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By J. W. Pugh, J. D. Nisbet

THIS study of the ternary has been made as one phase of a metallurgical investigation which began nearly four years ago in the General Electric Company's Research Laboratory in Schenectady, N. Y. The objective of this program is the discovery of new metallurgical information which will lead to the development of better high-temperature materials. Combinations of the four pure base elements—iron, chromium, nickel, and cobalt—are being studied at the present time. It is essential in an investigation such as this to know as much as possible about the constitutional diagrams involved. The study of the iron-chromium-nickel system has been made to this end. Preliminary Explanation of Experimental Procedure: In all, fifty-five alloys at steps of 10 at. pct were made for the investigation of this ternary. Several ternary alloys in the chromium rich corner had to be omitted because their extreme brittleness made testing impractical. All alloys were vacuum melted with hydrogen reduction and centrifugally cast. The apparatus and technique of this process has been described in detail by Nisbet.1,2 The purity of the alloys prepared in this way is considered to be quite good. Impurities are listed as follows: Pct Carbon.............................0.02 Oxygen................................0.02 Nitrogen.........................0.005 Magnesium..................0.03-0.05 Sulphur...........................trace Hydrogen....................trace Phosphorous..................trace Silicon........................ trace After casting, all samples were given a homo-genization treatment which consisted of holding them for 15 hr at 1150°C (2100°F) and water quenching. Testing was begun with the samples in this condition. The tests employed in the study of this system were (1) dilatometer, (2) hardness versus aging temperature, (3) tensile strength and elongation versus temperature, (4) microstructure analysis, and (5) electrical resistance versus temperature. Dilatometer tests were made at the rather rapid heating rate of 1093°C (2000°F) in one hour on a Bristol-Rockwell type instrument. Hardness data were taken on specimens cooled from 204", 427", 649°, 760°, 871°, 982°, and 1093°C under conditions which are thought sufficient to bring the specimens to equilibrium in all but the cases of the very sluggish transformations. Electrical resistance data for several specimens were taken for both heating and cooling conditions in a vacuum furnace especially designed for this work by D. W. Bainbridge, formerly of this laboratory. Provisions were made for heating and cooling standard specimens at a constant rate, while autographic records of resistance and temperature were made simultaneously. Micrographs of all the alloys were made in the quenched condition. Some question may exist as to how such physical values as hardness, tensile strength, and elongation were interpreted to indicate a change in phase. Original data were recorded on physical property versus temperature graphs, each of which was made from the data of a single alloy (fig. la). From these, another series of graphs were plotted with the physical property as a function of composition for constant temperatures (fig. 1b). Sharp deviations in the slope of these composition versus hardness curves often indicate a change in phase. The example of fig. 1 will serve to describe this experimental technique. The plotting of a single point from graph "a" to graph "b," and finally to the phase diagram "c," is illustrated. The location of the point on graph "b" is indicated as point (1). If all the alloys of the A-B binary system were solid solutions at temperature X, the hardness in this curve would be expected to rise at a fairly even rate as A is diluted with B to a maximum at some intermediate value between A and B, as

