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E. A. H. Tays, San Blas, Sinaloa, Mex. (communication to the Secretary*):—The results obtained by Messrs. Hofman and Hayward in their experiments, proving that a low percentage of copper sulphate with a variable percentage of salt, depending on the ore, gives the best results, confirm practical mill-work which I did in 1895. I have none of my notes, taken at the time, to refer to, so have to rely solely on memory, which precludes the conciseness that is alway desirable. In 1894 I took charge of the plant of the San Rafael Company, near Chinipas, Chihuahua, Mex., which at that time was treating a very refractory ore carrying about $15 in gold and from 20 to 25 oz. of silver per ton, the bullion being about 300 fine in gold. The silver in the ore was in the form of a sulphide. Although carrying an average of 0.75 oz. of gold per ton, free gold could rarely be seen by panning, but upon roasting a sample of the ore the gold became visible at once—a result which was discovered by chance and used to advantage later. In order to utilize the old mill to the best advantage, it was decided to use pan-amalgamation after roasting. The roasting, done in a lime-kiln, was similar to the ordinary " burning " operation. The roasted ore was trammed to the mill-bins and crushed by 10 stamps to pass a 30-mesh screen. The pulp was de-watered and fed to four 1-ton pans. My recollection is that upon starting the mill-work, the charge contained 1.5 lb. of copper sulphate and 5 per cent. of salt per ton. From the start the extraction was unsatisfactory and the loss of quicksilver was very large. Experiments were then carried out on a working scale. First, the quantity of copper sulphate was increased 4 oz. at a time; then it was reduced

Jan 1, 1910

By W. E. Forsythe

WHEN measuring ordinary temperatures, the instrument is generally placed in very close contact with the body the temperature of which is desired. However, if the temperature of the source is continually raised, a point is soon reached where no known substance will, in general, remain constant in any of its temperature-measuring properties if placed in direct contact with the source. Also, it is occasionally necessary to measure the temperature of a source that 'is so small or so situated that it would be very hard to bring the measuring instrument into direct contact with the source. When these conditions exist, advantage is taken of the well-known fact that all bodies, when at sufficiently high temperatures, send out radiation in amounts readily measurable. This radiation has been found to be related to the temperature. The temperatures of very hot bodies have probably always been judged by the color, or the brightness, of the light given off. With practice, one can estimate probably within 50° to 100° C. of the correct value. However, if judgment is left to the eye alone, very much larger errors are sometimes made, due to

Jan 9, 1919

By J. W. Hickman, E. A. Gulbransen

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By E. A. Gulbransen, J. W. Hickman

In a previous paper' the authors have investigated the structure of the oxide films formed on most of the metals that make up the alloys of this study. The metals were studied in order to provide basic information on the structures, both physical and chemical, of the oxide films and to determine how these structures are effected by the temperature, time of oxidation, and surface preparation. It was felt that an understanding of the physical and chemical structure as well as the stability of the oxide film might furnish clues as to the nature of the reaction process and the protective quality of the film. The oxidation of the metals was studied over the temperature range 300' to 7o0°C. except for copper, wherc the range selected was 100' to 500°C. The results of these studies were presented in graphical form as existence diagrams of the oxides on a time-temperature scale. For some of the metals the existence diagrams were simple and showed few chemical transitions, but there were numerous cases where the physical state of the oxide surface was a function of time and temperature. In general the physical state of the oxide surface changed with increasing temperature so as to increase the sharpness of the diffraction patterns and to cause orientation effects to be more pronounced. Deviatiois in lattice Darameters from X-ray values were noted. In general these deviations were of positive nature and may be due to solid solution of the metal in the oxide lattice. This effect might be expected in thin oxide films. In a study of the oxidation of alloys containing two or more metals, there may arise the complicating factor of identification of the oxides formed. A thorough understanding of the oxides formed on the pure metals, therefore, was, essential before investigation of the oxidation of alloys. In this paper it is our purpose to present a study of the following problems: 1. The existence diagrams of various alloys. 2. The effect of the structure of the alloying metal on the existence diagram of iron. 3. The effect of the percentage of chromium on the oxides formed on Fe-Cr alloys. 4. The relationships, if any, between the oxides formed and the protective quality of the oxides. The following alloys are included in this study: alloys of iron with body-centered cubic, face-centered cubic and other metals, 13 Cr-Fe, 18-8 stainless steel, K4²B, Nichrome V, Hipernik, Inconel, Stellite "²I," Refractaloy, Kovar, mild steel, a series of Cr-Fe alloys and a series of Co-Fe alloys. Since many of the commercial alloys in this list contain more than two metals, various complicating factors in the identification of the oxides formed may arise.

