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By Patrick M. Hurley

The relationships between mineral deposits and various plate margin mechanisms are examined under the constraints of radiogenic isotopes and other geochemical indicators. It seems like1 y that: (1) deposits of the spreading ridge association are fairly ubiquitious through most of geologic history and can be recognized by the lithologic assemblage and primitive lead isotope ratios; (2) most metals in the island arc association are not derived entirely from a subducting oceanic plate, and have a partly continental affinity; (3) subduction beneath a continental plate generates ores which are derived either from the downgoing plate or from the lower crust; (4) the heating of a continental plate by thickening or by mantle plumes may develop a metallogenic province involving extraction of metals from the curst; (5) rifts and grabens developing thick sections of marine sediments with evaporites may be the locus of base metal mineralization by movement of reducing brine solutions resulting from diagenesis and bacterial reduction of sulfates

Jan 1, 1978

By E. F. Bradley, R. I. Jaffee, H. R. Ogden, E. S. Bartlett, D. N. Williams

The mechanical properties of solid-solution-strengthened columbium alloys have been assessed as a function of alloying additions. Studies included the effects of tungsten, tantalum, molybdenum, and vanadium. Elevated temperature fabrication was required at alloying levels above about 15 pct W or 10 pct Mo. Tungsten, molybdenum, and vanadium additions increase tensile strength at room temperature and 2200°F, but tantalum additions exert little strengthening. Similarly, tungsten, molybdenum, and probably vanadium additions increase the ductile-to-brittle transition temperature, and tantalum additions decrease this parameter. The 2200°F stress-rupture strength is increased by tungsten and molybdenum additions; with 20 to 25 at. pct additions, 100-hr rupture strengths of 30,000 psi are obtainable. Small vanadium additions exhibit mild stress-rupture strengthening, and tantalum additions are innocuous. At 2500°F, tungsten additions retain stress-rutpure strengthening capability, but molybdenum additions are much less effective. Tantalum additions augment the stress-rupture strengthening of tungsten plus molybdenum additions at 2500°F. Of the refractory metals, columbium possesses specific potential for structural use in the temperature range from 2000" to about 2500°F. Desirable features of columbium are its good low-temperature ductility, ease of fabrication, oxidation mechanics (lack of a volatile oxide at moderate temperatures), good availability and reserves, and relatively low density. However, alloying is required to provide attractive strength at elevated temperatures. Published information concerning alloying be- havior of columbium relative to mechanical properties is sketchy, particularly in consideration for long-time applications at temperatures in excess of 2000°F. Only a few stress-rupture data at temperatures from 2000" to 2500°F have been reported;'-' these are too meager to allow rationalization of the effects of various alloying additions on creep or stress-rupture properties. Additional published data do, however, give some insight toward understanding of systematic alloying behavior for columbium relative to low-temperature strength4-' and ductility,' and elevated temperature tensile behavior.4,6 This paper is intended to augment previous knowledge, and to promote understanding of the alloying behavior of columbium for long-time structural service at elevated temperature. BASIC CONSIDERATIONS Solid-solution strengthening is recognized to be of prime importance in improving strength in columbium-base alloys. Other strengthening mechanisms may be (and are, in current alloys) used to augment solid-solution strengthening. As strengthening results primarily from lattice distortion, the strengthening effectiveness per atom depends upon atomic size mismatch between solvent and solute. Another factor in this regard is conformance to ideal solution behavior in the solid solution. Thus, for example, despite appreciable differences in the degree of mismatch between tungsten (5 pct), molybdenum (5 1/2 pct), and vanadium (7 1/2 pct) in solution in columbium, all are about equally effective in straining the columbium lattice at room temperature.'-' Similarly, tantalum additions do not strain the columbium lattice, and little strengthening is expected. Size effects being equal, maximum solution strengthening at high temperatures is anticipated to result from the addition of elements that increase the melting temperature of columbium. This expectation is based on an increase in the electronic bonding forces exhibited in the transition metal series as electronic structures approach those of the Group Vl metals. Of the metals that exhibit ex-