Jan 1, 1951

By Malcolm T. Hepworth

RECENT interest in thermoelectric devices has been directed toward studies of the properties of thermoelectric materials of semiconducting solid compounds with little attention given to ionic and semiconducting liquids such as aqueous solutions, fused salts, and mattes. One type of thermoelectric system is the thermocell: a nonisothermal galvanic cell with two identical electrodes at different temperatures connected by an electrolyte bridge. An electromotive force, v, is generated which is a function of the electrode reactions and the properties of the electrolyte according to the Eastman' equation: where S* is the entropy change of the system arising from the electrode reactions and by heat transferred by ion migration and by thermal conduction. The quantity nF is the product of equivalents passed and Faraday's constant. A value of S* of 23.06 cal per "C is equivalent to 1 mv-Faraday per "C. The symbol, a, is used for dV/dT in analog to the See-beck coefficient of solid-state thermoelements. de Bethune2 has calculated the temperature coefficients of the electromotive force of a large number of nonisothermal aqueous cells from measurements on the nonisothermal temperature coefficients of the standard hydrogen electrode, combined with data on the isothermal temperature coefficients of half-cells tabulated in the literature. Values of these coefficients (a) in de Bethune's compilation ranged up to 3 mv per C. In particular he reported a value of +2.059 mv per "C at 25'C for the cell: Fe (aqueous, unit activity) (aqueous, unit activity) written for the hot-electrode reaction. The positive sign indicates that the hot electrode is positive (an "n-type thermocell"). In analog to a solid-state p-n system, it would be possible to couple two thermocells together to form a system in which the figure of merit could be calculated by adding the temperature coefficients according to the relationship described by offee:' where a is the Seebeck coefficient in volts per "C, p is the specific resistivity in ohm-cm, and K is the thermal conductivity in watts per cm "C. Even though ionic systems have rather high electrical resistivities compared with semiconducting and metallic systems, it was felt that a preliminary study of one ionic system should be made to establish some basis for evaluating the possibility of a p-n thermocell for energy conversion. Accordingly the Fe", Fe"' system was studied as a possible component for a p-n system. A glass system was constructed consisting of two vertical water-jacketed tubes connected by a horizontal tube, Fig. 1. Platinum-black electrodes 1 cm by 1 cm in dimension were inserted in each vertical tube with thermometers to register the electrode-compartment temperatures. The temperature of the electrode compartments was controlled by circulating water from thermostatted baths around the electrode compartments. The electromotive force of the cell was then read by a potentiometer for zero current as a function of the temperature of the hotter electrode. Current output of the cell for varying external loads was also measured. The cell resistance was measured by means of a bridge circuit with 10,000 cps signal and oscilloscope. Resistance measurements were converted to specific resistivity by calibrating the cell with a solution of known conductivity.

Jan 1, 1965

By W. L. Honnold

AS BOTH South Africa and diamond mining are unfamiliar subjects it seems best that on such an occasion as this I should endeavor to reflect the atmosphere of the place and to picture the mines from an industrial rather than from a technical standpoint and, because of long absence, my remarks must necessarily be sketchy and in some particulars not up to date. The preferable route to South Africa is via England, direct steamers from America being inferior as to service and effecting no saving of time. The newer boats are of about 20,000 tons capacity and very comfortable. Seventeen days are required for the voyage and only one stop is made-that at the island of Madiera, three days out. Between Southampton, the port of departure, and Madiera the weather may be warm or cold and the

Jan 1, 1925

By Alexander B. Morris

Studies such as the investigations into the solubility of gases in crude oil under various conditions, which have been carried on during the past three or four years, are very interesting from an academic point of view, but this consideration alone is hardly sufficient to warrant the large contributions from the industry necessary to maintain them. Some definite benefit to the industry as a whole should be forthcoming. The purpose of this paper is to direct the attention of company engineers, and company executives, to some of the ways in which the information gained from these studies can be made directly profitable. This work has two principal economic aspects. One affects the investment budget, and through it the financial requirements of the companies. The other affects operations, and through this course is reflected in current earnings. It will be shown that, as a direct result of the investigations into gas solubility, undertaken in the recent past by various investigators, it is now possible: 1. To determine more accurately the amount of reservoir oil originally present. 2. To obtain closer control on operating conditions, to effect more economical recovery. 3. To predict earlier and more dependably when and how much surface lifting equipment will be needed. 4. To reduce, or entirely avoid the very large investment in gasoline recovery equipment now frequently found necessary. 5. To control the gravity of the pipe-line oil so as to secure the greatest possible revenue from the products of the well. 6. To effect the recovery of a large amount of gasoline now wasted while the practicability of a gasoline recovery system is being decided. 7. To plan operations, by comparison with the history of old properties operated without this new information, so as to avoid the mistakes of ignorance made in the past. These points will be discussed in the following pages, though not necessarily in the order stated. There is so much overlapping of the points themselves, and of the data from which they have been drawn as conclusions, that to treat them in any particular order would require

Jan 1, 1935

By V. Niemitz

Approximately 30 miles east of Chicago on the southern shores of Lake Michigan stands Bethlehem Steels newest fully integrated steelmaking facility-the billion dollar Burns Harbor plant. The first phase of what will ultimately be the most completely integrated and flexible materials handling system for a steel mill in the western hemisphere is now complete.