Jan 1, 1947

By Walter F. Bradley

CLOSE to 300 members and guests were registered at the Regional Meeting of the Institute in San Francisco. Oct. 3-6, and many other mining men were present at some of the sessions, but failed to register. Headquarters were at the Palace Hotel. Technical papers for the Metals Session were sponsored by the San Francisco Section, whereas the program for the Industrial Minerals Session was arranged by the Southern California Section. Walter W. Bradley, Chairman of the San Francisco Section, opened the General and Metals Session, introducing President Buehler, who gave a hearty welcome to those present. Clyde M. Eye, of the. Benguet Consolidated Mining Co., presented the first paper, entitled "The Economic and Strategic Value of Philippine Metals to the United States." In closing, he urged. that this country retain and control the Philippines because their large

Jan 1, 1935

An informal discussion on the application of physical chemistry to steelmaking was held during the Annual Meeting of the Institute in February, 1929. Alexander L. Feild presided. In opening the session, Mr. Feild said: We are all familiar with the cooperative mining and metallurgical studies that were begun in 1920 by the U. S. Bureau of Mines, the Carnegie Institute of Technology, and the Mining and Metallurgical Advisory Boards, and in particular with the work on the physical chemistry of steelmaking which was launched under the technical direction of Dr. C. H. Herty, Jr., in May, 1926. It was this work at Pittsburgh more than anything else that was the immediate cause of the formation within the Institute of a committee on the physical chemistry of steelmaking. During the latter part of 1927 a small group of Institute members interested in. the general subject of the physical chemistry of steelmaking undertook the organization of a subcommittee within the Iron and Steel Committee, to foster an active interest in this comparatively new field among the Institute membership and to obtain papers for publication in the Transactions, covering the various phases of the general subject. This plan was conceived by C. E. Meissner, to whose active efforts at the outset as well as during the past year is largely due whatever measure of success the plan has thus far attained. The subcommittee, now a committee of the Iron and Steel Division, was recognized and formally made a part of the Institute's organization at the February, 1928, meeting. As originally organized and as const,it,uted during the past year the committee has been made up as follows: C. H. Herty, Jr., C. D. King, A. B. Kinzel, John Johnston, C. E. Meissner, L. F. Reinartz, R. B. Sosman, and A. L. Feild, Chairman. Dr. C. H. Herty, Jr. has just been elected chairman for the coming year and C. E. Meissner has been reelected as secretary. From the outset it has been the settled policy of the committee to make membership an annual rather than a permanent matter and to reconstitute in part the membership of the committee each year by dropping a certain number of members and adding new members. In view of the fact that the work of the committee is still in a

Jan 1, 1929

Total U.S. mineral production reached an estimated $17.8 billion for 1960, 4 pct above 1959 and second only to the record high of $18.1 billion established in 1957. As a group, metals achieved a rise from $1.6 billion in 1959 to $2.0 billion this year, an increase of 28 pct. Similarly the value of nonmetallic production including fuels (i.e., natural gas, petroleum, natural-gas liquids, asphalt and related bitumens, carbon dioxide. anthracite. bituminous and lignite coal, peat, and helium) rose from $15.5 billion in 1959 to approximately $15.8 billion in 1960. However, this 2 pct increase in the total value of non-metallic production was due to an increase in the value of the fuels ($11.8 billion in 1959 to $12.2 billion in 1960) which offset a drop in value of the other nonmetallic minerals ($3.7 billion in 1959 to $3.6 billion in 1960).

