regularly prorated fields in the district were shut down 123 days. Major exceptions were the East Texas field, closed128 days; Hawkiis, shut down 106 days; and Cayuga, Sulphur Bluff, Talco, and Rodessa, which

Jan 1, 1943

By James W. Halley

' FINE-GRAINED " steels have been standard products for many years. This paper describes an investigation of the effects of some of the more common grain-growth; inhibitors used to produce these steels. The properties, response to heat-treatment, and the deoxidation practice necessary to produce "fine-grained" steels have been the subjects of numerous papers. It has been shown that a substantial quantity of' aluminum is necessary to produce this type of steel, and it has been indicated that titanium and zirconium produce a similar result. For some time there was a lively argument between those who felt that aluminum refined the grain and those who felt that aluminum oxide was the effective agent. This argument subsided with an apparent victory for those promoting aluminum oxide. Most of the work on grain size has divided steels into two broad classifications based upon McQuaid and Ehn's original carburizing test at 1700°F. or some similar test at this temperature. If the steel coarsened at this temperature, it was coarse grained, while if it did not it was fine grained. Quantitative data concerning how much a certain amount of aluminum raised the coarsening temperature and affected the properties, all other factors being constant, are very meager. Similar information regarding titanium and zirconium is practically nonexistent. The published information on aluminum yields some quantitative information. Epstein, Nead and Washburn' gave the first quantitative information on the amount of aluminum necessary to prevent grain growth at 1700°F. They showed that the addition of a pound to a pound and a half of aluminum per ton (0.05 to 0.075 per cent) would assure steel that would not .coarsen during a McQuaid-Ehn test at 1700°F. Herty, McBride and Hough2 reported that a steel containing 0.020 per cent acid-soluble aluminum coarsened between 1742° and 1832°F., while steels containing 0.016 per cent and 0.017 per cent acid-soluble aluminum coarsened between 1652~ and 1742°F. compared with similar aluminum-free steels that started to coarsen at 1580°F. Herty3 also showed a marked improvement in low-temperature notched impact resistance with increasing acid-soluble aluminum up to 0.030 per cent. McQuaid4 compared the coarsening of steels containing 0.011 to 0.204 per cent total aluminum and found a maximum coarsening temperature at 0.098 per cent aluminum. He had no samples between 0.015 and 0.098 per cent aluminum. Houdrement5 found a marked decrease in coarsening temperature with aluminum contents above 0.50 per cent. Kinzel, Crafts and Egan6 found that aluminum and zirconium improved thy low-temperature impact resistance of a low-alloy steel, while titanium was detrimental. Sims7 shows that sulphur increases the coarsening temperature and that the maximum coarsening temperature is between 0.04and 0.06 Per cent added aluminum. The

Jan 1, 1946

By S. WHINERP

(Cleveland Meeting, October, 1912.) I AM indebted to L. E. Bryant, of Danville, Ky., President of the Virginia Mining Co., operating coal-mines in Scott county, Tenn., for the following information relating to the existence of the Clinton iron-ore under the NW. slope of the Cumberland Plateau in Kentucky and Tennessee. During the past 15 years quite an important oil-field has been developed in a region having Wayne county, Ky., as its center, and a large number of wells have been drilled in that and adjacent territory in the search for oil. Many of' these wells have been carried to considerable depths below the recognized oil-bearing horizon, and one of them was drilled by Mr. Bryant at Pine Knot, a station on the Cincinnati, New Orleans & Texas Pacific railroad, a few miles north of the point where that road crosses the Kentucky-Tennessee State-line. The elevation of the surface at the crossing is about 1,400 ft. above sea-level. The railroad is located on the dividing ridge between the Cumberland river and Big South Fork. At a depth of 1,720 ft. below the surface the drill reached and passed through a formation which the drillers called " red rock," but which Mr. Bryant classified as Clinton iron-ore, as its geological position corresponded to that formation. The ore at this point was 6 ft. thick and appeared to be of uniform quality throughout. An analysis of the drillings gave : Fe, 33; Mn, 0.25; Si02? 3 ; Al203, 2 ; CaO, 13; MgO, 7 ; P,05, 0.333 per cent. ; S, trace. This analysis seems to confirm the belief that the ore is Clinton, and that it is of a quality equal to the average of the deep or unbleached Clinton ores in Tennessee and Alabama. This discovery led Mr. Bryant to make further examinations and inquiries, and he found that the stratum called " red rock " by the drillers had been passed through and noted in the great majority of the wells carried down to the same geological hori-