Jan 1, 1970

By G. D. Marshall, D. K. Sarin, V. E. Hampton

Ground support at the Thompson Mine emphasizes scaling, rock bolting and wire mesh screening on the backs and walls of all underground stoping and development areas and also full column grouted cable bolting in the bulk mining areas. This paper describes the equipment for the point anchored rock bolts as well as the full column cable bolts. Modifications in design and testing of all components and procedures has ensured a safe and efficient method of ground support for the mining conditions existing at the Thompson Mine.

Jan 1, 1983

The world's largest steam-driven mine hoist, built by Nordberg Manufacturing Co. a half century ago, has become a major tourist attraction in Michigan's Upper Peninsula. The hoist, designed by company founder Bruno V. Nordberg, is located in the Quincy Mine Number Two, just north of Hancock. Nordberg began construction of the mammoth machine before World War I, but delayed completion until after the war. The hoist became operational in 1920 and continued running until the mine was shut down in 1931.

Jan 9, 1968

By L. L. Seigle

Free energies, heats, and entropies of mixing of solid Fe-Au alloys have been measured by the galvanic cell method between 800° and 900°C. A positive deviation from Raoult's law and a large excess entropy of mixing were observed, both attributable to lattice distortion caused by the disparity in component atom sizes. Since the terminal solid solutortiontions are not regular, thermodynamic properties computed from the location of the mis-cibility gap do not agree well with measured quantities. The electromotive force data suggest some changes in the existing Fe-Au phase diagram. ALTHOUGH a considerable amount of information has been accumulated about the thermodynamic properties of metal solid solutions which exhibit negative deviation from Raoult's law, particularly those in which ordering occurs, relatively few experimental measurements have been made on solutions with positive deviation. This is due to the infrequency of broad homogeneous regions suitable for experimental measurement in solutions of this type, since any marked positive deviations from ideality lead to restricted solubility and the formation of miscibility gaps. Thermodynamic data reported in the literature for such systems have usually been calculated from the location of the miscibility gap boundaries under the assumption that the entropies of mixing are ideal, i.e., the terminal solutions are regular.' One of the few binary systems with both positive deviation and a wide homogeneous range in the solid is the Ni-Au system. A recent investigation of solid Ni-Au alloys' revealed that the entropies of mixing were much larger than ideal and consequently thermal data computed from the phase boundaries assuming regular solutions were seriously in error. Theoretical considerations put forward by Zener indicated that high entropy values should generally be associated with systems possessing a miscibility gap in the solid, when this is due to differences in the size of component atoms. These facts suggest that the regular solution assumption is a poor approximation for many solid solutions with positive deviation and that reliable thermodynamic data generally cannot be obtained by conventional methods from the location of miscibility gap boundaries. The Fe-Au system, Fig. 1, resembles the Ni-Au system in certain respects. The presence of a miscibility gap in the solid indicates a large positive deviation from ideality, but there is nevertheless an extensive single phase region suitable for experimental measurement. The following investigation of solid Fe-Au alloys was carried out in order to obtain additional data on the thermodynamic properties of metal solid solutions with positive deviation from Raoult's law and to further compare thermodynamic data computed from miscibility gap boundaries with those measured experimentally. Experimental Method The thermodynamic properties were derived from measurements of the potential developed between pure solid iron and Fe-Au alloys in a high temperature galvanic cell. The experimental apparatus and technique were the same as those used for the Ni-Au alloys and described in a previous report.' Cell electrodes were 1/16 in. diam rods swaged from chill-cast ingots and annealed for one week at 850°C. The alloys were prepared by melting fine gold granules under argon with pure iron obtained from the National Research Co. The cell electrolyte was

