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By J. A. Lund, A. M. Lawson

THE structures of quenched eutectoid and hypereu-tectoid Fe-Cu alloys have been examined by X-ray diffraction and by optical and electron microscopy. The relevant portion of the Fe-Cu phase diagram is given in Fig. 1. Several values have been reported for the solubility of copper in a Fe at the eutectoid temperature, including 1.4 wt pct by orton' and 2.13 wt pct by Wreidt and Darken.2 Alloys containing 4.8 and 7.5 wt pct Cu have been prepared from two batches of Ferrovac E iron (0.005C and 0.013C) and electrolytic tough pitch copper (99.90 Cu). Specimens of dimensions 0.8 by 0.8 by 0.1 in. were cut from hot-rolled material, austenitized, and quenched into brine at 25°C. Similar specimens were also cooled in the furnace, after a short soaking treatment at 1100°C, at a rate estimated to be 10°C per min in the temperature range of 900" to 500°C. X-ray diffractometry was performed on quenched and on furnace-cooled bulk specimens using iron radiation. Only a bcc phase could be detected in all samples. Lattice parameters were calculated from measurements on four lines, made up of two resolved high-angle doublets. Comparisons were made against a silicon standard. Results are shown in Table I. Based on X-ray diffraction studies of a series of alloys of lower copper concentrations, orton' estimated that the tattice constant of a Fe at 25°C increases 0.0014A per wt pct Cu in solution. Extrapolating Norton's data, it may be concluded that all copper was retained in solution in the brine-quenched 4.8 pct Cu alloy, and that approximately 5 pct Cu was also held in solution on quenching the 7.5 pct Cu alloy. Typical microstructures of brine-quenched specimens, as observed by optical microscopy, are shown in Figs. 2 and 3. Precipitation of the E phase (copper-rich) occurred along the y grain boundaries on quenching the 7.5 pct Cu alloy, rendering them readily detectable in the microstructure, Fig. 3. The original boundaries in the 4.8 pct Cu specimens were gener- ally not discernible, however. This indicates that the z phase which was seen in the higher-copper alloy was probably of proeutectoid origin. Thin foils for transmission electron microscopy were obtained from bulk specimens by spark machining to 0.006 in. thickness, followed by electrolytic polishing. Typical transmission electron micrographs

Jan 1, 1967

By Clyde E. Williams, V. N. Krivobok, C. H. Herty

THE extreme effect of the depression on the steel industry is well illustrated by the fact that the amount of iron ore shipped from the Lake Superior district was the lowest in 47 years. Something over 3 1/2 million tons of ore was shipped in 1932, compared with over 65 million tons in 1929. It is not surprising then that practically no advancement in iron ore beneficiation has been made. Improved research and development work, however, was continued at the Michigan College of Mines in the survey of the lean iron ores of Michigan with reference to the possibility of their concentration; at the University of Minnesota in its large-scale jigging studies of Lake :Superior ores; and at Battelle Memorial Institute in the development of improved jigging of iron ores. The successful operation of the new Hadsel mill at a gold property in California gave such low grinding costs on a quartz ore as to give much encouragement in the iron ore industry for a cheapening of the cost of grinding lean ores for concentration.

Jan 1, 1933

[New York Holds monthly meetings, except June, July and August. J. E. SPURR, Chairman A D. BROKAW, Vice-chairman SIDNEY ROLLE, Vice-chairman M. H. MERRISS, Secretary-treasurer, Nichols Copper Co., 25 Broad St., New York M. F. CHASE KARL HOFFMAN Boston Meets first Monday of each winter month. C. R. HAYWARD. Chairman E. C. GEITHER, Vice-chairman D. H. MCLAUGHLIN, Secretary-treasurer Rotch Bldg., Harvard Univ. Cambridge. Mass. GEO. H. GILMAN GEO. A. PACKARD]

Jan 1, 1928

By Walter R. Hibbard

Whether we have occasion to think of it or not, an adequate and economic supply of energy fuels is vital to each of us. It is interesting to look ahead at the way in which fuels from supplementary sources will begin to enter into the energy mix to help meet the long-term national energy needs. From 1947 to 1965, the average annual rate of growth of energy consumption was 2.7%, with total energy demand in 1965 being equivalent to 54 quadrillion Btu's. During this short period of 18 years, the cumulative output of coal in the U.S. was 9.6 billion tons; natural gas, 193.5 trillion cu ft; and crude oil, 45.9 billion bbl. During the next decade and a half the nation's energy requirements are expected to grow at an average rate of 3.3% yearly, with consumption of energy expected to reach an annual rate of about 88 quadrillion Btu's by 1980, or 63% over the 1965 level.