Jan 2, 1961

By I. Lowthian Bell

THERE has been probably no improvement introduced into the manufacture of iron which created more surprise in the minds of practical smelters and of scientific men than Neilson's discovery of the hot blast. In 1829, Messrs. Dunlop & Co. consumed at the Clyde Works, near Glasgow, nearly 7 3/4 tons of coal to make a ton of pig iron, of which about 20 cwts. was employed under the boilers of the blowing engines, leaving nearly 7 tons for the consumption of the furnace itself. In the year 1833, by heating the air to 612° F. (322° C.), they reduced the 7 3/4 tons to 3 tons by the mere burning of 8 cwts. of coal in the apparatus for raising the blast to this temperature. The statement just given is strictly true in a commercial sense, but when we come to consider the question as one of physical science, it is necessary to eliminate some of the conditions which conduced to so extraordinary a result. Anterior to Neilson's time the fuel employed in smelting iron was coke, and it was supposed at that period, erroneously, however, that coal in its raw state, when burned with cold air, was totally unfit for the purpose in question. This mineral, as it was obtained from the Lanarkshire coal-field, contained about 35 per cent. of volatile matter, but the process of charring it was performed in so unskilful a manner that instead of receiving 88 cwts. of coke from 135 cwts. of coal, 60 cwts. only was the product of the operation. Again, the reduced consumption of carbon in the furnace itself was accompanied by a corresponding diminution of blast, and this was followed by an economy of half a ton in engine coal. After making a proper allowance, however, for all these collateral circumstances, we are within the mark when we admit that in actual coke, which is really the form the fuel has to assume before it is burnt in the blast-furnace, not less than 30 cwts. was saved by heating the blast to 615° F. (322° C.). This unexpected economy, be it remembered, was obtained by the combustion of the 8 cwts. of coal, somewhat wastefully applied in the hot-air apparatus. Numerous have been the opinions advanced by different authorities in the scientific world to account for the apparent anomaly, but none,

Jan 1, 1877

By Paul T. Benson

MOST important of the various departments of a custom smelter, so far as the financial welfare of the plant and the confidence of shippers are concerned, is that responsible for correct weights, accurate moisture sampling, and the obtaining of control samples that are strictly representative of the lot of ore from which they come. Treatment rate schedules are based on the metal content of ores received, reduced to dry weight. These rates must be low enough to keep the ship- per from taking his business else- where and still must allow the smelter a profit. Assay results, likewise, must satisfy the shipper, but if they show too high a metal content for the ore they represent, the smelter will actually lose money. It is always considered, and constant checks through umpire assays prove, that laboratory results are closely correct, so the bur- den of the plant profit and loss and the satisfaction of the shipper rest squarely upon the sampling department.