Oct 1, 1912

By Jerome F. Kuzmick

Many investigations have been made on the effect of the variables of pressure, sintering temperature and sintering time on the physical and microstructural charactcristics of metal-powder compacts. Severa1 such investigations have indicatcd that pressure is the least important of these three factors in an attempt to secure a dense. strong compact by a simple coltl-pressing and sintering procedure. However, it was felt that a further study of the effect of pressure on pressed and sintered metal powder compacts might prove interesting, for the following reasons: In work done in the past on the effect of pressure, temperature. arid time, the, metal-powder compacts were subjected to long sintering periods, and temperatures right up to the melting point of the metal were applied. It was thought that pressure might exert a more profound effect under short-time simtering and within narrower ranges of temperature. such as normally would be applied in large-scale production of metal-powder parts. 2. It was hoped that something further might be learned of the nature of the bond in pressed and sintered metal-powder compacts. 3. It was thought that interesting infor mation concerning the work-hardening effect of pressure on the crystal structure. of sintered metal-powder compacts would be obtained. Procedure Rectangular bars, 2 by 1/2 by 1/4 in. were molded from the following metal powders: Atomizcd till powder, 325-mesh Atomized aluminum powder, 325-mesh Reduced copper powder, 100-mesh Electrolytic iron powder, 100-mesh Atomized 70-30 brass powder, l00-mesh The, till powder was molded at various pressures up to 40 tolls per sq. in. This was the maximum, because at higher molding pressures there was considerable extrusion of tin into the die wall, jamming the die plungers. The tin specimens were not -in tered, as this phase of the work was- done merely to see how much a very sold metal could be compressed. The aluminum powder was compressed at various pressures up to 50 lons per sq in. Higher pressures could not be used because of extrusion into the die wall The compacts were sintered one hour at 000 in pure dry hydrogen. The copper powder was molded at vari-ous pressures up to 96 tons per sq. in. One set was sintered at 750°C., another at 050 C. for one hour in pure dry hydrogen. The electrolytic iron powder was molded at various pressures up to 00 tons per sq. in. and sintered, one set at Soo°C and one set at 1300°C for one hour in pure dry hydrogen. Extra 325-mesh specimens were also prepared to study the effect of reduced particle size on grain structure. The brass powder was molded at various pressures up to 96 tolls per sq. in. and silltered for one hour. one set at 65o°C. and one set at 800°C, in pure dry hydrogeu.

Jan 1, 1945

Jan 1, 1914

By C. E. Mills

Studies of ground movement and subsidence resulting from mining operations cover a broad field. It is also a very important consideration and one that eventually affects nearly every mining operation of any extent. The damage to surface buildings, removal of mine surface plants and replacements of main hoisting shafts must reach an astounding expenditure were these cost figures available over a period of years. Were the subject one of mathematical formula and dependent only on the angle of draw of the walls or country rocks, the problem would be relatively simple. Consideration must be given to depth and extent of workings; structural conditions of the orebodies and enclosing country rock; physical properties of these same rocks, including schistosity, bedding, jointing, slips, dikes, faults, and other structural weaknesses. The method of mining, extent of openings, supporting pillars, and amount of moisture or water underground are other pertinent factors. With such a large number of variable factors, it is apparent that the subject of subsidence is one that must be based largely on experience and results at other mines where conditions are somewhat comparable. In presenting this paper, it is the intent to describe the progressive results of past ground movements at the United Verde, to bring out physical conditions largely responsible for this movement, but to refrain from theorizing on the ultimate extent of subsidence resulting from future mining operations. Geology and Structure1 The ore deposits of the United Verde are of the massive sulfide, schist-replacement type. A structural anticline formed by the intrusion of diorite between bedding planes of steeply dipping and severely folded greenstones and porphyry localized the deposit of sulfide. The mineralized zone is of great horizontal extent varying from 200,000 to 400,-000 sq. ft., and extends from the surface to the lowest levels at a steep dip of from 50° to 75. The irregular interfingering of the sulfide with