Jan 12, 1967

By J. Szekely, Robert G. Lee

Calculations are presented for the prediction of the combined radiative-convective heat loss from molten steel held in a ladle, covered by initially molten slag. A mathematical formulation is given and numerical solutions are presented of the resultant partial differential equation. It is shown that a slag layer of about 2 to 3 in. thick would prevent any significant heat loss from the top metal surface for Periods of up to 1 hr. For thinner slag layers (or in the absence of the protective slag) appreciable heat losses would occur; plots given in the paper allow the quantitative evaluation of the fall in the metal temperature due to this heat loss. The ironmaking-steel processing operation involves several intermediate steps where the molten metal is held or transfered in ladles. The quantitative assessment of the heat losses occurring under these conditions is of considerable importance in process design considerations since the temperature of the metal may have to meet rigid specifications in any given part of the processing sequence. While the metal is held in a ladle, heat is lost by two mechanisms: i) by conduction into the ladle walls; ii) by radiation and convection from the top surface. Calculations relating to the conductive heat loss, are readily made and information may be found in the literature both on data pertaining to metallurgical situations and on the techniques that are available for performing additional computations.'-3 The evaluation of the combined convective-radiative heat loss is less straightforward, especially when there exists a protective slag layer covering the metal. In this latter case, as the top slag surface loses heat partial solidification may occur and the latent heat thus given up by the slag may represent an effective barrier to the heat loss from the metal. A semiquantitative assessment of the role played by the slag in preventing heat loss from the metal has been made in a previous paper,4 where it was shown that a slag layer 6 in. thick would act as a near-perfect insulator for periods of up to 2 hr. However, this first paper reported on an essentially preliminary investigation that considered only one slag layer thickness; furthermore, the boundary conditions used for the calculations were somewhat restrictive since no allowance was made for changes in the metal temperature. The purpose of this second paper is to extend the scope of the preliminary investigation previously reported by: i) considering several slag layer thicknesses; ii) allowing for variations in the metal temperature; and finally iii) by performing calculations on the net loss from the metal rather than from the slag surface. FORMULATION Consider a slag phase extending from y = 0 to y = L1, covering a metal phase that occupies the region extending from y = Ll to y = L, as illustrated in Fig. 1. Denote the slag and metal temperatures by TS and Tm and assume that initially both slag and metal are molten, having a uniform temperature Ti. At time = zero the surface represented by the y = 0 plane (top slag surface) is brought into contact with cold air, the temperature of which is given as T Thus for time > zero, heat will be transfered from the slag to the air by natural convection and thermal radiation; as a result of this heat loss the slag temperature will fall and after some time a solid phase is formed and a solidification boundary (more realistically described as a zone) will move progressively from y = 0 toward y = L1. Once the region of temperature gradients, moving ahead of the solidification zone, reach the slag-metal interface (y = L1) there will be a net transfer of heat from the metal through the slag to the cold air, across the y = 0 plane. In the formulation of moving boundary problems, involving phase changes that require computer solution, it is convenient to represent both phases by a single equation, making allowance for the latent heat of solidification by assigning an appropriate temperature dependence to the specific heat content. Thus the energy equation for the whole of the slag may be written as follows:

Jan 1, 1969

By Thomas M. Plouf

Getting optimal performance from flotation cells can, in many cases, be critical to a project's economic viability. Simple testing procedures can sound early warning signals as well as maintain optimum recoveries from the flotation cycle. The materials required for a simple testing laboratory include: (1) pH meter or pH paper, (2) bottles of reagents used in plant flotation, (3) stop watch, (4) calibrated eye droppers. (5) laboratory flotation machine (1000-g tank, open impeller), (6) froth collection pans, (7) magnifying glass, (8) sizing screen sufficient to retain 10% of the flotation feed coarse fraction, (9) sizing screen for the size particles at which desliming of the plant flotation feed is to take place, and (10) a set of screens covering the complete range of feed particle size.