Jan 1, 1936

By C. M. Schwartz, A. E. Austin, W. B. Wilson

High-temperature X-ray diffraction studies were conducted with Th-U alloys with up to 10 wt pet U. The solid solubility of uranium in thorium as a function of temperature was determined by the method of lattice parameters. Thorium will dissolve up to 2.5 wt pet U at 950°, 4.5 wt pet U at 1150°, and 7.5 wt pet U at 1250°C. Determinations were made of the temperature of the transition of thorium and of the effect of uranium upon the transition. The a to ß transition for thorium was observed to occur at 1330' ±20°C. Mean coefficients of expansion were calculated for thorium and two alloys, and for ThO2 in contact with the thorium, using X-ray lattice-parameter data. Values obtained at 950° C for thorium and Tho2 were 12.1 and 9.40 X 10-6 per OC, respectively. Impurities obtained during the X-ray exposure were identified by diffraction and were essentially Tho2 and ThC, with two additional unknown phases being detected. The effect of the impurities upon the results is discussed. DIRECT investigation (i.e., high-temperature X-ray diffraction studies) of the phase diagram of thorium-rich uranium alloys has been shown to be necessary since recent work1 - has disclosed the presence of an allotropic transformation near 1400°C in pure thorium with the room temperature face-centered-cubic phase transforming to a body-cen-tered-cubic structure at the elevated temperature. The effect upon the transition of the addition of uranium to thorium and of the solubility of uranium in thorium at high temperatures remained unknown, yet was of interest in understanding fabrication procedures and elevated temperature use. The present work was undertaken to provide information in this area by determining the transition temperature, the effect of uranium on the transition temperature, and the solubility of uranium in thorium as a function of temperature. Experimental Work The high-temperature diffraction data were obtained using a camera especially designed for the purpose3 and capable of reaching temperatures in excess of 2000°C at pressures as low as 1 x 10." mm Hg. Temperature regulation was provided by regulating the power input to ±0.1 pet variation, and by regulating the water flow through the camera jacket to provide a constant thermal load. The X-ray sample was a rod nominally 80 mil diam, which was further turned down to 20 mil and then etched to 18 mil over 1/2 in. of one end. This was placed in the sample holder and mounted on the camera so that the smaller part was surrounded by a cylindrical tantalum-sheet radiation-type heating element. Diffraction from the sample was recorded on film after passing through a slot in the heating element and radiation-baffle shield and through beryllium vacuum windows. The X-ray film mounting was of the Straumanis type4 with a camera diameter of 114.59 mm. Since previous work of Chiotti' indicated that impurities considerably alter the transition temperature, chemical analysis of the arc melted iodide crystal-bar thorium samples was obtained prior to testing. The analysis disclosed the material to contain as low as 0.001 ±0,0002 wt pet H and 0.007 ±0.001 wt pet 0. Carbon was 0.003 wt pet and nitrogen less than 0.002 wt pet. This material was sealed in mild steel in an inert atmosphere and subsequently hot rolled to 3/8-in. diam rods at a temperature of 732°C. Following removal of the jacket, the material was pickled and cold swaged to 1/8-in. rods, from which the diffraction samples were prepared. The alloys were similarly prepared, with the uranium being added during arc melting. The uranium analyses of the alloys prepared appear in Table I. The experimental procedure for diffraction examination of the three samples of high-purity thorium differed from those of the Th-U alloys. The original practice, later modified, consisted of pumping down the camera with the diffusion pump on and then admitting liquid nitrogen to the cold trap of the system. This was modified for the Th-U alloys by maintaining liquid nitrogen in the cold trap at all times before and while the diffusion pump was heated. This minor change produced a reduction in the amount of carbon pickup by the sample during exposure to the diffusion-pump vapors. The sample was brought to the desired test temperature and exposed for 21/2 hr at pressures which were usually 2 x 10-6 mm Hg, or lower. Exposures were made at

Jan 1, 1959

By Cyril Smith

A COMPLETE discussion of the literature on the subject of the influence of copper on iron and steel will be published elsewhere.1 The present paper is concerned especially with the precipitation-hardening of copper steels, and brief mention will be made here only of the work of Kin-near,2,3 Nehl4 and Buchholtz and Koster,5 who alone have studied this phase of the subject. Kinnear found that normalized low-carbon steel castings containing about 1.0 per cent copper on drawing at temperatures in the neighbor-hood of 530° C. (1000° F.) increased in tensile strength and yield point, with little decrease in ductility. The maximum effect was obtained with about 0.9 to 1.0 per cent copper, and when the copper exceeded 3 per. cent no improvement occurred on reheating. Kinnear did not study the effect of time of reheating-an all important factor where precipitation is concerned. Nehl,6 who apparently was unaware of Kinnear's work, recognized the change as due to precipitation and studied the interdependence of time and temperature of reheating, the temperature of the initial solution heat treatment, and the speed of cooling necessary to retain the bulk of the copper in supersaturated solu-tion and to give an increase in hardness and tensile strength on reheating. Nehl found that if the final rolling or forging temperatures exceeded 700° C. (1300° F.) it was not necessary even to normalize the steel, but full precipitation occurred on merely reheating the forged or rolled shapes at 500° C. (930° F.).

Jan 1, 1933

By Paul D. V. Manning

MAGNESIUM is an exceedingly strategic material but the importance of its production at the time this war started was not realized. Our Government then suddenly became much alive to the need of a tremendous increase in magnesium output, and became a participator in the industry. In this paper an attempt will be made to given an over-all picture of the industry as it has been, and is being, developed. The present war is giving a great acceleration to the use of lighter metals. Development of facilities for production of great tonnages of aluminum and magnesium is bound to bring about some interesting changes in later peace times because costs will be low and production capacities high. As our knowledge of the metallurgy of magnesium alloys increases, this metal will become of vital peacetime importance and will be used in ways we do not now imagine. Household refrigerators, furniture, automobiles, even houses will all be lightened through the use of magnesium.