Jan 1, 1963

Jan 6, 1951

By I. W. Walling, F. B. Plummer

Bastin and others have demonstrated the presence of sulphate-reducing bacteria in oil wells producing salt water. Analyses show that at 125°F. bacteria alone reduce sulphates in East Texas salt water by only 3 per cent in 30 days, forming principally hydrogen sulphide and sodium or calcium hydroxide. The hydrogen sulphide reacts with soluble iron compounds to produce iron sulphide in the absence of oxygen, and ferric hydroxide where oxygen and air are present. Where iron or other metals and iron sulphide are already in the water containing bacteria, I00 per cent reduction of the sulphates is complete in 30 days or less; where magnesium is present, reduction is complete in 15 days. The effects of changes in temperature, of different bactericides, and of concentration of bactericides on sulphate reduction are described in detail and illustrated by tables and curves. The significance of sulphate reduction on corrosive properties of oil-field water is briefly discussed. Chemistry of East Texas Oil-field Water The chemical composition of the water in the East Texas field salt-water disposal pits is shown in Table I. This salt water corrodes pipes, pumps, and steel tanks excessively, principally because of its content of oxygen, hydrogen, sulphide, and carbonic acid. The carbonates in the water when exposed to air tend to give up carbon dioxide and to precipitate calcium carbonate in large quantities. This forms coatings in tanks, settling pits, and ditches, and soon, unless removed by acid treatment, will effectively clog an injection well and reduce the flow of water back into the ground. The iron compounds in the water, most of which are dissolved from tanks and pipes, are in the ferrous form, and when exposed to the air are oxidized from soluble ferrous carbonate to insoluble ferric hydroxide, resulting in the precipitation of a gelatinous precipitate that will clog oil-field sands effectively: 2Fe(HCO3)2 + O + H2O -> 2Fe(OH)3 + 4CO2 The sulphates in strong sulphate-bearing water may be attacked by swarms of sulphate-reducing bacteria and more hydrogen sulphide may be produced. The hydrogen sulphide reacts with soluble minerals in the water to form black sludges. A knowledge of the chemistry of each reaction in oil-field water is important to the oil-field engineer, since means must be devised to prevent the formation of harmful precipitates that clog injection wells and to prevent corrosion of tanks by harmful products of biochemical processes. Methods of Treating Water before Injection into Ground* The open system of handling the waste salt water in the East Texas field consists of aerating and chemically treating the water to precipitate the unstable iron,

Jan 1, 1946

By F. B. Plummer, I. W. Walling

Bastin and others have demonstrated the presence of sulphate-reducing bacteria in oil wells producing salt water. Analyses show that at 125°F. bacteria alone reduce sulphates in East Texas salt water by only 3 per cent in 30 days, forming principally hydrogen sulphide and sodium or calcium hydroxide. The hydrogen sulphide reacts with soluble iron compounds to produce iron sulphide in the absence of oxygen, and ferric hydroxide where oxygen and air are present. Where iron or other metals and iron sulphide are already in the water containing bacteria, I00 per cent reduction of the sulphates is complete in 30 days or less; where magnesium is present, reduction is complete in 15 days. The effects of changes in temperature, of different bactericides, and of concentration of bactericides on sulphate reduction are described in detail and illustrated by tables and curves. The significance of sulphate reduction on corrosive properties of oil-field water is briefly discussed. Chemistry of East Texas Oil-field Water The chemical composition of the water in the East Texas field salt-water disposal pits is shown in Table I. This salt water corrodes pipes, pumps, and steel tanks excessively, principally because of its content of oxygen, hydrogen, sulphide, and carbonic acid. The carbonates in the water when exposed to air tend to give up carbon dioxide and to precipitate calcium carbonate in large quantities. This forms coatings in tanks, settling pits, and ditches, and soon, unless removed by acid treatment, will effectively clog an injection well and reduce the flow of water back into the ground. The iron compounds in the water, most of which are dissolved from tanks and pipes, are in the ferrous form, and when exposed to the air are oxidized from soluble ferrous carbonate to insoluble ferric hydroxide, resulting in the precipitation of a gelatinous precipitate that will clog oil-field sands effectively: 2Fe(HCO3)2 + O + H2O -> 2Fe(OH)3 + 4CO2 The sulphates in strong sulphate-bearing water may be attacked by swarms of sulphate-reducing bacteria and more hydrogen sulphide may be produced. The hydrogen sulphide reacts with soluble minerals in the water to form black sludges. A knowledge of the chemistry of each reaction in oil-field water is important to the oil-field engineer, since means must be devised to prevent the formation of harmful precipitates that clog injection wells and to prevent corrosion of tanks by harmful products of biochemical processes. Methods of Treating Water before Injection into Ground* The open system of handling the waste salt water in the East Texas field consists of aerating and chemically treating the water to precipitate the unstable iron,