Jan 1, 1934

By D. T. Peters, S. Floreen

The age hardening behavior of an Fe-8Ni-13Mo alloy was studied after the matrix had been varied to produce either ferrite, cold u~orked ferrite, or nzassive nzartensite. The aging behavior of the cold worked ferrite and murtensite structures were very similar. The martensite aging kinetics were much different from those observed in earlier studies of aging of maraging steels, even though the martensite wzatri.r had the same dislocation structure as those found in maraging steels. The results suggest that the previously observed precipitation kinetics of maraging steels ?nay have been controlled by the nucleation be-haviov, which in turn were dictated by the alloy compositions and the resultant identities of the precipitating phases. IT is well known that the rate of precipitation from solid solution depends not only on the degree of super-saturation, but also on the density and distribution of dislocations in the matrix structure. These imperfections often act as nucleation sites, and may also enhance atomic mobility. 'Thus, the presence of dislocations is important since the type and distribution of precipitates may be determined by them. The precipitate density and morphology in turn affects the mechanical properties of the alloy. A number of studies have been devoted to the precipitation characteristics in various types of maraging steels.'-" These are iron-base alloys containing 10 to 25 pct Ni along with other substitutional elements such as Mo, Ti, Al, and so forth, that are used to produce age hardening. The carbon contents of these steels are quite low, and carbide precipitation is not believed to play any significant role in the aging reactions. After solution annealing and cooling these alloys generally transfclrm to a bcc lath or massive martensite structure characterized by elongated martensite platelets that are separated from each other by low angle boundaries, and that contain a very high dislocation den~it~.~~~~~~~~-~~ Age hardening is then conducted at temperatures on the order of 800" to 1000°F to produce substitutional element precipitation within the massive martensite matrix. Most of the aging studies to date have revealed several common traits in these alloys, regardless of the particular identity of the precipitation elements. Generally hardening has been found to be extremely rapid, with incubation times that approach zero. The agng kinetics, at least up to the time when reversion of the martensite matrix to austenite begins to predominate, frequently follow a AX/~~ = ktn type law, where x is hardness or electrical resistivity, t is the time, and k and n are constants. The values of n are frequently on the order of 0.2 to 0.5, which are well below the idealized values of n based on diffusion controlled precipitate growth models. Finally, the observed activation energy values are typically on the order of 30 kcal per mole, and thus are well below the nominal value of about 60 kcal per mole found for substitutional element diffusion in ferrite. The common explanation of these observations is that the precipitation kinetics are controlled by the massive martensite matrix structure. Thus, the absence of any noticeable incubation time has been attributed, after ~ahn," to the fact that the precipitate nucleation on dislocations may occur without a finite activation energy barrier. The low values of the activation energy are generally assumed to be due to enhanced diffusivity in the highly faulted structure. If this explanation that the precipitation kinetics are dominated by the matrix structure is correct then one should observe a distinct difference in lunetics between aging in a martensitic matrix and aging the same alloy when it has a ferritic matrix. Such a comparison cannot be made with conventional maraging compositions, but could be made with the alloy used in the present study. In addition, the ferritic structure of the present alloy could be cold worked to produce a high dislocation density so that one could determine whether ferrite in this condition would age similarly to martensite. EXPERIMENTAL PROCEDURE The composition of the alloy used in this study was 8.1 pct Ni, 13.0 pct Mo, 0.10 pct Al, 0.13 pct Ti, 0.012 pct C, bal Fe. The alloy was prepared as a 40 lb vacuum induction melt. The heat was homogenized and hot forged at 2100°F to 2 by 2 in. bar, and then hot rolled at 1900°F to $ in. bar stock. The aging lunetics were followed by Rockwell C hardness and electrical resistivity measurements. Samples for hardness testing were prepared as small strips approximately 2 by $ by 4 in. thick. Electrical resistivity was studied on cylindrical samples approximately 2 in. long by 0.1 in. diam. The method for making the alloy either martensitic or ferritic was based on the fact that the alloy showed a closed y loop type of phase diagram. At high temperatures, above approximately 24003F, the alloy was entirely ferritic. Small samples on the order of the dimensions described above remained entirely ferritic after iced-brine quenching from this temperature. In practice, a heat treatment of 1 hr in an inert atmosphere at 2500°F followed by water quenching was used to produce the ferritic microstructure. These samples were quite coarse grained and usually en-