Jan 4, 1978

By J. L. Martin, W. M. Campbell

A new electric logging method, called displacement logging, often gives a direct indication of the presence of mobile hydrocarbons in hydrocarbon-bearing formations. This method is based on the detection of a bank of connate water which is formed between the invading mud filtrate and virgin formation fluids in these cases. The existence of this phenomenon has beer, verified by laboratory studies and by actual field logs taken in known oil sands. INTRODUCTION During the past decade increasing use has been made of conventional electric logs to determine the amount of oil or gas in formations traversed by a borehole. This determination requires knowledge of several factors, such as true resistivity of the formation, formation factor, and water resistivity. Sometimes all of the factors necessary to make a reliable saturation calculation are not available. Also, the computations and corrections which are necessary in such a study often require the services of an experienced log analyst. It has long been the desire of exploration people to have a logging device which will locate hydrocarbon-bearing formations directly without requiring complex interpretation methods. The displacement log, while not completely fulfilling this desire, appears to be a Step in that direction. Basis for the Device The basis for this device stems from a phenomenon which occurs when mud filtrate invades a formation which contains displaceable hydrocarbons. As the mud filtrate invades the formation, most of the oil or gas is pushed out of the invaded zone, leaving residual oil. However, in addition to displacing most of the oil or gas, the connate water is also swept out, since the originally irreducible water is mobile in the presence of a water phase.1,2,3 Tonsequently, this irreducible water piles up as a bank between the virgin oil zone and the invading filtrate. If the mud filtrate is of higher resistivity than the formation water— as is commonly the case—the resulting annular zone, containing the bank of formation water, will be of lower resistivity than either the virgin oil-bearing formation resistivity or the invaded zone resistivity. This resistivity configuration, going from high to low to high again as the distance from the borehole increases, is found only in those zones which contain displaceable hydrocarbons. A device which would reliably detect this low resistivity zone would give a direct indication of mobile hydrocarbons. Illustrations This phenomenon is illustrated in Fig. 1 and 2. Fig. 1 shows a sketch of a zone containing salty connate water plus displaceable hydrocarbons, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 2 shows this zone, together with fluid content and resistivity graphs. after invasion by a fresh water mud. The resistivity pattern on moving away from the borehole is high: low: high. The absence of the low zone phenomenon in water zones is illustrated in Fig. 3 and 4. Fig. 3 shows a sketch of a zone containing salty formation water and residual oil, along with graphs showing fluid content and electrical resistivity vs distance from the borehole, before invasion occurs. Fig. 4 shows this water zone, together with fluid content and resistivity graphs, after invasion bv a fresh water mud. In this case the resistivity pattern on moving away from the borehole is high: low since there is no change in water saturation at the head ol

Jan 1, 1956

By R. P. Laforce, ZJ. R. Low, A. M. Turkalo, D. F. Stein

The interaction of the crlloying eletnenls, nickel and chromium, with the impurity elements, antimony, pIzosphorus, tin, and arsenic, to producse reversible temper brittleness in a series of high-purity steels containing 0.40 wt pct C has been investigated. The alloyed steels contained approximately 3.5 pcl Ni, 1.7 pct Cr, and 0.05 to 0.08 pct of the particular irnpurity to be investigated. Susceptibility to teirlper embrittlement was measured by comparing the notched-bar transition temperature of each steel after quenching from the final temper and after very slow cooling (step cooling;) following the final temper. A plain carbon steel without alloying elements, bu/ ud/h 0.08 pel Sh, does not embrittle when step-cooled through the emzbrittling range of temperatures. The same embrittling treatment, applied to a steel with about the same antinzony content but with nickel and chvonziunz added, causes a 700°C increase in transition temperature. If chromium or nickel is the only alloying element, the increase in transition temperature is only 50%, again with antimony present. A carbon-free iron containing nickel, chromium, and antimony shou~s a 200°C shift in transition temperature for the same thermal treatment. Specific alloy-impurily interactions are also observed for the other impurity elements, phosphorus, tin, and arsenic. Additional investigations involving electron microscopy, trzicrohard-ness tests of vain boundaries, minor additions of zirconiutn and the rare earth and noble metals, nzainly with negative results, are also described. HE particular type of embrittlement investigated is that which is encountered in alloy steels tempered in the temperature range from about 350" to 525'C or slowly cooled through this range of temperatures when tempered above this range. This type of embrittlement is sometimes called reversible temper brittleness to distinguish it from the embrittlement indicated by a minimum in the room-temperature V -notch Charpy energy vs tempering-temperature curve encountered in the range 28 0" to 350°C. Temper brittle-ness seriously restricts the use of many alloy steels since it precludes tempering or use in the embrittling range of temperatures and may significantly raise the ductile-brittle transition temperature of heavy-section forgings and castings tempered above the embrittling range, since such sections cannot be sufficiently rapidly cooled after tempering to avoid embrittlement. The very voluminous literature of temper brittle-ness up to about 1960 has been reviewed by woodfine' and LOW.' Of particular significance to the present investigation was the demonstration by Balajiva, Cook, and worn3 that high-purity Ni-Cr steel does not exhibit temper brittleness and the subsequent detailed and systematic study by Steven and Balajiva~ of the effect of impurity additions on the susceptibility to embrittlement of Ni-Cr steels. Steven and Balajiva showed that, of the impurities which may be found in commercial steels, Sb, As, P, Sn, Mn, and Si could all produce temper brittleness in a high-purity Ni-Cr steel. The principal purpose of the present investigation was to study the effects of particular alloy-impurity combinations on susceptibility to temper embrittlement. The steels used were high-purity 0.30 to 0.40 wt pct C steels containing 3.5 wt pct Ni and 1.7 wt pct Cr, separately or in combination. The susceptibility of these steels was then determined when approximately 500 ppm by weight of antimony, arsenic, phosphorus, or tin were added as an impurity. The melting, casting, and forging practices used in the preparation of the materials investigated are described in Appendix A. Table A-I in this appendix shows the analysis of all steels to be discussed. The steels were produced as 20- or 2-lb heats. The smaller heats were used after it had been demonstrated (see Appendix B) that a small, round, notched test specimen could be used to measure the shift in the ductile-brittle transition temperature caused by temper brittleness with about the same result as that obtained by Charpy testing. HEAT TREATMENT Unless otherwise noted, all steels were tested for embrittlement in the tempered martensitic condition. A typical heat treatment for a 0.40 C, 3.5 Ni, 1.7 Cr steel was: 1 hr at 870"C, in argon, quench into oil at 100"C, quench into liquid nitrogen, temper 1 hr at 625"C, and water-quench. The warm oil quench was used where quench-cracking was encountered; otherwise the initial quench was into room-temperature oil or water. For other compositions austenitizing temperatures were 50°C above Acs with the remainder of the thermal cycle the same. Steels in this condition, with no further heat treatment, are designated as non-embrittled. The above quenching and tempering cycle for the 0.40 pct C steels resulted in as-quenched hardnesses of 48 to 53 RC and as-tempered hardnesses of 24 to 31 Rc except in the case of the plain nickel or plain carbon steels. In these, the as-tempered hardness was as low as 80 to 90 Rg. No attempt was made to adjust the tempering temperature to obtain the same hardness in ali steels since it was felt that a uniform thermal cycle was more important than exactly equivalent hardness values. Pro- the standard quench and temper described above, the standard embrittling treatment was "step-cooling". For this the thermal cycle was: 593"C, 1 hr; furnace-cool to 538"C, hold 15 hr; cool to 524"C, hold 24 hr; cool to 496"C, hold 48 hr; cool to 468'C, hold 72