Jan 1, 1946

By John L. Walter

A sintered compact of iron containing 0.007 vol fraction of glass , prepared 6). powder rnetullurgtcal lechniques, was rolled lo foil, 0.001 in. /hick. The foil sullrples were anneuled a1 650° to 850°C in hydrogen. Pri,narj recryslullization prodtnced large grains which Lc3ere highly elongnled in the rolling direclion und which had an unusual prgferred orientation. The glass parlicles assumed a stringerlike dispersiorz on working; llie slrinyers were parallel lo the rolling direction and to the long axis of the grains. The same unusual grain structure, preferred orientation, and stringerlike dispersion of purticles are found in heal-ily rolled and annealed foil of tungsten which has heen doped wilh small amounts of aluminum, silicon, and polassiutvt. Both the proper dispersion of the particles and severe working (reductions in excess of 98 pct) are necessary to produce the elongzcted grain structure. RECENTLY, the author reported on the origin of the elongated or "nonsag" grain structure in tungsten foil which was doped with aluminum, silicon, and potassium.' It was observed that particles, identified as mullite (Al6Si2Ol3), were present in the doped ingot (as sintered) and at all stages of processing from ingot to sheet or wire. It was shown that the particles, being plastic at tungsten working temperatures (up to 1550"C), underwent a "stringing out" parallel to the working di-direction. It was concluded that these strings of particles were responsible for the formation of the highly elongated interlocking grains observed in doped tungsten wire or sheet. To give further credence to this explanation of a long-observed but not understood phenomenon, it was decided to design a new system, one which was analogous to the doped-tungsten system. Thus, a bcc metal, iron, was chosen to be doped with glass which would be plastic at reasonable working temperatures for iron. The glass chosen was a #0080 Corning lime glass which melts at about 810°C. This is approximately the same fraction of the melting point of iron (0.6) as the melting temperature of mullite is of tungsten. It will be shown that all the observed unusual features of the doped tungsten are duplicated in the glass. doped iron, even to the preferred orientation of the grains in the recrystallized sheet. In the tungsten sheet the preferred orientation consists of two components, (1i3)(691) and (013)(362), neither of which has been observed as a component in textures of primary recrystallized bcc metals. EXPERIMENTAL PROCEDURE The glass, in the form of fine powder, was added to high-purity electrolytic iron powder and mixed dry. The particular composition chosen was 0.007 vol fraction of glass. After mixing, the powder was mechanically pressed to a disk 0.5 in. diam and 0.15 in. thick at a pressure of 5000 psi. The pellet was sintered, in pure dry hydrogen, for 2 hr at 8 50°C. The sintered pellet was then heated to 750°C and rolled to 50 pct reduction of thickness in two passes, with reheating between passes. The rolling temperature was then reduced to 600°C and the slab was rolled to a thickness of 0.050 in. Rolling to 0.010 in. was accomplished in several passes at 300°C. Final reductions to 0.003 and 0.001 in. were taken at room temperature. This rolling temperature schedule was similar, in terms of the fraction of the melting point, to that used in the rolling of the doped tungsten. The total reduction of thickness was in excess of 99 pct. Samples of the rolled foil were lightly electro-polished and annealed for 1 to 6 hr at temperatures of 650" to 85O°C in hydrogen. Samples for transmission electron microscopy were thinned on a Disa Electropol using AC-1 electrolyte.

Jan 1, 1968

By D. J. Carney, R. R. Burt, E. J. Whittenberger

Hardenability (multiplying) factors for carbon, mongonese, silicon, chromium, nickel, and molybdenum have been developed for hypereutectoid low-alloy steels in which bainite is the first subcritical transformation product. These factors permit the calculation of 95, 80, and 50 pct martensite hardenability from chemical composition when steels with spheroidized structures are quenched from 1475°, 1525°, and 1575°F. The strong contributions to hardenability of the less expensive elements, silicon and manganese, suggest their use to obtain additional hardenability in hypereutectoid low-alloy steels. DURING the past decade a number of investigators'"11 have carefully developed information which permits calculation of the hardenability of medium -carbon low-alloy steels from chemical composition and grain size. These data have been especially valuable in developing less costly low-alloy steel compositions with equivalent or Improved