Jan 1, 1957

By W. E. Wrather

CURTAILMENT of production was a matter of far more serious concern to the oil industry through 1933 than the search for new supplies of oil. The huge reserves of crude, built up during past years, instead of inspiring a feeling of security, were viewed apprehensively. The status of past laws and court decisions seemed to guarantee to operators the right to produce oil at will, and this entrenched privilege was so widely adhered to that the market was-in a constant state of chaos. The more modern idea of the ownership of oil in place and correlative rights gained headway slowly, since usually there were enough belligerent producers, staunch believers in the old established order, to defeat the efforts of the majority who sought to' introduce order and restraint. State regulatory commissions were unable to cope, with the rebellion among producers with the result that those who abided by proration rulings were penalized, while those who flouted the rulings and produced unrestrainedly were able to make profits on large volumes of flush oil even at low prices. This situation, known in the vernacular as the "hot 'oil" problem, became so acute that the industry was threatened with ruin. The low price for 36c A.P.I. in the Mid-Continent came in April. at 25c per barrel 'but gradually moved upward to the long-hoped for price of $1.00 per barrel in October, after the Federal Government had taken a hand in the matter and effectively allocated production among the oil producing states and materially curbed the "hot oil" runs.

Jan 1, 1934

By C. A. Stetefeldt

FoR the convenience of those who do not care to enter into the details of this long essay, I begin with a summary of the most important results it presents. The extraction of silver by the lixiviation-process from ores which have been subjected to a chloridizing-roasting, is based upon the fact that silver chloride is easily soluble in solutions of sodium or calcium hyposulphite, and that silver is precipitated from such solutions by an alkaline sulphide, with regeneration of the hyposulphite salts. In case the ore contains lead a large portion of the latter is and dissolved, lead sulphate being soluble in hyposulphite solutions. If, at the same time, copper is present, the sulphides precipitated from the solution, contain silver, copper, and lead, a combination of metals not desirable for subsequent treatment. Mr. E. H. Russell, of Park City, Utah, is the inventor and the patentee in the United States and several foreign countries of a new lixiviation-process, based upon the chemical facts discussed in this paper. Mr. Russell has discovered that lead can be completely separated from a sodium hyposulphite solution, as lead carbonate, by sodium carbonate or purified soda-ash, without precipitating any copper or silver. After decanting the solution from the lead carbonate, silver and copper are obtained from it in the usual way. This method of separating lead prohibits the use of calcium poly-sulphide as a precipitant for the sulphides, because any calcium entering the regenerated lixiviationsolution would also be precipitated as a carbonate with the lead by soda-ash. Hence, a sodium sulphide must be employed. A full investigation has demonstrated that this is by no means detrimental. Sodium sulphide and hyposulphite are more advantageously used in the lixiviation-process than the corresponding calcium-salts. Another defect in the lixiviation-process consisted in the necessity of a very perfect chlorination of the silver in the ore, because silver in

Jan 1, 1885

By B. J. Nelson, F. N. Rhinos

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By F. N. Rhinos, B. J. Nelson