Jan 1, 1969

By Charles A. Kelliher

In November of 1957, the Aliquippa Works started operation of the third basic oxygen furnace shop in North America. This high speed basic steelmaking method provided a very economical increase in capacity at the Works. The success of these two (2) 81-ton furnaces led to the construction of a second B.O.F. shop, producing heats of 230 tons at J&L's Cleveland Works in 1962. The experience gained operating both shops provided the background for the design of the new steelmaking complex at the Aliquippa Works. This new complex consists of a three (3) furnace shop with two (2) furnaces blowing alternately producing heats ranging from 120 to 207 tons. This variation in heat size is predicated on the requirement that approximately 20% of the shop production will be used to supply steel to a six (6) strand casting machine, producing 4' through 7" billets. The new B.O.F. shop has replaced all other steelmaking units including the #1 Shop, where operations were discontinued in September of 1968. With the advent of the strand casting facilities in September of 1969, many of the standard shop practices had to be changed to compensate for higher tap temperatures, longer handling times, and reduced ladle availability. The subsequent changes in these areas led to the evolution of the strand cast ladle practice which is described in this paper.

Jan 1, 1972

By J. W. Hickman

INTRODUCTION MOST of the electron diffraction studies of oxide films which form on metals and alloys have been carried out by oxidizing the specimens in an auxiliary furnace, cooling down to room temperature and then inserting the sample in the camera and taking a diffraction photograph. Prior to the investigations at the Westinghouse Research Laboratories, no systematic study of the oxidation of any metal or alloy had been made over a wide temperature range with photographs taken at elevated temperatures except the investigation of iron by Jackson and Quarrell.1 In order to interpret the electron diffraction patterns of the oxides which may form on alloys, it seemed advisable to make a comprehensive study of the oxidation of the purest metals available in the bulk form. Thus far studies have been completed on iron,2 cobalt,2 nickel,2 chromium ,2 Copper2, tungsten,3 molybdenum,3 beryllium ,4 uranium,4 thorium4 titanium5 and zirconium5 while investigations are in progress on tantalum and columbium, The next step in the study is concerned with the investigation of the oxides which form on binary alloys. Some of the alloys consist of a single, phase while others contain more than one phase. The identification of the oxides on the surface of a binary alloy may be more difficult than on the metals since oxides containing both metals as well as those of each metal separately may form. Furthermore, it is possible that solid solutions of the various oxides may occur. In these cases the electron diffraction method may not be able to identify the oxidation products unequivocally, Examples of solid solutions which may present difficulties are MoO2 and W02, Fe3O4 and FeO-Cr2O3 since the diffraction patterns are so similar. Since electron diffraction can determine only the structure of the oxide, the chemical composition must be inferred from the diffraction data based upon X ray diffraction investigations of specimens of known composition. It is possible in some cases to decide whether a given solid phase reaction can occur on the surface of an alloy by a study of available thermodynamic data. Table I lists the equations for the formation of most of the oxides from the elements together with values of log10 KR for the several temperatures. [OF°R = -RT In KR 0 and-~75T = logi°KR] [?F°R] and KR are the free energy and equilibrium constant of the reaction. Calculations may be made using the values given in Table I to determine whether a given solid phase reaction is possible thermodynamically. For example, a solid phase reaction should occur between aluminum and chromium' oxide to form