Jan 1, 1957

By Charles R. Fettke

In the present day manufacture of glass nearly pure quartz sands are used almost exclusively as the source of the silica, which is the major constituent of all common varieties of glass. Ordinary soda-lime, such as bottle, common tableware, plate, and window glasses, contains from 65 to 75 per cent. of silica. Occurrence Glass sands occur in nature either in the form of loose, unconsolidated sediments or in deposits in which the individual grains have been more or less thoroughly bound together by some cementing agent so as to form sandstones. While deposits of sand and sandstones occur both widely and abundantly distributed, deposits that are sufficiently free from other constituents than quartz grains, so that they can be employed in the manufacture of the better grades of glass, are, comparatively speaking, of rare occurrence. The major portion of the glass sand produced in the United States comes from sandstones. In order to be suitable for glass sand, they should be rather friable. The rock should break down readily along the cementing material between the grains and should not break across the grains rather than along the bond. Some of the sandstones used are so friable that only light shots of slow-burning dynamite are necessary to disintegrate them sufficiently for hydraulic mining, while others have to be passed through crushers in order to disintegrate the rock into its individual grains. MINERALOGICAL COMPOSITION An ideal glass sand is made up entirely of grains of the mineral quartz free from inclusions of foreign substances. Sands containing 100 per cent. silica, however, are not found in nature, although some very nearly approach this composition.

Jan 1, 1926

By I. N. Knapp

Introduction.—The spccial object of these notes is to describe the mixing, testing, and use of mud-ladened water for rotary drilling in such a way as to make them helpful to the driller, the operator, or the engineer in solving his own special drilling problems. The structures, apparatus and tools used are indicated in a general way. No attempt is made to describe the art of rotary drilling; only such descriptions as are necessary to make plain the use of mud are given. The information is the result of actual experience in drilling in Coastal Plain formations. The materials encountered in the wells drilled were unconsolidated sands, gravels, and clays, in which thin layers of sandstones, shell conglomerates, and shales began to appear at about 1,200 ft, in depth, although one well was drilled to 3,018 ft. without encountering any cemented or indurated materials. Unusual Conditions.—-The general surface of the ground where the drilling was done being hardly a foot above mean tide, and the daily tidal variation being about 15 in., it was found necessary to plank over the sod surface with 3-in. plank to work from. A 30 by 30 ft. planked area was sufficient to carry the derrick with equipment and 2,500 ft. of 4-in. drill pipe stacked in it. The derrick was set up 3 ft. on cribbed blocking arranged to spread the load over the planking. The engine, bailers, and pipe yard were also carried on 3-in. planking. Drilling 0utfit.—This consisted of a derrick, 20 by 20 ft. and 84 ft. high, two 35-h.p., "oil country" boilers, one double 8 1/4 by 10 in. reversible engine, two 10 by 6 by 12 in. duplex mud pumps, one 15-in. rotary, "hoisting works" with chain drive, hoisting block with line, crown block with pulleys, rotary jetting swivels, hose, complement of tools, pipes and connections, and a mud mixer, with engine. Hydraulic Rotary Drilling Method.—This method of drilling is an adaptation of Fauvelle'sl invention made in France in 1833 for drilling

Jan 1, 1915

By Russell Salter, Edwin J. King

SINCE 1950, when perhaps two or three cyclones were being tested in Arizona, the number in use has grown to about 100. Most of these have come into operation within the last two or three years, and according to information supplied by various mining companies, the number will continue to grow for several years more. In mills that have been recently constructed, cyclones dominate the fine classification field, removing grit from lime slurries, producing smelter flux, reducing concentrate thickener overloads, classifying molybdenite in grinding circuits, and conditioning flotation feed. Four major copper companies are now testing cyclones in primary grinding circuits, and one concentrator soon to begin operation will classify entirely with cyclones. In at least two instances these versatile machines have been given a vital role in the construction of tailings disposal systems.