Studies upon the rates of oxidation of copper alloys containing small quantities of the alloying elementsl,2 have shown that steady growth of the scales at predictable rates is limited to a small concentration range and to oxidation at temperatures above 600°C., whereas unpredictable and erratic oxidation behavior is found with alloys containing larger additions and at low temperatures. The latter effect appears to be associated with modifications in the geometric disposition of the oxides. At low concentrations of the baser elements in copper, simple oxidation behavior is typified by the formation of two distinguishable zones of oxidation: (I) a subscale composed of discrete particles of the oxide of the alloying element embedded in substantially pure copper and (2) an external scale composed of cuprous oxide (with a very thin layer of cupric oxide on the outside) containing particles of the alloying element distributed throughout, but most profusely near the metal surface (see Fig. 2, top). Where this type of structure obtains, the process of oxidation is believed to be implemented, and its rate controlled, by the diffusion of the reacting elements through a' continuous matrix phase; i.e., through the alpha (metallic) phase of the subscale and alloy and through the cuprous oxide of the external scale. Copper is presumed to diffuse outward through the cuprous oxide layer to the external surface, where it reacts to form more cuprous oxide.3 Oxygen is delivered at the oxide-metal interface in the form of cuprous oxide, which may either react with the alloying element to deposit its oxide at the inner limit of the external scale or dissolve in the pure copper that remains at the surface of the metal after it has become depleted in its oxidiza-ble alloying elements. Both oxygen and the alloying element are pictured as diffusing through the metal, the oxygen inward and the alloying element outward. Where the two diffusion streams meet in sufficient concentration the oxide of the subscale is precipitated. If the oxygen pressure in the surrounding atmosphere is just below the pressure necessary to maintain cuprous oxide undecomposed, no cuprous oxide can be formed; some of the oxide of the alloying element may form upon the external surface, if its decomposition pressure is below that of cuprous oxide, and a normal sub-scale appears. This condition is achieved experimentally by enclosing the alloy with cuprous oxide together with an excess of copper. At temperatures from 600°C. downward, the precipitated oxides tend to accumulate at the grain boundaries of the alpha phase where a relatively small volume establishes a partial barrier to the diffusion of the reactants- Similarly, large volumes of Precipitated oxides tend to deposit in various patterns that may be expected to

Jan 1, 1944

By Arthur C. Spencer

(Glen Summit Meeting, June, 1911.) THREE great deposits of iron-ore, in Camaguey and Oriente Provinces, Cuba, are well known to me through careful field-examinations executed in the years 1901 and 1907. In 1901 I visited the Cubitas iron-ore district, which lies about 12 miles distant from the city of Camaguey in a northerly direction, and the Mayari district, which includes the Sierra Nipe, lying opposite Nipe bay on the north side of Oriente Province. In 1907 I again visited the Cubitas district, and also made a sojourn of several days in the Moa district, where the extensive deposits of iron-ore were observed and studied. The observations of 1901 were made under the auspices of the then Military Governor of Cuba; Gen. Leonard Wood, and my conclusions concerning the value of these deposits were incorporated in a report.1 The examination of certain denouncements of iron-ore in the Moa district in 1907 was made in behalf of iron-masters operating in the United States, to whom I reported the existence of large amounts of easily-workable limonitic iron-ore, properly designated " brown iron-ore " in the terminology now current among iron-ore producers in the United States. In 1908 I published a paper entitled Three Deposits of Iron Ore in Cuba, outlining the occurrence and origin of the surficial ores existing in the Cubitas, Mayari, and Moa districts.2 . 1 A Geological Reconnoissance of Cuba, by C. Willard Hayes, T. Wayland Vaughan and Arthur C. Spencer, printed as a part of the report of the Military Governor of Cuba for the year 1901, vol. i. 2 Bulletin No. 390, U. S. Geological Survey, pp. 318 to 329 (1908).

Mar 1, 1911

By A. E. Wells, H. O. Hofman, R. P. Reynolds

A Discussion of the Paper of H. O. Hofman, R. P. Reynolds and A. E. Wells, read by title at the London Meeting, July, 1906 ; presented at the New York Meeting, April, 1907, and printed in Bi-Monthly Bulletin, No. 13, January, 1907, pp. 37 to 52. GEORGE A. PACKARD, Boston, Mass. (communication to the Secretary*) :-The very interesting results obtained by Prof. Hofman and his assistants came to my attention when I had temporarily assumed charge of the metallurgical department of the Missouri School of Mines, and had found it, pending the completion of a new building, lacking a furnace in which to roast ore preparatory to the customary lead blast-furnace run. An attempt at lime-roasting had been already determined upon, but the use of a charge which would make a slag of definite composition was a new idea. The results following were obtained by Messrs. Aubrey Fellows, J. C. Long, E. R. Wash, and Dr. T. C. Tseung, under my supervision. It is regretted that the data are not more complete; but the work was done simply incidentally to securing the desired ore for the blast-furnace, with no idea of obtaining any results of especial interest. It is submitted because of the metallic lead obtained, no notice of which has been seen elsewhere. The ore was an aggregate of several lots of concentrates, apparently from Missouri ores. The analysis follows, with that of the limestone and sandstone used, as far as made:. Ore, SiO2, 3.04; Fe, 0.77; CaO, 2.53; Pb, 68.74; Zn, 5.77; S, 13.9 per cent.; limestone, SiO2, 1.0 ; CaO, 54.35 per cent.; sandstone, SiO2, 99.8 per cent. The converter was made in the shops from a sheet of No. 14 iron riveted in the shape of a truncated cone, 20 in. in diameter at the top, 15 in. at the bottom and 22 in. high. A grate of No. 8 iron, 17 in. in diameter, with 130 s-in. holes placed at about 1.25-in. centers, was held in place by the shape of the