Jan 1, 1948

By A. D. Schwope, L. R. Jackson, A. M. Hall

In the course of an extensive investigation of the comparative properties of several types of copper, data were obtained on the cold working and subsequent recovery and recrystallization of the copper. In this paper, relations between the degree of cold work and the course of re-crystallization are developed. In particular, it is shown that the course of recrystallization over long periods of time and at low temperatures can be predicted with reasonable accuracy from short-time high-temperature recrystallization data. Materials Used in The Investigation Three types of copper were used in this investigation; these were tough pitch, OFHC, and OFHC copper with 15 oz per ton of silver added identified herein as Lots C, D, and F, respectively. The material was supplied by the American Metal Co. Ltd., and processed by the Rome Cable Co. The analyses of the three types of copper are given in Table I. Originally, it started as wire bars 4 X 4 X 54 in. These bars were heated to 871° C in air and hot rolled to % in. rod. This rod was cold drawn to 0.204 in. rod (70 pct reduction) in three passes and annealed at 427°C for 4 hr. A portion of the 3/8 in. rod was saved for more detailed cold-drawing experiments. Starting with the annealed 0.204 in. rod, hard-drawn wires were produced by cold drawing to 0.081 in. wire in 7 passes (84.4 pct reduction in area). Half-hard wires were made by cold drawing the 0.204 in. rod to 0.102 in. wire, (75 pet reduction) in 6 passes and annealing at 427'C for 4 hr. This annealed wire was then drawn to 0.081 in. wire, (37.1 pet reduction) in 2 passes. Square rod was made by hot rolling wire bars to Re in. rod in 8 passes. This rod was then cold drawn to 0.445 in.-diam rod and annealed for 346 hr at 538°C. It was then cold drawn to 0.325 in. rod and again annealed at 538°Cf or 3 1/2 hr Hard square rods were then made by cold rolling this material to 0.257 X 0.257 in. rod, a reduction in area of 20.5 pct. Half-hard square rods were made by cold rolling to 0.268 x 0.268 in. square, annealing for 3 1/4 hr at 538°C and cold rolling to 0.257 x 0.257 in., a reduction of 8.5 pct. Soft wire or rod was made from all types of copper by annealing the hard-drawn material at 343°C for 3 hr in steam. The grain size of the annealed 0.081 in. wire varied slightly among the three lots: from o.o15+.oz5 mm in the silver-bearing OFHC to 0.035-0.045 mm in the OFHC copper. The annealed 0.257 in. wires were more uniform in grain size, averaging about 0.035-0.045 mm. Representative structures are shown in Fig I. Effect of Cold Drawing and Tensile Strain on Strength of Copper Conventional tensile tests were performed on the three types of copper in the various degrees of hardness described above. Results of these tests are tabulated in Table 2. The results in Table 2 are 6

Jan 1, 1949

By C. L. Dake

Chemistry of Iron Solution IRON is much more soluble in the ferrous than in the ferric form. Where, as in the case of the ferrous silicates and the sulphides, the iron is already in the ferrous form, it may go at once into solution and be removed, upon the breaking down of the parent rock. If in the ferric form, it must first be reduced; usually by the decay of organic matter, the demand of the decaying carbonaceous matter for oxygen being so great that the latter is abstracted from the ferric compounds and the iron is thereby reduced and rendered' soluble. The iron may go into solution as the sulphate, or in the presence of excess CO2 as ferrous carbonate. It is probably soluble as salts of the organic acids.1 Recent work indicates that these are important in the formation of bog ores.2 There is considerable variety of opinion concerning the behavior of these organic compounds.3 The secretions about the roots of plants and trees also cause the solution and removal of iron and a consequent bleaching of the soil.4 While the matter is not yet well understood, we can probably say definitely that the so-called organic acids are a group of colloids which possess slightly acid properties, and the salts of which are partly soluble

Jan 7, 1915

By A.J. PHILLIPS, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Win. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm.. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four, binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for-examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By A. J. Phillips, C. G. Grant, Wm. B. Price