Jan 8, 1957

By Reynold Q. Shotts

The small domestic underfeed stoker as now designed is unusually sensitive to the coking and plastic properties of coals, and when the attempt is made to burn the high rank coking and caking coals of the Appalachian fields, serious trouble may occur. Part of the trouble may be caused by the ash content and clinkering characteristics of the particular coal in use, but more often it is the result of an excessive ac-in of coke in the form of ''trees,, or masses in the fuel bed. Often the zone of burning becomes so restricted that the fire goes out, and in extreme cases the fire may be lifted completely out of the fuel bed and away from the air ports. Even if the fire is preserved, excessive coking may cause response to subsequent heat demand to be slow and irregular. Coke trees seem to grow most readily during periods of hold-fire operation, so that in order to preserve the fire in mild weather it is often necessary to set the timer for such a long operating period each hour that much unneeded and unwanted heat is developed, causing discomfort. During demand periods the fire may pick up so slowly that the intense burning which develops just before stoker cut-off causes a serious overshooting of the thermostat. Stoker coal performance tests which have been made in a number of labora- tories1,2,3,4,5 are one method of approach to the problem Of selecting stoker coals- As yet these tests have not been standardized and they are expensive and time-consuming. The value of the results probably increases with the length of the test. Sherman and co-workers at Battelle Memorial Institute believe that even a one-week test is not too reliable a trial2 and it is quite likely that Others will agree. A great advantage of such tests is that characteristics of coals, other than the tendency to form coke masses, may be evaluated from them. The selection of stoker coals would be greatly facilitated if there existed some simp1e measure Of the tendency Of a a to form coke in a fuel bed. Although possessing all Of the disadvantages Of any small-scale laboratory test, the test for the free-swelling index of coal has been found useful for evaluating the probable effects Of swelling properties upon combustion.7 Ostborg, Limbacherand Sherman, have shown that the test can Predict, roughly, the tendency Of coke to accumulate in the fuel bed Of a domestic stoker. They also gave instances of its value in predicting combustion behavior in some large installations. The use of the test for free-swelling index has become well established and has been adopted as a standard by the American Society for Testing Materials.8 When domestic stoker coal investigations began at the State Mine Experiment Station in the summer of 1944, it was decided

Jan 1, 1949

By Walter Knox, Charles H. Sawyer

All of the coals commonly used in domestic bituminous stokers form coke, and satisfactory operation depends upon the fact that the coke formed is so weakly bound together that it breaks readily in the normal operation of the stoker and automatically maintains a good fuel bed. Some coals, because of their tendency to form solid, blocky coke, are practically excluded from use in small domestic stokers as now built. Other coals, some among the best stoker coals available, can form this troublesome coke under certain conditions. Many contradictory methods have been offered as cures for coke formation. Generally the procedure has been to try various adjustments until a combination was found that seemed to give better results. Such random methods of treatment have not provided any reliable information as to causes. The present paper covers a comprehensive test program undertaken by the Koppers Company's Stoker Coal Research Laboratory at Kearny, N. J. The program had two main objectives; first, to discover what factors affected coke formation, and second; to define corrective steps that could be applied in stoker service work. Conclusions and Results i. The design of the stoker outweighs in importance all other factors capable of improving coke formation. 2. Insufficient air supply aggravates the formation of large blocky coke, although raising the air above 30 to 40 per cent excess (as determined during steady running) does not further improve the character of the coke formed and only reduces its accumulation at the expense of efficiency, increased fly ash, poorer clinker-ing, and other disadvantages. 3. Increasing the coal feed results in a somewhat more friable coke structure and is recommended for persistently troublesome jobs. 4. Increasing over-fire draft improves the character of the coke formed and reduces troublesome accumulations by accelerating off-period burning, although at some expense in efficiency and some increase in fly-ash accumulation. 5. Coke structure was not substantially improved by blocking some of 'the retort tuyeres, although the blocking of tuyeres at the feed-screw end of a rectangular retort did lead to somewhat improved performance, possibly because of considerably better distribution of coke in the fuel bed. 6. With the equipment tested no difference was shown between installation of the same stoker in a steam boiler and a warm-air furnace, or between a sand-filled and a ventilated type of hearth. 7. The following design features had no noticeable effect on coke formation: a. Presence or absence of coal-tube air as provided by many manufacturers to eliminate smoke-back. B. Presence or absence of a flap damper ill the air duct to minimize off-period burning. c. Continuous or intermittent (ratchet and pawl driven) movement of fuel feed screw.