Jan 1, 1970

Part 1. Coal Part 2. Industrial Minerals

Jan 3, 1977

By Shiro Ban-ya, John Chipman

Equilibrium in the reaction was investigated at temperatures of 1500°, 1550°, and 1600°C for sulfur concentrations up to 7.2 wt pct. Multisample crucibles contained the liquid alloys in a resistance-heated furnace using a technique especially designed for the study of more complex alloys to be reported separately. Modern free-energy data are used to correct the H2S:H2 ratio for dissociation of H2S and calculalion of the partial pressure of S2. Published data on the equilibrium are similarly corrected. Thermodynanzic treatment of the data employs the composition variable zs = nS/(nFe — nS) and the activity coefficient Gs = as/zs The data at 1500" and 1550°C are fitted by the equation log s = —2.30zs. Within the limits of experimental error the same coefficient is applicable to the data at higher temperatures. Equations are given for the free-energy change in Reaction [I] as well as for the solution of S, gas in the metal. The heat of solution of 1/2 s2 is -32.28 i2.5 kcal. Uncertainty in the free energy is very much smaller. For dilute solutions of interest in steelmaking, the activity coefficient of sulfur is unchanged from that listed in Basic Open Hearth Steel-making. DETERMINATIONS of the thermodynamic properties of sulfur in liquid iron by Morris and williams1 and by Sherman, Elvander, and chipman' provided a basis for control of sulfur in steelmaking processes. From the standpoint of understanding the chemistry of metal plus nonmetal in liquid solution they left several questions unanswered. The activity of sulfur in dilute solution at about 1600°C was well-established but temperature coefficients were uncertain, due at least in part to the use of the optical pyrometer and uncertainty regarding the effect of sulfur on emissivity. It appeared that deviation from Henry's law increased with increasing temperature, a most unusual behavior requiring either confirmation or disproof. These studies were based on experimental determination of equilibrium in the reaction: At high temperatures H2S is partially dissociated so that the gas mixture contains HS, S2, and S in addition to HS. At the time of the earlier studies the free energies of these constituents were unknown and it was therefore impossible to make adequate correction for dissociation. Observations on the effects of alloying elements by Morris and coworkers1, 3 and by Sherman and Chip-man4 enable us to assess the effects of alloying elements on the activity and to make corrections for incidental impurities in the binary liquid. These studies as well as a number of more recent investigations will be reviewed in detail after out own experimental results have been presented. It was our purpose in planning this study to avoid uncertainties regarding the emissivity of alloys and the errors of thermal diffusion which plagued some of the early attempts,5 by using a resistance furnace and thermocouple in preference to induction heating and optical pyrometer. Modern data on free energies of the gaseous species are to be applied to our data and to those of other investigators to obtain corrected values of K1 and of the activity coefficient and ultimately to relate the sulfur content of the bath to the equilibrium partial pressure of S,. Extension of the study to include ternary and complex solutions will be described in a later section. EXPERIMENTAL METHOD a) Preparation and Calibration of H2-H2s Gas Mixture. The source of hydrogen sulfide was a preparer mixture of 43 pct H2S, balance hydrogen, contained in a large aluminum cylinder. This was passed through anhydrone and through a microflowmeter. Hydrogen was passed through platinized asbestos, ascar-ite, and anhydrone, and through a capillary flowmeter. Argon was passed through copper wool at 500°C, then through ascarite, anhydrone, and a flowmeter. The flow rate of hydrogen was kept constant at 200 ml per min, to which an arbitrary amount of the hydrogen-hydrogen sulfide mixture was constantly added and then the prepared gas mixture was introduced into the reaction tube through a gas mixer. In certain experiments 200 ml per min of argon was added to the hydrogen-hydrogen sulfide gas mixture to increase the total flow rate of gas. The ratio of hydrogen-hydrogen sulfide in the inlet gas was checked for each run by chemical analysis. A sample of the gas taken from a bypass was bubbled through zinc and cadmium acetate solution (4 pct zinc acetate, 1 pct cadmium acetate, and 1 pct acetic acid) to remove hydrogen sulfide from the gas mixture, and the flow rate of the remaining hydrogen was measured by a soap bubble method to determine the volume of hydrogen. The amount of hydrogen sulfide absorbed in solution was determined by titration with iodine against sodium thiosulfate, with starch used as the indicator. The ratio of hydrogen sulfide to hydrogen in the inlet gas could be kept within ±2 pct in the range from 10-2 to 5 x 10"4 which corresponds to from 0.2 to 7.0 wt pct sulfur in liquid iron. b) Furnace Arrangement. Fig. 1 shows the furnace arrangement and the shape of the alumina crucible used in this experiment. A vertical-tube silicon carbide electric resistance furnace contained the reaction tube which consisted of two parts, the gas-tight