Jan 1, 1943

By J. K. Brooke, F. A. Renninger

During 1966, crushed stone production in the United States totaled just over 811 million tons valued at almost $1.2 billion. This represented in- creases of 4 % in tonnage and 5 % in value over that for 1965. Excluding the crushed stone used for agricultural and certain industrial purposes (cement, lime and flux), crushed stone mineral aggregate production totaled 616.3 million tons valued at almost $910 million, also up roughly 4% in tonnage and 5% in value over the 1965 figures. Limestone was by far the most widely used rock variety, followed by basalt, granite and sandstone in that order. Concrete aggregate and roadstone continued as the main uses for stone, accounting for 63% of all tonnage produced in 1966 and 60% of total stone value. Sand and gravel production in 1966 increased 3% over that for 1965. Total 1966 output was just in excess of 934 million tons valued at almost $985 million as compared with 908 million tons at $957 million for the previous year. Excluding the higher valued industrial sands, 903.2 million tons of sand and gravel valued at $891.6 million were used directly as mineral aggregates, representing a 2.9% increase in tonnage and a 2.4% increase in value over 1965.

Jan 2, 1968

By William E. Ford, Edward Salisbury Dana

Normal phosphoric acid is H3P04, and consequently normal phosphates have the formulas R3PO4, R3(P04)2 and RPO4, and similarly for the arsenates, etc. Only a comparatively small number of species conform to this simple formula. Most species contain more than one metallic element, and in the prominent Apatite Group the radical (CaF), (CaCI) or (PbCI) enters; in in the Wagnerite Group we have similarly (RF) or (ROH).

Jan 1, 1922

By W. P. Sykes

ThiS investigation was undertaken primarily to establish the relations existing between temperature and mechanical properties in molybdenum, nickel, and an aluminum-copper alloy. Mlolybdenutn (m.p. 2500" C.) was chosen because it is partly similar to tungsten and partly similar to the common ductile metals. Also it is known to furnish, by proper treatment, a desirable material to use in studying relation of grain size and physical properties. The molybdenum used was of the quality that is drawn into wire 0.003 in. in diameter for use as filament supports in incandescent lamps; Chemical analysis shows less than 0.1 per cent. of impurities. Nickel belongs to the same class as iron. Its melting point is 1450" C. and an allotropic change at about 370" C. results in a loss of magnetism above that temperature. This feature made nickel doubly valuable for the purposes of these tests. The nickel used was obtained from the Driver-Harris Co. as 0.090 in. (2.3-mm.) wire, annealed; analysis showed 99.8 per cent. nickel and 0.150 per ccnt. iron. Aluminum is one of the low melting-point metals. Some tensile tests at clevated temperatures have been reported by Bengough but the possibility of learning more with the low temperature and sensitive apparatus available rccommendcd this metal. The samples marked A1 arc an aluminum-copper alloy that contains 3 per cent. copper, 0.42 per cent. iron, and 0.21 per cent. silicon. The presence of the copper somewhat coniplicates the analysis of the results; but the action of copper in aluminum has been studied so that its influence might have been foretold, in part at least. The material and analyses were furnished by the Aluminum Castings Co. The nickel wire, which was deformed at 400" C., was drawn under a bath of molten lead and through a die, which also was immersed in the bath. A thermocouple was suspended in the molten metal to indicate the temperature. Hot oil was uscd as the heating bath for drawing the