Jan 1, 1944

By Charles H. Sawyer, Walter Knox

All of the coals commonly used in domestic bituminous stokers form coke, and satisfactory operation depends upon the fact that the coke formed is so weakly bound together that it breaks readily in the normal operation of the stoker and automatically maintains a good fuel bed. Some coals, because of their tendency to form solid, blocky coke, are practically excluded from use in small domestic stokers as now built. Other coals, some among the best stoker coals available, can form this troublesome coke under certain conditions. Many contradictory methods have been offered as cures for coke formation. Generally the procedure has been to try various adjustments until a combination was found that seemed to give better results. Such random methods of treatment have not provided any reliable information as to causes. The present paper covers a comprehensive test program undertaken by the Koppers Company's Stoker Coal Research Laboratory at Kearny, N. J. The program had two main objectives; first, to discover what factors affected coke formation, and second; to define corrective steps that could be applied in stoker service work. Conclusions and Results i. The design of the stoker outweighs in importance all other factors capable of improving coke formation. 2. Insufficient air supply aggravates the formation of large blocky coke, although raising the air above 30 to 40 per cent excess (as determined during steady running) does not further improve the character of the coke formed and only reduces its accumulation at the expense of efficiency, increased fly ash, poorer clinker-ing, and other disadvantages. 3. Increasing the coal feed results in a somewhat more friable coke structure and is recommended for persistently troublesome jobs. 4. Increasing over-fire draft improves the character of the coke formed and reduces troublesome accumulations by accelerating off-period burning, although at some expense in efficiency and some increase in fly-ash accumulation. 5. Coke structure was not substantially improved by blocking some of 'the retort tuyeres, although the blocking of tuyeres at the feed-screw end of a rectangular retort did lead to somewhat improved performance, possibly because of considerably better distribution of coke in the fuel bed. 6. With the equipment tested no difference was shown between installation of the same stoker in a steam boiler and a warm-air furnace, or between a sand-filled and a ventilated type of hearth. 7. The following design features had no noticeable effect on coke formation: a. Presence or absence of coal-tube air as provided by many manufacturers to eliminate smoke-back. B. Presence or absence of a flap damper ill the air duct to minimize off-period burning. c. Continuous or intermittent (ratchet and pawl driven) movement of fuel feed screw.

Jan 1, 1944

By N. F. Neumann, A. W. Schlechten

Metal chlorides were formed by reacting metal oxides and calcium chloride; the effect of additions to the reaction mixture was studied. It was found that by use of proper additions, metal chlorides could be prepared from mixtures that were not reactive under ordinary conditions. ManY recent metallurgical developments involve the use of chlorine or chlorides as primary reagents; good examples are found in the production of ductile zirconium and titanium by reduction of their chlorides with magnesium. Various methods of preparing metal chlorides are used and many others have been proposed. Some chlorides are formed by the direct combination of a metal or alloy with chlorine. Other processes react chlorine and metallic oxides; carbon or other reducing agents are usually employed to reduce the metal oxides and so promote chlorination. Metallic chlorides have also been produced by the exchange of chlorine between metal oxides and a chloride, such as sodium chloride. This type of reaction was the basis for the old process of chloride roasting in which metal ores were roasted in the presence of salt. Soluble chlorides thus formed

Jan 1, 1959

By E. Buehler, H. J. Levinstein

The temperature ranges in which the three inter-metallic phases in the Nb-Sn system form have been determined and the composition and structure of two of the three phases has been established. The kinetics of the formation of Nb3Sn in cored wire samples has been studied in the temperature range of 800° to 1050°C. From 800°to 950°C the rate of formation increases by four orders of magnitude. The rate-controlling step for the formation process in this temperature range appears to be the diffilsion of tin through NbSn. At higher temperatu~es a change occurs in the mechanism of the formation process such that up to a temperature of 1050°C the rate of formation of Nb3Sn does not increase above the rate observed at 950°C. For temperatures helow 950°C the current-carrying capacity of the wire increases with increased percent reaction reaching a maximum value when the formation process is 90 to 95 pct complete. The maximum current-carrying capacity obtainable in this temperature range is independent of the temperature. Above 950°C tlze current-carrying capacity obtainable in the wire decreases with increasing temperature of formation. A model is proposed which accounts for the ohserved behavior. RECENTLY, Buehler et a1.l reported the results of an investigation of the process variables which influence the superconducting properties of Nb3Sn-cored wire. These results indicated that at least four variables affect the properties of the manufactured wire. These include composition, particle size of the starting powder mix, temperature of heat treatment, and time of heat treatment. In order to understand completely the role of these variables, it is necessary to have an accurate knowledge of the phase equilibria in the Nb-Sn system. At the present time, phase-equilibrium diagrams for the Nb-Sn system have been published by a number of investigators.2-5 The diagrams differ as to the number of phases present, the composition of the phases, and the temperature range of stability of the phases. The present investigation was undertaken in order to resolve these differences. Since the investigation of Buehler et al. demon- strated that the length of time at the temperature of heat treatment affected the superconducting properties of Nb3Sn, it is apparent that it is necessary to understand the kinetics of the formation process as well as the equilibrium conditions before a complete understanding of the system is possible. As a result, the kinetics of formation of the various phases in the system were also studied in this investigation. EXPEFUMENTAL PROCEDURE Diffusion couples and sintered powdered compacts were employed in the phase-diagram investigation. The diffusion couples were made by filling 1/8-in.-ID monel-sheathed niobium tubes with tin. The monel sheath was employed to facilitate drawing.' The tubes were then drawn to a tin-core diameter of 32 mils. Samples approximately 3 in. long were then cut from the drawn composite. The tin was drilled out of the ends to a depth of 1/4 in. and niobium-wire plugs were inserted into the ends and peened over. The monel was removed by etching in concentrated nitric acid, after which the samples were sealed in evacuated quartz bulbs and heat-treated in a resistance-wound tube furnace. The samples were quenched into ice water upon removal from the furnace. The diffusion couple samples were examined metallographically employing a chemical etching solution consisting of 10 ml of saturated chromic acid per g of NaF. In addition, two anodizing solutions were used for phase-identification purposes. The first was the picklesimer7 solution; the second consisted of equal parts by volume of 30 pct H2O2 and concentrated NH4OH to which 1 g of NaF was added per 25 ml of solution. The anodizing conditions for the second solution were 2 v and 100 ma with a tin cathode. The powdered compacts were made by pressing previously mixed powders of 99.9 pct pure Sn and 99.6 pct pure Nb supplied by the United Mineral Co. into cylinders 3/8 in. in diameter by 1/2 in. long. The cylinders were then sealed in quartz tubes and heat-treated in the same manner as the diffusion couples. The samples were examined metallographically and by X-ray diffraction techniques. Since it was desirable to be able to correlate the kinetic data with current-carrying capacity, the type of specimen chosen for this part of the investigation had to be a compromise between the optimum system for studying kinetics and one which was suitable for making current-carrying capacity