Jan 1, 1969

Albin, B. R. Billings, Mont. 28 Amster, Nathan L 25 Broad St., New York, N. Y. '28 Bache, Jules S. 42 Broadway, New York, N. Y. 28 Barrett, C. P. 5338 Harper Ave., Chicago, 111. '28 Baum, Frank G., Cons. Hydro-Electric Engr Cassel, Shasta Co., Cal. '28 Bayless, William S. Russ Bldg., San Francisco, Cal. '28 Bean, Louis H.60 E. 42nd St., New York, N. Y. '28 Beatty, Roes J. 1105 First National Bank Bldg., Chicago, Ill. '28 Benwell, Oswald F. Hold Mags. '28 Beymer, Albert S., V.P., Keystone National Bank Pittsburgh, Pa. '28 Blumenthal, Hugo 44 Pine St., New York, N. Y. '28 Boettcher, Charles Ideal Cement Bldg., Denver, Colo. '28 Bowlus, Thomas H. Iola, Kan. '28 Brown, Colvin B. Chamber of Commerce, Washington, D. C. '28 Bart, Maxwell Struthers Southern Pines, N. C. '28

Jan 1, 1932

By E. S. Machlin, W. R. Yankee

IN a previous study1 of the effect of heating com-mercial titanium in air on its subsequent friction coefficient against other metals, as well as itself, it was found that the friction coefficient markedly decreased from a value of about 0.7 to about 0.3. A tentative explanation was given that surfaces normally produced at room temperature are not contaminated sufficiently to prevent seizing or welding of the titanium to the softer mating metals. The latter tend to cleanse themselves during rubbing over the harder titanium. It was thought that the lack of a contaminant protective film on the titanium was due to the high solubility of titanium for oxygen and nitrogen and hence an inability to form a contaminant oxide or nitride. This explanation requires the ratio of the surface absorption rate to the diffusion rate to become much lower at room temperature than it is at high temperatures. In order to check the phenomenon further, commercial titanium specimens were nitrided or oxidized at 800°C for 20 hr in flows of prepurified N2 and 01, respectively, at about 1/2 in. H2O above atmospheric pressure. Friction runs were made in argon using a freshly cut copper hemisphere (cut in argon) on surfaces cut successively into the diffusion layers in the titanium (cut in argon) using the techniques described in a previous publication.' DPH values (100 gram load) were made as a function of depth into the diffusion layer using a Tukon tester. Also, micrographs were taken at separate cross sections to indicate the diffusion layers. The results obtained are presented in Figs. 1 and 2, which show the "static" friction coefficient vs hardness for the nitrided and oxidized specimens, respectively. A separate measurement of the friction coefficient of clean copper vs iodide titanium also was made. From results reported in the literature' giving the oxygen and nitrogen contents as functions of the hardness, cross plots were made showing the friction coefficients as functions of the amount of interstitial solute. These plots are given in Figs. 3 and 4. From micrographs of the diffusion layers and the phase diagrams, it was deduced that the data in Figs. l through 4 correspond to the single phase a region. The points observed on the compound regions have been excluded from the figures. It is apparent that nitrogen or oxygen in solution in the a titanium markedly affects the friction coefficient against a softer mating metal. Discussion of Results These results are extremely interesting from both a practical and theoretical viewpoint. The theoretical implications will be discussed first. According to Bowden, the friction coefficient should be given to a good approximation by the relation where a is the fraction of contact area that has welded, a is the shear strength of weaker component, and H is the hardness of softer component. Using this relation alone, it is difficult to understand the results because none of the terms should be affected by a variation in the oxygen or nitrogen content of the harder and stronger metal, titanium. Even if the ratio of S/H for titanium is used in Eq. 1, the ratio has been shown to be independent of oxy-gen or nitrogen content.' If a more rigorous equa-tion is used combining Eq. 1 and a result given pre-viously" for the case where welding is absent, then the relation obtained is µ = a S/H + (1-a) a W aß/H where a is constant and Waß is the work of adhesion between the two metals comprising the friction couple. This relation states that if a is less than 1/2 or so, variation in the work of adhesion Waß between copper and the titanium should affect the friction coefficient markedly. It is reasonable to expect that the work of adhesion will depend on the oxygen or nitrogen content of the titanium. Available data4 show that clean metals and oxides have much lower works of adhesion than the same metals against the