ADMIRALTY nickel is a new corrosion-resisting and heat-resisting white metal alloy composed of 70 per cent. copper, 29 per cent. nickel and 1 per cent. tin. It has been given the trade name "Adnic." In 1924, Wm. B. Price1 described this alloy and its successful use as a diaphragm metal. The physical properties of Adnic at ordinary and elevated temperatures were given in Mining & Metallury.2 A patent3 was granted on Adnic, April 28, 1925. Work was first started on this alloy during December, 1921. An investigation of the patent situation in this country and abroad, and also a search of the literature, did not reveal any work on the ternary diagram, copper-nickel-tin; and the only wrought copper-nickel-tin alloy found was that known as "Newloy," composed of copper, 64 per cent.; nickel, 35 per cent.; tin, 1 per cent. This was being manufactured and sold by Wm. Gallimore & Sons, Ltd., Sheffield, England, for unplated spoon and fork stock, and first came to our attention in January, 1922. The preliminary work in connection with the development of Adnic was started by casting four binary copper-nickel alloys of the compositions shown in Table 1. Various amounts of tin were added to each of these mixtures, to produce the series of ternary copper-nickel-tin alloys also given in Table 1. A 200-gm. sample of each of these was cast by melting in a clay graphite crucible and allowing the melt to slowly cool with the furnace. A longitudinal section from each of these castings was polished and etched for examination. The castings were not homogeneous solid solutions, but showed the usual cored structure associated with cast alloys. However, from an examination of these sections we roughly determined

Jan 1, 1928

By R. E. Robbins, H. R. Brager

THIS note describes an unusual result obtained in an electron microscope investigation of cavities produced in commercial type 304 stainless steel irradiated in a thermal reactor (ETR) at 290°C to a high neutron flu-ence, 6 x loz1 n per sq cm. The analysis of the steel used is given in Table I. The unusual result is that the calculated quantity of helium gas produced by transmutation during the irradiation, 12 ppm, is less than one-tenth the amount of gas necessary to balance the surface tension of the observed cavities produced in the steel during ETR irradiation. Therefore, the cavities would be expected to behave like voids; however, they behave like "gas filled" bubbles. The maximum quantity of helium produced in the steel by B" transmutation was 8 ppm. In addition, the amount of helium formed by (n, (1) fast neutron reactions with the major alloy constituents and nitrogen was calculated to be 4 ppm based on the tabulated differential or effective fission-averaged cross sections of elements in type 304 stainless steel irradiated in typical thermal reactors.', In previous investigations concerning commercial austenitic stainless steel irradiated in a thermal reactor, the amount of helium gas calculated to be produced by transmutation has always been significantly greater than the amount calculated on the basis that the bubbles were gas filled, PPs= 2y/R. The balance of the gas was assumed to be in bubbles smaller than could be detected on the electron micrographs. Accordingly, the bubbles were attributed to helium produced from transmutation of impurity boron by thermal neutrons. These bubbles were not uniformly dispersed in the matrix but were located principally at grain boundaries, or were radially positioned around a few precipitates located in the matrix and at the grain bundaries., 4 Voids have also been observed in austenitic stainless steel irradiated at high temperature to high neutron fluences in the EBR-I1 and Dounreay Fast Reactors. The voids were uniformly distributed throughout the matrix. The amounts of helium gas produced by transmutation during these irradiations were less than one-tenth the amounts needed to balance the surface tension of the voids formed by the fast reactor irradiation. The fast reactor results are quite analogous to those reported here for the ETR irradiated steel. Electron microscope examination of the fast reactor irradiated material after a 1 hr postirradiation annealing at 900°C disclosed that essentially all the voids had been eliminated. The authors stated that the voids had developed due to the high concentration of vacancies produced during irradiatin., 6, ' The microstructure of the ETR irradiated material as-tested at 75O°C, Fig. 1, contained about 2 X lot5 cavities per cm3 with an average diameter of 110A. With the Van der Waals b correction and y = 1500 ergs per cm2, 300 ppm He would balance the surface tension of the observed cavities. Stereoscopic examination of the electron micrographs showed that the cavities were neither preferentially located near the grain boundaries nor highly concentrated at specific regions or precipitates. The cavities were nearly uniformly distributed throughout the matrix, on dislocations and at grain boundaries. These observations imply that the cavities were not the sole results of B'O