Jan 1, 1964

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Marie L. V. Gayler

Without diffusion taking place in liquid metals and alloys, no castings could be made; it is therefore the most important factor affecting the structure of metals. Diffusion involves the interchange of atoms, a process which takes place during the life history of an ingot. In the liquid, atoms are in a state of high thermal agitation, but this thermal vibration is reduced in amplitude with falling temperature. When solidification sets in, the atoms arrange themselves on an ordered space lattice and the changes in structure which take place in the solid are due to the interchange of atoms on this space lattice. The rate of atomic interchange—e.g., of diffusion—is most rapid at temperatures close to the melting point and decelerates as the temperature is lowered. At room temperature, the rate of diffusion is practically negligible in most alloys, and any change in structure can only be brought about by using methods which will accelerate the rate of diffusion. The rate of diffusion depends on three factors (I) temperature; (2) concentration gradient and (3) activation energy. The growth of grains and particles in the solid alloy also depend on these factors and are therefore intimately associated with diffusion. The rate of homogenization in a cast alloy depends on several factors, such as: (I) rate of solidification, which involves grain and particle size which, in their turn, depend on diffusion: (2) the nature of the constituents; (3) the temperature interval between the melting point of the metal or alloy and the temperature at which it is being heat-treated. It is well known that coarse, cast structures are extremely difficult—if possible— to homogenize, and the finer the grain size and particle size, the more readily solid solution will take place. The rate of diffusion depends, also, largely on the nature of the constituents; for instance, copper and magnesium form solid solutions with aluminum quite readily but nickel and iron do not; neither do certain intermetallic compounds, such as alpha and beta FeSi. Furthermore, the actual formation of intermetallic compounds may be a very slow process, particularly when they are formed in the solid state as equilibrium products. For example, BFeSi is formed in the solid as the result of the reaction aFeSi + A1 —+ PFeSi. The particles of aFeSi become surrounded with a reaction ring of PFeSi. This layer is formed as the result of diffusion of atoms taking place between the aluminum matrix and aFeSi. As the amount of aFeSi surrounding the core of aFeSi increases the concentration gradient becomes low and so the rate of diffusion of atoms also decreases until it practically ceases. This occurs after a comparatively thin layer of ßFeSi has been formed. It follows that when intermetallic compounds of this type are formed in the solid, as the result of diffusion, it is generally impossible ever to attain equilibrium, since the forma-

Jan 1, 1944

By Kalman N. Isaacs

BY minimizing time that must be spent in the field, intelligent application of photogeology offers tremendous savings in exploration programs. In areas so remote and hazardous that ground exploration must be deferred, photogeology assumes its most important role, often in conjunction with airborne geophysics. There is still another advantage. Aerial photography may give the geologist a relatively quick understanding of large-scale structures and relationships that are difficult to interpret on the ground.