Jan 1, 1955

Organization Place - Date 1918 American Iron and Steel Institute New York, N. Y. May American Water Works Association :.. St. Paul, Minn. May 20-25 American Institute of Chemical Engineers Berlin, N. H.. June 19-22 American Concrete Institute Atlantic City, N. J. June 24-26 American Society for Testing Materials Atlantic City, N. J. June 25-28 New York Electrical Society New York, N. Y. June National Association of Stationary Engineers Cincinnati, 0. Sept. 9-13 National Exposition of Chemical Industries New York, N.Y.. Sept.23-28 American Chemical Society Cleveland, 0. Sept. National Petroleum Association Atlantic' City, N. J. Sept.

Jan 5, 1918

By Nicholas J. Grant, Robert F. Wilde

TAYLOR and Floyd's"" work in establishing phase diagrams based on the elements Ni-Cr-Ti-A1 has led to an understanding of the precipitation hardening mechanism in alloys based on these elements. Nordheim and Grant4 concluded that in simple alloys, and where the aluminum to titanium atomic ratio was such that less than three out of five aluminum atoms were replaced by titanium, the precipitate on aging is the face-centered-cubic Ni 3A 1 phase, called They further found that increasing amounts of hexagonal ? phase, Ni3Ti, precipitated from these alloys when the titanium content exceeded the solid solubility of both matrix and Ni3A1. For alloys of Ni-Cr-Ti-Al, in which the titanium and aluminum contents each ranged from 0 to 4 wt pct, the titanium-rich was superior for strengthening to either pure ?' or 7. It was also noted that the combined titanium plus aluminum content (atomic pct) was a direct measure of the high temperature strength and overaging temperatures for these alloys.4 The present investigation was undertaken to extend existing data on precipitation hardening in the more complex commercial alloys containing higher titanium plus aluminum, and with significant quantities of cobalt, molybdenum, and carbon. Experimental Procedure Reforging of As-Received Bar Stock—The alloys were received as ground, forged bar stock. Chemical analyses and the as-received bar diameters are shown in Table I along with the ASTM grain size after the various treatments. All stock except the Waspaloy was reforged to % in. diam to gain material and to facilitate machining of stress-rupture specimens. Forging was carried out at 2100°F, and discontinued when the bar temperature fell to 1800°F. Heat Treatments—For experixental simplicity it was desirable to heat treat all of the alloys at, the

Jan 1, 1958

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938

By Charles N. Becker

The practice of drying phosphate in Florida is as old as the industry, which began a little more than half a century ago. The methods, however, have changed considerably. At first, the natural process of exposure to the sun and air was used, later supplemented by wood fires beneath open-air stationary dry kilns and drying towers of various designs. It was not until the early nineties that rotary driers came into use, and at first they were of very small design and fired with wood. As the industry grew and tonnage increased, so likewise grew the number and size of rotary driers, until today the largest installations are 6 ft. up to 7 ft. 6 in. in diameter, and 55 to 60 ft. long, fired with crude oil. The reasons for drying phosphate rock are: (1) to eliminate freight on water in the shipment and (2) to facilitate the good grinding qualities required by the buyers in their acidulation. Phosphate pebbles vary materially in natural characteristics and each property has a direct bearing on the processing. In making comparisons of cost and operating conditions, the following are usually taken into consideration: 1. The hard dense pebbles, which contain very little interior moisture and 6 to 8 per cent total moisture, usually produced from the low-grade deposits. 2. The lighter, porous pebbles, which contain 4 to 5 per cent interior moisture and a total moisture ranging from 9 to 15 per cent. 3. The product of recovery operations using oily reagents, containing from 15 to 25 per cent moisture. 4. The size of the pebbles Usually the plus 5-mesh material is considered as "coarse rock"; the minus 5-mesh plus 24-mesh is "fine rock," and the minute particles below 24 mesh are called "concentrate." 5. The amount of moisture allowed in the dried product. The practice is generally to dry down to 1.5 to 2 per cent moisture. There is, however, an actual range in guarantee of from 1 per cent maximum to 3 per cent maximum.

Jan 1, 1938