Jul 1, 1907

By Russell C., Fleming

FOK, many years the officials of the Magma Copper Co. mine at Superior, Ariz., have had to contend with adverse conditions underground in the form of high rock temperatures, hot water, and high relative humidity. These conditions in the mine have been such that working the mine would have been impossible were it not for the constantly expanding and improved sys- tem of ventilation to produce bearable conditions in the working places. Results that have already been achieved make an interesting study of what can be done along those lines. From the time the mine was first opened in 1910 it has been hot. An idea of the conditions that have persistently been encountered can be obtained from parts of the mine that are not being worked at present or that do not yet have sufficient ventilation. Virgin rock temperatures as determined in drill holes at the faces range from 104° to 116°*. An observation made at the face of No. 5 West footwall drift on the 2800-ft. level.

Jan 1, 1930

By W. Armstrong Price

INVESTIGATION by German chemists during the World War showed that particles of iron oxide form rapidly in iron pipes carrying hydrogen gas under pressure when the gas contains small amounts of water. Under these conditions, the gas frequently exploded when expanding into a dirigible. The explanation of the explosions lies in the building up of a charge of static electricity in the flow just beyond the orifice and the ignition of the gas by a spark accompanying discharge of the electricity. Friction between the moving particles and the pipe generated the electric charge, which was manifested by a pale blue glow formed in the flow at pressures above two atmospheres. In one experiment, this glow, at eighty atmospheres, extended for a distance of forty to fifty centimetres, but did not ignite hydrogen and air mixtures until the charge was col-lected by a conductor and discharged across a gap between electrodes placed at the side of the column of gas. Autoignition did not occur when this discharge was effected at a distance from the gas column, nor if the gas used was thoroughly dried and free from impurities. The electric charge has been studied by placing various wire and screen conductors in the outcoming stream of gas, Guest having summarized these experiments. The application of these conclusions to fires in petroleum and natural gas issuing uncontrolled from wells is made in the following paper, citing the ignition of a wild gas well in Texas.

Jan 1, 1936

By Alexander R. Troiano, Taylor Lyman

Studies of the transformation of aus-tenite at constant subcritical temperatures have been numerous since the work of Davenport and Rain.' Considerable information has been obtained on low-alloy steels and on high-carbon alloys containing undissolved carbide or graphite at the austenitizing temperature. Little is known of the isothermal transformation of aus-tenite containing in solution large amounts of both carbon and a single alloying element. In this investigation four steels containing one per cent carbon and with chromium in the range 3 to 9 per cent have been examined with the view to establishing the fundamental character of the isothermal reactions when all carbon and chromium are initially in solution in austenite. Experimental Procedure Alloys The chemical compositions of the steels investigated are given in Table I. The 4 per cent Cr alloy is a commercial steel. The other steels were made by the Carpenter Steel Co. as 50-lb., induction-furnace heats and rolled to 5/8 -in. round bars. Bars were softened at 650' to 700°C. before the specimens were cut. Most of the lines on the transformation diagrams presented here have been placed on the basis of the microscopic examinatioll of partially reacted specimens, Thees specimens were approximately 1/2 by 1/4 by 1/8 in. ill size, specimens of the 9 per cent cr steel were held 10 to 12 hr, at 1200°to 1225°C. before quenching to the various subcritical temperatures. The other steels were held for 2 to 2 1/2 hr. at 12ooOC. before quenching. These treatments, carried out in an atmosphere of purified nitrogen, produced an austenite grain size larger than A.S.T.M. So. I, some grains being 1 to 2 mm. in diameter. There were a few undissolved carbide particles in some specimens of the 9 per cent Cr steel. It is believed, however, that any errors in the results due to incomplete solution of carbon and chromium in austenite are negligible; that is, austenite compositions may be considered as being those listed ill Table I. X-ray Methods Constituents were identified and mar-tensite axial ratios determined from Debye