Jan 4, 1958

By E. W. Johnson, M. L. Hill

Cold working of iron-carbon alloys was found to increase greatly the hydrogen solubility and to decrease the diffusivity at temperatures up to 400° C. These effects are increasing functions of both the carbon content and the degree of deformation. The hydrogen behavior is consistent with the idea that cotd working creates "traps", which are concluded to be microcracks in which the hydrogen is chemisorbed. Hydrogen embrittlement is explained by the Petch theory of metal crack surface energy loss due to hydrogen adsorption. HYDROGEN embrittlement of steel has been studied for many years and has been the subject of an extensive literature, but the mechanism of the effect has not been completely understood. The embrittlement is unusual in that the ductility loss is not accompanied by an increase of the yield strength, being primarily a decrease of the fracture strength alone. The loss of fracture strength is usually most severe in the temperature range between 0°and 100°C. Here the solubility of hydrogen in the iron lattice at ordinary H2 pressures is extremely low while the diffusivity is still quite high. From the relationships between the ductility and the hydrogen content, test temperature and strain rate, it is apparent that the hydrogen atoms causing the ductility loss difbse to and concentrate in small regions of the metal which are especially susceptible to the initiation and propagation of fracture. This hydrogen segregation apparently occurs after plastic straining has begun. Below 0°C the ductility loss persists only at low strain rates in confirmation of the view that the embrittlement is diffusion .controlled. The tendency of the embrittlement to disappear above 100°C can be explained by the increasing lattice solubility of hydrogen with rising temperature. A common view of hydrogen embrittlement of steel is that the hydrogen initially dissolved in the metal lattice diffuses to structural discontinuities and there precipitates as H2 gas at very high pressures which assist the external stress in causing premature failure.1,2 The idea of a high H2 pressure in equilibrium with ordinary amounts of hydrogen in steel at room temperature is due to observations of hydrogen behavior in fully annealed material, for which the Sieverts' law constant relating solute concentration to H2 pressure is extremely small. Hydrogen-embrittled steel, however, is always plastically deformed to some extent, and therefore it is important that hydrogen embrittlement be explained primarily in terms of hydrogen behavior in plastically deformed material. Such an explanation is attempted in this paper. Previous studies of hydrogen in cold-worked steel have shown that both the solubility and the diffusion rate are significantly chaned when the steel is cold worked. Darken and Smith discovered that the amount of hydrogen absorbed from acid by cold-rolled steel at 35°C is many times greater than that absorbed by hot-rolled steel. They found also that the hydrogen permeability of the steel is unaffected by cold working. Keeler and Davis4 confirmed the high apparent solubility of hydrogen in cold-worked iron-carbon alloys at temperatures up to and even beyond the recrystallization temperature. They also found that this solubility increase accompanying cold work is a sensitive function of the carbon content, being absent when no carbon is present. The present experimental study was undertaken primarily to obtain an improved understanding of the behavior of hydrogen in cold-worked steel. Data were obtained on the effects of temperature, H, pressure, carbon content, and degree of cold work on the hydrogen solubility and diffusivity in iron-carbon alloys. These data have been helpful in elucidating the nature of the cold-worked steel structure as well as in providing information on the mechanism of hydrogen embrittlement of steel. EXPERIMENTAL Cylindrical specimens for hydrogen absorption and diffusion rate measurements were prepared from three iron-carbon binary alloys and a commercial SAE 1010 steel. The iron-carbon alloys were prepared by vacuum melting electrolytic iron with graphite in a magnesia crucible. The alloys were cast in vacuum as 2 1/2-in. sq ingots weighing about 20 lb each. The ingots were hot rolled (above 1900°F) to 5/8-in.-diam round bars and then cooled in air to room temperature. The resulting metallographic structure consisted of islands of fine pearlite surrounded by free ferrite. Chemical analyses of the materials are given in Table I. The 5/8-in. diam bars were turned to diameters such that cold reduction to the desired final specimen diameters would result in either 30 or 60 pct reduction in area (RA). The machined bars were then cold worked by swaging at room temperature

Jan 1, 1960

By William E. Ford, Edward Salisbury Dana

THIS Appendix contains a series of tables, more or leas complete, of minerals arranged according to chemical composition or to certain prominent crystallograhic or physical characters. These, it is believed, will be of service not only to the student, but ago to the skilled mineralogist. The type used in the printing of the mineral names indicates their relative importance. Table I is a complete list of the species named in this book arranged fist according to the prominent basic elements which they contain and secondly according to their acid radicals. Table II is of Minerals arranged according to their System of Crystallization The other tablets make no claim to completeness, being limited often to common ah important species. For an exhaustive system of Determinative Tables based particularly upon blowpipe and chemical characters, the student is referred to the work of Professors Brush and Pen- field, mentioned on p. 330.

Jan 1, 1922