Jan 1, 1969

By Wayne L. Worrell

Thermodynamic data for the stable carbides and oxides of chromium, molybdenum, and tungsten have been critically eualuuted and are used to determine the stable condensed phases at 1 atm total pressure in each metal-carbon-oxygen system. Pourbaix-Ellingham diagrams have been constructed and are used to estimate the minimum temperatures neces.see)*y to oblain these metals by corbolhermic redlrction under reduced pressures. USING recently reported data for the carbides and oxides of chromium, molybdenum, and tungsten, the stable phases in the Group VI metal-carbon-oxygen systems at specific temperatures and pressures can be determined. The thermodynamically stable regions in each metal-carbon-oxygen system can be completely pictured using a Pourbaix-Ellingham diagram in which the two coordinates are oxygen potential (-RT In Po2) and temperature. Worrell and chipman' have described and constructed such diagrams for the metal-carbon-oxygen systems of vanadium, columbium, and tantalum. Downing2 has used similar diagrams to provide a description of the reactions in submerged arc furnaces. One of the examples which he cited was the Cr-C-O system; however, an improved diagram is presented in this paper using recently obtained data for the carbides of chromium. Although some of the oxides and carbides of the Group VI metals exist over slight ranges of composition,3 all solid phases are represented as stoi-chiometric compounds in the subsequent diagrams. Any error introduced into the calculated equilibria by neglecting the compositional variation of these phases is less than the uncertainty in the thermodynamic data. In a Pourbaix-Ellingham diagram for a three-component system, the phase rule requires that at equilibrium four condensed phases specify a point, three condensed phases determine a line, and two condensed phases define an area. To obtain a well-defined area at high oxygen potentials and teniperatures, the initial carbon to oxygen mole ratio is specified to be more than sufficient to reduce the oxide but not enough to convert all the metal to carbide. Thus, the lowest regions in the subse- quent Pourbaix-Ellingham diagrams represent areas in which the metal and its carbide are the stable condensed phases. Cr-C-O SYSTEM A) Thermodynamic Data. To simplify the subsequent calculations, all thermodynamic data are presented in the form of linear Gibbs-energy-of-formation* equations which were derived for the temperature range 505° to 2000°K and are reasonably accurate over the entire temperature ranges of the diagrams. The thermodynamic data for the compounds occurring in the Cr-C-O system are summarized in Table I. Several volatile chromium oxides have been reported,4 but their influence is negligible in the Cr-C-O system. Thermodynamic data for CO and CO2 were taken from the compilation of Coughlin.5 The only solid chromium oxide sufficiently stable to exist below 1800°K in the Cr-C-O system is Cr2Os.11 The Gibbs-energy-of-formation equation for Cr2O3 was obtained by revising the data tabulated in Coughlin,5 using the heat of formation of ah' and the high-temperature thermal data for chromium.7 In 1953 Richardson8 re-evaluated the original work of Kelley and coworkers,9 who measured the thermodynamic properties of the chromium carbides. However, the high-temperature equilibrium results of Boericke9 yield values for ?G°f of Cr2O3 which are 2 kcal more positive than the accepted data. His results for the chromium carbides are based on the same questionable equilibria. Gleiser10 recently determined the Gibbs energy of formation of Cr3C2 and the equation in Table I was calculated from her data and the thermal data of Kelley and coworkers.9 Thermodynamic data for the Cr7C3 and Cr23C6 carbides were obtained by combining the Cr3C2 data

Jan 1, 1965

By G. C. Rauch, T. H. Courtney, J. Wulff

The superconducting behavior of Nb-Ti alloys containing 40 and higher wt pct of Nb and variable oxygen content was studied as a function of thermomechanical processing. Critical current density (Jc) us applied transverse magnetic field (H) data were obtained for 0.010 in. diam wires at 4.2° Kin steady fields up to 120 kOe. The precipitate responsible for increase in Jc in each of the alloys studied was related to niobium and oxygen content. In alloys containing 40 to 60 wt pct Nb with less than about 1600 ppm of oxygen, w precipitation in the range 350° to 450°C appears to be responsible for the maximum value of Jc observed. In alloys of higher oxygen content (-2500 ppm), the oxygen-enriched a phase which precipitates in the temperature range 450° to 550°C is a more effective fluxoid pinner. Maximum Jc in low oxygen (350 ppm) 80 wt pct Nb alloys was achieved by 600°C aging heat treatments. Measurements of resistive critical field also reflect the changes in composition accompanying precipitation in these alloys. It is well known that the superconducting critical current density, Jc, of solid solution superconducting alloys can be increased by precipitation heat treatments.1-4 The precipitate, to serve as an effective superconzlucting fluxoid pinner and increase Jc, must be of proper size and spacing.' Its electronic properties must also be different from those of the matrix.6 As in age-hardenable systems, optimum temperature and time of aging are dictated by the composition and history of the particular solid-solution alloy under consideration. The alloy diagram of Ti-Nb7-9 shown in Fig. 1 is typical of ß-stabilized Ti alloys. Precipitation to achieve high Jc in Ti-Nb and Ti-Ta alloys is usually carried out in what is believed to be a two-phase a + ß region.1,2,4,10 Previous work on Ti-Nb4,11 and on other ß-stabilized systems such as Ti-V, Ti-Mo,12-14 has shown, however, that the first precipitate to appear is not necessarily (Y. Under specific conditions the meta-stable w phase is precipitated instead. A further complication arises in such alloys from the strong influence of contained oxygen on the phase stability and on the kinetics of precipitation.15,16 The superconducting critical current density of Nb-Ti alloy containing less than 36 wt pct Nb has been studied by Vetrano and Boom1 and Kramer and Rhodes.4 The most effective aging temperature was found to be about 425°C; fluxoid pinning was attributed to the precipita- tion of a by Vetrano and Boom and of w by Kramer and Rhodes. Although the latter workers used recrystal-lized material and the former cold-worked, studies carried out in our laboratory lead us to believe that the type of precipitate responsible for increased Jc is unaffected by prior cold-work.17 That other types of precipitates may also be effective, especially in higher oxygen-containing alloys, has been demonstrated by Reuter, et al.2 in this laboratory with the aid of electron microscopy. Reuter et al. found that at an aging temperature of 600°C, fee-TiO is precipitated, resulting in high values of Jc. Even higher values of Jc were observed after heat treatment at 500°C, but the precipitate could not be indexed as fee-TiO. Whether the precipitate was oxygen-rich w or a could not be clearly distinguished. The work nevertheless indicates that appreciable amounts of oxygen alter the nature of the phases precipitated at different temperatures, at least in alloys containing more than 36 wt pct Nb. Since such compositions are more readily worked into suitable wire than lesser niobium content alloys, it was decided to study the response to aging of the alloy compositions reported in the present paper with the hope of clarifying the effect of composition on the precipitation processes responsible for high values of Jc. I. EXPERIMENTAL Nb-Ti alloys containing 40, 50, 60, and 80 wt pct Nb were prepared by are-melting 35 g ingots of iodide crystal bar titanium and electron-beam melted niobium.