Jan 1, 1921

By R. O. Williams

Analytical representation of the thermodynamics of solutions is highly desirable from the standpoint of accuracy, compactness, and numerical manipulations. In particular, computer calculations are greatly implemented. Mathematical considerations show that previous expressions have one or more serious defects. This investigation shows a Fourier series to be satisfactory but that it is also possible to derive a new series which fits certain additional conditions. Included examples show the value of analytical expressions in giving a simple characterization of each system using some two to five parameters, the elimination of the Gibbs-Duhem integration, and the es timation of the error for the experimental function as well as derived functions. It is further shown that the present characterization provides easy comparison between systems. IN the past, thermodynamic calculations have depended to a considerable extent on tabular and graphical methods. As the volume and precision of such data increase such methods become less satisfactory. Specifically, the selection of the optimum representation and the estimation of errors require statistical methods which in turn require analytical representation. The utilization of such data require further manipulations which are best done analytically for maximum precision. For example, phase equilibria are determined by common tangents to free-energy curves: a graphical determination is normally of low accuracy. As computers are increasingly used analytical representations become almost mandatory. Insufficient mathematical consideration has been given previously to the selection of empirical expressions. Those expressions having some theoretical justification are generally too inflexible and mathematically unattractive. We consider the problem in some detail and show that a Fourier series can be effectively used. Also a new series is defined which has certain advantages. ANALYSIS We wish to consider the analytical representation of the heat of mixing, AH, the excess free energy, ?Gxs, and the excess entropy, ?sXS, as a function of composition, X, for binary solutions relative to the pure components in the same state. When a distinction is not required, we use W to denote any one of the above functions. One may use a Taylor expansion around X = 0 to generate a power series. As the derivatives are un- known we represent the series as W = A + BX + CX2 + DX3 + EX4 + ... [l] where the constants A , B, C , ..- are to be selected to provide some optimum fit. For the extremes of composition W is necessarily zero so it follows that A = 0 [2a] B +C + D + E +••• = 0 [2b] Nonelectrolytes, which we are considering, appear to satisfy the condition that d3W/dx3 = 0 [3] in the terminal regions. This is the basis of the a, ß, and Q functions used by Hultgren et al.' and others. While this condition does not have a strong theoretical basis it does appear desirable that any analytical relation should satisfy this condition. Darken2 and Turk-dogan and Darken3 have shown that many systems exhibit this behavior over an extended range from each terminal region, departure being restricted to a limited intermediate region. Since we have no a priori knowledge as to where this transition occurs we can require that this condition be satisfied only as a limit at the extreme compositions as a general condition. We will show later how more restricted conditions can be included in specific solutions. Darken2 has called this behavior the quadratic formalism; we call our application the limiting quadratic formalism, LQF. This condition applied to the above power series requires that D = 0 [4a] 4-3-2E +5-4-3_F + 6 • 5 . 4G + ••• =0 [4b] The form of the power series normally used, due to Margules,4 is W=X(1-X)(A + BX + CX2 + DX3 + EX4 + •••) [5] where A, B, C, --. are a new set of constants. (Guggenheim5 has given a variation of this expression in a more desirable form. Since, however, it is contained in the above expression it does not require separate consideration.) This form is precisely what results by incorporating the conditions in Eq. [2] into the power series and regrouping the constants. The LQF requires that B =C [6a] and 4.3.2(D-C) +5-4-3(E-D) + ••• =0 [6b] Thus, the correct form of the Margules expression with two adjustable parameters is w =X(1-X)[A + B +X2-2/3x3)] 171 and the EX4 term must be included before three adjustable parameters are permitted.

Jan 1, 1970

By L. W. McKeehan, W. C. Elmore

THE magnetic powder method, long used for roughly mapping magnetic fields, has recently been refined 1,2 for investigating the microscopic variations in the surface magnetization of ferromagnetic crystals. Bitter' first discovered regular powder patterns connected with the crystal structure of such specimens. Several other investigators3 have used Bitter's original technique, with slight modifications, to study the variation of the patterns with variations in the magnetizing field applied parallel to the surface, and their dependence upon the state of strain, of polish and of crystal cut. All of the explanations of these patterns on metallic ferromagnetics have been couched in general terms. In a preliminary report we have described an improvement in the powder technique which led us to the discovery of a new effect throwing considerable light on the magnetic secondary structure of alpha iron4 and of nickel' single crystals. We now report additional evidence confirming the existence and stability of a magnetic block secondary structure. SPECIMENS The following list describes the specimens used in the present investigation. DESIGNATION DESCRIPTION A1 Silicon ferrite furnished to us by Dr. W. E. Ruder, of the General Electric Co., for which he gave the following typical analysis: C, 0.05; P, 0.038; 5, 0.026; Mn, 0.15; Si, 3.24. Disk, 0.60 cm. diameter, about 0.05 cm. thick.