Jan 1, 1945

By L. Thomassen, N. Spooner, J. M. Thomas

NI-CR and some Ni-Cr-Fc alloys, when used as electrical resistance heating elements in reducing atmospheres, at times suffer rapid breakdowns due to so-called "green rot." These reducing atmospheres are most frequently used in bright annealing and heat-treating furnaces which are kept for long periods of time at 1500' to 1800°F. The green rot is a preferential oxidation of the chromium in the alloy to such an extent that the remaining metal frequently becomes ferromagnetic. The Curie point (magnetic transition point) at room temperature for a pure Ni-Cr alloy is known to be at about 7 pct Cr.¹ This represents a severe loss in chromium for one popular grade of resistance alloy, which is nominally 80 pct Ni-20 pct Cr. The formation of oxides along the grain boundaries makes the ribbon brittle and gives the fracture a green, earthy appearance—hence the name. The authors have studied this phenomenon, simulating the industrial conditions by heating resistance ribbons in various reducing atmospheres, such as moist hydrogen or the atmosphere specified in the ASTM test.² This atmosphere contains 16 pct H2, 10 pct CO, 4 pct C02, 1 pct CH1, 1.5 to 2.5 pct H2O, balance N2. Little success was had in producing severe corrosion with the commercial 80 pct Ni-20 pct Cr alloys. It had been noticed, however, that 90 pct Ni-10 pct Cr alloy wires deteriorated very rapidly when placed in the bottom of narrow thermocouple protection tubes. The bottoms of the tubes with the wires were heated in air. This took place both in porcelain tubes and in Inconel* tubes either with the cold end open or loosely stoppered with asbestos. On examination the wires showed microstructures which would be classified as green-rot corrosion. Subsequent investigations with various alloy wires confirmed the observation that corrosion occurred in some wires, including 80 pct Ni-20 pct Cr alloys, much more rapidly in such tubes than had occurred previously in test atmospheres mentioned above. When 90 pct Ni-10 pct Cr alloys are oxidized with an abundant air supply, the oxide coat consists of both nickel and chromium oxides. In this case thermodynamic equilibrium between the oxides is not established. However, when oxidized 90 pct Ni-10 pct Cr alloy specimens were heated to 1500" to 1800°F inside small diameter tubes, the oxide coat transformed to a bright metallic outer layer of nickel or nickel-rich alloy, beneath which appeared a green oxide, followed by intergranularly attacked metal. The obvious explanation is that in the narrow tubes, thermodynamic equilibrium is being established according to the equation NiO + Cr (in alloy) ? Ni + Cr2O3 This reaction is favored due to the fact that the oxygen pressure over nickel oxide is more than 10"' times the oxygen pressure over the green chromium oxide. The initial oxygen in the tubes is depleted very rapidly by oxidation of the wire and of the tube, if it is metallic. A confirmation of the occurrence of the reaction, reduction of NiO by the chromium in the alloy, was obtained by putting oxidized nickel foil into an evacuated quartz tube along with a piece of bright 90 pct Ni-10 pct Cr alloy ribbon, and heating the tube at 1820°F for a number of hours. The nickel oxide on the foil was completely reduced to pure nickel, leaving a bright foil. The 90 pct Ni-10 pct Cr alloy became strongly magnetic and showed the typical green-rot structure. Weights of the samples before and after testing showed the weight loss of the foil to approximately equal the weight gain of the ribbon. Evidently the bottom of long, narrow protection tubes, stoppered or not, may under certain conditions act just as the sealed quartz tubes in respect to being a confined space in which oxygen is not freely replenished. This condition of oxygen depletion can be prevented by introducing a small amount of air into the bottom of the tube. Many conditions becloud the green-rot phenomenon, such as carburization, sulphidization, and the presence of other corrosive agents. However, these experiments have shown that the basic reaction is a case of internal oxidation which can occur simply by adjusting the oxygen pressure to a low enough level so that the atmosphere will leave the nickel intact and oxidize the chromium. The action of the other agents in commercial atmospheres can then be taken up as individual cases. From these and numerous other tests completed to date or still in progress, it is believed that a more critical evaluation of electrical resistance alloys for their resistance to green-rot corrosion can be made. A much better understanding of the mechanism for this type of corrosion should also result. A more complete report on these experiments will be published later. In the May 1953 issue: TP 35213 Discussion: Solubility of Carbon and Oxygen in Molybdenum by W. E. Few and G. K. Manning, discussion by N. A. Gokcen: p. 747, first column, the fifth, sixth, and seventh lines should be the first, second, and third lines, followed by the present first, second, third, fourth, eighth, ninth, and tenth lines.