Jan 1, 1969

(Butte Meeting, August, 1913.) IN metallurgical circle it is. known widely, but somewhat vaguely, that the ease of reduction of metallic .oxides. depends largely on the way they have been prepared. It is likewise known that. different forms of carbon have different and greatly varying reducing powers. It is the purpose of, this paper to show somewhat more definitely and scientifically these facts. Sonic years ago the writer published an account of pyrometric determinations of the reduction temperature of zinc oxides variously prepared and of several kinds.1 In said paper it was shown that the temperature at which zinc oxide evolves zinc according to the equation, ZnO+C? Zn+CO depends upon the nature of -the two reacting bodies. The determinations bad a range of accuracy of from 2°to 6°C.,whereas differences were found to, amount to an extreme of 90° C. So the differences are real ones and must have a definite cause. The equation of boiling water, (H2 O)4 = 4 (H20) has a fixed temperature for? equilibrium of 100° C. at 760 mm. pressure. In general, all equations reacting in the liquid or the gaseous phase have well-defined constant physical conditions which govern the equilibrium point and reaction velocities.

Jan 7, 1913

By C. H. Li, R. J. Stokes, S. H. Bendel, J. A. Sartell, T. L. Johnston

The mechanism of the oxidation of high-purity copper has been studied at temperatures from 500° to 981°C employing gravimetric, high-temperature microscopic and inert marker techniques. An investigation of the adhesion of copper oxides was also made. The oxidation of copper is found to be parabolic at all temperatures. It is concluded that the controlling mechanism is the outward diffusion of CU+ ions through the Cu2O layer, but the mechanism of diffusion is modified by the state of compressive stress in the oxide layer at the oxidation temperature. At temperatures below the transition from elastic to plastic behavior of Cu2O the growth stresses reach a value sufficiently high to cause CuO whiskers to be extruded. The extrusion of whiskers results in the injection of a large number of vacancies into the CuO. The Cu20 layer grows by the advance of the CuzO/CuO interface into vacancy-rich CuO. Since there is an adequate supply of non -thermally created vacancies, the activation energy for oxidation is that required to move the Cu+ ion through the appropriate saddle point to a neighboring vacancy, which has been determined to be 20,000 cal per mole. At temperatures at which the Cu20 can deform plastically the stresses are never high enough to cause whiskers to form. thus vacancies must be supplied by themal activation and as a result the activation energy increases to 40.000 cal per mole. ALTHOUGH extensive studies of the oxidation kinetics of pure copper have been made in the past. the mechanism has received relatively little attention. As a result, certain features of the kinetic data have not been satisfactorily explained' For example, several workers1,2 have reported that the activation energy for oxidation in the range from 500° to 700° C was about 20,000 cal per mole whereas that above

Jan 1, 1960

By R. A. Haney, S. J. Gigliotti

Over the past ten years, analysis of the acceptability of face ventilation systems has been based on numerical criteria rather than solely a study of air flow and methane patterns in the face area. This type of analysis has become possible primarily because of the instrumentation and mathematical models developed by the Ventilation Division, Pittsburgh Health Technology Center, Mine Safety and Health Administration (MSHA). To properly use these mathematical models, large amounts of methane and airflow data must be collected in the face area during mining activities. To supplement underground testing of face ventilation systems, a full scale model of a face area was built. This model includes a full scale model continuous miner, a face ventilation system, a gas release system, and a remote methane detection system. The remote methane detection system consists of an array of twelve methane sensors located throughout the face area. Data from the sensors are transmitted to strip chart recorders. Methane, air quantity, and other data collected during a test are entered into a computer for analysis. This paper presents the data entry system, the models used for data analysis, the test results, and the application of these results to a face ventilation system.

Jan 1, 1983