Jan 1, 1935

By J. B. Hess, C. S. Barrett

TO reach equilibrium between different phases in cobalt-rich alloys requires prohibitively long annealing cobalt-richalloystimes when temperatures are below about 700°C. The fact that a transformation from face-centered cubic to close-packed hexagonal readily tered takes place at temperatures below this in the cobalt-rich solid solutions is not an indication that thermally activated processes occur at an appreciable rate, for the transformation is well established as martensitic in nature. Wide divergence between heating and cooling experiments and high sensitivity to prior heat treatment make it difficult to judge temperatures of equilibrium between the phases.&apos; One object of the present work was to see if the information object of on the relative stability of phases could be gained by substituting plastic deformation for thermal agitation. Procedures were worked out that led to the determination of a diffusionless type of phase diagram, which represents the temperature of of phase equal stability for phases of the same composition, and the technique was applied to the Co-Ni system. Another object of the work was to see whether or not deformation would generate frequent stacking faults when these were thin lamellae of quentstackingfaultsa phase having higher free energy than the parent phase. The alloys were prepared in 80 to 100 g melts from cobalt (with metallic impurities estimated spectrochemically as follows: Ni, 0.05 pct; Fe, 0.001 pct.; Mg, Si, Cu, Cr, Al, < 0.001 pct) and Mond Car-bony1 nickel (with Fe, 0.05 pct; Si, 0.003 pct; C, 0.61 pct.; Cu, 0.001 pct; Co, Cr not detected, < 0.01 pct). The metals were melted in pure Al2O3 crucibles. An atmosphere of argon, that had been purified by passing over hot magnesium chips, was used for the alloys that, by analysis of the portions of the ingots actually used, were found to contain 15.3, 25.7, and 35.0 pct Ni, and vacuum melting (after degassing) was used for those containing 29.4 and 31.5 pct Ni. After induction melting the alloys were allowed to solidify in the crucible, and slices % in. thick x ½ in. in diam were annealed 12 hr at 1350°C for homogenization. These same specimens were used throughout the series of experiments, with annealing treatments of 4 hr at 900°C in purified hydrogen followed by furnace cooling, alternating with the deformation and X-ray tests discussed below. Results Spontaneous transformation was observed on cooling to room temperature in all alloys containing 29.4 pct Ni or less and by cooling the 31.5 pct alloy to — 195°C but was not observed in the 35 pct alloys after cooling to —195°C. These results are in satisfactory agreement with the cooling experiments of Masimoto.4 From these data it is clear that the temperature of beginning transformation M,,, drops to 20°C with the addition of about 30 pct Ni. The test for spontaneous transformation was metallographic. Specimens were thermally polished by annealing 10 hr in hydrogen at 1350°C, then furnace cooled; if trans- formation had occurred there were relief effects visible on the thermally polished surfaces. These markings were narrow straight lines, usually resolvable at high magnification as clusters of fine lines that resembled slip lines. It was concluded that they resulted from displacements on (111) planes, for the number of directions in individual grains often reached but never exceeded four, and lines could always be found parallel to the thermally etched (111) boundaries of annealing twins. The markings were thus consistent with the idea that the transformation occurs by (111) plane displacements (Shockley partial dislocations moving on (111) planes). This was further confirmed by X-ray tests for stacking disorders. Using an oscillating crystal technique previously employed to detect strain-induced faulting in Cu-Si alloys," streaks indicative of the stacking faults were looked for and found on X-ray films of the spontaneously transformed 25.7 pct Ni alloys, as expected by analogy with Edwards and Lipson&apos;s results on pure cobalt." The streaks were much intensified after rolling at room temperature. Transformation induced by plastic strain was investigated as a function of alloy composition and temperature of deformation. A series of tests was made to determine suitable straining and X-raying techniques. Filing was found inferior to abrasion in converting cubic samples to hexagonal, and abrasion was less effective than peening in producing smooth unspotty Debye rings in the X-ray patterns. Because the diffraction lines were broad, Geiger-counter spectrometer records of filings were less sensitive in revealing small amounts of transformed material than X-ray patterns recorded on films in a small diameter camera. After these exploratory tests the following methods were adopted. Specimens that had been annealed at least 4 hr at 900°C and furnace cooled were mounted in a block of aluminum, brought to temperature, and peened thoroughly with a mullite pestle preheated to the same temperature. The specimens were then quenched to room temperature. In peening, a circular area of % in. diam was given 500 blows. A few control tests showed that an additional 1000 blows did not detectably change the proportions of the phases present. The amount of transformation was judged by X-ray reflection patterns from the peened surface, using the innermost four lines of the cubic and the hexagonal patterns with filtered CoKa radiation,