Jan 1, 1954

By J. B. Clark

In multiphase ternary diffusion studies, plots of the variation bf the composition on the isotherm constitutes one of the most effective methods of presenting experimental results, especially if such plots are made in a manner which relates the composition path on the isotherm with the diffusion layer structure in the couple. Unfortunately, if different conventions for plotting are used serious misinterpretations occur readily, causing apparent disagreement between investigators who actually share the same viewpoint. A common convention for mapping these diffusion paths is needed at this time because with the increasing use of the electron-probe X-ray microanalyzer, a much greater number of ternary diffusion studies can be expected in the near future. In an effort to prevent unnecessary confusion in the future litera- ture, a convention for these plots is proposed, as outlined below. A hypothetical example of the use of these conventions is given in Fig. 1 where the path of composition through the diffusion structure of the 100 pct A/50 pct B, 50 pct C couple is plotted on the appropriate isotherm of the ABC system. The lower case letters relate the region in the diffusion layer structure to the appropriate composition on the ternary isotherm. 1) The diffusion path is plotted on the isothermal section corresponding to the diffusion temperature of the couple. 2) The terminal compositions of the plotted diffusion path are the initial compositions of the couple halves—provided infinite boundary conditions are maintained. If, in either couple half, infinite conditions are not maintained, then the path terminates at the composition of the exterior surface of the couple. If, at this surface, the composition varies with time or if the plotted path is time dependent, then the diffusion time should be noted beside the plotted path. 3) A solid line crossing a single phase field (e.g., line a-b in Fig. 1) denotes an existing layer of that phase in the diffused couple. 4) A dashed line crossing a two-phase field parallel to the tie lines (e.g., line g-h) represents an interface between the two phases with interfacial compositions designated by the ends of the tie-line. The line represents no spatial extent. 5) A solid line crossing a two-phase field so as to cut tie lines (e.g., line b-c or line j-k) represents a locally equilibrated columnar two-phase layer. The solid line should cut those tie lines which correspond to the lateral interfacial equilibria along the columnar

Jan 1, 1963

By D. M. Dunbar, H. C. SCHLILTZ

HE Chile Exploration Co.'s mine and reduction plant are at Chuquicamata, Chile, on the eastern edge of the Atacama Desert, 163 miles northeast of Antofagasta, 80 miles from the Pacific Ocean, and 70 miles from the Bolivian border and at an altitude of 10,000 ft. Guggenheim Brothers started prospecting in -4pri1, 1912, and purchased the main property, in October of that year; the property is now controlled by the Anaconda Copper Mining Co., which acquired it in January, 1923. The orebody strikes north 10" east, and has a dip of about 64" west. The length, as far as developed, is approximately 1% miles; the width averages sightless than mile.

Jan 1, 1925