Jan 1, 1953

By E. A. Gulbransen, W. S. Wysong

THE behavior of tungsten and its surface oxides in oxidizing and reducing atmospheres and in high vacua at elevated temperatures is a question of considerable technical importance. The use of tungsten as a metal or as an important component in alloys in high temperature oxidizing atmospheres has been limited because of the unprotective nature of its oxide film and the volatility of its oxide. This paper will present results of a microbalance study1,2 of the following problems: (I) the oxidation behavior in the temperature range of 25 to 550°C (2) the reduction with pure hydrogen of thin oxide films formed on tungsten, and (3) the volatility of thin oxide films on tungsten. Tungsten is an interesting metal to study for the following reasons: (1) although the oxide to metal volume ratio is greater than one, the oxide is not considered protective, (2) the metal readily oxidizes at temperatures from 300° to 550°C (3) the oxides W02 and WO3 are reduced at temperatures as low as 500°C. by hydrogen, and (4) the oxide W02 is volatile at temperatures from 800 to 1100°C. LITERATURE The oxidation of tungsten in its thin film range has not been studied critically. In the thick film range Dunn3 has made the only systematic study. He found the oxidation rate to obey the parabolic rate law in the temperature range of 700 to 900°C. The temperature variation of the oxidation rate constant was found to follow an exponential law of the Arrhenius type. An inflection was noticed in the temperature plot of the rate law constant at 850 to 900°C. This was attributed to a phase change in the oxides. Scheil4 has studied the oxidation rate at 500 and 700°C over long periods of time and found a linear rate law. This result was interpreted as evidence for the presence of a nonprotective film. Pilling and Bedworth5 analyses of the oxide volume to metal volume ratio would indicate that a compact protective film should form. McAdam and Geil6 have studied the oxidation of tungsten in the thin film range using the interference color method. A parabolic rate law was found. Their curves showed that tungsten oxidizes faster than nickel but more slowly than iron. The lattice structures found in the oxidation of tungsten surfaces have been studied by Hickman and Gulbransen.7 They have reported that W03 is the stable oxide in contact with the metallic substrate up to approximately 600°C while W02 forms first at 700°C. Hägg and Magneli8 have recently reported a study of the lattice structures observed in the tungsten oxides using the X-ray diffraction method. In addition to an a-phase W03 and a d-phase W02, they reported the existence of two new phases. A ß&apos; phase, homogeneous between

Jan 1, 1947

By R. M. Brick

AN increased demand for information in regard to the effect of gaseous elements in steel has accompanied the recognition of the importance of grain size. Attempts to correlate grain-size characteristics with gas con-tent, particularly oxygen in solution or in the form of included metallic oxides, have not been universally successful. Certain definite effects of dissolved gases are recognized; specifically, the role of hydrogen in causing internal cracks or "flakes" and that of nitrogen in preventing excessive grain growth of ferritic chromium steels. When irregular behavior or properties are found in a well-known steel and no definite cause for the abnormality may be assigned on the basis of chemical and metallographic tests, dissolved gases are frequently blamed as the culprits. The solubilities of hydrogen1 and nitrogen2 in pure liquid iron are known but of the ternary systems, iron-alloying element-gas, only the Fe-Si-N3 and Fe-Cr-N systems have received attention and here the study was confined to liquid alloys. Krivobok4 published a curve show-ing the solubility of nitrogen in liquid Fe-Cr alloys but gave no informa-tion on the experimental procedure employed. The considerable experimental work reported on the Cr-N binary alloys has been reviewed by Hansen.5 It is generally agreed that the nitride CrN is a stable phase although the existence of nitrides within limited temperature ranges of stability, viz., Cr3N2 and Cr2N, has been disputed, Adcock6 and others7 have reported a eutectic between Cr and CrN at 1580°C., although the supporting evidence is not complete.

Jan 1, 1940